EP4551643A1 - Particules de polymère thermoplastique expansé ayant une teneur en matériau recyclé, et leur procédé de production - Google Patents

Particules de polymère thermoplastique expansé ayant une teneur en matériau recyclé, et leur procédé de production

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Publication number
EP4551643A1
EP4551643A1 EP23739261.8A EP23739261A EP4551643A1 EP 4551643 A1 EP4551643 A1 EP 4551643A1 EP 23739261 A EP23739261 A EP 23739261A EP 4551643 A1 EP4551643 A1 EP 4551643A1
Authority
EP
European Patent Office
Prior art keywords
styrene
expanded
polymer particles
weight
copolymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23739261.8A
Other languages
German (de)
English (en)
Inventor
Bianca WILHELMUS
Yvonne VAN VEEN
Johannes MEUCHELBÖCK
Holger RUCKDÄSCHEL
Nick WEINGART
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ineos Styrolution Group GmbH
Original Assignee
Ineos Styrolution Group GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ineos Styrolution Group GmbH filed Critical Ineos Styrolution Group GmbH
Publication of EP4551643A1 publication Critical patent/EP4551643A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • 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
    • 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
    • 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
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/30—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
    • C08J2425/00—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
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene

Definitions

  • thermoplastic polymer particles with recycled content and process for their production
  • the invention relates to expanded polymer particles with recycled content based on styrene polymers, a process for their production and the use of the expanded polymer particles for foam moldings.
  • Particulate foams have been used for years in a variety of applications, including construction insulation, packaging, and structural, lightweight automotive wall materials.
  • Particle foams usually consist of many foamed polymer beads that are welded together.
  • particle foams offer the advantage of weight reduction compared to solid materials while at the same time having good mechanical properties.
  • Particle foams made from polyolefins such as polyethylene have been known for decades and are described, for example, in US 6,028,121.
  • CN 107501595A describes a process for producing expanded polypropylene particles.
  • a disadvantage of particle foams made from polyolefins is that they have to be completely foamed during production because the blowing agent does not remain in the polymer material for a long time. In these cases, the blowing agent is loaded immediately before the expansion of the particles, which are then welded together to form molded parts in subsequent steps.
  • US 4,108,806 describes a process for producing expanded and expandable polymer particles based on a polyolefin matrix into which expandable microspheres are introduced.
  • the microspheres consist of a thermoplastic shell and a core made of a volatile liquid blowing agent, which causes the polymer mass to expand when heated. This manufacturing method is complex and results in a polymer mixture of two or more polymer types.
  • Expandable polymer particles including styrene polymers and copolymers, and processes for their production are also described in the literature.
  • WO 2013/085742 describes the provision of an extruded polymer foam made of styrene-acrylonitrile copolymer (SAN), which is produced using a blowing agent mixture of 74-78% by weight of 1,1,1,2-tetrafluoroethane, 13-16% by weight. CO2 and 7-9% by weight of water is produced.
  • SAN styrene-acrylonitrile copolymer
  • US 5,480,599 describes a process for producing particle foams, including from styrene polymers and copolymers. The process makes it possible to at least partially recover the blowing agent after the particles have expanded.
  • EP-A 2384355 describes expandable, thermoplastic polymer particles containing a styrene polymer and a polyolefin. Since the polymers used are not miscible with one another, a compatibilizer must be used to adjust the morphology. The use of polyolefins and compatibilizers is necessary to achieve particle foams with high rigidity and good elasticity, which cannot be achieved with particle foam consisting only of polystyrene.
  • US 3,945,956 describes a process for producing expandable polymer particles in which a volatile liquid blowing agent is enclosed in a hollow sphere made of a styrene-acrylonitrile copolymer.
  • the blowing agent is enclosed in a polymer particle but is not homogeneously distributed in a polymer matrix. When such polymer particles expand, a foam with inhomogeneously distributed cavities is formed.
  • EP-A 0712885 claims expandable beads made of acrylonitrile-butadiene-styrene copolymers (ABS). These are manufactured in a batch process in which ABS beads are impregnated with a blowing agent in an autoclave. It is necessary to modify the bead surface with electrolytes so that the loading of the beads with the propellant can take place in an aqueous medium. This is disadvantageous because the electrolytes remain on the surface and affect the weldability of the beads. can become pregnant. In addition, the quantities that can be produced are limited by the complex coating process, the size of the autoclave required, the discontinuous operation and the long loading time with the blowing agent.
  • EP-A 2614111 discloses expandable, vinyl aromatic polymers which contain 0.5 to 2% by weight of talc and 1 to 5% by weight of carbon black.
  • Vinylaromatic polymers include polystyrene (PS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS) or copolymers of styrene and butadiene.
  • US 2013/059933 teaches a method for producing an expandable, pelletized polymer material consisting of a styrene polymer component with a glass transition temperature of > 130 ° C, and one or more thermoplastic polymers selected from the group consisting of aromatic polyethers; polyolefins; polyacrylates; polycarbonates; polyesters; polyamides; polyethersulfones; Polyether ketones and polyether sulfides. Since the polymer material comprises at least two different polymer classes, the expandable granules obtained are not mechanically recyclable or can only be recycled with difficulty.
  • PS 90-100% by weight (based on P) of a styrene copolymer component, consisting of PS1) one or more styrene-acrylonitrile copolymers (SAN) or
  • PS2 a mixture of one or more styrene-acrylonitrile copolymers (SAN) and one or more styrene-maleic anhydride copolymers (SMA) and/or PS3) one or more styrene-acrylonitrile-maleic anhydride copolymers (SANMA) and
  • thermoplastic polymers 0 to 10% by weight (based on P) of one or more thermoplastic polymers from the group consisting of aromatic polyethers; polyolefins; polyacrylates; polycarbonates (PC); polyesters; polyamides; polysulfones; polyethersulfones (PES); polyether ketones (PEK) and polystyrene;
  • T 2 to 8 parts by weight (based on P) of a physical blowing agent component (T), containing 80 to 100% by weight (based on T)) of one or more hydrocarbons with 2 to 7 carbon atoms, F) a flame retardant system containing 1 up to 10 parts by weight, based on P, of one or more brominated trialkyl phosphates as flame retardants (F1).
