WO2017204635A1 - Fibre-reinforced plastic objects - Google Patents

Fibre-reinforced plastic objects Download PDF

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Publication number
WO2017204635A1
WO2017204635A1 PCT/NL2017/050329 NL2017050329W WO2017204635A1 WO 2017204635 A1 WO2017204635 A1 WO 2017204635A1 NL 2017050329 W NL2017050329 W NL 2017050329W WO 2017204635 A1 WO2017204635 A1 WO 2017204635A1
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WO
WIPO (PCT)
Prior art keywords
plastic
plastic object
fibres
rest fraction
fibre
Prior art date
Application number
PCT/NL2017/050329
Other languages
French (fr)
Inventor
Jozef Maria Hubertus Lemmens
Martin Jean José VRÖSCH
Maria Geertruida Johanna SIJBERS -WISMANS
Robert Benno Wiegers
Original Assignee
Ibr Consult B.V.
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Publication date
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Publication of WO2017204635A1 publication Critical patent/WO2017204635A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • B29B17/0042Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting for shaping parts, e.g. multilayered parts with at least one layer containing regenerated plastic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2309/00Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
    • B29K2309/08Glass
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/62Plastics recycling; Rubber recycling

Definitions

  • the invention relates to fibre-reinforced plastic objects, more particularly to fibre- reinforced plastic objects comprising a rest fraction from plastic recycling comprising more than 95 wt% polyolefins.
  • the invention further relates to methods of producing said fibre- reinforced plastic objects and the use of fibres to improve the mechanical properties of recycled plastic objects comprising said rest fraction from plastic recycling.
  • this rest fraction comprises more than 95 wt% polyolefins of which the major part consists of polyethylene and polypropylene.
  • the rest fraction typically comprises additives used in the production of the plastics such as plasticizers, colorants and fillers.
  • the resulting fibre-reinforced polymers or fibre-reinforced plastics are composite materials made of a polymer matrix with fibres embedded therein.
  • the fibres are usually glass, carbon or aramid fibres, although other fibres such as paper, wood, or asbestos have also been applied.
  • the reason for adding the fibres is to improve mechanical properties such as strength, stiffness or toughness of virgin plastics to make them for example suitable as a substitute for infrastructure components that are constructed of traditional civil engineering materials such as concrete and steel. In this respect, reference is made to M.A.
  • GB1,095,700A relates to the reinforcement of virgin plastics obtained from polymers of a- olefins such as polypropylene and polyethylene with mineral fillers such as glass fibres, asbestos fibres or mica.
  • GB1,095,700A discloses an embodiment wherein glass fibres coated with the reaction product of ⁇ -aminopropyl triethoxysilane and a copolymer of ethylene and glycidyl methacrylate are compounded with virgin polypropylene.
  • a reinforcement factor, defined as the ratio of the tensile modulus of the reinforced virgin polypropylene at a given strain to that of unreinforced virgin polypropylene, of about 1.5 was reported.
  • DE19830913A1 concerns a process for recycling and production of plastics.
  • mechanical properties of a plastic object obtained from (a) a rest fraction from plastic recycling comprising 80 wt% LDPE, 10 wt% PP, 5 wt% HDPE, 2 wt% PVC, 2 wt% polystyrene and 1 wt% of further recycled plastics, (b) 2 wt%, based on the weight of the rest fraction, of a mixture consisting of 65 wt% linseed oil and 35 wt% safflower oil, (c) 0.025 wt%, based on the weight of the rest fraction, of a cross-linker, and (d) 30 wt%, based on the total weight of (a), (b) and (c), of glass wool fibres.
  • 'virgin polymer' as used herein relates to polymer that has never been put into a finished product. It is the 'new' polymer that a factory uses directly from the polymer manufacturer. Likewise, the term 'virgin plastic' relates to plastic or a plastic article comprising only virgin polymer. On the other hand, 'recycled plastic' is, at least partially, made of plastic material that has been made into a finished product before. Virgin plastics already find many commercially interesting applications and reinforcement of virgin polymers with fibres to form plastic composite materials even extends this range of applications.
  • a rest fraction from plastic recycling comprises different grades of polyethylene, polypropylene and further recycled plastics. These recycled plastics may be partially degraded due to impact of weather and thermal processing. Moreover, these recycled plastics may contain all kinds of additives commonly used in the production of plastic consumer products such as colorants, plasticizers, fillers, antimicrobials and the like. Consequently, the rest fraction from polymer recycling is a mixture of many diverse components which can in no way be compared to a virgin polymer or virgin plastic.
  • the present inventors have found that the above objects can be met by adding mineral fibres to the rest fraction from plastic recycling and by processing the mixture into fibre-reinforced plastic products.
  • the present invention thus provides a fibre-reinforced plastic object comprising, based on the weight of the plastic obj ect:
  • the rest fraction from plastic recycling comprises 10 - 90 wt% of recycled polyethylene, 10 - 90 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than
  • the present inventors have established that the addition of glass wool fibres to a rest fraction from polymer recycling greatly improves the otherwise inferior mechanical properties such that the resulting fibre-reinforced plastic objects find interesting applications.
  • the inventors have further unexpectedly found that the addition of stone wool instead of glass wool further improves mechanical properties of the fibre-reinforced plastic object.
  • the present invention further provides a method for producing a fibre-reinforced plastic object as defined herein before, said method comprising the steps of:
  • step d) (i) cooling the homogenized material of step c) and collecting the fibre-reinforced plastic object in the form of a masterbatch or (ii) hot cutting the homogenized material of step c) and collecting the fibre-reinforced plastic object in the form of pellets or a granulate or (iii) feeding the homogenized material of step c) to the mould of an injection- moulding device to form an injection- moulded fibre-reinforced plastic object.
  • the present invention further relates to the use of mineral fibres, preferably stone wool fibres, to improve the mechanical properties of recycled plastic objects comprising a rest fraction from plastic recycling, said rest fraction from plastic recycling comprising 10 - 90 wt% of recycled polyethylene, 10 - 90 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
  • mineral fibres preferably stone wool fibres
  • a fibre-reinforced plastic object comprising, based on the weight of the plastic object:
  • the rest fraction from plastic recycling comprises 10 - 90 wt% of recycled polyethylene, 10 - 90 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
  • recycled polyethylene encompasses different kinds of polyethylene that may appear in waste streams such as ultra-high-molecular-weight polyethylene (UHMWPE), ultra-low-molecular-weight polyethylene (ULMWPE or PE-WAX), high- molecular-weight polyethylene (HMWPE), high-density polyethylene (HDPE), medium- density polyethylene (MDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), very-low-density polyethylene (VLDPE), and polyethylene- polypropylene random or block copolymers.
