WO2009072150A1 - Procédé et installation pour la production de thermoplastiques composites et matières ainsi obtenues - Google Patents

Procédé et installation pour la production de thermoplastiques composites et matières ainsi obtenues Download PDF

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Publication number
WO2009072150A1
WO2009072150A1 PCT/IT2007/000841 IT2007000841W WO2009072150A1 WO 2009072150 A1 WO2009072150 A1 WO 2009072150A1 IT 2007000841 W IT2007000841 W IT 2007000841W WO 2009072150 A1 WO2009072150 A1 WO 2009072150A1
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Prior art keywords
materials
filler
organic solvent
polymers
thermoplastic
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Inventor
Maurizio Avella
Maria Emanuela Errico
Giuseppe Fabozzi
Cristina Lucchesi
Giovanni Lucchesi
Mario Malinconico
Maurizio Petrucci
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PONZECCHI EDOARDO
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PONZECCHI EDOARDO
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Priority to PCT/IT2007/000841 priority Critical patent/WO2009072150A1/fr
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    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/30—Polymeric waste or recycled polymer
    • 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
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/02—Copolymers with acrylonitrile
    • 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
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides

Definitions

  • the present invention concerns a process and a plant for the production of thermoplastic composites and materials made therefrom. More in particular, the present invention concerns a process in which thermoplastic materials and fillers are blended to produce a composite material in which at least one between the thermoplastic material or materials and the filler o fillers are recycled material, at least in part.
  • composite thermoplastic materials we mean materials consisting of an "emulsion" of filler particles of various forms and natures in rigid or flexible thermoplastic polymers. These materials combine the low density, typical of plastic materials, with the rigidity and strength of the fillers, both as particles and as fibrous reinforcements and-with acceptable costs; for this reason they are now widely used in sectors such as means of transportation by land, sea and air, in building construction, furnishing and alike.
  • Composite materials consisting of a resin matrix and a reinforcing component that can be of various kinds, such as powders (CaC ⁇ 3 , etc.) fibers (glass, polymers, graphite), ranging from 30 to 60% by weight, are known; for economic reasons, in the most widely used composites the fibrous component consists of glass fibers (which may be long or short), while for reasons of resistance to high temperatures the polymer matrix often consists of thermosetting materials; thermoplastic composites filled with 30-50% (w/w) of short fibers, particularly in the automotive sector, are known.
  • the object of the present invention is thermoplastic composite materials.
  • One particular object of the invention is materials in which at least part of the polymers or filler, or both, is recycled materials.
  • homogeneous regenerated polymers in the form of PP, PE, PET, PUR, PA, PS-EPS, ABS, PC, PMMA, PVC, etc. deriving from process waste as well as from selective waste collection from different product sectors such as packaging (films, bottles, drums, shopping bags, etc.), agriculture (films for greenhouses covering, films for silage, irrigation hoses, etc.), textiles (tubes for yarn cones, synthetic fibers, nonwoven fabrics, etc.), motor vehicles (dashboards, tank, bumpers and padding, exhausted batteries, etc.), electrical/electronic appliances (TV cases, refrigerators, computers, etc.), containers for environmental hygiene (waste bins, bells, etc.), building construction and furniture (films, pipes and joints, window frames, fittings, etc.); heterogeneous regenerated polymers consisting of different polymer matrixes mainly coming from selective waste collection.
  • packaging films, bottles, drums, shopping bags, etc.
  • agriculture films for greenhouses covering, films for silage, irrigation
  • These recycled materials can be in the form of granules, pellets, flakes, ground materials, micronized materials, semifinished products (such as bars and sheets, etc.).
  • the fillers known and used for this invention can be in powder form, granules or fibers, and can be of mineral, vegetable or even animal nature. These fillers can perform different functions, from increasing rigidity, thermoregulation, phonoregulation, resistance to abrasion, fire, ultraviolet rays, etc. to mere pigmentation and cost reduction.
  • the most widely used fillers are mineral- or fibrous-based of vegetable origin, but often they are also obtained from other production cycles, after being ground, granulated or treated in other ways, such as inert materials like ash obtained from energy production plants and waste materials from construction activities.
