Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
  • B29C44/34—Auxiliary operations
  • B29C44/36—Feeding the material to be shaped
  • B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
  • B29C44/44—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form
  • B29C44/445—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form in the form of expandable granules, particles or beads
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
  • B29C44/34—Auxiliary operations
  • B29C44/3461—Making or treating expandable particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
  • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
  • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
  • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
  • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
  • B29C67/205—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising surface fusion, and bonding of particles to form voids, e.g. sintering
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
  • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
  • B29C67/207—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising impregnating expanded particles or fragments with a binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/22—After-treatment of expandable particles; Forming foamed products
  • C08J9/224—Surface treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/22—After-treatment of expandable particles; Forming foamed products
  • C08J9/228—Forming foamed products
  • C08J9/232—Forming foamed products by sintering expandable particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/10—Homopolymers or copolymers of propene
  • C08J2323/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
  • C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

• the present invention relates to a method for producing molded parts from particle foams and to particle foam molded parts themselves.
• molded parts made from particle foams and their manufacturing processes are known per se.
• molded parts made of EPP expanded polypropylene
• the tools have to be more stable than comparable tools, for example for the production of molded parts from expanded polystyrene (EPS).
• EPS expanded polystyrene
• the production itself can be described as a kind of sintering process in which the individual EPP particles, after filling a mold, are heated and softened by means of water vapor, as a result of which the air trapped in the particles develops a foam pressure, which ultimately turns the particles into a molded part be sintered.
• the present inventors had already developed a method for the production of EPP molded parts which is described in EP 2 937 379 B1. This process manages with moderate process conditions, i.e. essentially without pressure and at temperatures below the melting range of EPP.
• the EPP particles are wetted with an aqueous emulsion of at least one polyolefin modified with chlorine and maleic anhydride and thus functionalized so that they are shaped and bonded to one another (but not sintered or welded) by moderate heating.
• particle foams can continue to be used increasingly for special areas of application. Examples of this are the areas of sport, logistics (storage and transport of mechanical sensitive components), furniture and design (prototype construction) or model construction (custom-made products). Therefore, in addition to an increased need for small series of particle foam molded parts or individual pieces, there is also a need for composite materials made of particle foams and other materials that can be produced easily and quickly in large series, but which do not have the aforementioned disadvantages of the chlorine-containing activator. These processes and products are also of great interest to the automotive sector (keyword e-mobility), particularly with regard to insulation and weight savings.
• the present invention is based on the object of specifying an improved method with which, on the one hand, small series and individual pieces of particle foam molded parts and, on the other hand, large series of composite materials from particle foams and other materials can be produced simply and inexpensively .
• Another goal is simple and inexpensive particle foam moldings and particle foam composite moldings themselves.
• the aqueous emulsion of the at least one polyolefin is an aqueous emulsion which comprises at least one polyolefin converted into the liquid state with an anhydride of an unsaturated carboxylic acid and modified with methacrylic acid ester copolymers.
• the above-mentioned object is achieved by a particle foam molded part which can be obtained by the method according to the invention.
• the present invention generally has the advantage over the prior art that the particle foam particles are added under moderate process conditions Molded parts can be processed which are free of chlorine and its products such as chloroform.
• the first aspect of the present invention relates to a method for producing molded parts from particle foams.
• particle foam refers to thermoplastics which have already been processed by the manufacturer to form individual particles by foaming. These particle foams are in the form of foam beads or foam beads. In their raw state they form free-flowing materials.
• the particle foams have densities in the range from 15 kg / m 3 to 300 kg / m 3 , some special foams also have densities over 300 kg / m 3 , and are characterized by very good specific mechanical properties, high thermal insulation properties and enormous potential for lightweight construction.
• the particle foam particles used in the present invention are essentially finished intermediate products, for example commercially available materials.
• Examples of commercially available materials are for EPP (expanded polypropylene) Neopolen® P from BASF SE and Eperan® ⁇ PP from Kaneka, for EPS (expanded polystyrene) Styropor®, Neopor® and Peripor® from BASF SE, for EPE (expanded polystyrene) Polyethylene) Eperan®-EP from Kaneka or for EPET (expanded polyethylene terephthalate) ArmaShape® from armacell.