  • UHMWPE ultra-high-molecular-weight polyethylene
  • ULMWPE or PE-WAX ultra-low-molecular-weight polyethylene
  • HMWPE high-density polyethylene
  • HDPE high-density polyethylene
  • MDPE medium- density polyethylene
  • LLDPE linear low-density polyethylene
  • LDPE low-density polyethylene
  • VLDPE very-low-density poly
  • recycled polypropylene encompasses different kinds of polypropylene that appear in waste streams such as isotactic, syndiotactic and atactic polypropylene, high crystalline polypropylene (HcPP) and expanded polypropylene (EPP).
  • the 0.1 - 3 wt% of further recycled plastics typically comprise cross-linked polyethylene (PEX or XLPE), high-density cross-linked polyethylene (HDXLPE), polyamides, polyethylene terephthalate and/or thermosetting plastics.
  • the amount of further recycled plastics is between 0.15 and 2 wt%, more preferably between 0.2 and 1 wt%, based on the weight of the rest fraction from plastic recycling.
  • Typical examples of inorganic impurities are sand, glass and metals, such as aluminium.
  • the amount of inorganic impurities is less than 1 wt%, in a more preferred embodiment less than 0.5 wt%, based on the weight of the rest fraction from plastic recycling.
  • the amounts of these inorganic impurities can be further reduced by enhanced separation techniques. However, the better the separation, the higher the costs and at some point, the separation costs do not outweigh the commercial value of the fibre-reinforce plastic objects anymore.
  • the recycled polyethylene, recycled polypropylene and further recycled plastics are so-called postconsumer plastics that have been produced and possibly also used for a specific application.
  • these recycled plastics may contain all kinds of additives commonly used in the production of plastic consumer products such as colorants, plasticizers, fillers, antimicrobials and the like. Consequently, the rest fraction from polymer recycling may comprise small amounts of many diverse components.
  • the rest fraction of polymer recycling as defined herein before is a typical rest fraction obtained from industrial and domestic plastic waste streams after separating off the otherwise useful fractions.
  • the overall composition of industrial and domestic plastic waste streams may depend on time and location, it is possible to obtain a rest fraction having a composition as defined herein before using separation techniques that are well-known in the art of plastic recycling.
  • separation techniques that are well-known in the art of plastic recycling.
  • J. Brandrup, M. Bittner, W. Michaeli, G. Menges, Eds. Recycling and recovery of plastics, Hanser, Kunststoff, Germany, 1996 and to V. Goodship, Introduction to plastics recycling, Smithers Rapra Press, 2nd edition, 2008.
  • the rest fraction from plastic recycling as used in the fibre- reinforced plastic object as defined herein before comprises 30 - 70 wt% of recycled polyethylene, 30 - 70 wt% of recycled polypropylene, and 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
  • the rest fraction from plastic recycling as used in the fibre-reinforced plastic object as defined herein before comprises 40 - 60 wt% of recycled polyethylene, 40 - 60 wt% of recycled polypropylene, and 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
  • the 0 - 5 wt% of further additives typically comprise colorants such as dyes or pigments, preferably pigments, compatibilizers, emulsifiers, fillers, antimicrobials, waxes, stabilizers, flame retardants and antioxidants.
  • the rest fraction of polymer recycling is in fact a waste stream.
  • the fibre- reinforced plastic object comprises, based on the weight of the plastic object, 0 - 4 wt% of further additives, more preferably 0 - 3 wt%, still more preferably 0 - 2 wt%.
  • the further additives do not include a cross-linker.
  • the rest fraction from plastic recycling in the fibre-reinforced plastic object is very important for obtaining good mechanical properties.
  • the rest fraction from plastic recycling may comprise based on the weight of the plastic object and as part of the further additives, between 1 and 5 wt% of a compatibilizer.
  • compatibilizers are chosen from the group consisting of ionomers, ethylene vinyl acetate, elastomers such as EPDM, LLDPE and polyethylene-polypropylene grafts.
  • a compatibilizer is only needed in case the rest fraction from polymer recycling show macroscopic phase separation in the melt. In a preferred embodiment, no compatibilizer is used.
  • the fibre-reinforced plastic objects according to the invention can be coloured using colorants such as dyes or pigments.
  • the rest fraction from plastic recycling comprises based on the weight of the plastic object and as part of the further additives, between 1 and 5 wt% of a colorant. Pigments are preferred colorants because of their better lightfastness.
  • the fibre-reinforced plastic objects according to the invention can further comprise one or more emulsifiers or wetting agents for improving the wetting of the mineral fibres by the rest fraction from plastic recycling and for improving the adhesion between the mineral fibres and the rest fraction from plastic recycling.
  • the plastic object may comprise based on the weight of the plastic object and as part of the further additives, between 1 and 5 wt% of one or more emulsifiers and/or wetting agents.
  • Preferred examples of emulsifiers or wetting agents are glycol and glycerol. Surprisingly, the inventors found that sufficient wetting and adhesion can be obtained when no wetting agents or emulsifiers are used. In a preferred embodiment, no emulsifiers or wetting agent is used.
  • Preferred examples of fillers that can be applied in the plastic object are calcium carbonate and talc.
  • Preferred examples of antimicrobials that can be applied in the plastic object are silver- based antimicrobials.
  • the fibre-reinforced plastic object according to the invention can further comprise one or more waxes.
  • Waxes may be applied to lower the melt flow index (mfi) of the plastic material during injection moulding.
  • mfi is a measure of the ease of flow of the melt of a thermoplastic polymer. It is defined as the mass of polymer, in grams, flowing in ten minutes through a capillary of a specific diameter and length by a prescribed pressure at a prescribed temperature.
  • the melt flow index should be high enough that the molten polymer can be easily formed into the intended article.
  • Preferred examples of waxes that can be applied in the plastic object are paraffin, polyolefin waxes and amide waxes. For injection moulding and extrusion mfi-values of 1 or higher are required.
  • the fibre-reinforced plastic object comprises, based on the weight of the plastic object, 0.2 - 15 wt% of mineral fibres, preferably 0.4 - 10 wt%, more preferably 0.6 - 6 wt%.
  • the mineral fibres are chosen from the group consisting of glass wool fibres, stone wool fibres, or combinations thereof.
  • the mineral fibres are glass wool fibres.
  • the fibre-reinforced plastic object comprises, based on the weight of the plastic object, 0.8 - 10 wt% of glass wool fibres, preferably 0.9 - 6 wt%.
  • the mineral fibres are stone wool fibres.
  • Stone wool is also called rock wool in the art. Both terms are considered interchangeable herein.
  • the fibre-reinforced plastic object comprises, based on the weight of the plastic object, 0.4 - 10 wt% of stone wool fibres, preferably 0.6 - 6 wt%, more preferably 0.7 - 3 wt%, even more preferably 0.8 - 2.5 wt%.
  • Stone wool can be manufactured from various types of diabase rock, mainly basalt, which is melted at high temperature. Through the furnace product of molten rock at a temperature of about 1600 °C, air or steam is blown. More advanced production techniques are based on spinning molten rock in high-speed spinning heads. The final product typically is a mass of fine, intertwined fibres with a typical diameter of 2 to 6 ⁇ .
