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WO2025027149A1 - Article composite en polymère vinylaromatique recyclable et son procédé de production - Google Patents

Article composite en polymère vinylaromatique recyclable et son procédé de production Download PDF

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Publication number
WO2025027149A1
WO2025027149A1 PCT/EP2024/071859 EP2024071859W WO2025027149A1 WO 2025027149 A1 WO2025027149 A1 WO 2025027149A1 EP 2024071859 W EP2024071859 W EP 2024071859W WO 2025027149 A1 WO2025027149 A1 WO 2025027149A1
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WO
WIPO (PCT)
Prior art keywords
vinylaromatic
vinylaromatic polymer
polymer composition
segment
total weight
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
PCT/EP2024/071859
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English (en)
Inventor
Norbert Niessner
Bianca WILHELMUS
Yvonne VAN VEEN
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
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Publication of WO2025027149A1 publication Critical patent/WO2025027149A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • F25D23/06—Walls
    • F25D23/065—Details
    • F25D23/066—Liners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a vinylaromatic polymer composite article comprising at least two segments comprising vinylaromatic polymer compositions, each of which comprises at least one vinylaromatic (co)polymer, wherein the percentages of repeating units derived from vinylaromatic monomers in each vinylaromatic (co)polymer differ from each other by less than 25 wt.-%.
  • the vinylaromatic polymer composite article is characterized by reduced delamination tendency and improved recyclability.
  • the invention further relates to a process for producing the vinylaromatic polymer composite article and to the use of the obtained vinylaromatic polymer composite article as component of refrigerating devices or freezing devices.
  • Refrigerating devices and freezing devices are widely used in the industry and private households. They typically comprise different materials including metals, glass, and different types of polymer compositions, in particular insulation material (often made of polyurethane foams) and liner (often made of vinylaromatic polymers). Due to the variety of different materials used in refrigerators and freezers, end-of-life recycling often requires complex processes.
  • the technology of recycling waste refrigerators and freezers mainly consists of two steps.
  • the first step includes the manual disassembly to recover the accessories, such as drawers, shelfs, compressors, condensers, cooling equipment, wires and other easy-to-disassemble parts.
  • Manual dismantling, mechanical separation and other methods are typically used to recycle the housings of waste refrigerators and freezers. Manual dismantling is a generally accepted solution in the industry.
  • a second step the remaining polymeric materials that have not been dismantled in the first step are subjected to thermal treatment for energy recovery, as it is currently difficult to mechanically recycle this mixture of different materials, which are often bonded or welded together. This is disadvantageous, because the materials are lost, and the material cycle is not closed. Moreover, improper incineration may produce carcinogenic substances, such as dioxin and furans.
  • CN-A 101670355 describes a method for the treatment of waste refrigerators, with a manual disassembly step, followed by an extraction of the refrigerant liquids and a subsequent crushing process.
  • the polyurethane foam is removed by wind-sifting, it is not further processed to a valuable recyclate.
  • Other plastics are also not recycled. The majority of the polymers are wasted and not recycled.
  • CN-A 106269803 describes a dismantling and resource classification recycling procedure for waste refrigerators, in which iron, polyurethane foam, copper, aluminum, and ABS and other plastics can be recovered.
  • the process of separation is often not complete and leads to contamination of the recovered polymers.
  • EP-A 1747870 relates to a method and equipment for recycling plastic material, particularly plastic material combined with other materials, such as materials deriving from the recycling of household appliances, refrigerators, microwave ovens, air-conditioners, computers, telephones and other electronic devices.
  • the recycling method comprises at least one isolating step and one surface purification step to obtain a polymer recyclate, in which said surface purification step is a simultaneous heat and abrasive treatment.
  • EP-A 1747823 relates to a cryo-treating method and equipment for recycling of various materials, particularly plastic materials combined with materials of a different nature, such as the one deriving from household appliances, e.g. refrigerators or the like.
  • US 2008/190819 relates to a method for separating differently additivated polymers based on polystyrene, copolymers and/or blends thereof. Said method is used in particular for recycling of flame-retardant plastic materials, as can be found in old electrical appliances.
  • the method is characterized by a density separation with at least one liquid or gaseous separation medium.
  • EP-A 2399719 describes the removal of specific polystyrene parts as a first step in refrigerator recycling, to recover high quality polystyrene flakes.
  • ABS acrylonitrile-butadiene- styrene copolymer
  • PS polystyrene
  • Expandable polystyrene compositions are known in the art.
  • CN-A 113444280 describes the use of a polystyrene bead foam in refrigeration housings.
  • JP 2020-063904 and JP 2017-133784 describe the use of styrene foam for insulation of a refrigerator, providing a low delamination between liner and foam and a good miscibility in the recycling process.
  • no details are disclosed how a high insulation behavior could be maintained over the lifetime of the appliance.
  • WO 2009/120624 describes a method of preparing a refrigeration insulation liner in the shape of a multilayer polymeric sheet with at least one foam layer and at least one solid layer adjacent to the foam layer.
  • a method of preparing a refrigerator liner by co-extruding a foamed polystyrene layer between two solid layers of high impact polystyrene to form a sheet, thermoforming the sheet into the liner, and incorporating the liner into the refrigeration device is described.
  • the insulation performance of the foam layer is not sufficient for today's refrigerators and does not make the additional use of polyurethane based insulation obsolete.
  • JP 2004-075926 discloses expandable acrylonitrile-styrene resin particles.
  • the resin particles are impregnated with foaming agent and the surface is coated with a fluorine-containing vinyl type copolymer.
  • the foamed shaped article obtained by foam molding is recommended for refrigerators because it excels in preventing the permeation of water that is contaminated with undesired ingredients such as surfactants and oils.
  • the use of fluorinated copolymers is not desirable from an environmental and recycling point of view.