• EPC expanded polycarbonate
• ETPU expanded thermoplastic polyurethane
• EPMI expanded polymethacrylimide
• EPBT expanded polybutylene terephthalate
• particle foam can also be used to denote renewable raw materials which are foamed into individual particles by thermal treatment.
• a process analogous to the production of popcorn (“popcorn”) is used for this purpose.
• Water is bound in the starchy tissue of the renewable raw materials used. When these raw materials are heated up quickly, the water changes its physical state very quickly from liquid to gaseous, so that the starch liquefied by the heat and pressure is transformed into the The foamy structure of the tissue expands rapidly and then immediately cools and solidifies.
• the wetting in step b) is preferably carried out by spraying, in particular metered spraying, of the particle foam particles in a closed or in a partially open container.
• aqueous emulsion used according to the invention of at least one polyolefin converted into the liquid state with an anhydride of an unsaturated carboxylic acid and modified with methacrylic acid ester copolymers is referred to below as “aqueous AMP emulsion” for the sake of easier readability.
• the polyolefin which is present as a solid at room temperature under normal conditions, is converted according to the invention into the liquid state of the aqueous AMP emulsion by the anhydride of an unsaturated carboxylic acid, so that it can easily be applied to the particle foam particles.
• aqueous AMP emulsion developed by the present inventors within the scope of the present invention is currently being prepared for commercial sale as a finished activator, for which a safety data sheet has already been created.
• a finished activator for which a safety data sheet has already been created.
• the offer and commercial sale of the finished activator will only be started after the publication of the present application.
• the anhydride of an unsaturated carboxylic acid is particularly preferably maleic anhydride.
• polyolefin according to the Geneva nomenclature, more correctly describes a “polyalkene”.
• the modified polyolefin in the aqueous AMP emulsion can preferably be selected to match or at least materially related to the particle foam material.
• the modified polyolefin in EPP as a particle foam material is especially polypropylene (PP).
• PP polypropylene
• PE polyethylene
• PE polyethylene
• the particle foam particles for wetting in step b) can be mixed in a closed container in which the particle foam particles are moved in the aqueous AMP emulsion.
• the particle foam particles and the aqueous AMP emulsion are pumped together between separate containers.
• the particle foam particles can be filled into a container with a sieve bottom and flooded with the aqueous AMP emulsion without pressure.
• the aim of wetting in step b) is, on the one hand, to completely wet the particle foam particles and, on the other hand, to collect and reuse the aqueous AMP emulsion that is not required.
• the particle foam particles are made up of a very thin solid layer from the aqueous AMP emulsion coated. Despite this solid layer, the particle foam particles remain optically unchanged, but their surface can be functionalized.
• the drying has a particularly positive effect on the physical properties of the functionalizable particle foam particles.
• the drying process can mean that the functionalizable particle foam particles can be packed (e.g. bagged) and made up in a timely manner in order to send them as an intermediate product.
• “functionalizable” is understood to mean that the thin solid layer of the aqueous AMP emulsion on the particle foam particles behaves inertly under ambient conditions (normal pressure of approx. 1 bar, standard temperature of approx. 25 ° C), ie the physical properties (eg the flowability) of the particle foam particles are not significantly changed.
• the thin solid layer of the aqueous AMP emulsion is functionalized in the manner described below only at an elevated temperature, as is specified in more detail below.
• the functionalizable particle foam particles pretreated in this way can be stored for an almost unlimited time before being shaped in step d).
• the functionalizable particle foam particles can be introduced into a simple, suitable shape and, if necessary, compacted. Despite the fact that the particle foam particles can be functionalized according to the invention, their flowability is retained, so that a mold can be filled without any problems.
• step e) the functionalizable particle foam particles are heated at a temperature below this melting range that of the actual material depends, whereby the shaped, functionalizable particle foam particles are functionalized.
• the hitherto non-polar surfaces of the particle foam particles are polarized in that heteroatoms are deposited on them from the functionalizing layer (solid layer from the aqueous AMP emulsion).
• the adhesion of the particle foam particles to one another is no longer brought about by a substitution of hydrogen by chlorine, as is explicitly described in patent EP 2 937 379 B1 granted to the present inventor. Rather, the required adhesion of the particle foam particles to one another is achieved by an adhesion caused by the aqueous AMP emulsion.