  • the binding agent typically is a thermosetting resin such as phenolic resins, like phenol formaldehyde resins or phenol formaldehyde urea resins.
  • the mineral fibre that is applied in the rest fraction from polymer recycling is a waste stream.
  • the inventors have found that the offcuts resulting from the production of stone wool isolation material can be used in the fibre-reinforced plastic object as defined herein before. These offcuts mainly consist of intertwined stone wool fibres comprising small amounts of cured binder.
  • the mineral fibres are stone wool fibres in the form of offcuts resulting from the production of stone wool isolation. These stone wool fibres may comprise small amounts of binder.
  • stone wool fibres without binder can also be applied in the plastic objects according to the invention.
  • the mechanical properties of the fibre-reinforced plastic objects as defined herein before are sufficient for the production of different plastic products.
  • the plastic object as defined herein before is an injection- moulded product, preferably a pallet, bin, container, paver, tube or garden furniture. Relevant mechanical properties for such injection- moulded products are E-modulus, flexural modulus and impact strength.
  • the minimum preferred values for the mechanical properties of such injection- moulded products are an E- modulus of at least 450 MPa, as determined in accordance with ISO 527-1 (version 1996), a flexural modulus of at least 450 MPa, as determined in accordance with ASTM D790 (version 1995), and an impact strength (unnotched) of at least 60 kJ/m 2 as determined in accordance with ISO 179-1 (version 2001).
  • the fibre-reinforced plastic object as defined herein before has one or more of the following mechanical properties:
  • an E-modulus as determined in accordance with ISO 527-1 (version 1996), of at least 450 MPa, more preferably at least 900 MPa, even more preferably at least 950 MPa, still more preferably at least 1000 MPa;
  • a flexural modulus as determined in accordance with ASTM D790 (version 1995), of at least 450 MPa, more preferably at least 780 MPa, even more preferably at least 790 MPa, still more preferably at least 800 MPa;
  • the fibre-reinforced plastic object as defined herein before has all of the following mechanical properties:
  • an E-modulus as determined in accordance with ISO 527-1 (version 1996), of at least 450 MPa, more preferably at least 900 MPa, even more preferably at least 950 MPa, still more preferably at least 1000 MPa;
  • a flexural modulus as determined in accordance with ASTM D790 (version 1995), of at least 780 MPa, more preferably at least 785 MPa, even more preferably at least 790 MPa, still more preferably at least 800 MPa;
  • an impact strength (unnotched), as determined in accordance with ISO 179-1 (version 2001), of at least 60 kJ/m 2 , more preferably no fracture resulting from said impact strength test.
  • the fibre-reinforced plastic object is an intermediate product that takes the form of pellets, a granulate or masterbatch that can be used in injection- moulding processes to produce further fibre-reinforced plastic objects.
  • the fibre-reinforced plastic objects as defined herein before can also be applied in multilayer plastic products.
  • a fibre-reinforced plastic object as defined herein before in the form of a layer is combined with one or more layers of virgin plastic.
  • a multi-layer plastic object is provided, said multi-layer plastic object comprising a fibre-reinforced plastic object as defined herein before in the form of a first layer and a second plastic layer comprising virgin plastic attached to a first side of said first layer.
  • a multi-layer plastic object comprising a fibre-reinforced plastic object as defined herein before in the form of a first layer and a second plastic layer comprising virgin plastic attached to a first side of said first layer and a third plastic layer comprising virgin plastic is attached to a second side of said first layer.
  • a method for producing a fibre-reinforced plastic object as defined herein before comprising the steps of:
  • the melt homogenization device is a compounder or an injection- moulding device.
  • the injection-moulded fibre-reinforced plastic object is chosen from the group consisting of pallets, bins, containers, pavers, tubes and garden furniture.
  • the total residence time of the material in the melt homogenization device is less than 60 seconds.
  • the highest temperature in the melt homogenization device must be above the melting point of the highest melting component in the rest fraction from polymer recycling. Typically, the highest temperature in the melt homogenization device is between 200 and 230 °C.
  • the initial length of the fibres is as long as possible without negatively influencing the processability.
  • at least 90 wt% of the mineral fibres before melt homogenization have a length of between 30 and 70 mm, more preferably between 40 and 60 mm.
  • the mineral fibres are applied as individual fibres and not as wool.
  • Individual glass wool fibres or stone wool fibres of this length can be obtained by size reduction techniques such as cutting and/or shredding of glass wool, stone wool or offcuts resulting from the production of stone wool isolation.
  • the invention relates to the use of mineral fibres, preferably glass wool fibres or stone wool fibres, more preferably stone wool fibres, to improve the mechanical properties of plastic objects comprising a rest fraction from plastic recycling, said rest fraction from plastic recycling comprising 10 - 90 wt% of recycled polyethylene, 10 - 90 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
  • plastic recycling comprising 10 - 90 wt% of recycled polyethylene, 10 - 90 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
  • said use encompasses the incorporation of further additives as defined herein before, the use of preferred mineral fibres as defined herein before and the use of preferred rest fraction compositions as defined herein before.
  • the use of mineral fibres relates to improving the mechanical properties of plastic objects comprising the rest fraction from plastic recycling as defined herein before, wherein the plastic objects comprise, based on the weight of the plastic object:
  • Example 1 preparation of plastic objects from recycled plastic
  • a rest fraction from polymer recycling was obtained from curbside collection.
  • the composition of the rest fraction from polymer recycling as used in this example was determined using differential scanning calorimetry (DSC) in accordance with ISO 11357-1 (version 2009).
  • the composition of the rest fraction from polymer recycling comprised 58 wt% polyethylene, 39 wt% polypropylene, 2wt% of other plastics and 1 wt% of inorganics.
  • Mineral fibres were milled to obtain a product containing fibres having a length of between about 30 mm and 70 mm. Such a milled product mainly consisting of individual fibres can be dosed more easily than a mineral fibre wool.
  • the rest fraction from polymer recycling was gravimetrically fed to a hopper of twin screw compounder (Collin ZK 25T SCD 15, Teachline Cooling WB 850T and granulator Teachline CSG 171T) without or with mineral fibres.
  • the homogenized fibre-reinforced plastic material was obtained as an extruded strand which was subsequently cooled and cut into a granulate.
  • the total residence time of the material in the twin screw compounder was 30 seconds.
  • the granulate thus obtained was used in an injection moulding device (BOY XS) to produce plastic objects for testing (thermo-)mechanical properties.
  • thermo-mechanical properties of plastic test samples comprising glass wool fibres are presented in Table 1.
  • the sample not comprising glass wool fibres ('R + 0 wt%') is used as a reference.
  • the property 'rmT stands for melt flow index.
  • the abbreviation 'R' stands for rest fraction from polymer recycling.
  • the test sample not comprising glass wool fibres has a low E-modulus and impact strength.
  • Such inferior mechanical properties do not enable the production of useful plastic products.