  • the invention relates to a vinylaromatic polymer composite article comprising (or consisting of):
  • A-1 50 to 98 wt.-%, based on the total weight of the vinylaromatic polymer composition A, of at least one vinylaromatic copolymer A-1 , comprising or consisting of: A-11 : 50 to 100 wt.-%, based on the total weight of the vinylaromatic copolymer
  • A-1 of repeating units selected from the group of monomers consisting of styrene, alpha-methylstyrene, para-methylstyrene, and mixtures of at least two of the afore-mentioned;
  • A-12 0 to 50 wt-%, based on the total weight of the vinylaromatic copolymer A-
  • A-2 2 to 50 wt.-%, based on the total weight of the vinylaromatic polymer composition A, of at least one rubbery polymer A-2, dispersed in the vinylaromatic copolymer A-1 ;
  • A-3 0 to 48 wt.-%, based on the total weight of the vinylaromatic polymer composition A, of at least one further polymer;
  • A-4 0 to 20 wt.-%, based on the total weight of the vinylaromatic polymer composition
  • A of at least one additive, wherein the sum of components A-1 , A-2, A-3 and A-4 is 100 wt.-%;
  • B-1 50 to 100 wt.-%, based on the total weight of the vinylaromatic polymer composition B, of at least one vinylaromatic polymer B-1 , comprising or consisting of: B-11 : 50 to 100 wt.-%, based on the total weight of the vinylaromatic copolymer
  • B-1 of repeating units selected from the group of monomers consisting of styrene, alpha-methylstyrene, para-methylstyrene, and mixtures of at least two of the afore-mentioned;
  • B-12 0 to 50 wt.-%, based on the total weight of the vinylaromatic copolymer B-
  • B-3 0 to 48 wt.-%, based on the total weight of the vinylaromatic polymer composition B, of at least one further polymer;
  • B-4 0 to 20 wt.-%, based on the total weight of the vinylaromatic polymer composition B, of at least one additive, wherein the sum of components B-1 , B-2, B-3 and B-4 is 100 wt.-%;
  • C-1 of repeating units selected from the group of monomers consisting of styrene, alpha-methylstyrene, para-methylstyrene, and mixtures of at least two of the afore-mentioned; and C-12: 0 to 50 wt-%, based on the total weight of the vinylaromatic copolymer C-
  • C-4 0 to 20 wt.-%, based on the total weight of the vinylaromatic polymer composition C, of at least one additive C-4, wherein the sum of components C-1 , C-2, C-3 and C-4 is 100 wt.-%; wherein the vinylaromatic polymer composite article is characterized in that the percentages of repeating units A-11 , based on the total weight of the vinylaromatic polymers A-1 , repeating units B-11 , based on the total weight of the vinylaromatic polymers B-1 , and optionally repeating units C-11, based on the total weight of the vinylaromatic polymers C-1 , differ from each other by ⁇ 25 wt.-%, preferably by ⁇ 20 wt.-%, often ⁇ 15 wt.-%, for example ⁇ 10 wt.-%. This ensures a good compatibility of the polymers A and B and optionally C.
  • the percentage of repeating units A-11, based on the total weight of the vinylaromatic polymers A-1 and the percentage of repeating units B-11 , based on the total weight of the vinylaromatic polymers B-1 differ from each other by ⁇ 25 wt.-%, for example ⁇ 24 wt.-%, ⁇ 23 wt.-%, ⁇ 22 wt.-%, or ⁇ 21 wt.-%, preferably by ⁇ 20 wt.-%, for example ⁇ 19 wt.-%, ⁇ 18 wt.-%, ⁇ 17 wt-%, or ⁇ 16 wt.-%, often ⁇ 15 wt.-%, for example ⁇ 12 wt.-% or ⁇ 10 wt.-%.
  • the percentage of repeating units A-11, based on the total weight of the vinylaromatic polymers A-1 and the percentage of repeating units C-11 , based on the total weight of the vinylaromatic polymers C-1 differ from each other by ⁇ 25 wt- %, preferably by ⁇ 20 wt.-%, often ⁇ 15 wt.-%, for example ⁇ 10 wt.-%.
  • the percentage of repeating units B-11 based on the total weight of the vinylaromatic polymers B-1 and the percentage of repeating units C-11 , based on the total weight of the vinylaromatic polymers C-1 , differ from each other by ⁇ 25 wt-%, for example ⁇ 24 wt.-%, ⁇ 23 wt.-%, ⁇ 22 wt.-%, or ⁇ 21 wt.-%, preferably by ⁇ 20 wt.-%, for example ⁇ 19 wt.-%, ⁇ 18 wt.-%, ⁇ 17 wt.-%, or ⁇ 16 wt.-%, often ⁇ 15 wt.-%, for example ⁇ 12 wt.-% or ⁇ 10 wt.-%.
  • the percentage of repeating units A-11, based on the total weight of the vinylaromatic polymers A-1 , the percentage of repeating units B-11 , based on the total weight of the vinylaromatic polymers B-1, and the percentage of repeating units C-11 , based on the total weight of the vinylaromatic polymers C-1 differ from each other by ⁇ 25 wt.-%, for example ⁇ 24 wt.-%, ⁇ 23 wt.-%, ⁇ 22 wt.-%, or ⁇ 21 wt.-%, preferably by ⁇ 20 wt.-%, for example ⁇ 19 wt.-%, ⁇ 18 wt.-%, ⁇ 17 wt-%, or ⁇ 16 wt.-%, often ⁇ 15 wt.-%, for example ⁇ 12 wt.-% or ⁇ 10 wt.-%.
  • the invention relates to a process for producing a vinylaromatic polymer composite article according to the invention as component of a refrigerating device or a freezing device.
  • the invention relates to the use of a vinylaromatic polymer composite article according to the invention as component of a refrigerating device or a freezing device.
  • the vinylaromatic polymer composite article comprising or consisting of:
  • the vinylaromatic polymer composite article comprises:
  • the vinylaromatic polymer composite article comprises:
  • segment (b) is positioned between segment (a) and segment (c).
  • Segment (b) comprises two opposing surfaces, also referred to as first surface and second surface.