• the aqueous AMP emulsion according to the invention as such envelops the particle foam particles and, after drying, forms an extremely thin, mechanically adhering film.
• the anhydride of this unsaturated carboxylic acid which hydrolyzes in water to form the carboxylic acid easily enters into addition reactions because of its unsaturated compounds. As a result, this leads to electrochemical interactions and bonds between the surfaces of the particle foam particles and thus to a stable and permanent connection of the individual particle foam particles to a ready-to-use particle foam molding.
• the heating in step e) can take place in different ways. It can be done quite conventionally in an oven or a corresponding heating device. However, heating between two heating plates is also provided without the need for a completely closed tool. This variant can be used when, for example, continuous production of profiles, semi-finished products or the production of very long molded parts is required. With the methods known today, this can only be done to a very limited extent, if at all.
• energy sources based on radiation laser, infrared
• step f) can take place quite simply after the particle foam molded part has been removed from the mold at ambient temperature. However, the mold as such can also be cooled before the particle foam molded part is removed.
• the inventive method has the advantage over the prior art that the particle foam particles under moderate process conditions, ie at a low pressure of 1 bar to 5 bar, preferably at 2 bar to 3 bar, and at temperatures below the melting range of Particle foam particles are connected to one another (but not sintered or welded).
• a major advantage is that the activating aqueous AMP emulsion does not contain any chlorine or chlorine compounds. This is an important step forward in terms of environmental aspects and health risks. In addition, chlorine is problematic if particle foam moldings that are no longer used are recycled later.
• chlorine-containing activators such as the aqueous emulsion previously used by the present inventors, of at least one polyolefin modified with chlorine and maleic anhydride ("aqueous CMP emulsion”) always contains an amount, albeit a small amount, of chloroform (in the range of ⁇ 0 , 5%). However, even such a small amount must be mentioned in a safety data sheet, which significantly reduces the acceptance of such an activator.
• the present inventors are not aware of any manufacturer or supplier of chlorinated polyolefins who do not also contain a certain amount of chloroform in these chlorinated polyolefins.
• the particle foam moldings produced with the aqueous AMP emulsion according to the invention are qualitatively equivalent to those parts which the present inventors have described in EP 2 937 379 B1.
• aqueous AMP emulsion according to the invention leads to a significant expansion of the application possibilities of the method according to the invention compared to the methods known from the prior art, which is explained further below.
• the aqueous emulsion is a chlorine-free aqueous emulsion of at least one polyolefin which has been converted into the liquid state with maleic anhydride and modified with an acrylate resin.
• a polypropylene modified with the chlorine-free emulsion of an acrylate resin and maleic anhydride is used as the aqueous AMP emulsion.
• the epoxy-terminated silane leads to improved adhesion of the functionalizing layer to the particle foam particles, a high-boiling ester alcohol also being able to serve as a coalescing agent.
• the at least one epoxy-terminated silane is preferably added to the aqueous emulsion of the at least one polyolefin (aqueous AMP emulsion) which has been converted into the liquid state with an anhydride of an unsaturated carboxylic acid and modified with methacrylic acid ester copolymers immediately before step b).
• the epoxy-terminated silane can be added to the aqueous AMP emulsion by simply stirring.
• At least one epoxy resin can be added to the aqueous emulsion of the at least one polyolefin (aqueous AMP emulsion) which has been converted into the liquid state with an anhydride of an unsaturated carboxylic acid and modified with methacrylic acid ester copolymers.
• the epoxy resin is in particular a difunctional bisphenol A / epichlorohydrin derivative, which is preferably undiluted and / or liquid and / or colorless and / or clear.
• the epoxy resin stabilizes the emulsion. Since it is not - as is common with paints, casting resins and the like - with amines or Isocyanates is crosslinked, the epoxy resin acts on the other hand as an elasticizing component in the functionalizing layer.
• a preferred embodiment of the present invention provides that the particle foam particles provided in step a) comprise two or more different particle foam materials.
• Particle foam materials here refer in particular to different plastics such as EPP, EPE, EPC, EPS, EPET, ETPU, EPMI or EPBT and the like.