  • the addition of glass wool fibres clearly improves E-modulus, impact strength and flexural modulus, while the influence of the addition of glass wool fibres on tensile strength and elongation is only limited.
  • Example 3 (thermo-)mechanical properties of test samples comprising stone wool fibres Several (thermo-)mechanical properties of plastic samples comprising stone wool fibres

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

This invention relates to fibre-reinforced plastic objects comprising a rest fraction from plastic recycling comprising based on the weight of the plastic object: a) 65 - 99.9 wt% of a rest fraction from plastic recycling; b) 0.1 - 30 wt% of mineral fibres; c) 0 - 5 wt% of further additives; wherein the rest fraction from plastic recycling comprises 10 - 90 wt% of recycled polyethylene, 10 - 90 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction. The invention further relates to methods of producing said fibre- reinforced plastic objects and the use of fibres to improve the mechanical properties of recycled plastic objects comprising said rest fraction from plastic recycling. The addition of mineral fibres, particularly glass wool fibres or stone wool fibres, to a rest fraction from polymer recycling greatly improves the otherwise inferior mechanical properties such that the resulting fibre-reinforced plastic objects find interesting applications.

Description

FIBRE-REINFORCED PLASTIC OBJECTS
FIELD OF THE INVENTION
The invention relates to fibre-reinforced plastic objects, more particularly to fibre- reinforced plastic objects comprising a rest fraction from plastic recycling comprising more than 95 wt% polyolefins. The invention further relates to methods of producing said fibre- reinforced plastic objects and the use of fibres to improve the mechanical properties of recycled plastic objects comprising said rest fraction from plastic recycling. BACKGROUND OF THE INVENTION
The huge amounts of plastic waste resulting from industrial and domestic use presents our society with major challenges. Due to the very limited economically feasible options for processing plastic waste into valuable products, a large fraction of the plastic waste is incinerated along with other industrial and domestic waste streams or ends up at landfill sites. Even large parts of the plastic waste collected separately is incinerated. The fraction that is not incinerated is typically sorted out into different useful fractions that are processed into different products and a rest fraction. This rest fraction from plastic recycling, which amounts to up to 60 wt% of the plastic waste collected separately, can as such, due to its heterogeneity, not be processed into useful products and cannot be efficiently separated further into valuable fractions. Typically, this rest fraction comprises more than 95 wt% polyolefins of which the major part consists of polyethylene and polypropylene. Apart from the polyolefins, the rest fraction typically comprises additives used in the production of the plastics such as plasticizers, colorants and fillers.
It is known in the art to reinforce virgin thermosetting polymers, and sometimes also thermoplastic polymers, with fibres. The resulting fibre-reinforced polymers or fibre-reinforced plastics are composite materials made of a polymer matrix with fibres embedded therein. The fibres are usually glass, carbon or aramid fibres, although other fibres such as paper, wood, or asbestos have also been applied. The reason for adding the fibres is to improve mechanical properties such as strength, stiffness or toughness of virgin plastics to make them for example suitable as a substitute for infrastructure components that are constructed of traditional civil engineering materials such as concrete and steel. In this respect, reference is made to M.A. Masuelli, Introduction of fibre-reinforced polymers - polymers and composites: concept, properties and processes, 2013, open access article available via http://dx.doi.org/10.5772/54629. GB1,095,700A relates to the reinforcement of virgin plastics obtained from polymers of a- olefins such as polypropylene and polyethylene with mineral fillers such as glass fibres, asbestos fibres or mica. GB1,095,700A discloses an embodiment wherein glass fibres coated with the reaction product of γ-aminopropyl triethoxysilane and a copolymer of ethylene and glycidyl methacrylate are compounded with virgin polypropylene. A reinforcement factor, defined as the ratio of the tensile modulus of the reinforced virgin polypropylene at a given strain to that of unreinforced virgin polypropylene, of about 1.5 was reported.
DE19830913A1 concerns a process for recycling and production of plastics. In Example 3 of DE19830913A1, mechanical properties of a plastic object obtained from (a) a rest fraction from plastic recycling comprising 80 wt% LDPE, 10 wt% PP, 5 wt% HDPE, 2 wt% PVC, 2 wt% polystyrene and 1 wt% of further recycled plastics, (b) 2 wt%, based on the weight of the rest fraction, of a mixture consisting of 65 wt% linseed oil and 35 wt% safflower oil, (c) 0.025 wt%, based on the weight of the rest fraction, of a cross-linker, and (d) 30 wt%, based on the total weight of (a), (b) and (c), of glass wool fibres.
The term 'virgin polymer' as used herein relates to polymer that has never been put into a finished product. It is the 'new' polymer that a factory uses directly from the polymer manufacturer. Likewise, the term 'virgin plastic' relates to plastic or a plastic article comprising only virgin polymer. On the other hand, 'recycled plastic' is, at least partially, made of plastic material that has been made into a finished product before. Virgin plastics already find many commercially interesting applications and reinforcement of virgin polymers with fibres to form plastic composite materials even extends this range of applications.
As will be understood by those skilled in the art, a rest fraction from plastic recycling comprises different grades of polyethylene, polypropylene and further recycled plastics. These recycled plastics may be partially degraded due to impact of weather and thermal processing. Moreover, these recycled plastics may contain all kinds of additives commonly used in the production of plastic consumer products such as colorants, plasticizers, fillers, antimicrobials and the like. Consequently, the rest fraction from polymer recycling is a mixture of many diverse components which can in no way be compared to a virgin polymer or virgin plastic.
One of the problems that arises when one would process the rest fraction from polymer recycling into products is a (too) low tensile modulus and flexural modulus, a low elongation and a low impact strength. In this respect, reference is made to DE19830913A1. Further reference is made to Recycling and Recovery of Plastics, Hanser/Gardner Publications, Inc., Cincinnati, 1996, J. Brandrup, Ed., which is incorporated herein by reference. Because of these inferior mechanical properties, plastics objects obtained from the rest fraction of polymer recycling hardly find interesting applications.
Accordingly, there is a need for new processes for producing valuable products from the heterogeneous rest fraction obtained from plastic recycling. It is therefore an object of the invention to provide valuable products from the heterogeneous rest fraction obtained from plastic recycling. It is a further object of the invention to provide products from the heterogeneous rest fraction obtained from plastic recycling having improved tensile modulus, flexural modulus, elongation and/or impact strength. SUMMARY OF THE INVENTION
The present inventors have found that the above objects can be met by adding mineral fibres to the rest fraction from plastic recycling and by processing the mixture into fibre-reinforced plastic products.
The present invention thus provides a fibre-reinforced plastic object comprising, based on the weight of the plastic obj ect:
a) 65 - 99.9 wt% of a rest fraction from plastic recycling;
b) 0.1 - 30 wt% of mineral fibres;
c) 0 - 5 wt% of further additives;
wherein the rest fraction from plastic recycling comprises 10 - 90 wt% of recycled polyethylene, 10 - 90 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than
2 wt% of inorganic impurities, based on the weight of the rest fraction.