  • Segment (a) is positioned on at least a part of the first surface of segment (b).
  • Segment (c) is positioned on at least a part of the second surface of segment (b).
  • Segment (a) and/or segment (c) may have the same shape and/or size as segment (b).
  • Segment (a) and/or segment (c) may have different shapes and/or sizes as segment (b).
  • Segment (a) may have the same shape and/or size as segment (c).
  • segment (a) and/or segment (c) have a larger size than segment (b).
  • segment (a) and segment (c) are in contact with each other at at least some sections which extent beyond the shape of segment (b). This allows to encase segment (b) by segments (a) and (c).
  • the vinylaromatic polymer composite article comprises at least two segments (a), (b) and optionally (c), which have a different chemical composition.
  • segment (a) and segment (b) have a different chemical composition.
  • the vinylaromatic polymer composite article comprises at least three segments (a), (b) and (c), wherein segment (a) is different from segment (b) with regards to their chemical composition and segment (b) is different from segment (c) with regards to their chemical composition.
  • Segment (a) and segment (c) may have the same chemical composition or may be different with regards to their chemical composition.
  • segment (a) and segment (c) have the same chemical composition and segment (b) has a chemical composition different from segments (a) and (c).
  • the terms “different chemical composition” or “different with regards to their chemical composition” refer to vinylaromatic polymer compositions A, B and/or C, which differ at least in one of the constituents A-1 , A-2, A-3, A-4, B-1 , B-2, B-3, B-4, C-1 , C-2, C-3, and/or C-4.
  • the vinylaromatic polymer compositions A, B and/or C may differ in the monomers of which they are composed, the vinylaromatic polymer compositions A, B and/or C may differ in the ratios of comonomers of which they are composed, the vinylaromatic polymer compositions A, B and/or C may differ in the selection or ratio of the polymer constituents A-1 , A-2, A-3, B-1 , B-2, B-3, C-1 , C-2, and/or C-3 of which they are composed, or the vinylaromatic polymer compositions A, B and/or C may differ in the selection or ratio of the additives A-4, B-4, and/or C-4.
  • At least one of the segments (a), (b) and/or (c) is (at least partially) configured in the shape of a polymer foam, preferably the at least one segment (b) comprising or consisting of the at least one second vinylaromatic polymer composition B is (at least partially) configured in the shape of a polymer foam.
  • Polymer foams are known in the art and may be produced by known processes.
  • the vinylaromatic polymer composition to be foamed i.e. A, B, or C
  • the vinylaromatic polymer composition to be foamed is impregnated with at least one physical foaming agent (as additive B-4) and subsequently foamed by reducing the ambient pressure and/or increasing the ambient temperature.
  • the vinylaromatic polymer composition to be foamed i.e. A, B, or C
  • at least one chemical foaming agent as additive B-4
  • Foaming may be facilitated by reducing the ambient pressure, e.g. to a pressure at least 200 mbar below the ambient pressure.
  • Physical and chemical foaming agents may also be used in combination with each other as additive B-4.
  • Suitable physical foaming agents include gases like carbon dioxide, nitrogen, noble gases or mixtures thereof, preferably carbon dioxide, nitrogen and mixtures thereof. Further suitable physical foaming agents include lower hydrocarbons, for example Ci-Ce alkanes, in particular butane and pentane. Suitable chemical foaming agents may, for example, be a mixture of sodium bicarbonate and citric acid or carbodiimide. Preferably, the foaming agent is not a fluorinated foaming agent, more preferably not a halogenated foaming agent.
  • the vinylaromatic polymer composite article is a layered vinylaromatic polymer composite article comprising:
  • the vinylaromatic polymer composite article is a layered vinylaromatic polymer composite article comprising:
  • thermoformed layered segment (a) comprising or consisting of the at least one first vinylaromatic polymer composition A;
  • the at least one thermoformed layered segment (a) is a thermoformed refrigerator liner and the at least one foamed layered segment (b) is a refrigerator insulation foam.
  • the thermoformed layered segment (a) is a thermoformed refrigerator liner having a thickness of ⁇ 10 mm, often ⁇ 8 mm, for example from 0.5 to 8 mm, often from 1 to 6 mm.
  • the thermoformed layered segment (b) has a thickness of ⁇ 10 mm, often
  • thermoformed layered segment (b) is a foamed insulation layer having a thickness of 5 to 100 mm, often 10 to 80 mm, for example from 15 to 60 mm.
  • thermoformed layered segment (c) has a thickness of ⁇ 10 mm, often
  • ⁇ 8 mm for example from 0.5 to 8 mm, often from 1 to 6 mm.
  • the first vinylaromatic polymer composition A may comprise at least one further polymer A-3
  • the second vinylaromatic polymer composition B may comprise at least one further polymer B-3
  • the optional further vinylaromatic polymer composition C may comprise at least one further polymer C3.
  • the optional polymers A-3, B-3 and C-3 are each independently selected from vinylaromatic polymers.
  • the optional polymers A- 3, B-3 and C-3 are different form the vinylaromatic polymers A-1, B-1 and C-1, respectively.
  • the first vinylaromatic polymer composition A does not comprise a further polymer A-3.
  • the second vinylaromatic polymer composition B does not comprise a further polymer B-3.
  • the optional further vinylaromatic polymer composition C does not comprise a further polymer C3.
  • the first vinylaromatic polymer composition A consists of the constituents A-1 , A-2 and optionally A-4.
  • the second vinylaromatic polymer composition B consists of the constituents B-1 , B-2 and optionally B-4.
  • the at least one further vinylaromatic polymer composition C consists of the constituents C-1 , C-2 and optionally C-4.
  • melt blending of constituents A-1 and A-2 with constituents B-1 and B-2 and optionally with constituents C-1 and C-2 at temperatures below 250 °C in a mixing device results in a micro-dispersed morphology with either a single-phase morphology or a 2-phase morphology having an average domain size of less than 20 pm, preferably less than 15 pm, often less than 12 pm. It is understood that melt blending of the constituents requires a temperature, which allows to obtain a substantially liquid melt of the polymer constituents, i.e. a temperature above the melt temperature of the polymer constituents.