  • this secondary raw material (recycled), valorized by being compounded with resins, either virgin or also recycled, can represent a strategy capable of giving added value to the material and developing its potential fully.
  • other types of manufacturing waste or products and by-products of agriculture and industry can be used, such as ash from biomasses with or without pretreatment, sand and quarry dust, metal powders, acetone-insoluble polymers, sawdust, fibrous waste and residues from agriculture, construction materials, textile scraps, residues from leather tanning and in general anything that normally can be considered as a cost since it must be disposed in landfill and often in special landfill sites.
  • a blown product made from HDPE must be produced using at least 50% granules of recycled HDPE (high density polyethylene), in turn containing no less than 95% post- consumption plastics (i.e. materials from selected waste collection) while a product made of PET (Polyethylene Terephthalate) by injection molding must be produced using at least 70% granules or flakes of recycled PET, in turn containing not less than 95% post-consumption plastics.
  • HDPE high density polyethylene
  • PET Polyethylene Terephthalate
  • Another problem is caused by the fact that materials from selected waste collection comprise different types of blended polymers and it is therefore difficult to recycle the above-mentioned blends of heterogeneous polymers as they are often composed of polymers that are incompatible.
  • the known techniques for processing materials to be recycled normally used require chemical reactions and high cost procedures.
  • the aim of this invention is to obtain materials with a thermoplastic matrix and very high filler content, using simple chemical-physical procedures that do not involve any chemical reactions, preferably starting from materials normally destined to be disposed in landfill, or incinerated, or in any case used for products having a low added value.
  • a further aim of this invention is to obtain stable materials which can be processed in machines that are normally used for injection molding and with low costs. Still a further aim of the present invention is to provide an industrial process at low energy and economic cost. Another aim of the invention is to provide a process that will permit recycling of plastics from urban and industrial waste. Another aim of this invention is to provide a plant for the production of composite thermoplastic materials with very high filler content. Summary of the invention
  • thermoplastic composite materials obtained in accordance with this invention comprise preferably more than 60% by weight of filler with respect to the end product (free of organic solvents and dried) and may contain up to about 94-95% by weight of filler with respect to the composite material.
  • the end product effectively consists of an emulsion of fillers in the solubilized polymer matrix and is therefore endowed with a uniform structure as the fillers are uniformly distributed in the thermoplastic. This differentiates it from products with high filler content already known in the art, where the fillers are irregularly distributed in the polymer.
  • the filler can be produced with polymers different from and incompatible with the materials used for the base in solution (PS, ABS polyvinylidene fluoride).
  • the polymers used as filler generally (and preferably) have a glass transition temperature lower than that of polystyrene (PS) and make it possible, in addition to or in substitution of ABS, to provide the resulting composite material with characteristics of flexibility and tenacity that PS alone is incapable of.
  • PS polystyrene
  • the filled composite obtained with the invention is generally extruded or drawn and in any case subjected to a process of plastification and subsequent granulation, a process that leads to better amalgamation of the incompatible polymers with the polymer base.
  • the high quantity of filler is dispersed uniformly in the polymer base so as to obtain, in effect, an emulsion of particles of various size and nature, in rigid or flexible thermoplastic polymers the binder of which ensures their uniformity at the micro and macroscopic level.
  • the filler which can be composed of various types of materials, contributes to the attainment and maintenance of its technological properties.
  • the process employed makes it possible to obtain the compatibility of different polymers, that is, to obtain a homogeneous material composed of different polymers, by including polymer materials in the PS and/or ABS base in solution, in the form of "thermoplastic filler", preferably in granular form with dimensions of less than 0.1 mm.
  • the fillers (inorganic or not) used have a granulometry in the range between 0.003 mm and 0.5 mm, with preference up to 0.1 mm.
  • the quantity of "thermoplastic filler” is between 0% and 50% of the total filler of the blend.
  • Polymers suitable for transformation into thermoplastic filler that is to say a filler of thermoplastic materials, for example HDPE, PP, PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PA6, PA66 (polyamide 6 and 66), POM (polyoximethylene).