• the particle foam particles provided in step a) can be a mixture of at least two different types of the respective particle foam material, which makes it possible, for example, to produce porous or partially porous density distributions and gradients.
• the method further includes, before step d), the step dO) providing a foreign material that comprises forming a composite molding with the particle foam particles, wherein in step d) the functionalizable particle foam particles are shaped in direct contact with the foreign material.
• foreign material is initially understood to mean materials that have no chemical and / or physical relationship to particle foam materials, such as textiles, metals, high-density plastics, natural materials (wood, etc.).
• Functional components represent another type of foreign material, for example electrical connection cables or sensors for recording mechanical or physical states (e.g. pressure, temperature, humidity, etc.)
• the particle foam molded parts to be produced can be provided with a lamination, mechanical reinforcement, physical sealing or optical finishing.
• the molded particle foam parts to be produced can also be provided with a functional component.
• some combinations of particle foam materials and foreign materials are shown as examples.
• step dO) can in particular take place in that a mold for the particle foam molded part to be produced is at least partially equipped or lined with a foreign material before the mold is filled with the particle foam particles.
• a Reinforcing material can be provided before particle foam particles are filled around this reinforcing material.
• step dO can also take place alternately, for example by first inserting a foreign material (e.g. a film), then a first pouring of the functionalizable particle foam particles takes place, on which a further foreign material (e.g. in the form of a reinforcing rib) is placed before a final pouring with functionalizable particle foam particles takes place.
• a foreign material e.g. a film
• a further foreign material e.g. in the form of a reinforcing rib
• Another foreign material can also be placed on the final fill before the shaping takes place in step d).
• in direct contact means that the particle foam particles are filled onto, into or around the foreign material without further pretreatment of the foreign material, so that the particle foam particles come into direct contact with the surface of the foreign material.
• the method according to the invention according to this development can be used to produce permanent connections from a wide variety of particle foam materials to a wide variety of foreign materials in order to provide the particle foam moldings obtained in combination with one or more foreign materials. This is particularly possible without subjecting the foreign materials to a special pretreatment, for example with adhesion promoters or the like.
• laminate is understood to mean the joining of several layers of the same or different materials, in particular in order to protect and / or decorate the particle foam molded parts obtained and / or to achieve an addition of favorable material properties.
• reinforcement is familiar to the person skilled in the art. Reinforcements serve in particular to improve the mechanical properties of a molded part.
• Laminations or similar foreign materials are usually implemented in a second work step that is separate from the manufacturing process of the molded part, by first applying a lamination agent (e.g. paint, glue, wax) to the finished molded part before the actual lamination is applied.
• a lamination agent e.g. paint, glue, wax
• a particle foam molding can now be produced with foreign material in a single operation.
• an already finished particle foam molded part is also connected to a further particle foam molded part or provided with a foreign material.
• step b the aqueous emulsion of the at least one which has been converted into the liquid state with an anhydride of an unsaturated carboxylic acid and modified with methacrylic acid ester copolymers
• Polyolefins are applied to the relevant surfaces of the parts to be joined together, dried according to step c) and then joined analogously to step d) before the composite to be created is heated for joining according to the method according to the invention.
• these finished particle foam molded parts do not necessarily have to be produced by the method according to the invention; they can also be commercially available molded parts which, according to the prior art, can only be produced with difficulty or only with great effort.
• This embodiment also enables the production of more complex particle foam molded parts, which according to the invention can be composed of geometrically simple particle foam elements.
• the shaping in step d) takes place at least temporarily under mechanical pressure, which has proven to be advantageous for the stability of the particle foam molded part to be produced.
• the pressure to be applied at least temporarily can be between 1 bar and 5 bar, in particular between 2 bar and 3 bar, depending on the intended use of the particle foam molded part.
• the resulting porous structure offers additional areas of application.
• the mechanical pressure in step d) is only applied temporarily. This means that pressure is only applied to shape or compress the bed of particle foam particles, for example with a stamp, which is then relaxed again. According to the invention, a degree of compression between 1, 5 and 2 is preferred.
• the heating in step e) takes place without pressure.