  • melt blending of constituents A-1 and A-2 with constituents B-1 and B-2 at temperatures below 250 °C in a mixing device results in a micro-dispersed morphology with either a single phase morphology or a 2-phase morphology having an average domain size of less than 20 pm, preferably less than 15 pm, often less than 12 pm.
  • melt blending of constituents A-1 and A-2 with constituents C-1 and C-2 at temperatures below 250 °C in a mixing device results in a micro-dispersed morphology with either a single phase morphology or a 2-phase morphology having an average domain size of less than 20 m, preferably less than 15 pm, often less than 12 pm.
  • melt blending of constituents B-1 and B-2 with constituents C-1 and C-2 at temperatures below 250 °C in a mixing device results in a micro-dispersed morphology with either a single phase morphology or a 2-phase morphology having an average domain size of less than 20 pm, preferably less than 15 pm, often less than 12 pm.
  • melt blending of constituents A-1 and A-2 with constituents B-1 and B-2 and constituents C-1 and C-2 at temperatures below 250 °C in a mixing device results in a micro-dispersed morphology with either a single phase morphology or a 2-phase morphology having an average domain size of less than 20 pm, preferably less than 15 pm, often less than 12 pm.
  • the vinylaromatic polymer composite article comprises further segments (c’), (c”), and so on, which are defined as segment (c) described herein.
  • Vinylaromatic copolymers A-1 , B-1 and C-1 Vinylaromatic copolymers A-1 , B-1 and C-1
  • the at least one segment (a) of the vinylaromatic polymer composite article comprises or consists of at least one first vinylaromatic polymer composition A, comprising:
  • A-1 50 to 98 wt.-%, based on the total weight of the vinylaromatic polymer composition A, of at least one vinylaromatic copolymer A-1 , comprising or consisting of:
  • A-11 50 to 100 wt.-%, preferably 70 to 100 wt.-%, for example 80 to 100 wt.-% or 75 to 95 wt.-%, based on the total weight of the vinylaromatic copolymer A-1, of repeating units selected from the group of monomers consisting of styrene, alpha-methylstyrene, para-methylstyrene, and mixtures of at least two of the afore-mentioned; and
  • A-12 0 to 50 wt-%, preferably 0 to 30 wt-%, for example 0 to 20 wt-% or 5 to 25 wt-
  • the monomers A-11 are selected from styrene, alpha-methylstyrene, and mixtures thereof. Particular preferred is styrene.
  • Suitable comonomers A-12 include monomers selected from the group consisting of Ci-Cs alkyl(meth)acrylate (preferably C1-C4 alkyl(meth)acrylate, e.g. methyl methacrylate or ethyl methacrylate), acrylonitrile, methacrylonitrile, acrylamide, vinlymethyl ether, anhydrides of unsaturated carboxylic acids (e.g. maleic anhydride or phthalic acid anhydride) and imides of unsaturated carboxylic acids (e.g. N-substituted maleimides, like N-cyclohexylmaleimide or N- phenylmaleimide).
  • Preferred are methyl methacrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, in particular acrylonitrile.
  • the at least one segment (b) of the vinylaromatic polymer composite article comprises or consists of at least one second vinylaromatic polymer composition B, comprising:
  • B-11 50 to 100 wt.-%, preferably 70 to 100 wt.-%, for example 80 to 100 wt.-% or 75 to 95 wt.-%, based on the total weight of the vinylaromatic copolymer B-1, of repeating units selected from the group of monomers consisting of styrene, alpha-methylstyrene, para-methylstyrene, and mixtures of at least two of the afore-mentioned; and
  • B-12 0 to 50 wt.-%, preferably 0 to 30 wt-%, for example 0 to 20 wt-% or 5 to 25 wt- %, based on the total weight of the vinylaromatic copolymer B-1 , of repeating units of at least one comonomer, which is copolymerizable with the monomer(s) B-11 ; wherein the sum of components B-11 and B-12 is 100 wt.-%.
  • the monomers B-11 are selected from styrene, alpha-methylstyrene, and mixtures thereof. Particular preferred is styrene.
  • Suitable comonomers B-12 include monomers selected from the group consisting of Ci-Cs alkyl(meth)acrylate (preferably C1-C4 alkyl(meth)acrylate, e.g. methyl methacrylate or ethyl methacrylate), acrylonitrile, methacrylonitrile, acrylamide, vinlymethyl ether, anhydrides of unsaturated carboxylic acids (e.g. maleic anhydride or phthalic acid anhydride) and imides of unsaturated carboxylic acids (e.g. N-substituted maleimides, like N-cyclohexylmaleimide or N- phenylmaleimide).
  • Preferred are methyl methacrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, in particular acrylonitrile.
  • the at least one segment (c) of the vinylaromatic polymer composite article comprises or consists of at least one second vinylaromatic polymer composition C, comprising:
  • C-11 50 to 100 wt.-%, preferably 70 to 100 wt.-%, for example 80 to 100 wt.-% or 75 to 95 wt.-%, based on the total weight of the vinylaromatic copolymer C-1, of repeating units selected from the group of monomers consisting of styrene, alpha-methylstyrene, para-methylstyrene, and mixtures of at least two of the afore-mentioned; and
  • C-12 0 to 50 wt.-%, preferably 0 to 30 wt.-%, for example 0 to 20 wt.-% or 5 to 25 wt.- %, based on the total weight of the vinylaromatic copolymer C-1 , of repeating units of at least one comonomer, which is copolymerizable with the monomer(s) C-11 ; wherein the sum of components C-11 and C-12 is 100 wt.-%.
  • the monomers C-11 are selected from styrene, alpha-methylstyrene, and mixtures thereof. Particular preferred is styrene.