The present inventors have established that the addition of glass wool fibres to a rest fraction from polymer recycling greatly improves the otherwise inferior mechanical properties such that the resulting fibre-reinforced plastic objects find interesting applications. The inventors have further unexpectedly found that the addition of stone wool instead of glass wool further improves mechanical properties of the fibre-reinforced plastic object.
The present invention further provides a method for producing a fibre-reinforced plastic object as defined herein before, said method comprising the steps of:
a) gravimetric of volumetric feeding 65 - 99.9 wt%, based on the weight of the plastic object, of a rest fraction from plastic recycling, 0.1 - 30 wt% of mineral fibres and 0 - 5 wt% of further additives, all as defined herein before, to a hopper of a melt homogenization device; b) feeding the components fed to the hopper to a feeding zone of the melt homogenization device wherein at least part of the air is removed and wherein the material is compacted; c) conveying, heating, melting and homogenizing the compacted material from step b) at a temperature of between 170 and 230 °C; and subsequently
d) (i) cooling the homogenized material of step c) and collecting the fibre-reinforced plastic object in the form of a masterbatch or (ii) hot cutting the homogenized material of step c) and collecting the fibre-reinforced plastic object in the form of pellets or a granulate or (iii) feeding the homogenized material of step c) to the mould of an injection- moulding device to form an injection- moulded fibre-reinforced plastic object.
The present invention further relates to the use of mineral fibres, preferably stone wool fibres, to improve the mechanical properties of recycled plastic objects comprising a rest fraction from plastic recycling, said rest fraction from plastic recycling comprising 10 - 90 wt% of recycled polyethylene, 10 - 90 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction. DETAILED DESCRIPTION
In a first aspect of the invention, a fibre-reinforced plastic object is provided, said plastic object comprising, based on the weight of the plastic object:
a) 65 - 99.9 wt% of a rest fraction from plastic recycling;
b) 0.1 - 30 wt% of mineral fibres;
c) 0 - 5 wt% of further additives;
wherein the rest fraction from plastic recycling comprises 10 - 90 wt% of recycled polyethylene, 10 - 90 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
The term recycled polyethylene as used herein encompasses different kinds of polyethylene that may appear in waste streams such as ultra-high-molecular-weight polyethylene (UHMWPE), ultra-low-molecular-weight polyethylene (ULMWPE or PE-WAX), high- molecular-weight polyethylene (HMWPE), high-density polyethylene (HDPE), medium- density polyethylene (MDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), very-low-density polyethylene (VLDPE), and polyethylene- polypropylene random or block copolymers.
The term recycled polypropylene as defined herein encompasses different kinds of polypropylene that appear in waste streams such as isotactic, syndiotactic and atactic polypropylene, high crystalline polypropylene (HcPP) and expanded polypropylene (EPP). The 0.1 - 3 wt% of further recycled plastics typically comprise cross-linked polyethylene (PEX or XLPE), high-density cross-linked polyethylene (HDXLPE), polyamides, polyethylene terephthalate and/or thermosetting plastics. In a preferred embodiment, the amount of further recycled plastics is between 0.15 and 2 wt%, more preferably between 0.2 and 1 wt%, based on the weight of the rest fraction from plastic recycling.
Typical examples of inorganic impurities are sand, glass and metals, such as aluminium. In a preferred embodiment, the amount of inorganic impurities is less than 1 wt%, in a more preferred embodiment less than 0.5 wt%, based on the weight of the rest fraction from plastic recycling. Obviously, the amounts of these inorganic impurities can be further reduced by enhanced separation techniques. However, the better the separation, the higher the costs and at some point, the separation costs do not outweigh the commercial value of the fibre-reinforce plastic objects anymore.
As will be understood by those skilled in the art, the recycled polyethylene, recycled polypropylene and further recycled plastics are so-called postconsumer plastics that have been produced and possibly also used for a specific application. Hence, these recycled plastics may contain all kinds of additives commonly used in the production of plastic consumer products such as colorants, plasticizers, fillers, antimicrobials and the like. Consequently, the rest fraction from polymer recycling may comprise small amounts of many diverse components.
The rest fraction of polymer recycling as defined herein before is a typical rest fraction obtained from industrial and domestic plastic waste streams after separating off the otherwise useful fractions. Although the overall composition of industrial and domestic plastic waste streams may depend on time and location, it is possible to obtain a rest fraction having a composition as defined herein before using separation techniques that are well-known in the art of plastic recycling. In this respect, reference is made to J. Brandrup, M. Bittner, W. Michaeli, G. Menges, Eds., Recycling and recovery of plastics, Hanser, Munich, Germany, 1996 and to V. Goodship, Introduction to plastics recycling, Smithers Rapra Press, 2nd edition, 2008.
In a preferred embodiment, the rest fraction from plastic recycling as used in the fibre- reinforced plastic object as defined herein before comprises 30 - 70 wt% of recycled polyethylene, 30 - 70 wt% of recycled polypropylene, and 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
In another preferred embodiment, the rest fraction from plastic recycling as used in the fibre-reinforced plastic object as defined herein before comprises 40 - 60 wt% of recycled polyethylene, 40 - 60 wt% of recycled polypropylene, and 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction. The 0 - 5 wt% of further additives typically comprise colorants such as dyes or pigments, preferably pigments, compatibilizers, emulsifiers, fillers, antimicrobials, waxes, stabilizers, flame retardants and antioxidants. The rest fraction of polymer recycling is in fact a waste stream. As will be understood by those skilled in the art, further additives increase the price of the plastic object obtained from the rest fraction of polymer recycling. Hence, the amount of further additives is preferably kept as low as possible. In a preferred embodiment, the fibre- reinforced plastic object comprises, based on the weight of the plastic object, 0 - 4 wt% of further additives, more preferably 0 - 3 wt%, still more preferably 0 - 2 wt%.
In a preferred embodiment, the further additives do not include a cross-linker.
It is known in the art that mixtures of different types of polyethylene and polypropylene can be miscible, partially miscible or immiscible dependent on their relative concentration. In this respect, reference is made to L.A. Utracki, Thermodynamics of Polymer Blends, Polymer Blends Handbook (2003), page 123-201, Kluwer Academic Publishers. Homogeneity of the rest fraction from polymer recycling in the fibre-reinforced plastic object is very important for obtaining good mechanical properties. Hence, the rest fraction from plastic recycling may comprise based on the weight of the plastic object and as part of the further additives, between 1 and 5 wt% of a compatibilizer. Preferred examples of compatibilizers are chosen from the group consisting of ionomers, ethylene vinyl acetate, elastomers such as EPDM, LLDPE and polyethylene-polypropylene grafts. As will be appreciated by those skilled in the art, a compatibilizer is only needed in case the rest fraction from polymer recycling show macroscopic phase separation in the melt. In a preferred embodiment, no compatibilizer is used.