• “without pressure” means that no (additional) pressure is applied from the outside during the heating, as is customary according to the prior art. Since, according to the present invention, it is preferable not to use any pressure-stable molds, there is also essentially no high pressure to build up during heating.
• “pressureless” also means that the in step d) for shaping the functionalizable particle foam particles can still be maintained at least at the beginning of the heating in step e).
• the pressure applied can be completely relaxed and the method according to the invention can also be carried out.
• a particle foam molded part with a very loose and open structure is obtained from a relatively loose bed of the particle foam particles.
• Such special particle foam moldings are desirable for use as ventilation or drainage.
• these special particle foam molded parts can be used in sandwich structures, where the main concern is to keep the supporting surfaces apart.
• step e heat in step e) at a temperature of 80.degree. C. to 220.degree. C., in particular at 110.degree 160 ° C. This means that the heating can take place “dry”, i.e. without a potentially disruptive liquid phase.
• functional components in particular sensors
• a special embodiment of the present invention provides for the method that in a modified step d) the shaping takes place in individual layers and / or structures of functionalizable particle foam particles.
• desired geometries can first be specified with the functionalizable particle foam particles.
• the heating takes place with a locally focusable energy source, so that the functionalizable particle foam particles are connected to one another in the individual layers or structures.
• This energy source can be, for example, a laser or an infrared source.
• the focusable energy source can heat individual areas of the functionalizable particle foam particles in lines, grids or punctually and only connect there with the method according to the invention.
• the cooling takes place by deactivating the locally focusable energy source, so that initially a partial particle foam molding is obtained. This partial particle foam molding essentially reproduces the geometry specified in modified step d).
• step g at least one further layer and / or one further structure of functionalizable particle foam particles is provided in contact with the partial particle foam molding. In this way, the geometries generated above can be further built up.
• step g) are repeated until the finished particle foam molding is reached.
• This particular embodiment provides a type of 3D printing with the means of the present invention. According to the invention, it is also possible to produce more complex geometries with cavities, undercuts or the like from particle foam particles. It is also possible to insert foreign materials and combine them with those made of particle foam particles or a partial particle foam molding.
• the aim of the present invention is achieved in a second aspect by a particle foam molded part that can be obtained by the method according to the invention.
• Such a particle foam molded part has the advantage that it can be produced more simply and cost-effectively than comparable molded parts from the prior art. In addition, it does not contain any residues of chlorine or chlorine compounds such as chloroform, since the aqueous AMP emulsion according to the invention, which is chlorine-free, is used for production.
• Composites can also be produced in a single process step (“in mold”).
• the particle foam moldings according to the invention can also have a porous or partially porous density distribution in order to obtain tailor-made properties.
• the molded part densities to be achieved can be varied to a greater extent by the method according to the invention. In this way it is not only possible to produce molded parts of different densities, but also partially porous structures, since even small contact areas between the individual particle foam particles lead to a connection and enable the formation of a molded part.
• a further, third aspect of the present invention forms the use of a chlorine-free aqueous emulsion of at least one polyolefin which contains at least one an anhydride of an unsaturated carboxylic acid converted into the liquid state and modified with methacrylic acid ester copolymers, for the production of particle foam moldings, the particle foam being selected from thermoplastics.
• the inventive use of this aspect now enables the production of molded particle foam parts without any residual chlorine content.
• the AMP emulsion used has the advantage over the emulsion used in the present inventors' earlier invention of not only functioning essentially with expanded polypropylene as the polyolefin, but of being applicable to a wide range of polyolefins such as those listed above .
• the fourth aspect of the present invention extends the use of a chlorine-free aqueous emulsion of at least one polyolefin, which comprises at least one polyolefin converted into the liquid state with an anhydride of an unsaturated carboxylic acid and modified with methacrylic acid ester copolymers, to the production of particle foam molded parts, the Particle foam is selected from natural renewable raw materials.
• Naturalally renewable raw materials are used here to describe all natural substances that can be converted into particle foams or foam particles. These include, among other things, starchy natural substances that foam up by themselves when exposed to temperature. Natural substances that can be foamed by external blowing agents are also included.
• the AMP emulsion according to the invention can also be used to combine particle foams made from renewable raw materials to form molded parts.