  • a flame retardant system containing 1 up to 10 parts by weight, based on P, of one or more brominated trialkyl phosphates as flame retardants (F1).
  • DE 103 58 801 discloses particle foam moldings, obtainable by welding pre-foamed foam particles from expandable, thermoplastic polymer granules, containing 5 - 100% by weight of a styrene copolymer A), 0 to 95% by weight of polystyrene B) and 0 to 95% by weight one of a) and b) different thermoplastic polymer C), characterized in that the particle foam has a density in the range from 8 to 100 g / l.
  • DE 10 2008 023702 teaches a process for the continuous production of expandable polymer particles by incorporating a polymer stream into a second polymer stream containing the expanding system and additives.
  • the addition of additives makes it difficult for the polymer foam to be recycled after the end of its use or service life.
  • DE 103 58 804 discloses expandable styrene polymer granules with at least bi- or multi-modal molecular weight distribution.
  • US 5,049,328 describes a process for producing foam without organic blowing agents. Only inert gases such as CO2, nitrogen or air are used as blowing agents. The process is not suitable for providing expandable polymer particles that can be stored for a certain period of time because the gases consisting of small molecules quickly escape from the polymer mass.
  • inert gases such as CO2, nitrogen or air are used as blowing agents.
  • the process is not suitable for providing expandable polymer particles that can be stored for a certain period of time because the gases consisting of small molecules quickly escape from the polymer mass.
  • foamed materials are combined with non-foamed materials.
  • the foamed material and the non-foamed material consist of the same thermoplastic polymer matrix. Then, at the end of its lifespan, the object can be shredded and melted down again without the material suffering any loss of mechanical properties.
  • a styrene polymer or copolymer is used as a non-foamed material. It would therefore be desirable to have a compatible material also in foamed form, so that overall there is good recyclability when both materials are combined in one object. This can be achieved, for example, with a particle foam made from a styrene polymer or copolymer.
  • plastic recyclates offers several advantages over the production of plastics from fossil sources, such as energy savings, waste reduction, less resource consumption.
  • energy savings in order not to suffer any loss of quality compared to primary plastics when using recyclates and to compensate for the quality fluctuations of the recyclates used, it is advantageous to adjust the properties of the recyclates using suitable additives, as described in WO 2021/074084.
  • KR 101789704 describes the use of recyclates to produce expandable polystyrene particles, but only post-industrial waste is used as recyclates, i.e. waste that is created, for example, when cutting molded parts. Post-consumer waste is not used.
  • CN-A 110105677 teaches the use of recyclates to produce expanded polypropylene particles.
  • the proportion of recyclate is very low at a maximum of 40% by weight, and the resulting polypropylene foam structure is very inhomogeneous.
  • EP-A 1694753 discloses a process for producing expandable, pelletized thermoplastic polymer materials, from a mixture of 50 to 90% by weight of polystyrene and 10 to 50% by weight of styrene copolymer, selected from styrene-butadiene block copolymers, styrene-a -Methylstyrene copolymers, acrylonitrile butadiene styrene (ABS), styrene- Acrylonitrile (SAN), Acrylonitrile Styrene Acrylate (ASA), Methacrylate Butadiene Styrene (MBS) and Methyl Methacrylate Acrylonitrile Butadiene Styrene (MABS).
  • ABS acrylonitrile butadiene styrene
  • SAN styrene- Acrylonitrile
  • ASA Acrylonitrile Styrene Acrylate
  • MMS Methacrylate Buta
  • polymer recyclates can also be added to the styrene polymer melt, but states a maximum proportion of 50% by weight, in particular 1 to 20% by weight.
  • the mechanical properties of expanded polymer compositions with a high polystyrene content are usually disadvantageous. This also applies to the expandable styrene polymer granules described in EP 1 694 755 with at least 70% by weight of polystyrene and 0.1 to 30% by weight of a low molecular weight styrene copolymer consisting of styrene, acrylic acid and alpha-methylstyrene.
  • An object of the present invention is therefore to provide expanded, thermoplastic polymer particles which consist of a high proportion of recyclates and can themselves be easily recycled and which can be processed into particle foams with high rigidity and at the same time good elasticity.
  • a further object is to provide a process for producing such expanded, thermoplastic polymer particles.
  • the expanded, thermoplastic polymer particles contain (or consist of):
  • At least one primary polymer (B), which is at least one styrene polymer (B-1 ) includes, C) 0 to 6% by weight, based on the total weight of (A), (B), (C), (D) and (E), of at least one blowing agent (C);
  • E 0 to 8% by weight, based on the total weight of (A), (B), (C), (D) and (E), of at least one additive (E); where the sum of (A) and (B) amounts to 83 to 100% by weight, based on the total weight of (A), (B), (C), (D) and (E), and where the expanded, thermoplastic polymer particles contain essentially no other polymers in addition to the at least one recyclate (A) and the at least one primary polymer (B).
  • the expanded, thermoplastic polymer particles do not contain more than 5% by weight, preferably not more than 3% by weight, often not more than 1% by weight, based on the total weight of (A), (B).
  • the expanded, thermoplastic polymer particles preferably contain 0% by weight, based on the total weight of (A), (B), (C), (D) and (E), of polymers that do not meet the definition of recyclate (A). and the primary polymer (B).
  • the small amount of foreign polymers improves the recyclability of the expanded polymer particles according to the invention.
  • Styrene polymers are polymers whose polymer chain contains repeating units made of styrene monomers.
  • the styrene polymers according to the invention are selected from the group consisting of styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), acrylate-styrene-acrylonitrile copolymers (ASA), styrene-butadiene block copolymers ( SBC), methyl methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS), methyl methacrylate-butadiene-styrene copolymers (MBS), a(alpha)-methylstyrene-acrylonitrile copolymers (AMSAN), styrene-methyl methacrylate -Copolymers (SMMA), amorphous polystyrene (PS) and impact-
  • the expanded, thermoplastic polymer particles contain at least 10% by weight, often at least 20% by weight, preferably at least 30% by weight, in particular at least 40% by weight, often more than 50% by weight, based on the total weight of (A), (B), (C), (D) and (E), at least one recyclate (A), which comprises at least one styrene polymer (A-1) and consists predominantly of styrene polymers.