  • Suitable comonomers C-12 include monomers selected from the group consisting of Ci-Cs alkyl(meth)acrylate (preferably C1-C4 alkyl(meth)acrylate, e.g. methyl methacrylate or ethyl methacrylate), acrylonitrile, methacrylonitrile, acrylamide, vinlymethyl ether, anhydrides of unsaturated carboxylic acids (e.g. maleic anhydride or phthalic acid anhydride) and imides of unsaturated carboxylic acids (e.g. N-substituted maleimides, like N-cyclohexylmaleimide or N- phenylmaleimide).
  • Preferred are methyl methacrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, in particular acrylonitrile.
  • the amounts of monomers A-11, B-11 and - if present - C-11 are selected in that the percentages of repeating units A-11 , based on the total weight of the vi- nylaromatic polymers A-1 , repeating units B-11 , based on the total weight of the vinylaromatic polymers B-1 , and optionally repeating units C-11 , based on the total weight of the vinylaromatic polymers C-1 , differ from each other by ⁇ 25 wt.-%, preferably by ⁇ 20 wt.-%, often ⁇ 15 wt.-%, for example ⁇ 10 wt.-%.
  • the at least one segment (a) of the vinylaromatic polymer composite article comprises or consists of at least one first vinylaromatic polymer composition A, comprising:
  • A-2 2 to 50 wt.-%, based on the total weight of the vinylaromatic polymer composition A, of at least one rubbery polymer A-2, dispersed in the vinylaromatic copolymer A-1.
  • the rubbery polymer A-2 comprises or consists of:
  • A-21 rubber obtained by a emulsion polymerization reaction.
  • A-22 rubber obtained by a solution polymerization reaction, and/or
  • A-23 rubber obtained by a mass polymerization reaction
  • A-24 rubber obtained by an anionic and/or living polymerization reaction.
  • Each of the rubbers A-21 , A-22, A-23 and A-24 preferably comprises butadiene, isoprene and/or acrylate.
  • the rubbers A-21 , A-22, A-23 and A-24 respectively, comprise at least one monomer selected from acrylonitrile, methacrylonitrile and vinylaromatic monomers, preferably selected from styrene, alpha-methylstyrene, para-methylstyrene, and mixtures of at least two of the afore mentioned.
  • the rubbers A-21 , A-22, A-23 and A-24 comprise at least one monomer selected from acrylonitrile and vinylaromatic monomers, preferably selected from styrene, alpha-methylstyrene, and mixtures thereof, preferably acrylonitrile and styrene.
  • the rubbers A-21 , A-22, A-23 and A-24 comprise at least one monomer selected from vinylaromatic monomers, preferably selected from styrene, alphamethylstyrene, and mixtures thereof, in particular styrene.
  • the rubbers A-21 , A-22, A-23 and A-24, respectively are graft/shell copolymers which are compatible with component A-1, preferably the rubber A-21 is a graft/shell copolymer which is compatible with component A-1.
  • Suitable rubbers include acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile-sty- rene-acrylate copolymers (ASA), and styrene-butadiene copolymers (SBC),
  • ABS Acrylonitrile-butadiene-styrene copolymers
  • ABS are graft copolymers known in the art and consist of a graft core comprising repeating units of butadiene and optionally styrene and at least one graft shell comprising styrene and acrylonitrile, which is obtained by graft copolymerization of the styrene and acrylonitrile in the presence of the graft core.
  • ABS is preferably used in combination with styrene-acrylonitrile copolymers (SAN) as component A-1.
  • SAN styrene-acrylonitrile copolymers
  • the ABS and SAN are mixed.
  • ASA Acrylonitrile-styrene-acrylate copolymers
  • ASA are graft copolymers known in the art and consist of a graft core comprising repeating units of acrylates, preferably Ci-Cs alkyl(meth)acrylate (e.g. n-butylacrylate) and optionally styrene and at least one graft shell comprising styrene and acrylonitrile, which is obtained by graft copolymerization of the styrene and acrylonitrile in the presence of the graft core.
  • ASA is preferably used in combination with styrene-acrylonitrile copolymers (SAN) as component A-1 .
  • SAN styrene-acrylonitrile copolymers
  • the ASA and SAN are mixed.
  • Styrene-butadiene copolymers are block copolymer known in the art and consists of at least one soft polymer block B, which predominantly comprises repeating units of butadiene and at least one hard polymer block S which predominantly comprises or consists of repeating units of styrene.
  • the SBC comprises a triblock structure SBS.
  • SBC is preferably used in combination with styrene-acrylonitrile copolymers (SAN) as component A- 1.
  • SAN styrene-acrylonitrile copolymers
  • the SBC and SAN are mixed.
  • the rubbers A-21 , A-22, A-23 and A-21, respectively comprise polybutadiene rubber particles (BR).
  • BR is preferably used in combination with styrene homopolymers.
  • styrene monomers are polymerized in the presence of BR particles, and optionally mixed with further styrene homopolymers.
  • the resulting composition is known in the art as high impact polystyrene (HIPS).
  • the rubbers A-21 , A-22, A-23 and/or A-24 optionally create lamellae, cylinders, spheres, and/or bi-continuous morphologies.
  • the rubbers A-21 , A-22, A-23 and A-24, respectively, may be mixed with the further constituents A-1 and optionally A-3 and A-4.
  • the rubbers A-21, A-22, A-23 and A-24, respectively can be mixed with the monomers of A-1, which are subsequently polymerized in the presence of the rubbers A-21 , A-22, A-23 and A-24, respectively.
  • the at least one segment (b) of the vinylaromatic polymer composite article comprises or consists of at least one second vinylaromatic polymer composition B, comprising:
  • B-2 2 to 50 wt.-%, based on the total weight of the vinylaromatic polymer composition B, of at least one rubbery polymer B-2, dispersed in the vinylaromatic copolymer B-1.
  • the rubbery polymer B-2 comprises or consists of:
  • B-21 rubber obtained by an emulsion polymerization reaction
  • B-23 rubber obtained by a mass polymerization reaction
  • B-24 rubber obtained by an anionic and/or living polymerization reaction.