• a simple example is a type of “popcorn” in which particle foams based on corn starch are processed into molded parts.
• the particle foams based on renewable raw materials are not used in a mixing station like particle foams based on plastic Treated with the AMP emulsion, because depending on the specific material, there is the possibility that these particle foams absorb too much water and thereby swell. It is therefore preferred to apply the AMP emulsion undiluted and by means of a spraying process to the particle foams made from renewable raw materials. After subsequent air drying, the particle foams made from renewable raw materials are just as free-flowing as their plastic-based equivalents and can be processed into molded parts using the same process as these.
• a further, fifth aspect of the present invention consists in the use of a chlorine-free aqueous emulsion of at least one polyolefin, which comprises at least one polyolefin converted into the liquid state with an anhydride of an unsaturated carboxylic acid and modified with methacrylic acid ester copolymers, for the permanent connection of metallic surfaces.
• the AMP emulsion according to the invention is not only suitable for the production of molded parts from particle foams on an artificial or natural basis, but also for the permanent connection of metallic surfaces, i.e. for connecting metal objects to one another.
• the metals that can be used are not restricted as long as the objects produced from them have a smooth or flat surface for connection to a similarly opposite smooth or flat surface.
• pairings made of the same metals can also be connected, the pairings made of different metals, without being subject to particular restrictions.
• contact surfaces are preferably provided with a thin layer of the AMP emulsion according to the invention by dabbing or wiping. After complete drying, the treated parts are then joined together with the maximum possible contact area, tempered at an elevated temperature and held together in a stable manner until they cool. In practice, a time of one to 5 minutes, in particular one to two minutes, and at a temperature of 100 ° C. to 140 ° C. has proven to be particularly suitable.
• the chlorine-free aqueous emulsion is in particular an aqueous emulsion of at least one polyolefin which has been converted into the liquid state with maleic anhydride and modified with an acrylate resin.
• FIG. 1 shows a photographic illustration of a particle foam molded part made of EPP using the method according to the invention
• FIG. 2 shows a photographic illustration of a particle foam molded part made of EPP with an applied textile material, produced using the method according to the invention
• FIG. 3 shows a photographic illustration of a particle foam molded part made of EPP with an applied aluminum foil, produced using the method according to the invention
• FIG. 4 shows a photographic illustration of a particle foam molded part made of EPP with an aluminum sheet applied using the method according to the invention
• FIG. 5 shows a photographic illustration of a particle foam molded part made of EPP using the method according to the invention with an applied GRP plate
• FIG. 6 shows a photographic illustration of a particle foam molded part made of EPP using the method according to the invention with an applied steel sheet
• FIG. 7 shows a photographic illustration of a particle foam molded part made of EPP with an applied wood decor using the method according to the invention
• FIG. 8 shows a photographic illustration of a particle foam molded part made of EPC with an applied wood decor using the method according to the invention
• FIG. 9 shows a photographic illustration of a particle foam molded part made of EPC with an organic sheet applied using the method according to the invention
• FIG. 10 shows a photographic illustration of a particle foam molded part made of EPS with an applied GRP plate, produced using the method according to the invention
• 11 shows a photographic illustration of a particle foam molded part made of EPS with a steel sheet applied using the method according to the invention
• FIG. 12 shows a photographic illustration of a particle foam molded part made of ETPU with an applied textile material, produced using the method according to the invention
• FIG. 13 shows a photographic illustration of a particle foam molded part made from EPP and ETPU using the method according to the invention
• 16 is a photographic illustration of a semi-automatic mixing device
• 17 is a photographic illustration of a semi-automatic mixing device
• 21 is a photographic illustration of a closed mold
• FIG. 24 shows a photographic illustration of a particle foam molded part made from foamed corn granulate using the method according to the invention, in a top view;
• FIG. 25 shows a photographic illustration of the particle foam molding shown in FIG. 24 made of foamed corn granulate in a sectional view
• 26 shows a photographic illustration of a particle foam molded part made from foamed corn granules with an embedded power cable in a sectional view, produced using the method according to the invention
• FIG. 27 is a photographic illustration of aluminum blocks connected with the aqueous AMP emulsion according to the invention.
• 29 is a photographic illustration of brass rings connected to the aqueous AMP emulsion according to the invention.