  • the expanded thermoplastic polymer particles contain not more than 99% by weight, usually not more than 98% by weight, often not more than 89% by weight, preferably not more than 84% by weight, often not more than 79% by weight, based on the total weight of (A), (B), (C), (D) and (E), of the at least one recyclate (A ).
  • the expanded, thermoplastic polymer particles often contain 40 to 79% by weight, preferably 45 to 74% by weight, often 51 to 72% by weight, based on the total weight of (A), (B), (C), (D) and (E), the at least one recyclate (A).
  • the expanded, thermoplastic polymer particles contain at least 1% by weight, often at least 10% by weight, preferably at least 15% by weight, often at least 20% by weight, based on the total weight of (A), (B), (C), (D) and (E), at least one primary polymer (B), which comprises at least one styrene polymer (B-1) or consists of at least one styrene polymer (B-1).
  • the expanded, thermoplastic polymer particles contain not more than 90% by weight, usually not more than 79% by weight, often not more than 69% by weight, preferably not more than 59% by weight, often less than 49% by weight .-%, based on the total weight of (A), (B), (C), (D) and (E), of the at least one primary polymer (B).
  • the expanded, thermoplastic polymer particles often contain 20 to 59% by weight, preferably 25 to 54% by weight, often 27 to 48% by weight, based on the total weight of (A), (B), (C), (D) and (E), of the at least one primary polymer (B).
  • the expanded thermoplastic polymer particles comprise less than 5% by weight, in particular less than 3% by weight, based on the total weight of (A), (B), (C), (D) and (E).
  • Polymers that do not have repeating units derived from styrene are small amounts of impurities caused by polymers that do not have repeating units derived from styrene can be introduced when the recyclates (A) are obtained due to incomplete separation by type in the recycling process.
  • recyclate (A) is defined as plastics whose origin comes from plastic objects that were recycled and processed at the end of their service life.
  • the processing into recyclate can be carried out using various processes known in industry, see for example Köhnlechner, R. (2014): “Generation of clean PS and ABS fractions from mixed electronic scrap”, in DG Karl J. Thome-Kozmiensky ( Ed.), Recycling and Raw Materials, Volume 7 (pp. 379-400), TK Verlag Karl Thome-Kozmiensky, Neuruppin.
  • additives and/or primary materials may have been added during the production of the recyclates in order to achieve the required material quality.
  • the recyclates (A) differ from the primary polymers (B) in particular in that the recyclates (A) have undergone at least one separate thermal compounding step before use in the expanded, thermoplastic polymer particles according to the invention, such as. B. an extrusion process or an injection molding process.
  • the recyclates (A), in contrast to the primary polymers (B), are therefore often in one at least once at a temperature above the melting range temperature of the recyclate (A), for example at a temperature in a range from 180 ° C to 320 ° C Range from 200 °C to 300 °C, such as 220 °C to 280 °C, determined according to ISO 294, has been mechanically stressed by mixing, in particular by shear forces, for example in an extruder, e.g. B. single-screw or twin-screw extruders, or in other conventional plasticizing devices such as Brabender mills or Banbury mixers.
  • an extruder e.g. B. single-screw or twin-screw extruders
  • other conventional plasticizing devices such as Brabender mills or Banbury mixers.
  • the recyclate (A) may also have been subjected to other processing steps in which the recyclate (A) was subjected to mechanical stress at temperatures below the melting range temperature, such as calendering.
  • the at least one recyclate (A) comprises at least one styrene polymer (A-1) and consists predominantly of styrene polymers.
  • the recyclate (A) preferably consists of at least 80% by weight, often at least 85% by weight, preferably at least 90% by weight or at least 92% by weight, based on the recyclate (A), of at least a styrene polymer (A-1).
  • the recyclate (A) can often contain other components which were added to the composition of the recyclate for the primary use or which ended up in the recyclate (A) due to inadequate separation during the recycling process.
  • the recyclates (A) may contain other components (A-2) such as additives, pigments, foreign polymers or contaminants such as metal parts, in particular aluminum particles.
  • the recyclate (A) does not contain any substances that have a negative effect on further use according to the invention. These include, in particular, halogen-containing flame retardants.
  • the components (A-2) generally make up not more than 20% by weight, often not more than 15% by weight, preferably not more than 10% by weight or not more than 8% by weight on the recyclate (A), the recyclate (A).
  • the recyclate (A) preferably contains essentially no other polymers.
  • the recyclate (A) contains not more than 5% by weight, preferably not more than 3% by weight, often not more than 1% by weight, based on the total weight of the recyclate (A), of polymers contains that do not meet the definition of styrene polymer (A-1) are equivalent to.
  • the recyclate (A) preferably contains 0% by weight, based on the total weight of the recyclate (A), of polymers that do not correspond to the definition of the styrene polymer (A-1).
  • the small amount of foreign polymers improves the recyclability of the expanded polymer particles according to the invention.
  • primary material and primary polymers are plastics that are made from fossil raw materials and have not yet been recycled during their service life.
  • the at least one primary polymer (B) comprises or consists of at least one styrene polymer (B-1).
  • the primary polymer (B) preferably comprises at least 80% by weight, often at least 85% by weight, preferably at least 90% by weight or at least 92% by weight, based on the primary polymer (B), of at least one styrene polymer (B -1).
  • the primary polymer (B) can contain components (B-2) which are usually used during the production of the styrene polymers and serve, for example, to improve processability. Examples of the component (B-2) include additives such as lubricants and mold release agents.
  • the primary polymer comprises 100% by weight, based on the primary polymer (B), of at least one styrene polymer (B-1).
  • the primary polymer of this embodiment comprises 0% by weight, based on the primary polymer (B), of a component (B-2).
  • the primary polymer (B) preferably contains essentially no other polymers. This means that the primary polymer (B) contains not more than 5% by weight, preferably not more than 3% by weight, often not more than 1% by weight, based on the total weight of the primary polymer (B), of polymers contains that do not meet the definition of styrene polymer (B-1).
  • the primary polymer (B) preferably contains 0% by weight, based on the total weight of the primary polymer (B), of polymers that do not correspond to the definition of the styrene polymer (B-1). The small amount of foreign polymers improves the recyclability of the expanded polymer particles according to the invention.