  • the filler consists entirely of the above- mentioned thermoplastic materials (that is, there is only the "thermoplastic filler”), in the desired granulometry.
  • the process makes it possible to obtain the compatibility of different polymers for a macroscopically heterogeneous end product, whose properties will depend on the composition used.
  • the process used makes it possible to produce the composite materials processable at low temperatures.
  • the process employed does not imply significant changes to the traditional systems and machinery used for molding the polymers, other than a different organization of the production line.
  • the process employed makes it possible to obtain high quality esthetic effects.
  • the plant 1 according to the invention for the production of composite thermoplastic materials with a very high filler content comprises a coarse grinder 2, a metal separator 3; a fine grinder 4; a system 5 for feeding the emulsifying substances; a mechanical feeder 6 for plastic material in granular form or as secondary raw material, after being ground, crushed, flaked, etc.; a silos 7 with vertical mixing auger conveyor in stainless steel equipped with a suction system 8 for the recovery of fumes; a mixing system 9; a dosage system 10 using a system of load cells; a crusher/cuber 11 ; a conveyor belt 12 with a stainless steel tank 13 equipped with a temperature control system; a suction system 14 for the recovery of fumes; a ventilated furnace 15 with an internal conveyor system 16 and fume recovery 17; a complete extrusion system 18, with a gravimetric dosage system 19 provided with load cells for the addition of additives; a cooling system 20; a cutter 21 ; and a bagging machine 22.
  • the materials to be recycled are initially fed into in the coarse grinder 2, then passed into system 3 where they are separated from metals, and finally ground in the fine grinder 4.
  • the granules of ground plastic material are conveyed, by a mechanical feeder 6, in a stainless steel silos 7 in which the emulsifying substances are also fed by a feeding system 5 so as to achieve the solubilization of the polymers in organic solvent and to obtain an emulsion.
  • Said stainless steel silos 7 is equipped with a mixing auger conveyor and a suction system 8 for recovery of fumes.
  • the solubilized polymers are cold mixed with the inert fillers in powder form in a mixing system 9 in order to obtain a homogeneous product.
  • the inert materials and additives making up the filler components are added by means of a load-cell dosage system 10.
  • the product obtained is passed through a cuber/crusher 11 for optimized cutting of the semi-finished materials loaded; however this passage is not strictly necessary since many processing machine will accept even irregular shapes of material.
  • the mixture in acetone can be poured into water with mechanical paddle stirring so as to break the mass into small fragments.
  • the cubed/crushed material is passed in water into a stainless steel tank 13, equipped with a temperature control system, on a conveyor belt 12 also immersed in water. In this step, there is also a suction system 14 for fume recovery. After the passage in water, the material is conveyed by the belt 16 into a ventilated furnace 15 provided with a fume recovery system 17.
  • the material is drawn at a temperature above 200° C by sending it through an extruder 18, preferably equipped with a double counter-rotating screw, where other additives can be added by a gravimetric dosage system 19 provided with load-cells, to characterize the final products, such as pigmentation additives.
  • a gravimetric dosage system 19 provided with load-cells, to characterize the final products, such as pigmentation additives.
  • the material On exiting the extruder 18 the material is cooled in water by a cooling system 20, then passed through a cutter 21 and finally packaged by a bagging machine 22.
  • the process according to the invention provides for creating a solution of polymeric thermoplastic base in which one or more filler materials can be dispersed and removing the organic solvent from the blend thus obtained by evaporation or water extraction.
  • the polymers used to prepare the solution are PS (polystyrene), ABS and other polymers, such as polyvinylidene fluoride, which can be solubilized in volatile organic solvents and preferably in the solvents indicated here below. More in particular, suitable solvents are aliphatic ketones, aromatic ketones, amide solvents, aliphatic and aromatic chlorinated solvents.
  • the organic solvent employed is selected between acetone and other water-miscible solvents or mixtures thereof, in consideration of their low environmental impact, ease of removal and condensability, low cost.