  • Each of the rubbers B-21 , B-22, B-23 and B-24 preferably comprise butadiene, isoprene and/or acrylate.
  • the rubbers B-21, B-22, B-23 and B-24 respectively comprise at least one monomer selected from acrylonitrile, methacrylonitrile and vinylaromatic monomers, preferably selected from styrene, alpha-methylstyrene, para-methylstyrene, and mixtures of at least two of the afore mentioned.
  • the rubbers B-21 , B-22, B-23 and B-24 comprise at least one monomer selected from acrylonitrile and vinylaromatic monomers, preferably selected from styrene, alpha-methylstyrene, and mixtures thereof, preferably acrylonitrile and styrene.
  • the rubbers B-21 , B-22, B-23 and B-24 respectively, comprise at least one monomer selected from vinylaromatic monomers, preferably selected from styrene, alphamethylstyrene, and mixtures thereof, in particular styrene.
  • the rubbers B-21 , B-22, B-23 and B-24, respectively are graft/shell copolymers which are compatible with component B-1, preferably the rubber B-21 is a graft/shell copolymer which is compatible with component B-1.
  • the rubbers C-21, C-22, C-23 and C-24 respectively comprise at least one monomer selected from acrylonitrile, methacrylonitrile and vinylaromatic monomers, preferably selected from styrene, alpha-methylstyrene, para-methylstyrene, and mixtures of at least two of the afore mentioned.
  • the rubbers C-21 , C-22, C-23 and C-24 comprise at least one monomer selected from acrylonitrile and vinylaromatic monomers, preferably selected from styrene, alpha-methylstyrene, and mixtures thereof, preferably acrylonitrile and styrene.
  • the rubbers C-21 , C-22, C-23 and C-24 comprise at least one monomer selected from vinylaromatic monomers, preferably selected from styrene, alphamethylstyrene, and mixtures thereof, in particular styrene.
  • the rubbers C-21, C-22, C-23 and C-24, respectively are graft/shell copolymers which are compatible with component C-1 , preferably the rubber C-21 is a graft/shell copolymer which is compatible with component C-1 .
  • Suitable rubbers include acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile-sty- rene-acrylate copolymers (ASA), styrene-butadiene copolymers (SBC), Acrylonitrile-butadiene-styrene copolymers (ABS) are graft copolymers known in the art and consist of a graft core comprising repeating units of butadiene and optionally styrene and at least one graft shell comprising styrene and acrylonitrile, which is obtained by graft copolymerization of the styrene and acrylonitrile in the presence of the graft core.
  • ABS is preferably used in combination with styrene-acrylonitrile copolymers (SAN) as component C-1.
  • SAN styrene-acrylonitrile copolymers
  • ASA Acrylonitrile-styrene-acrylate copolymers
  • ASA are graft copolymers known in the art and consist of a graft core comprising repeating units of acrylates, preferably Ci-Ca alkyl(meth)acrylate (e.g. n-butylacrylate) and optionally styrene and at least one graft shell comprising styrene and acrylonitrile, which is obtained by graft copolymerization of the styrene and acrylonitrile in the presence of the graft core.
  • ASA is preferably used in combination with styrene-acrylonitrile copolymers (SAN) as component C-1 .
  • SAN styrene-acrylonitrile copolymers
  • the ASA and SAN are mixed.
  • Styrene-butadiene copolymers are block copolymer known in the art and consists of at least one soft polymer block B, which predominantly comprises repeating units of butadiene and at least one hard polymer block S which predominantly comprises repeating units of styrene.
  • the SBC comprises a triblock structure SBS.
  • SBC is preferably used in combination with styrene-acrylonitrile copolymers (SAN) as component C-1.
  • SAN styrene-acrylonitrile copolymers
  • the SBC and SAN are mixed.
  • the rubbers C-21, C-22, C-23 and C-21 comprise polybutadiene rubber particles (BR).
  • BR is preferably used in combination with styrene homopolymers.
  • styrene monomers are polymerized in the presence of BR particles, and optionally mixed with further styrene homopolymers.
  • HIPS high impact polystyrene
  • the rubbers C-21 , C-22, C-23 and/or C-24 optionally create lamellae, cylinders, spheres, and/or bi-continuous morphologies.
  • the rubbers C-21 , C-22, C-23 and C-24, respectively, may be mixed with the further constituents C-1 and optionally C-3 and C-4.
  • the rubbers C-21 , C-22, C-23 and C-24, respectively can be mixed with the monomers of C-1 , which are subsequently polymerized in the presence of the rubbers C-21 , C-22, C-23 and C-24, respectively.
  • the at least one segment (a) of the vinylaromatic polymer composite article comprises or consists of at least one first vinylaromatic polymer composition A, optionally comprising up to 48 wt.-%, preferably up to 38 wt.-%, more preferably up to 23 wt.-%, for example up to 13 wt.-%, based on the total weight of the vinylaromatic polymer composition
  • the polymer A-3 may be selected from thermoplastic homopolymers or copolymers, which are compatible with the vinylaromatic copolymer A-1 , such as polycarbonates, polyamides, or vinylaromatic (co)polymers different from the vinylaromatic copolymer A-1 and the rubbery polymer A-2. If present, the polymer A-3 is preferably a vinylaromatic (co)polymer such as polystyrene, poly(alpha-methyl styrene), poly(styrene methyl methacrylate), or poly(styrene acrylonitrile). However, in a preferred embodiment, the at least one first vinylaromatic polymer composition A does not comprise a further polymer A-3.