  • the expanded, thermoplastic polymer particles consist of the at least one recyclate (A) and the at least one primary polymer (B). In another embodiment, the expanded, thermoplastic polymer particles consist of the at least one recyclate (A), the at least one primary polymer (B) and the at least one blowing agent (C). In a further embodiment, the expanded, thermoplastic polymer particles consist of the at least one recyclate (A), the at least one primary polymer (B) and the at least a nucleating agent (D). In a further embodiment, the expanded, thermoplastic polymer particles consist of the at least one recyclate (A), the at least one primary polymer (B), the at least one blowing agent (C) and the at least one nucleating agent (D).
  • the expanded, thermoplastic polymer particles consist of the at least one recyclate (A), the at least one primary polymer (B), and the at least one additive (E).
  • the expanded, thermoplastic polymer particles consist of the at least one recyclate (A), the at least one primary polymer (B), the at least one blowing agent (C), and the at least one additive (E).
  • the expanded, thermoplastic polymer particles consist of the at least one recyclate (A), primary polymer (B), the at least one nucleating agent (D) and the at least one additive (E).
  • the expanded, thermoplastic polymer particles consist of the at least one recyclate (A), the at least one primary polymer (B), the at least one blowing agent (C), the at least one nucleating agent (D) and the at least one additive (E) .
  • the at least one recyclate (A) and the at least one primary polymer (B) comprise or consist of polymers that belong to the same polymer class.
  • the expanded polymer particles according to the invention can be recycled particularly well, for example in mechanical recycling processes.
  • the at least one recyclate (A) and the at least one primary polymer (B) comprise or consist of polymers that belong to miscible polymer classes. Even then, there is good recyclability, e.g. in mechanical recycling processes.
  • polymer class refers to polymers that are made up of repeating units of the same monomers.
  • miscible means that no domains of a first polymer form in a continuous matrix of a second polymer, i.e. the first polymer is dissolved in the second polymer.
  • miscible polymer classes also includes polymers which form polymer blends in which a continuous phase and a discontinuous phase are formed, but the discontinuous phase has domains with an average domain size of less than 5 pm.
  • the primary polymer (B) is preferably dispersed in the form of discontinuous phase domains in a continuous phase of the recyclate (A), where- in which the discontinuous phase domains of the primary polymer (B) comprise at most phase domains with an average diameter of ⁇ 2 pm, more preferably ⁇ 200 nm, often ⁇ 100 nm.
  • the expanded thermoplastic polymer particles contain a total of 83 to 100% by weight, based on the total weight of (A), (B), (C), (D) and (E), at least one recyclate (A) and at least one primary polymer ( B), which comprise styrene polymers (A-1) or styrene polymers (B-1), the styrene polymers (A-1) and styrene polymers (B-1) preferably being selected from the group consisting of styrene-acrylonitrile copolymers ( SAN), acrylonitrile-butadiene-styrene copolymers (ABS), acrylate-styrene-acrylonitrile copolymers (ASA), styrene-butadiene block copolymers (SBC), methyl methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS), methyl methacrylate-butadiene -St
  • the styrene polymers (A-1) or styrene polymers (B-1) are preferably selected from the group consisting of styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS) or acrylonitrile-styrene-acrylate. copolymers (ASA).
  • SAN styrene-acrylonitrile copolymers
  • ABS acrylonitrile-butadiene-styrene copolymers
  • ASA acrylonitrile-styrene-acrylate. copolymers
  • the expanded thermoplastic polymer particles comprise at least 89% by weight, often at least 94.5% by weight, based on the total weight of (A), (B), (C), (D) and (E) , at least one recyclate (A) and at least one primary polymer (B).
  • the expanded thermoplastic polymer particles often comprise 93 to 99.5% by weight, particularly preferably 96 to 99% by weight, based on the total weight of (A), (B), (C), (D) and (E ), at least one recyclate (A) and at least one primary polymer (B).
  • the recyclate (A) or the primary polymer (B) contains less than 50% by weight, preferably less than 25% by weight, more preferably less than 10% by weight, based on the recyclate (A) or the primary polymer (B), on styrene homopolymer. In one embodiment, the recyclate (A) and the primary polymer (B) do not contain any styrene homopolymer. In one embodiment, the expanded, thermoplastic polymer particles contain no polymers other than the recyclate (A) and the primary polymer (B), which preferably do not contain any styrene homopolymer.
  • the recyclate (A) or the primary polymer (B) contains less than 50% by weight, preferably less than 25% by weight, more preferably less than 10% by weight, based on the recyclate (A) or the primary polymer (B), to copolymers which include maleic anhydride and/or maleimide.
  • the recyclate (A) and the primary polymer (B) do not contain a copolymer which comprises maleic anhydride and/or maleimide.
  • the expanded, thermoplastic polymer particles do not contain any polymers other than the recyclate (A) and the primary polymer (B), which preferably do not contain any copolymers which include maleic anhydride and/or maleimide.
  • the recyclate (A) or the primary polymer (B) contains less than 50% by weight, preferably less than 25% by weight, more preferably less than 10% by weight, based on the recyclate (A) or the primary polymer (B), on styrene-maleic anhydride copolymer (SMA). In a further embodiment, the recyclate (A) and the primary polymer (B) do not contain any styrene-maleic anhydride copolymer (SMA).
  • the expanded, thermoplastic polymer particles contain no polymers other than the recyclate (A) and the primary polymer (B), which preferably do not contain any styrene-maleic anhydride copolymer (SMA).
  • SMA styrene-maleic anhydride copolymer
  • the recyclate (A) and the primary polymer (B) contain less than 50% by weight, preferably less than 25% by weight, more preferably less than 10% by weight, based on the recyclate (A ) or the primary polymer (B), on a (alpha)-methylstyrene-acrylonitrile copolymer (AMSAN).
  • the recyclate (A) and the primary polymer (B) do not contain any a(alpha)-methylstyrene-acrylonitrile copolymer (AMSAN).
  • the expanded, thermoplastic polymer particles contain no polymers other than the recyclate (A) and the primary polymer (B), which preferably do not contain any ⁇ (alpha)-methylstyrene-acrylonitrile copolymer (AMSAN).