  • thermoplastic filler of incompatible polymers ground to a granulometry between 0.003 and 0.1 mm, either in combination with other fillers (minerals, fibers, etc.) or alone.
  • the process continues then with removal of the organic solvents from the filled blend; said removal can be accomplished by evaporation (necessarily when water-immiscible solvents like chlorinated solvents are used) or by extraction in water of the organic solvent of the filled blend, the process being possible if water-miscible solvents, i.e. water-soluble, are used.
  • the water temperature is preferably between 40 and 80 0 C, most preferably 65-70 0 C, at the latter temperatures obtaining rapid extraction of the acetone from the filled polymer mass. At 40 0 C extraction is slower and at even lower temperatures, for example at 25°C, part of the acetone remains instead in the filled polymer mass.
  • the solidified mass is dried to remove water and any residue of acetone or other organic solvent.
  • the organic solvent removal by drying in the furnace occurs at temperatures suitable to cause evaporation of the organic solvent, such as between 35°C and 70°C in the process using acetone.
  • the dried product is then extruded and reduced, for example, into pellets in the manner known in the art; during extrusion, or drawing, other additives can be added to the polymer mass previously filled.
  • additives can be added to the polymer mass previously filled.
  • the weight ratio between said at least one polymer and the above-mentioned at least one organic, volatile solvent is preferably in the range between 20/80 and 70/30 (w/w); both PS and ABS can be used in a 100% concentration of soluble polymer, that is to say, as the materials composing 100% of the polymeric matrix in which the fillers are dispersed, or in intermediate blends between these extreme values, depending on the flexibility degree and on the characteristics to give to the final product.
  • the blend includes acetone from 10 % to 30%, ABS from 20 to 50% and a filler consisting of polyamide from 10% to 40% and fiberglass from 20% to 70%, all percentages being by weight.
  • the acetone is between 10% and 20%
  • the ABS is between 20% and 40%
  • the polyamide is between 10% and 30%
  • the fiberglass is preferably between 30% and 60% by weight of the blend in the presence of organic solvent.
  • the blend includes from 10% to 30% of acetone, preferably from 10 to 20%, and from 20% to 50% of PS, preferably from 20 to 40%, to which a filler is added consisting of 50 to 70% of inert material from quarry or other waste, preferably from 60 to 70%, and 20 to 5% of fiberglass, preferably from 10 to 5%.
  • This blend gives a final product having processability, mechanical and impact properties, surface aspect, abrasion resistance higher than similar materials produced in the absence of organic acetone solvent.
  • the preparation provides for a blend consisting of 10% to 30% of acetone, preferably from 10 to 20%, and from 20% to 50 % of PS, preferably from 20 to 40%, to which a filler is added consisting of 50 to 70% of inert minerals, preferably from 60 to 70%, from 10 to 5% of limestone, preferably from 7 to 5%, providing a material with processability, mechanical and impact properties, surface aspect, and abrasion resistance higher than similar materials produced without organic acetone solvent.
  • a filler consisting of 50 to 70% of inert minerals, preferably from 60 to 70%, from 10 to 5% of limestone, preferably from 7 to 5%
  • Another embodiment provides for use of a blend consisting of 10% to 30% of acetone, preferably from 10 to 20%, and from 20% to 50 % of PS, preferably from 20 to 40%, to which a filler is added consisting of 50 to 70% of bottom ash (from power plants), preferably from 60 to 70%, and 20 to 5% of fiberglass, preferably from 10 to 5%.
  • the resulting composite material has processability, mechanical and impact properties, surface aspect, abrasion resistance higher than similar materials produced in the absence of organic acetone solvent.
  • a further example concerns a blend consisting of 10% to 30% of acetone, preferably from 10 to 20%, and from 20% to 50% of PS, preferably from 20 to 40%, to which a filler is added consisting of 50 to 70% of waste powder from aluminum processing, preferably from 60 to 70%, and 20 to 5% of fiberglass, preferably from 10 to 5%, with processability, mechanical and impact properties, surface aspect, and abrasion resistance higher than similar materials produced without organic acetone solvent.