• FIG. 30 is a photographic illustration of steel bolts connected with the aqueous AMP emulsion according to the invention.
• FIG. 31 shows a photographic illustration of metal parts made of steel and aluminum and bonded with the aqueous AMP emulsion according to the invention
• FIGS. 1 to 13 show the large bandwidth of possible combinations of particle foam particles with foreign materials for the formation of particle foam molded parts. These photographic images are self-explanatory in themselves, but cannot exhaustively portray the possible combinations. Successful trials have been carried out with EPE. All of the particle foam materials shown in FIGS. 1 to 13 can be combined with all of the foreign materials shown there.
• the particle foam molded parts shown in FIGS. 1 to 13 were each produced in a single operation, using what is known as an in-mold process.
• the foreign materials can preferably be selected from foils, textiles, plates, solid bodies and combinations thereof.
• the foils can be both polymer foils and metal foils.
• the textiles can be natural fibers, polymeric fibers, metallic fibers and combinations thereof and be present as woven fabrics, scrims, rovings, knitted fabrics, braids, knitted fabrics and combinations thereof. Plates are understood to mean bodies whose area is a multiple of their thickness.
• the panels can also be made from natural materials, polymeric materials, metallic materials, and combinations thereof.
• Solid bodies mean bodies whose three dimensions are essentially of the same order of magnitude. These bodies can also include natural materials, polymeric materials, metallic materials, and combinations thereof.
• EPP expanded polypropylene
• EPC expanded polycarbonate
• EPS expanded polystyrene
• ETPU expanded thermoplastic polyurethane
• EPE expanded polyethylene
• GTK glass fiber reinforced plastic.
• organic sheet describes a fiber composite material in which fibers such as glass, aramid (aromatic polyamides) or carbon are placed in a thermoplastic matrix.
• a finely divided aqueous emulsion of a polyolefin modified with maleic anhydride is mixed with 1% to 2% (based on the polyolefin solids) of an epoxy-terminated silane.
• This silane can be added to the aqueous AMP emulsion simply by stirring.
• the desired reactions should not take place in the storage container, but only when the particle foam particles are functionalized.
• aqueous AMP emulsion to a pH of 8.3 to 8.4 by adding diethylethanolamine.
• diethylethanolamine At the Application of the following film formation increases the pH to 8.8 to 9.2 and the following reactions occur:
• Step 1 preparing the particles
• Particle foam based on PP e.g. under the brand name ARPRO from JSP, Neopolen P from BASF or Eperan P from Kaneka
• Particle foam based on PS is known, among other things, under the name Styropor from BASF.
• Other processable particle foams are e.g. Piocelan from Sekisui, Infinergy from BASF, ArmaShape from Armacell, to name just a small selection.
• the particle foam particles are mixed with a small amount of the activator (i.e. the aqueous AMP emulsion according to the invention) in a suitable plant / device / vessel. It is important to ensure that the particle foam particles have a film that is as uniform as possible on the surface. Overdosing does not damage the production process, but can extend it if necessary, which is uneconomical. After uniform mixing, the particle foam particles that can now be functionalized are dried again in the mixing device until they are free-flowing. The activator is now firmly attached to the surface of the functionalizable particle foam particles.
• the activator i.e. the aqueous AMP emulsion according to the invention
• Step 2 Intermediate storage or drying of the particle foam particles
• Step 3 preparing the mold and machine
• the general basic structure is very similar to an injection molding tool. It is important that the intended mold can reproduce fast and absolutely dry cycles over a large temperature curve, whereby the temperature window can be between 60 ° C and 220 ° C, depending on the particle foam used.
• the use of external temperature control devices, such as those also known from classic injection molding, has proven itself here. Variothermal controls can also be used to advantage.
• the mold intended for use must be provided with a suitable non-stick coating, e.g. with PTFE (polytetrafluoroethylene / Teflon®), so that a bond between the particle foam and the mold surface that cannot be detached is avoided.
• the mold is built on a correspondingly modified particle foam press. The modifications largely relate to the integration of the temperature control unit and the adaptation of the process software to the steam- and water-free process.