  • A recyclate
  • B primary polymer
  • AMSAN ⁇ (alpha)-methylstyrene-acrylonitrile copolymer
  • the recyclate (A) and the primary polymer (B) contain less than 50% by weight, preferably less than 25% by weight, more preferably less than 10% by weight, based on the recyclate (A ) or the primary polymer (B), on styrene-isoprene-styrene block copolymer (SIS).
  • the recyclate (A) and the primary polymer (B) do not contain any styrene-isoprene-styrene block copolymer (SIS).
  • the expanded, thermoplastic polymer particles contain no polymers other than the recyclate (A) and the primary polymer (B), which preferably do not contain any styrene-isoprene-styrene block copolymer (SIS).
  • the recyclate (A) or the primary polymer (B) contains less than 50% by weight, preferably less than 25% by weight, more preferably less than 10% by weight, based on the recyclate (A) or the primary polymer (B), on styrene-acrylonitrile copolymer (SAN).
  • the recyclate (A) and the primary polymer (B) do not contain any styrene-acrylonitrile copolymer (SAN).
  • the expanded, thermoplastic polymer particles contain no polymers other than the recyclate (A) and the primary polymer (B), which preferably do not contain any styrene-acrylonitrile copolymer (SAN).
  • the recyclate (A) and the primary polymer (B) contain only styrene polymers of the same polymer class, selected from the group consisting of styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), acrylate Styrene-acrylonitrile copolymers (ASA), styrene-butadiene block copolymers (SBC), methyl methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS), methyl methacrylate-butadiene-styrene copolymers (MBS), a(alpha)-methylstyrene -Acrylonitrile copolymers (AMSAN), styrene-methyl methacrylate copolymers (SMMA), styrene-maleic anhydride copolymers (SMA), styrene-maleic
  • the recyclate (A) and the primary polymer (B) contain only styrene polymers of the same polymer class, selected from the group consisting of styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), acrylate Styrene-acrylonitrile copolymers (ASA), and a(alpha)-methyl-styrene-acrylonitrile copolymers (AMSAN).
  • SAN styrene-acrylonitrile copolymers
  • ABS acrylonitrile-butadiene-styrene copolymers
  • ASA acrylate Styrene-acrylonitrile copolymers
  • AMSAN a(alpha)-methyl-styrene-acrylonitrile copolymers
  • the recyclate (A) and the primary polymer (B) contain only styrene polymers of the same polymer class, selected from the group consisting of acrylonitrile-butadiene-styrene copolymers (ABS) and acrylate-styrene-acrylonitrile copolymers (ASA ), preferably acrylonitrile-butadiene-styrene copolymers (ABS).
  • ABS acrylonitrile-butadiene-styrene copolymers
  • ASA acrylate-styrene-acrylonitrile copolymers
  • the recyclate (A) and the primary polymer (B) contain polymer blends comprising styrene-acrylonitrile copolymers (SAN) and acrylonitrile-butadiene-styrene copolymers (ABS); Styrene-acrylonitrile copolymers (SAN) and acrylate-styrene-acrylonitrile copolymers (ASA); a(alpha)-methylstyrene-acrylonitrile copolymers (AMSAN) and acrylonitrile-butadiene-styrene copolymers (ABS); or a(alpha)-methylstyrene-acrylonitrile copolymers (AMSAN) and acrylate-styrene-acrylonitrile copolymers (ASA).
  • Polymer blends comprising styrene-acrylonitrile copolymers (SAN) and acrylonitrile-butadiene-styrene copolymers (ABS
  • the expanded thermoplastic polymer particles comprise less than 5% by weight, preferably less than 3% by weight, often less than 2% by weight, of the total weight of (A), (B), ( C), (D) and (E), other thermoplastic polymers, in particular selected from the group consisting of polyamides (PA), polyolefins such as polypropylene (PP) or polyethylene (PE), polyacrylates such as polymethyl methacrylate (PMMA), polycarbonate ( PC), polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyether sulfone (PES), polyether ketones (PEK), polyether sulfides (PES), polylactates, polyphenylene ethers (PPO/PPE), ethylene-vinyl acetate copolymers (EVA), Styrene-ethylene-butylene-styrene copolymers (SEES), styrene-ethylene-propylene cop
  • PA polyamides
  • the expanded thermoplastic polymer particles do not include any thermoplastic polymers selected from the group consisting of polyamide (PA), polyolefins such as polypropylene (PP) or polyethylene (PE), polyacrylates such as polymethyl methacrylate (PMMA), polycarbonate (PC), polyesters such as polyethylene terephthalate (PET ) or polybutylene terephthalate (PBT), polyethersulfone (PES), polyether ketones (PEK), polyether sulfides (PES), polylactates, polyphenylene ethers (PPO/PPE), ethylene-vinyl acetate copolymers (EVA), styrene-ethylene-butylene-styrene copolymers ( SEES), styrene-ethylene-propylene copolymers (SEP), and styrene-butyl acrylate copolymers.
  • PA polyamide
  • PE polyolefins
  • PE polypropylene
  • PE poly
  • the styrene polymers according to the invention usually have a weight-average molecular weight Mw in a range from 10,000 g/mol to 1,000,000 g/mol, preferably in a range from 50,000 to 500,000 g/mol, often in a range from 80,000 to 250,000 g/mol.
  • the molecular weight Mw can be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as eluent and with polystyrene calibration.
  • the styrene polymer of the recyclate (A) has a weight-average molecular weight Mw that is not more than 75%, preferably not more than 50%, often not more than 30%, of the weight-average molecular weight Mw of the styrene polymer of the primary polymer (B) differs.
  • the weight-average molecular weight Mw of the primary polymer (B) is in a range from 25,000 g/mol to 175,000 g/mol, preferably 50,000 g/mol to 150,000 g/mol, often 70,000 g/mol to 130,000 g/mol.
  • the styrene polymers according to the invention usually have a melt volume flow rate MVR (220 ° C/10 kg) according to ISO 1133 of 1 to 30 cm 3 /10 min, preferably 10 to 25 cm 3 /10 min.
  • the blowing agent (component C) is homogeneously distributed in the expanded, thermoplastic polymer particles in a polymer matrix consisting of the one or more recyclates (A) and the at least one primary polymer (B).