  • the at least one segment (b) of the vinylaromatic polymer composite article comprises or consists of at least one first vinylaromatic polymer composition B, optionally comprising up to 48 wt.-%, preferably up to 38 wt.-%, more preferably up to 23 wt.-%, for example up to 13 wt.-%, based on the total weight of the vinylaromatic polymer composition
  • the polymer B-3 may be selected from thermoplastic homopolymers or copolymers, which are compatible with the vinylaromatic copolymer B-1 , such as polycarbonates, polyamides, or vinylaromatic (co)polymers different from the vinylaromatic copolymer B-1 and the rubbery polymer B-2. If present, the polymer B-3 is preferably a vinylaromatic (co)polymer such as polystyrene, poly(alpha-methyl styrene), poly(styrene methyl methacrylate), or poly(styrene acrylonitrile). However, in a preferred embodiment, the at least one first vinylaromatic polymer composition B does not comprise a further polymer B-3.
  • the optional segment (c) of the vinylaromatic polymer composite article comprises or consists of at least one vinylaromatic polymer composition C, optionally comprising up to 48 wt-%, preferably up to 38 wt.-%, more preferably up to 23 wt.-%, for example up to 13 wt-%, based on the total weight of the vinylaromatic polymer composition
  • the polymer C-3 may be selected from thermoplastic homopolymers or copolymers, which are compatible with the vinylaromatic copolymer C-1 , such as polycarbonates, polyamides, or vinylaromatic (co)polymers different from the vinylaromatic copolymer C-1 and the rubbery polymer C-2. If present, the polymer C-3 is preferably a vinylaromatic (co)polymer such as polystyrene, poly(alpha-methyl styrene), poly(styrene methyl methacrylate), or poly(styrene acrylonitrile). However, in a preferred embodiment, the at least one first vinylaromatic polymer composition C does not comprise a further polymer C-3.
  • the vinylaromatic polymer composition A may comprise 0 to 20 wt.- %, preferably 0 to 10 % by weight, preferably 0 to 5 % by weight, often 0.1 to 5 %, based on the vinylaromatic polymer composition A, of one or more additive A-4. More preferably, the at least one additive A-4 is present in an amount of 0.001 to 10 % by weight, more preferably 0.01 to 5 % by weight, based on the vinylaromatic polymer composition A. In particular, the additive A-4 is not a polymeric compound defined as components A-1 , A-2 or A-3.
  • the vinylaromatic polymer composition B may comprise 0 to 20 wt- %, preferably 0 to 10 % by weight, preferably 0 to 5 % by weight, often 0.1 to 5 %, based on the vinylaromatic polymer composition B, of one or more additive B-4. More preferably the at least one additive B-4 is present in an amount of 0.001 to 10 % by weight, more preferably 0.01 to 5 % by weight, based on the vinylaromatic polymer composition B. In particular, the additive B-4 is not a polymeric compound defined as components B-1 , B-2 or B-3.
  • the vinylaromatic polymer composition C may comprise 0 to 20 wt- %, preferably 0 to 10 % by weight, preferably 0 to 5 % by weight, often 0.1 to 5 %, based on the vinylaromatic polymer composition C, of one or more additive C-4. More preferably the at least one additive C-4 is present in an amount of 0.001 to 10 % by weight, more preferably 0.01 to 5 % by weight, based on the vinylaromatic polymer composition C.
  • the additive C-4 is not a polymeric compound defined as components C-1 , C-2 or C-3.
  • the optional additive A-4, B-4, and - if present - C-4 may be selected from commonly known additives and/or auxiliaries for plastic materials.
  • auxiliaries and additives reference is made by way of example to “Plastics Additives Handbook”, Hans Zweifel 6th Edition, Hanser Publ., Kunststoff, 2009.
  • the at least one additive K may be selected from fillers, reinforcing agents, dyes, pigments, lubricants or mold-release agents, processing aids stabilizers, in particular light and heat stabilizers, antioxidants, UV absorbers, plasticizers, impact modifiers, antistatic agents, flame retardants, bactericides, fungicides, optical brighteners, and blowing agents.
  • the optional additive A-4, B-4, and - if present - C-4 is preferably selected from foaming agents, dyes, pigments, lubricants or mold-release agents, processing aids, stabilizers, in particular foaming agents, processing aids, antistatic agents, flame retardants and fillers.
  • Suitable foaming agents least include physical foaming agents, chemical foaming agent and mixtures thereof.
  • Suitable physical foaming agents include gases like carbon dioxide, nitrogen, noble gases or mixtures thereof, preferably carbon dioxide, nitrogen and mixtures thereof.
  • Further suitable physical foaming agents include lower hydrocarbons, for example Ci-Ce alkanes, in particular butane and pentane.
  • Suitable chemical foaming agents may, for example, be a mixture of sodium bicarbonate and citric acid or carbodiimide.
  • the foaming agent is not a fluorinated foaming agent, more preferably not a halogenated foaming agent.
  • the additive(s) B-4 include at least one foaming agent.
  • fillers which may be selected from particulate fillers or reinforcing agents, are silicates, amorphous silica, calcium silicates, such as wollastonite, powdered quartz, mica, metal oxides, metal hydroxides, carbon black, graphite, barium sulfate, calcium carbonate, magnesium carbonate, bentonites, talc, kaolin, carbon fibers or glass fibers in the form of glass woven, glass mats, or glass silk rovings, chopped glass, or glass beads.
  • at least one particulate fillers preferably a mineral filler, can be used as additive A-4, B-4, and - if present - C-4.
  • Common stabilizers for thermoplastic polymers encompass stabilizers for improving thermal stability, which are commonly agents to counteract thermal decomposition, light stabilizers (stabilizers for increasing lightfastness), and stabilizers for raising resistance to hydrolysis and to chemicals.
  • suitable light stabilizers are various substituted resorcinols, salicylates, benzotriazoles, and benzophenones.
  • Suitable stabilizers are hindered phenols, but also vitamin E and compounds whose structure is analogous thereto.
  • HALS stabilizers Hindered Amine Light Stabilizers
  • benzophenones benzophenones
  • resorcinols resorcinols
  • salicylates and benzotriazoles are also suitable.
  • thermoformed layered segment (a) comprising or consisting of the at least one first styrenic polymer composition A;
  • co-extrusion refers to a process wherein substantially melt-liquid vinylaromatic polymer compositions are separately provided and then the obtained polymer melts are extruded together using a co-extrusion die.