  • Another example regards a blend consisting of 10% to 30% of acetone, preferably from 10 to 20%, and from 20% to 50 % of PS, (expanded polystyrene from landfill), preferably from 20 to 40%, to which a filler is added consisting of 20 to 50% of undifferentiated plastic from landfill, preferably from 20 to 30%, and inert minerals from 50 to 70%, preferably from 50 to 60% and from 20 to 5% of fiberglass, preferably from 10 to 5%, with processability, mechanical and impact properties, surface aspect, and abrasion resistance higher than similar materials produced without organic acetone solvent.
  • PS expanded polystyrene from landfill
  • a filler consisting of 20 to 50% of undifferentiated plastic from landfill, preferably from 20 to 30%, and inert minerals from 50 to 70%, preferably from 50 to 60% and from 20 to 5% of fiberglass, preferably from 10 to 5%, with processability, mechanical and impact properties, surface aspect, and abrasion resistance higher than similar materials produced without organic acetone solvent.
  • Example 1 Ash-based materials from power plants using fossil fuel.
  • an acetone emulsion of a series of materials is produced.
  • This emulsion is obtained by dispersing in 1.5 liters of acetone 1 kilo consisting of (on a base of 100) 50 parts fly ash (Enel, Brindisi), 30 parts fiberglass (FV, produced by vetrofil ) 15 parts ABS (produced by BASF), 5 parts PA6 (produced by Rhodia).
  • the product obtained is dried in a ventilated furnace at 70 0 C, while the acetone in gas phase obtained is condensed using a cooling coil with water or coolant and collected so as to be completely recycled.
  • Example 2 an acetone emulsion of a series of materials is produced.
  • This emulsion is obtained by dispersing in 1 ,5 liters of acetone 1 kilo consisting of (on a base of 100) 50 parts fly ash (Enel, Brindisi), 30 parts fiberglass (FV, produced by vetrofil ) 15 parts ABS (produced by BASF), 5 parts PA6 (produced by Rhodia).
  • the product obtained is poured in water at 70 0 C, obtaining immediate extraction of the acetone by the water and thus complete solidification of the product.
  • Example 3 According to this example, an acetone emulsion of a series of materials is produced. This emulsion is obtained by dispersing in 1 ,5 liters of acetone 1 kilo consisting of (on a base of 100) 50 parts wollastonite ash, 30 parts fiberglass (FV, produced by vetrofil ) 15 parts ABS (produced by BASF), 5 parts PA6 (produced by Rhodia).
  • the product obtained is dried in a ventilated furnace at 70 0 C, while the resultant gas phase acetone is condensed using a water or coolant cooling coil and collected so as to be completely recycled.
  • the granulate is molded in an injection press for the production of handlebar test specimens and tested in accordance with the internationally accepted standards listed in Table 1.
  • Example 4 - According to this example, an acetone emulsion of a series of materials is produced.
  • This emulsion is obtained by dispersing in 1 ,5 liters of acetone 1 kilo consisting of (on a base of 100) 50 parts wollastonite ash, 30 parts fiberglass (FV, produced by vetrofil ) 15 parts ABS (produced by BASF), 5 parts PA6 (produced by Rhodia).
  • the product obtained is poured in water at 70 0 C, obtaining immediate extraction of the acetone by the water and thus complete solidification of the product.
  • the resultant water/acetone mixture is distilled and the condensation products are returned to the production cycle.
  • the granulate is molded in an injection press for the production of handlebar test specimens and tested in accordance with the internationally accepted standards listed in Table 1.
  • Table 1 The following are other illustrative and non limiting examples of the application of said process to materials from the recycle chain, and the functional properties obtainable with these materials. In particular these examples call for the use of floral ABS, undifferentiated plastics from urban waste and granules of quarry waste or inert construction site waste.
  • Example 5 - According to this example, an acetone emulsion of a series of materials is produced.
  • This emulsion on a base of 100, consists of 30 parts of granules from quarry waste or inert construction site waste, 10 parts fiberglass (FV, produced by vetrofil ) 15 parts ABS (produced by BASF), 30 parts of undifferentiated polymers (pulverized) from urban waste (PS PE PP POM PMMA PET) and 15 parts acetone.