The fibre-reinforced plastic objects according to the invention can be coloured using colorants such as dyes or pigments. Hence, in a preferred embodiment, the rest fraction from plastic recycling comprises based on the weight of the plastic object and as part of the further additives, between 1 and 5 wt% of a colorant. Pigments are preferred colorants because of their better lightfastness.
The fibre-reinforced plastic objects according to the invention can further comprise one or more emulsifiers or wetting agents for improving the wetting of the mineral fibres by the rest fraction from plastic recycling and for improving the adhesion between the mineral fibres and the rest fraction from plastic recycling. Hence, the plastic object may comprise based on the weight of the plastic object and as part of the further additives, between 1 and 5 wt% of one or more emulsifiers and/or wetting agents. Preferred examples of emulsifiers or wetting agents are glycol and glycerol. Surprisingly, the inventors found that sufficient wetting and adhesion can be obtained when no wetting agents or emulsifiers are used. In a preferred embodiment, no emulsifiers or wetting agent is used.
Preferred examples of fillers that can be applied in the plastic object are calcium carbonate and talc.
Preferred examples of antimicrobials that can be applied in the plastic object are silver- based antimicrobials.
The fibre-reinforced plastic object according to the invention can further comprise one or more waxes. Waxes may be applied to lower the melt flow index (mfi) of the plastic material during injection moulding. The mfi is a measure of the ease of flow of the melt of a thermoplastic polymer. It is defined as the mass of polymer, in grams, flowing in ten minutes through a capillary of a specific diameter and length by a prescribed pressure at a prescribed temperature. The melt flow index should be high enough that the molten polymer can be easily formed into the intended article. Preferred examples of waxes that can be applied in the plastic object are paraffin, polyolefin waxes and amide waxes. For injection moulding and extrusion mfi-values of 1 or higher are required.
In a preferred embodiment, the fibre-reinforced plastic object comprises, based on the weight of the plastic object, 0.2 - 15 wt% of mineral fibres, preferably 0.4 - 10 wt%, more preferably 0.6 - 6 wt%.
In another preferred embodiment, the mineral fibres are chosen from the group consisting of glass wool fibres, stone wool fibres, or combinations thereof. In a more preferred embodiment, the mineral fibres are glass wool fibres. In an very preferred embodiment, the fibre-reinforced plastic object comprises, based on the weight of the plastic object, 0.8 - 10 wt% of glass wool fibres, preferably 0.9 - 6 wt%.
Most preferably, the mineral fibres are stone wool fibres. Stone wool is also called rock wool in the art. Both terms are considered interchangeable herein. In a very preferred embodiment, the fibre-reinforced plastic object comprises, based on the weight of the plastic object, 0.4 - 10 wt% of stone wool fibres, preferably 0.6 - 6 wt%, more preferably 0.7 - 3 wt%, even more preferably 0.8 - 2.5 wt%.
Stone wool can be manufactured from various types of diabase rock, mainly basalt, which is melted at high temperature. Through the furnace product of molten rock at a temperature of about 1600 °C, air or steam is blown. More advanced production techniques are based on spinning molten rock in high-speed spinning heads. The final product typically is a mass of fine, intertwined fibres with a typical diameter of 2 to 6 μπι. Nowadays, the main application of stone wool is for thermal and/or sound isolation of buildings. For this purpose, small quantities of binding agents are added to bond the individual fibres together, the binder is cured and the resulting wool is processed by cutting it to the required size and shape, for example into rolls or boards. The binding agent typically is a thermosetting resin such as phenolic resins, like phenol formaldehyde resins or phenol formaldehyde urea resins.
In order to reduce costs, it would be advantageous if the mineral fibre that is applied in the rest fraction from polymer recycling is a waste stream. The inventors have found that the offcuts resulting from the production of stone wool isolation material can be used in the fibre-reinforced plastic object as defined herein before. These offcuts mainly consist of intertwined stone wool fibres comprising small amounts of cured binder. Hence, in a preferred embodiment, the mineral fibres are stone wool fibres in the form of offcuts resulting from the production of stone wool isolation. These stone wool fibres may comprise small amounts of binder. However, stone wool fibres without binder can also be applied in the plastic objects according to the invention.
The mechanical properties of the fibre-reinforced plastic objects as defined herein before are sufficient for the production of different plastic products. In a preferred embodiment, the plastic object as defined herein before is an injection- moulded product, preferably a pallet, bin, container, paver, tube or garden furniture. Relevant mechanical properties for such injection- moulded products are E-modulus, flexural modulus and impact strength. The minimum preferred values for the mechanical properties of such injection- moulded products are an E- modulus of at least 450 MPa, as determined in accordance with ISO 527-1 (version 1996), a flexural modulus of at least 450 MPa, as determined in accordance with ASTM D790 (version 1995), and an impact strength (unnotched) of at least 60 kJ/m2 as determined in accordance with ISO 179-1 (version 2001).
In a preferred embodiment, the fibre-reinforced plastic object as defined herein before has one or more of the following mechanical properties:
a) an E-modulus, as determined in accordance with ISO 527-1 (version 1996), of at least 450 MPa, more preferably at least 900 MPa, even more preferably at least 950 MPa, still more preferably at least 1000 MPa;
b) a flexural modulus, as determined in accordance with ASTM D790 (version 1995), of at least 450 MPa, more preferably at least 780 MPa, even more preferably at least 790 MPa, still more preferably at least 800 MPa; and
c) an impact strength (unnotched), as determined in accordance with ISO 179-1 (version 2001), of at least 60 kJ/m2, more preferably no fracture resulting from said impact strength test. In a more preferred embodiment, the fibre-reinforced plastic object as defined herein before has all of the following mechanical properties:
a) an E-modulus, as determined in accordance with ISO 527-1 (version 1996), of at least 450 MPa, more preferably at least 900 MPa, even more preferably at least 950 MPa, still more preferably at least 1000 MPa;
b) a flexural modulus, as determined in accordance with ASTM D790 (version 1995), of at least 780 MPa, more preferably at least 785 MPa, even more preferably at least 790 MPa, still more preferably at least 800 MPa; and
c) an impact strength (unnotched), as determined in accordance with ISO 179-1 (version 2001), of at least 60 kJ/m2, more preferably no fracture resulting from said impact strength test.
In another preferred embodiment, the fibre-reinforced plastic object is an intermediate product that takes the form of pellets, a granulate or masterbatch that can be used in injection- moulding processes to produce further fibre-reinforced plastic objects.
The fibre-reinforced plastic objects as defined herein before can also be applied in multilayer plastic products. In such a product, a fibre-reinforced plastic object as defined herein before in the form of a layer is combined with one or more layers of virgin plastic. In a preferred embodiment, a multi-layer plastic object is provided, said multi-layer plastic object comprising a fibre-reinforced plastic object as defined herein before in the form of a first layer and a second plastic layer comprising virgin plastic attached to a first side of said first layer. In another preferred embodiment, a multi-layer plastic object is provided, said multi-layer plastic object comprising a fibre-reinforced plastic object as defined herein before in the form of a first layer and a second plastic layer comprising virgin plastic attached to a first side of said first layer and a third plastic layer comprising virgin plastic is attached to a second side of said first layer.