• Step 4 filling the mold
• the functionalizable particle foam particles are then filled into the molding tool by means of a conventional filling device for particle foam, pressure hoses and filling injectors.
• the filling device enables the functionalizable particle foam particles to be compressed in the molding tool (pneumatic, mechanical or in combination), the compression rate being up to 50% of the original bulk density.
• the compression in the molding tool significantly influences the subsequent density of the molded part.
• the materials to be connected i.e. foreign materials
• the positions of the fill injectors remain free or are arranged in such a way that the inflow of the functionalizable particle foam particles is not hindered.
• Step 5 process flow
• the mold filled with the functionalizable particle foam particles is now brought to the required process temperature by means of the temperature control device already described.
• the duration of the heating depends largely on the particle foam used and the maximum wall thickness of the molded part.
• the mold is cooled to a demolding temperature of approx. 40 ° C to 80 ° C.
• the mold After reaching the demolding temperature, the mold is opened and the formed part usually remains in the so-called hood part of the mold.
• the molded part is then removed either manually or with the aid of suction cups and removal devices such as handling robots. Mechanical demolding using a special ejector function of the filling injectors is also possible.
• the formed part can be processed further immediately. Further process steps are not required.
• a general production sequence is shown in FIGS. 15 to 23.
• FIG. 15 shows a schematic representation of a suitable, fully automatic mixing device.
• FIG. 16 shows a photographic image of a semi-automatic mixing device in which particle foam particles and activator have already been mixed but not yet dried. The photographic image of the semi-automatic mixing device is then shown in FIG. 17, in which particle foam particles and activator are mixed and dried. The free-flowing, functionalizable particle foam particles can now be removed.
• FIG. 18 shows a photographic image of an opened molding tool which is installed on the prepared machine.
• the (green) tool surface is created by the non-stick coating with Teflon.
• Teflon On the right half of the mold, the closed deep-hole bores for the indirect temperature control are clearly visible.
• FIG. 19 shows a photographic image of the hood side of the molding tool. The two filling injectors and the completely closed mold surface can be seen.
• FIG. 20 A filling device is shown in FIG. 20 on the basis of a photographic image.
• the functionalizable particle foam particles are located in the pressure vessel.
• the functionalizable particle foam particles are fed to the filling injectors during the process via the partially transparent pressure hoses.
• FIG. 21 shows a photographic image of the closed mold.
• FIG. 22 shows a photographic image in which the particle foam molded part formed is, for example, a black EPP that is still in the side of the hood.
• FIG. 23 shows a photographic image in which the particle foam molding formed is, for example, white EPS that is still in the side of the hood.
• FIGS. 24 to 26 show the further bandwidth for the use of the aqueous AMP emulsion according to the invention, in which in this embodiment a foamed corn granulate can be processed into particle foam molded parts.
• the procedure is essentially the same as for particle foams made of plastics.
• dimensionally stable and mechanically solid particle foam molded parts are obtained, as can be seen from FIGS. 24 and 25.
• a power cable was embedded in the foamed corn granulate and subjected to shaping together with it.
• FIGS. 27 to 32 examples are given for very special embodiments and uses in which metals are bonded to one another by means of the aqueous AMP emulsion according to the invention. It can be seen in FIG. 27 that two aluminum blocks were connected to one another in a manner which was not to be expected from the aqueous AMP emulsion according to the invention. The right of the two aluminum blocks rests partially on a table top and is held there by hand, while the left aluminum block is free in the air and is only held by the connection according to the method according to the invention.
• FIG. 30 shows two steel bolts connected to one another by the connection according to the method according to the invention, the left of the steel bolts partially resting on a table top and being held there by hand, while the right steel bolt is free in the air.
• What is remarkable here is the small connection area between the two steel bolts in comparison to the other examples against the background of the high density (high weight) of the two parts.
• FIGS. 31 and 32 show that, according to the method according to the invention, pairs of different metals can also be firmly connected to one another, in FIG. 31 the pairing of steel and aluminum, in FIG. 32 the pairing of steel and brass, with the heavier steel bolt in the latter hangs freely and is only held by the connection according to the method according to the invention on the brass part.

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• 2019
  • 2019-07-18 DE DE102019119488.1A patent/DE102019119488A1/de active Pending
• 2020
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