  • the expanded, thermoplastic polymer particles contain 0 to 6% by weight, preferably 0 to 4% by weight, often preferably 0 to 2% by weight, based on the total weight of (A), (B), (C), (D) and (E), at least one physical blowing agent, for example an inorganic physical blowing agent such as CO2 or nitrogen, and / or an organic, physical blowing agent such as C3 to C8 aliphatic hydrocarbons, alcohols, Ketones, ethers or halogenated hydrocarbons, preferably CO2 or alternatively iso-butane, n-butane, iso-pentane, n-pentane, cyclo-pentane, or mixtures thereof.
  • the blowing agent comprises at least one organic, physical blowing agent.
  • the blowing agent comprises less than 5% by weight, more preferably less than 2% by weight, based on the total weight of component (C), of water.
  • the blowing agent is essentially free of water, i.e. it comprises not more than 0.5% by weight, preferably not more than 0.1% by weight, based on the total weight of component (C), of water.
  • the expanded, thermoplastic polymer particles contain 0 to 3% by weight, preferably 0 to 2% by weight, particularly preferably 0 to 0.5% by weight, based on the total weight of (A), (B ), (C), (D) and (E), at least one nucleating agent, for example talc, aluminum oxide or silicon dioxide.
  • at least one nucleating agent for example talc, aluminum oxide or silicon dioxide.
  • no talc, aluminum oxide or silicon dioxide is added as component (D) to the expanded thermoplastic polymer particles during production.
  • no nucleating agent is added as component (D) to the expanded, thermoplastic polymer particles during production, ie 0% by weight, based on the total weight of (A), (B), (C), (E) and (E).
  • the expanded, thermoplastic polymer particles contain nucleating agents, in particular from the recyclate (A) originate. It was found that the additives and impurities optionally contained in the recyclate (A) are generally sufficient to induce the desired pore formation in the expanded, thermoplastic polymer particles.
  • the expanded, thermoplastic polymer particles according to the invention can comprise further additives (E) in amounts that do not impair the pore formation and the resulting foam structure.
  • the expanded, thermoplastic polymer particles according to the invention often comprise at least one additive (E) in amounts of 0 to 8 wt.%, preferably 0 to 5 wt.%, more preferably 0 to 3 wt.%, for example 0.1 to 3 % by weight, based on the total weight of (A), (B), (C), (D) and (E).
  • Suitable additives (E) are known to those skilled in the art and include, for example, plasticizers, flame retardants, preferably non-halogen-containing flame retardants, soluble and insoluble inorganic and/or organic dyes and pigments, fillers or reinforcing materials (glass fibers, carbon fibers, etc.), co-blowing agents , antioxidants, heat stabilizers, UV stabilizers, peroxide destroyers, antistatic agents, lubricants, mold release agents, antiblocking agents, processing aids, and combinations of two or more thereof.
  • the expanded thermoplastic polymer particles do not contain halogen-containing flame retardants.
  • Preferred flame retardants include components based on phosphorus compounds that are known for this application in particular.
  • antioxidants and heat stabilizers are halides of metals from group I of the periodic table, for example sodium, potassium and/or lithium halides, possibly in combination with copper (1) halides, for example chlorides, bromides, iodides, sterically hindered phenols , hydroquinones, various substituted representatives of these groups and their mixtures in concentrations of up to 1% by weight, based on the total weight of the expanded, thermoplastic polymer particles.
  • thermoplastic polymer particles Various substituted resorcinols, salicylates, Benzotriazoles and benzophenones are called.
  • organic dyes such as nigrosine, pigments such as titanium dioxide, phthalocyanines, ultramarine blue and carbon black can be contained as dyes in the thermoplastic polymer particles, as well as fibrous and powdery fillers and reinforcing agents. Examples of the latter include carbon fiber, glass fiber, amorphous silica, calcium silicate (wollastonite), aluminum silicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica and feldspar.
  • Lubricants and mold release agents which can generally be used in amounts of up to 1% by weight, often 0.1 to 0.8% by weight, based on the total weight of the expanded, thermoplastic polymer particles, are, for example, long-chain fatty acids such as stearic acid or behenic acid, their salts (e.g. Car or Zn stearate) or esters (e.g. stearyl stearate or pentaerythritol tetrastearate) as well as amide derivatives (e.g. ethylenebisstearylamide).
  • long-chain fatty acids such as stearic acid or behenic acid
  • their salts e.g. Car or Zn stearate
  • esters e.g. stearyl stearate or pentaerythritol tetrastearate
  • amide derivatives e.g. ethylenebisstearylamide
  • mineral-based antiblocking agents can be included in amounts of up to 0.1% by weight, based on the total weight of the expanded, thermoplastic polymer particles.
  • examples include amorphous or crystalline silica, calcium carbonate or aluminum silicate.
  • mineral oil preferably medical white oil
  • plasticizers which may be mentioned are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N-(n-butyl)benzenesulfonamide and o- and p-tolylethyl sulfonamide.
  • One subject of the invention is a process for producing expanded, thermoplastic polymer particles, comprising the steps: a) adding the at least one blowing agent (C) and optionally the at least one blowing agent (C) to a mixture of the at least one recyclate (A) and the at least one primary polymer (B). at least one nucleating agent (D) and/or the at least one additive (E), so that a polymer mixture (I) is created; b) granulating the blowing agent-loaded polymer mixture (I) to obtain expandable polymer particles; and c) expanding the expandable polymer particles.
  • only the at least one recyclate (A), the at least one primary polymer (B) and the at least one blowing agent (C) are used as starting materials in the process according to the invention.
  • only the at least one recyclate (A), the at least one primary polymer (B), the at least one blowing agent (C) and the at least one nucleating agent (D) are used in the process.
  • only the at least one recyclate (A), the at least one primary polymer (B), the at least one blowing agent (C), the at least one nucleating agent (D) and the at least one additive (E) are used in the process.
  • only the at least one recyclate (A), the at least one primary polymer (B), the at least one blowing agent (C), and the at least one additive (E) are used in the process.
  • Process step a) preferably takes place at a temperature above the glass transition temperature of the at least one recyclate (A) or the mixture of the at least one recyclate (A) and the at least one primary polymer (B).