  • the product obtained is dried in a ventilated furnace at 70°C, while the resultant gas phase acetone is condensed using a water or coolant cooling coil and collected so as to be completely recycled.
  • the granulate is molded in an injection press for the production of handlebar test specimens and tested in accordance with the internationally accepted standards listed in Table 2.
  • Example 6 an acetone emulsion of a series of materials is produced.
  • This emulsion on a base of 100, consists of 30 parts of granules from quarry waste or inert construction site waste, 10 parts fiberglass (FV, produced by vetrofil) 15 parts ABS (produced by BASF), 30 parts of undifferentiated polymers from urban waste (PS PE PP POM PMMA - polymethylmetacrylate - PA), and 15 parts acetone.
  • the product obtained is poured in water at 70 0 C, obtaining immediate extraction of the acetone by the water and complete solidification of the product.
  • the resultant water/acetone mixture is distilled and the condensation products are returned to the production cycle.
  • the granulate is molded in an injection press for the production of handlebar test specimens and tested in accordance with the internationally accepted standards listed in Table 2.
  • the process is carried out at lower temperatures than those indicated above, generally around 30-50 0 C with removal of the organic solvent by evaporation.
  • the base polymer is solubilized in ketone (acetone) in the ratio of polymer to organic solvent ranging between 1/1 up to 1/1.5 depending on its characteristics,
  • a filler of various composites is prepared, as listed above, also containing limestone, said limestone being present in an extent of 5% of the total mass
  • the filler thus obtained i.e. the filler containing up to 5% limestone, is blended with the polymer solubilized in ketone.
  • the maximum quantity of filler with respect to the finished composite material (without organic solvent) is 85% by weight.
  • the material thus obtained (containing the organic solvent) is ready for use in the form of moldable and shapeable paste for the production of tiles, objects, flooring and similar products.
  • the finished molded or shaped product obtained is dried in a furnace at 40°, while the acetone obtained is condensed using a water or coolant cooling coil and collected so as to be completely recycled.
  • Example 7 According to this example, an acetone emulsion of a series of materials is produced. This emulsion, on a base of 100, consists of 75 parts granules from quarry waste or inert construction site waste, 5 parts limestone, 10 parts expanded polystyrene from urban waste and 10 parts acetone. The product obtained is a shapeable mass with which molded elements are produced. The samples obtained were dried in a furnace at 40° and left wet for 7 days. The tests performed refer to the NORMAL (standard CNR - Consiglio Nazionale delle Ricerche, Italy) except for the HDT. The results are shown in Table 3.
  • NORMAL standard CNR - Consiglio Nazionale delle Ricerche, Italy
  • Example 8 According to this example, an acetone emulsion of a series of materials is produced.
  • This emulsion on a base of 100, consists of 50 parts granules from quarry waste or inert construction site waste, 25 parts fiberglass, 5 parts limestone, 10 parts expanded polystyrene from urban waste and 10 parts acetone.
  • the product obtained is a shapeable mass with which molded elements are produced.
  • the samples obtained were dried in a furnace at 40° and left wet for 7 days. The tests performed refer to the NORMAL except for the HDT. The results are shown in Table 3.
  • Example 9 According to this example, an acetone emulsion of a series of materials is produced.
  • This emulsion on a base of 100, consists of 50 parts granules from quarry waste or inert construction site waste, 25 parts tomato fiber, 5 parts limestone, 10 parts PLA and 10 parts acetone.
  • the product obtained is a shapeable mass with which molded elements are produced.
  • the samples obtained were dried in a furnace at 40° and left wet for 7 days. The tests performed refer to the NORMAL except for the HDT. The results are shown in Table 4.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé et une installation pour la production de matières thermoplastiques composites ayant une teneur très élevée en matière de charge, à partir de matières normalement mises en décharge ou envoyées pour incinération, ou en tout cas destinées à des utilisations avec une faible valeur ajoutée, par préparation d'une solution dans au moins un solvant organique d'un polymère sélectionné parmi le polystyrène, l'ABS, le poly(fluorure de vinylidène) et autres polymères solubles dans les solvants organiques ; mélange avec la solution de polymère ainsi obtenue d'au moins une matière de charge ; élimination du solvant organique à partir du mélange de matières de charge et de polymères pour obtenir une matière thermoplastique chargée.