In a second aspect of the invention, a method for producing a fibre-reinforced plastic object as defined herein before is provided, said method comprising the steps of:
a) gravimetric of volumetric feeding 65 - 99.9 wt%, based on the weight of the plastic object, of a rest fraction from plastic recycling, 0.1 - 30 wt% of mineral fibres and 0 - 5 wt% of further additives, all as defined herein before, to a hopper of a melt homogenization device; b) feeding the components fed to the hopper to a feeding zone of the melt homogenization device wherein at least part of the air is removed and wherein the material is compacted; c) conveying, heating, melting and homogenizing the compacted material from step b) at a temperature of between 170 and 230 °C; and subsequently d) (i) cooling the homogenized material of step c) and collecting the fibre-reinforced plastic object in the form of a masterbatch or (ii) hot cutting the homogenized material of step c) and collecting the fibre-reinforced plastic object in the form of pellets or a granulate or (iii) feeding the homogenized material of step c) to the mould of an injection- moulding device to form an injection- moulded fibre-reinforced plastic object.
In a preferred embodiment, the melt homogenization device is a compounder or an injection- moulding device.
In another preferred embodiment, the injection-moulded fibre-reinforced plastic object is chosen from the group consisting of pallets, bins, containers, pavers, tubes and garden furniture.
Too much mechanical burden during melt homogenization leads to undesirable break-up of the mineral fibres and plastic degradation. It is within the skills of the artisan to adjust the screw geometries in such devices in order to minimize mechanical burden and plastic degradation. In this respect, reference is made to B. Jakob et al, Relevant Process Parameters for Twin Screw Compounding, Thermo Fisher Scientific, Material Characterization, Karlsruhe, Germany, Application Notes LR-70, 2012, to T. Sakai, Screw extrusion technology - past, present and future, Polimery, 2013 (58), pp 847-857, to K. Ramani et al, Effect of screw design on fibre damage in extrusion compounding and composite properties, Polymer Composites, 1995 (16), pp 258-266, and to A. L. Kelly et al, The effect of screw geometry on melt temperature profile in single screw extrusion, Polymer Engineering & Science, 2006 (46), pp 1706-1714.
In a preferred embodiment, the total residence time of the material in the melt homogenization device is less than 60 seconds.
The highest temperature in the melt homogenization device must be above the melting point of the highest melting component in the rest fraction from polymer recycling. Typically, the highest temperature in the melt homogenization device is between 200 and 230 °C.
Since the mineral fibres may break up into smaller fibres during processing steps such as compounding and/or injection moulding, it is preferred that the initial length of the fibres is as long as possible without negatively influencing the processability. Preferably, at least 90 wt% of the mineral fibres before melt homogenization have a length of between 30 and 70 mm, more preferably between 40 and 60 mm.
Preferably, the mineral fibres are applied as individual fibres and not as wool. Individual glass wool fibres or stone wool fibres of this length can be obtained by size reduction techniques such as cutting and/or shredding of glass wool, stone wool or offcuts resulting from the production of stone wool isolation. In a third aspect, the invention relates to the use of mineral fibres, preferably glass wool fibres or stone wool fibres, more preferably stone wool fibres, to improve the mechanical properties of plastic objects comprising a rest fraction from plastic recycling, said rest fraction from plastic recycling comprising 10 - 90 wt% of recycled polyethylene, 10 - 90 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
In further embodiments, said use encompasses the incorporation of further additives as defined herein before, the use of preferred mineral fibres as defined herein before and the use of preferred rest fraction compositions as defined herein before.
In a preferred embodiment, the use of mineral fibres relates to improving the mechanical properties of plastic objects comprising the rest fraction from plastic recycling as defined herein before, wherein the plastic objects comprise, based on the weight of the plastic object:
a) 65 - 99.9 wt% of the rest fraction from plastic recycling;
b) 0.1 - 30 wt% of the mineral fibres as defined herein before; and
c) 0 - 5 wt% of further additives as defined herein before.
Thus, the invention has been described by reference to certain embodiments discussed above. It will be recognized that these embodiments are susceptible to various modifications and alternative forms well known to those of skill in the art.
Furthermore, for a proper understanding of this document and its claims, it is to be understood that the verb 'to comprise' and its conjugations are used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. In addition, reference to an element by the indefinite article 'a' or 'an' does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be one and only one of the elements. The indefinite article 'a' or 'an' thus usually means 'at least one'.
All patent and literature references cited in the present specification are hereby incorporated by reference in their entirety.
The following examples are offered for illustrative purposes only, and are not intended to limit the scope of the present invention in any way. EXAMPLES
Example 1: preparation of plastic objects from recycled plastic
A rest fraction from polymer recycling was obtained from curbside collection. The composition of the rest fraction from polymer recycling as used in this example was determined using differential scanning calorimetry (DSC) in accordance with ISO 11357-1 (version 2009). The composition of the rest fraction from polymer recycling comprised 58 wt% polyethylene, 39 wt% polypropylene, 2wt% of other plastics and 1 wt% of inorganics. Mineral fibres were milled to obtain a product containing fibres having a length of between about 30 mm and 70 mm. Such a milled product mainly consisting of individual fibres can be dosed more easily than a mineral fibre wool.
The rest fraction from polymer recycling was gravimetrically fed to a hopper of twin screw compounder (Collin ZK 25T SCD 15, Teachline Cooling WB 850T and granulator Teachline CSG 171T) without or with mineral fibres. The homogenized fibre-reinforced plastic material was obtained as an extruded strand which was subsequently cooled and cut into a granulate. The total residence time of the material in the twin screw compounder was 30 seconds. The granulate thus obtained was used in an injection moulding device (BOY XS) to produce plastic objects for testing (thermo-)mechanical properties.
In total, 12 types of granulates and test samples were produced using the method described above. The first granulate and test sample consisted only of the rest fraction from polymer recycling. In addition, 3 granulates and test samples obtained therefrom, respectively having 1 wt%, 2 wt% and 5 wt% of glass wool fibres, based on the weight of the granulate, were produced. Moreover, 4 granulates and test samples obtained therefrom, respectively having 1 wt%, 2 wt%, 5 wt% and 10 wt% of stone wool fibres, based on the weight of the granulate, were produced. These stone wool fibres were offcuts resulting from the production of stone wool isolation (obtained from the wool fibre producing industry) and contained small amounts of cured binder.