  • the temperature in process step a) is often in a range from 150°C to 250°C, often in a range from 170 to 220°C.
  • At least process step b), often process steps b) and c), takes place at a temperature around the glass transition temperature of the at least one recyclate (A) or the mixture of the at least one recyclate (A) and the at least one primary polymer (B).
  • the temperature in process step b) and optionally c) is often in a range from 50°C to 250°C.
  • At least process step a), particularly preferably process steps a) and b), takes place under a pressure which exceeds atmospheric pressure.
  • Process step c) preferably takes place under a pressure that does not exceed atmospheric pressure.
  • process steps a), b) and c) take place in an extruder with subsequent underwater granulation at a water pressure in the range 0 to 11 bar, preferably 0 to 5 bar, particularly preferably 0.5 to 1.5 bar.
  • the water temperature during underwater granulation is below the glass transition temperature of the at least one recyclate (A) or the mixture of the at least one recyclate (A) and the at least one primary polymer (B), often in a range from 20 ° C to 80 ° C.
  • the extruder temperature is above the glass transition temperature of the at least one recyclate (A) or the mixture of the at least one recyclate (A) and the at least one primary polymer (B), often in a range from 170 ° C to 250 ° C.
  • process steps a), b) and c) take place in an autoclave.
  • the granulated mixture of the recyclates (A) and the primary polymers (B), which has optionally been mixed with a nucleating agent (D) and/or further additives (E), is impregnated with the blowing agent (C) under pressure. The pressure is then released so that foamed polymer particles are obtained.
  • a recyclate for example recycled SAN (rSAN), recycled ABS (rABS) or recycled ASA (rASA), and a primary polymer (B), for example SAN, ABS or ASA, optionally mixed with the nucleating agent (D) and/or other additives (E), is melted in a twin-screw extruder and impregnated with the blowing agent (C).
  • a preferred embodiment is the use of a separately produced mixture of the recyclate (A) and the primary polymer (B), which has, if necessary, already been adjusted to a desired material quality with the addition of additives.
  • the blowing agent-laden melt can then be extruded and cut into foam sheets, strands or particles in process step b) through a corresponding nozzle.
  • a preferred embodiment is extrusion through a micro-hole plate with one or, as a rule, several holes with a hole diameter of 0.1 to 2.4 mm, preferably 0.2 to 1.2 mm, particularly preferably 0.5 to 0.8 mm, so that particles are created.
  • the melt emerging from the micro-perforated plate is guided into a stream of water, where the melt is cut into individual particles by a suitable device. Setting the appropriate low counterpressure and a suitable temperature in the water flow of this so-called underwater granulation enables targeted production of expandable or expanded polymer particles.
  • process steps a) and/or b) can take place entirely or partially in a suspension.
  • the recyclate (A) and the primary polymer(s) (B), as well as optionally nucleating agent (D) and/or additive(s) (E), can be converted into a suspension, preferably an aqueous suspension, which is then mixed with at least is loaded with a gaseous propellant (C) such as CO2 or nitrogen under increased pressure.
  • a gaseous propellant (C) such as CO2 or nitrogen under increased pressure.
  • the pressure at which the propellant (C) is introduced is, for example, in the range from 1 bar to 20 bar, often in the range from 1.2 bar to 15 bar, or 1.5 bar to 10 bar.
  • the polymer particles obtained are isolated, for example by filtration and/or centrifugation, and, if necessary, washed.
  • the expansion step c) can be carried out by reducing the ambient pressure and/or increasing the ambient temperature.
  • the expanded, thermoplastic polymer particles according to the invention with recycled content preferably have an average particle diameter in the range from 0.1 to 10 mm, preferably from 0.3 to 5 mm, particularly preferably from 0.5 to 4 mm. Expanded polymer particles with a narrow particle size distribution and an average particle diameter in the specified range lead to better filling of the mold when the polymer particles are welded to form a molded part. They enable a more delicate molded part design and a better molded part surface.
  • the specific density of the expanded polymer particles with recyclate content is preferably in the range from 10 to 250 g/L, particularly preferably from 20 to 200 g/L, particularly preferably from 25 to 150 g/L and particularly preferably from 30 to 100 g/L.
  • the expanded thermoplastic polymer particles preferably have an average cell size between 50 and 400 pm, more preferably between 100 and 300 pm.
  • the expanded, thermoplastic polymer particles according to the invention with recycled content can be filled into a mold, which is then closed and hot air and/or steam flows through it and is thus heated. Alternatively, heating can be done using radio waves or infrared radiation.
  • the polymer particles fuse together and thus form a foam molding.
  • the processing pressure and temperature are chosen so low that the pore structure in the cell membranes is preserved. The pressure is usually in the range from 0.5 to 1.0 bar.
  • the expanded, thermoplastic polymer particles according to the invention can be further processed immediately after production.
  • the application of a coating to the surface of the expanded thermoplastic polymer particles according to the invention is not necessary, but can be done optionally if, for example, an antistatic finish is desired. Antistatic coatings are known to those skilled in the art.
  • antistatic coatings are quaternary ammonium salts, polyoxyethylene alkylphenol ether, glycerol esters, stearic acid monoglyceride, stearic acid triglyceride, ethylene bi-stearamide, polyethylene glycol sorbitan monooleate, zinc stearate, sodium alkanesulfonate, bis-(2-hydroxyethyl)-octyl -Methyl ammonium p-toluenesulfonate, polyvinyl propionate and surfactants.
  • Suitable antistatic coatings are, for example, under the trade name Larostat (manufacturer BASF, Germany). Neostatic® (manufacturer Peter H. Urdahl GmbH, Germany) or Chemstat® (manufacturer PCC Chemax Inc., Poland) are commercially available.
  • a further object of the invention is the use of the expanded, thermoplastic polymer particles according to the invention with recycled content for the production of molded parts such as foam bodies, which are preferably formed by welding the expanded polymer particles using hot air, steam, radio waves and / or infrared radiation.
  • the molded parts obtained can be used in numerous applications, in particular as insulation material, damping material, packaging material or as lightweight construction material, for example in the automotive sector.
  • the molded part preferably has a specific density of less than 250 g/L, preferably less than 200 g/L, particularly preferably less than 150 g/L.