PCT/IT2007/000841 2007-12-03 2007-12-03 Procédé et installation pour la production de thermoplastiques composites et matières ainsi obtenues Ceased WO2009072150A1 (fr)

Priority Applications (1)

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PCT/IT2007/000841 WO2009072150A1 (fr) 2007-12-03 2007-12-03 Procédé et installation pour la production de thermoplastiques composites et matières ainsi obtenues

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PCT/IT2007/000841 WO2009072150A1 (fr) 2007-12-03 2007-12-03 Procédé et installation pour la production de thermoplastiques composites et matières ainsi obtenues

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT201700023848A1 (it) * 2017-03-20 2018-09-20 Avella Maurizio Nuovo processo per il riutilizzo di scarti e materiali a fine vita provenienti dal settori trasporti, energetico e imballaggi e materiali cosi ottenuti
EP3971231A1 (fr) 2020-09-18 2022-03-23 Maurizio Avella Procédé d'exécution d'au moins un élément homogène de matériau composite thermoplastique

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3628991A (en) * 1969-01-21 1971-12-21 Johns Manville Method of bonding epoxy resins to polyvinyl chloride
GB1578517A (en) * 1977-06-07 1980-11-05 Ugine Kuhlmann Acrylonitrile-butadiene-styrene resin/polyvinylidene fluoride resin composite material
JPS6162526A (ja) * 1984-09-05 1986-03-31 Human Ind Corp ゴム細片を主体とした粒状物の製造方法
US5229448A (en) * 1991-06-12 1993-07-20 Hoechst Celanese Corp. Formation of filled molding powders of polybenzimidazole and other polymers
WO1997011127A1 (fr) * 1994-03-25 1997-03-27 Asahi Kasei Kogyo Kabushiki Kaisha Composition de resine thermoplastique renforcee par caoutchouc et contenant des particules de polymere greffe
US6395419B1 (en) * 1997-03-28 2002-05-28 Tdk Corporation Solid polymer electrolyte, method of making, and electrochemical device using the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3628991A (en) * 1969-01-21 1971-12-21 Johns Manville Method of bonding epoxy resins to polyvinyl chloride
GB1578517A (en) * 1977-06-07 1980-11-05 Ugine Kuhlmann Acrylonitrile-butadiene-styrene resin/polyvinylidene fluoride resin composite material
JPS6162526A (ja) * 1984-09-05 1986-03-31 Human Ind Corp ゴム細片を主体とした粒状物の製造方法
US5229448A (en) * 1991-06-12 1993-07-20 Hoechst Celanese Corp. Formation of filled molding powders of polybenzimidazole and other polymers
WO1997011127A1 (fr) * 1994-03-25 1997-03-27 Asahi Kasei Kogyo Kabushiki Kaisha Composition de resine thermoplastique renforcee par caoutchouc et contenant des particules de polymere greffe
US6395419B1 (en) * 1997-03-28 2002-05-28 Tdk Corporation Solid polymer electrolyte, method of making, and electrochemical device using the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 198619, Derwent World Patents Index; AN 1986-122697, XP002492461 *
HERMAN F. MARK ET AL. EDITORS: "Encyclopedia of Polymer Science and Engineering, Volume 12", 1988, WILEY-INTERSCIENCE, NEW YORK, XP002492460 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT201700023848A1 (it) * 2017-03-20 2018-09-20 Avella Maurizio Nuovo processo per il riutilizzo di scarti e materiali a fine vita provenienti dal settori trasporti, energetico e imballaggi e materiali cosi ottenuti
EP3971231A1 (fr) 2020-09-18 2022-03-23 Maurizio Avella Procédé d'exécution d'au moins un élément homogène de matériau composite thermoplastique

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