The 4 stone wool fibre granulates and test samples were reproduced using stone wool in the form of offcuts resulting from the production of stone wool isolation from which the small amounts of cured binder had been removed. Example 2: (thermo-)mechanical properties of test samples comprising glass wool fibres
Several (thermo-)mechanical properties of plastic test samples comprising glass wool fibres, produced in accordance with Example 1, are presented in Table 1. The sample not comprising glass wool fibres ('R + 0 wt%') is used as a reference. The property 'rmT stands for melt flow index. The abbreviation 'R' stands for rest fraction from polymer recycling.
Table 1 : (thermo-)mechanical properties of test samples comprising glass wool fibres
Figure imgf000014_0001
As can be inferred from Table 1, the test sample not comprising glass wool fibres ('R + 0 wt%') has a low E-modulus and impact strength. Such inferior mechanical properties do not enable the production of useful plastic products. The addition of glass wool fibres clearly improves E-modulus, impact strength and flexural modulus, while the influence of the addition of glass wool fibres on tensile strength and elongation is only limited.
Example 3: (thermo-)mechanical properties of test samples comprising stone wool fibres Several (thermo-)mechanical properties of plastic samples comprising stone wool fibres
(off cuts with small amounts of cured binder), produced in accordance with Example 1, are presented in Table 3. The properties were determined using the test methods indicated in Table 2. The composition of the rest fraction from polymer recycling was identical to the composition used in Example 2. Similar (thermo-)mechanical properties were obtained for stone wool fibres (off cuts) without cured binder.
Table 3 : (thermo-)mechanical properties of test samples comprising stone wool fibres
Figure imgf000015_0001
The addition of stone wool fibres clearly improves E-modulus, elongation, impact strength and flexural modulus, while the influence of the addition of stone wool fibres on tensile strength is limited. The improvement of these mechanical properties is much more pronounced than for glass wool fibres.

Claims

A fibre-reinforced plastic object comprising, based on the weight of the plastic object: a) 65 - 99.9 wt% of a rest fraction from plastic recycling;
b) 0.1 - 30 wt% of mineral fibres;
c) 0 - 5 wt% of further additives;
wherein the rest fraction from plastic recycling comprises 10 - 90 wt% of recycled polyethylene, 10 - 90 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
Plastic object according to claim 1, comprising based on the weight of the plastic object 0.2 - 15 wt% of mineral fibres, preferably 0.4 - 10 wt%, more preferably 0.6 - 6 wt%.
Plastic object according to claim 1 or 2, wherein the mineral fibres are chosen from the group consisting of glass wool fibres, stone wool fibres, or combinations thereof, preferably stone wool fibres.
Plastic object according to any one of claims 1 to 3, wherein the wherein the mineral fibres are offcuts resulting from the production of stone wool isolation material.
Plastic object according to any one of claims 1 to 4, wherein the rest fraction from plastic recycling comprises 30 - 70 wt% of recycled polyethylene, 30 - 70 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
Plastic object according to claim 5, wherein the rest fraction from plastic recycling comprises 60 - 40 wt% of recycled polyethylene, 40 - 60 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
Plastic object according to any one of claims 1 to 6, wherein the further additives are chosen from the group consisting of colorants such as dyes or pigments, preferably pigments, compatibilizers, emulsifiers, fillers, antimicrobials, waxes, stabilizers, flame retardants and antioxidants.
8. Plastic object according to any one of claims 1 to 7, wherein said plastic object is an intermediate product that takes the form of pellets, a granulate or masterbatch that can be used in injection- moulding processes to produce further plastic objects.
9. Plastic object according to any one of claims 1 to 7, in the form of an injection- moulded product, preferably a pallet, bin, container, paver, tube or garden furniture.
10. Multi-layer plastic object comprising the plastic object according to any one of claims 1-7 in the form of a first layer and a second plastic layer comprising virgin plastic attached to a first side of said first layer.
11. Multi-layer plastic object according to claim 10 wherein a third plastic layer comprising virgin plastic is attached to a second side of said first layer.
12. Plastic object according to any one of claims 1 to 11, having one or more of the following mechanical properties:
a) an E-modulus, as determined in accordance with ISO 527-1 (version 1996), of at least 450 MPa, more preferably at least 900 MPa, even more preferably at least 950 MPa, still more preferably at least 1000 MPa;
b) a flexural modulus, as determined in accordance with ASTM D790 (version 1995), of at least 780 MPa, more preferably at least 785 MPa, even more preferably at least 790 MPa, still more preferably at least 800 MPa; and
c) an impact strength, unnotched, as determined in accordance with ISO 179-1 (version 2001), of at least 60 kJ/m2, more preferably no fracture resulting from said impact strength test.
13. A method for producing a fibre-reinforced plastic object according to any one of claims 1 to 12, said method comprising the steps of:
a) gravimetric of volumetric feeding 65 - 99.9 wt%, based on the weight of the plastic object, of a rest fraction from plastic recycling, 0.1 - 30 wt% of mineral fibres and 0 - 5 wt% of further additives to a hopper of a melt homogenization device;
b) feeding the components fed to the hopper to a feeding zone of the melt homogenization device wherein at least part of the air is removed and wherein the material is compacted; c) conveying, heating, melting and homogenizing the compacted material from step b) at a temperature of between 170 and 230 °C; and subsequently
d) (i) cooling the homogenized material of step c) and collecting the fibre-reinforced plastic object in the form of a masterbatch or (ii) hot cutting the homogenized material of step c) and collecting the fibre-reinforced plastic object in the form of pellets or a granulate or (iii) feeding the homogenized material of step c) to the mould of an injection- moulding device to form an injection- moulded fibre-reinforced plastic object.
14. Method according to claim 13 wherein the melt homogenization device is a compounder or an injection- moulding device.
15. Method according to claim 14, wherein the injection- moulded fibre-reinforced plastic object is chosen from the group consisting of pallets, bins, containers, pavers, tubes and garden furniture.
16. Method according to any one of claims 13 to 15, wherein at least 90 wt% of the mineral fibres before melt homogenization have a length of between 30 and 70 mm, more preferably between 40 and 60 mm.
17. Use of mineral fibres, preferably glass wool fibres or stone wool fibres, to improve the mechanical properties of plastic objects comprising a rest fraction from plastic recycling, said rest fraction from plastic recycling comprising 10 - 90 wt% of polyethylene, 10 - 90 wt% of polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities.
18. Use according to claim 17, wherein the plastic objects comprise, based on the weight of the plastic object:
a) 65 - 99.9 wt% of the rest fraction from plastic recycling;
b) 0.1 - 30 wt% of the mineral fibres; and
c) 0 - 5 wt% of further additives.
19. Use according to claim 17 or 18, wherein the rest fraction from plastic recycling comprises 30 - 70 wt% of recycled polyethylene, 30 - 70 wt% of recycled polypropylene, 0.1 - 3 wt% of further recycled plastics, and less than 2 wt% of inorganic impurities, based on the weight of the rest fraction.
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CN112714738B (en) * 2018-09-05 2023-02-28 Sabic环球技术有限责任公司 Bicycle frame

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