  • the molded part preferably has a compressive strength at 10% elongation of more than 250 kPa.
  • the molded part preferably has a flexural modulus of more than 15 MPa.
  • the polymer mixture (I) thus obtained was then cooled in a single-screw extruder (type E 45 M, manufacturer Collin GmbH) with a screw diameter of 45 mm and a length-to-diameter ratio of 30 and the melt was extruded through a heated perforated plate.
  • the polymer strand was chipped off using underwater granulation, so that a blowing agent-loaded mini-granulate with a narrow particle size distribution was obtained.
  • the counter pressure in the underwater granulation was set to 0.5 to 1.5 bar.
  • the expanded polymer particles were welded in a TVZ 162/100 PP molding machine (manufacturer Teubert Maschinenbau GmbH) at approx. 120-125 °C in order to produce test specimens for measuring the thermal and mechanical properties.
  • the density of the expanded particles was determined using an AG245 density balance (manufacturer Mettler Toledo) in accordance with ISO 1183.
  • the cell size was measured by measuring the cell diameters using a profilometer, manufacturer Keyence, and the ImageJ software on foam particles halved using cryofracture. 50 cells per particle of three particles per material were evaluated.
  • the thermal characterization of the test specimens was carried out in accordance with DIN EN 12667 using a heat flow measuring plate apparatus type HMF Lambda Small (manufacturer Netzsch) using test specimens with dimensions of 200 x 200 x 20 mm and a temperature gradient of 20 K.
  • Example pairs 1 and 2 as well as 3 and 4 each have the same recycled content, but differ in their degree of foaming, which is specifically adjusted by varying the process parameters. The degree of foaming is reflected in the foam density. To compare mechanical and thermal properties, foams with the same density should be used, as these properties are strongly influenced by the foam density. Examples 1 and 3 and comparative examples 5 and 6 are foamed more than examples 2 and 4.
  • the thermal conductivity of Examples 1 and 3 according to the invention is significantly lower than that of Comparative Examples 5 and 6 not according to the invention, i.e. the insulating effect of the examples according to the invention is significantly better if the polymer mass contains a recycled content (see also FIG. 1).
  • the foam from Comparative Example 5 was produced without nucleating agents, which leads to inhomogeneous foam structures in the polymer compositions without recycled content.
  • the use of nucleating agents improves the foam structure (comparative example 6), but the thermal conductivity is still higher (and the insulation effect is therefore worse) than that of the foams with recycled content (examples 1 and 3). Even without nucleating agents, very good insulating foams can be produced if the polymer mass contains a high proportion of recycled material.
  • Examples 1 and 3 according to the invention also show a finer and more homogeneous cell structure than comparative example 5 (see FIGS. 4 and 5).
  • Fig. 4 shows the cell structure of a polymer foam according to the invention with 50% by weight of recyclate content according to Example 1.
  • Fig. 5 shows the cell structure of a foam not according to the invention without recyclate content according to Comparative Example 5. The foam without recyclate content is inhomogeneous, with large cells. In the foams not according to the invention, a good cell structure can only be achieved through the use of nucleating agents, as shown in FIG. 6. In Fig. 6 the foam structure of Comparative Example 6 can be seen; it is a foam not according to the invention without any recycled content, but with a nucleating agent.
  • Example 1 The average cell size of Example 1 according to the invention is significantly smaller than the cell size in Comparative Example 5 not according to the invention without nucleating agents, so the cell structure in the examples according to the invention is significantly better than in the examples not according to the invention.
  • Test specimens that were produced from the compositions according to the invention (Examples 1 and 3) have better compressive strength than test specimens according to the comparative examples 5 and 6 not according to the invention (see also FIG. 2).
  • Comparative example 5 shows only a very low compressive strength.
  • the addition of nucleating agents in Comparative Example 6 improves the compressive strength, but does not reach the good values of the examples according to the invention with recycled content.
  • the compositions according to the invention with a high proportion of recyclate are suitable for producing foams with very good compressive strength even without the addition of nucleating agents.
  • the measurement data of the flexural modulus of the test specimens also clearly show that the foams according to the invention with recycled content have significantly improved properties compared to the foams not according to the invention. In the latter case, the addition of nucleating agents improves the flexural modulus (comparative example 6), but the good values of the examples according to the invention with recycled content are still not achieved (see also FIG. 3).
  • foam bodies By using a high proportion of recyclate, foam bodies can be produced that have better mechanical and thermal properties than foam bodies made only from primary material, even without the addition of nucleating agents.
  • Fig. 1 shows the graphical representation of the experimentally obtained data of the thermal conductivity at 25 ° C in W / m * K of Examples 1 and 3 and Comparative Examples 5 and 6.
  • Fig. 2 shows the graphical representation of the experimentally obtained data of the compressive strength at 10% elongation in kPa of Examples 1 and 3 and Comparative Examples 5 and 6.
  • Fig. 3 shows the graphical representation of the experimentally obtained data of the flexural modulus in MPa of Examples 1 and 3 and Comparative Examples 5 and 6.
  • Example 4 shows an electron microscope image of an expanded particle according to the invention, which was obtained from Example 1.

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Abstract

L'invention concerne des particules de polymère thermoplastique expansé ayant une teneur en matériau recyclé à base de polymères de styrène, un procédé de production de celles-ci, et l'utilisation des particules de polymère expansé dans une partie de mousse moulée. Les particules de polymère thermoplastique expansé contiennent de 10 à 99 % en poids, par rapport au poids total, d'au moins un matériau recyclé (A), qui comprend au moins un polymère de styrène (A-1) et qui est largement constitué de polymères de styrène, de 1 à 90 % en poids, sur la base du poids total, d'au moins un polymère primaire (B), et éventuellement d'au moins un propulseur (C), d'au moins un agent de nucléation (D), et/ou d'au moins un additif (E).
EP23739261.8A 2022-07-08 2023-07-07 Particules de polymère thermoplastique expansé ayant une teneur en matériau recyclé, et leur procédé de production Pending EP4551643A1 (fr)

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PCT/EP2023/068823 WO2024008914A1 (fr) 2022-07-08 2023-07-07 Particules de polymère thermoplastique expansé ayant une teneur en matériau recyclé, et leur procédé de production

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