  • substantially melt-liquid means that the polymer mixture, as well as the predominant meltliquid (softened) fraction, may further comprise a certain fraction of solid constituents, examples being unmolten fillers and reinforcing material such as glass fibers, metal flakes, or else unmolten pigments, colorants, etc.
  • Melt-liquid means that the polymer mixture is at least of low fluidity, therefore having softened at least to an extent that it has plastic properties.
  • the constituents of the vinylaromatic polymer compositions (A) and (B) are provided in the predetermined amounts to an optionally heatable mixing device, separately for each vinylaromatic polymer composition. Subsequently, the constituents for each vinylaromatic polymer composition (A), (B), and optionally (C) are blended in the optionally heatable mixing device at temperatures above the glass transition point of the polymer constituents to obtain homogenous, substantially melt-liquid polymer melts of the vinylaromatic polymer compositions separately.
  • Suitable blending processes are those known by the person skilled in the art and include, for example, joint extrusion, kneading, or rolling.
  • a preferred mixing apparatus used is an extruder or a kneader. Particularly suitable for melt extrusion are, for example, single-screw or twin- screw extruders. A twin-screw extruder is preferred.
  • the mechanical energy introduced by the mixing apparatus in the course of mixing is enough to cause the mixture to melt, meaning that the mixing apparatus does not have to be heated. Otherwise, the mixing apparatus is generally heated.
  • the temperature for blending and extrusion is guided by the chemical and physical properties of the vinylaromatic polymer compositions and should be selected such as to result in a substantially melt-liquid polymer mixture.
  • the temperature is not to be unnecessarily high, in order to prevent thermal damage of the polymer mixture.
  • the mechanical energy introduced may, however, also be high enough that the mixing apparatus may even require cooling.
  • Mixing apparatus is operated customarily at 150 to 400 °C, preferably 170 to 300 °C. Extrusion of the polymer melt is typically made in the same temperature ranges.
  • melt-liquid vinylaromatic polymer compositions are subsequently fed together in a co-extrusion die, resulting in co-extrusion layers (“layered segment” in the sense mentioned above).
  • Subsequent cooling of the co-extrusion layers to temperatures below the glass transition point of the constituents provides the vinylaromatic polymer composite article according to the invention. Cooling of the co-extrusion layers may be achieved with the help of calendar rolls, and/or by air or other means.
  • Multi-layer composite articles may be obtained in one single co-extrusion process, or in repeated extrusion processes (e.g. in an over-molding process).
  • the extrusion setup contains a ring-shaped co-extrusion die and the molten co-extruded multilayer composite leaves the co-extrusion die in form of a ring-shaped tube.
  • the tube is transversally and/or longitudinally stretched on the plastic phase, so that the obtained multilayer composite film is stretched. This stretch process often results in a stronger, mechanically improved film.
  • the film tube is cooled down (e.g. by air), often laid flat with the help of rolls.
  • these single layer films are still composed of multiple polymer segment layers (e.g. segments (a), (b) and optionally (c), as outlined before).
  • the vinylaromatic polymer composite article according to the invention is preferably used as component of a refrigerating device or a freezing device, in particular as a component of a refrigerator or a freezer.
  • the invention relates to the use of a vinylaromatic polymer composite article according to the invention as component of refrigerating devices or freezing devices, in particular refrigerators or freezers.
  • automotive interior parts such as consoles, dashboard carriers, knobs, decorative parts, covers
  • electric/electronical applications such as housing for tools, kitchen appliance housing, housing and/or parts for vacuum cleaners, coffee machine parts, edge bands, decorative covers
  • toys healthcare applications and/or parts of healthcare applications, such as housings, carriers for diagnostics/analytics: single layer and/or multilayer laminates or coextruded films or sheets; and other industrial applications requiring a combination of impact resistance and stiffness.
  • vinylaromatic polymer composite article according to the invention examples include (but are not restricted to) multilayer articles such as ABS liner with two ABS layers of different composition (as segments (a) and (b)); ABS liner with an ABS main layer (as segment (a)) and a foamed back layer (as segment (b)), e.g. for thermal insulation; ABS liner with an ABS main layer (as segment (a)) and at least one SAN-containing layer (as segment (b)), e.g.
  • multilayer articles such as ABS liner with two ABS layers of different composition (as segments (a) and (b)); ABS liner with an ABS main layer (as segment (a)) and a foamed back layer (as segment (b)), e.g. for thermal insulation; ABS liner with an ABS main layer (as segment (a)) and at least one SAN-containing layer (as segment (b)), e.g.
  • the vinylaromatic polymer composite article comprises a main layer (segment (a)) made of “high impact polystyrene” (HIPS)), and a foamed back layer (segment (b)) made of polystyrene (e.g.
  • this vinylaromatic polymer composite article contains at least one additional layer (segment (c)), e.g. a layer with superior aesthetic properties such as surface gloss (“gloss cap layer”) containing polystyrene, preferably “general purpose polystyrene” (GPPS).
  • additional layer e.g. a layer with superior aesthetic properties such as surface gloss (“gloss cap layer”) containing polystyrene, preferably “general purpose polystyrene” (GPPS).
  • a further example of vinylaromatic polymer composite article according to the invention includes multilayer articles such as polystyrene liner with polystyrene main layer (as segment (a)) and at least one polystyrene-containing layer (as segment (b)), e.g. as “gloss cap layer”.
  • both layers are made of “high impact polystyrene” (HIPS).
  • the main layer is made of “high impact polystyrene” (HIPS) and the gloss cap layer contains “general purpose polystyrene” (GPPS).
  • HIPS high impact polystyrene
  • GPPS general purpose polystyrene
  • vinylaromatic polymer composite article according to the invention include food packaging films made of different polymers, for example different styrenic polymers; laminated structures containing different polymers, for example different styrenic polymers; and co-injection molded and/or over-molded structures containing different polymers, for example different styrenic polymers.
  • refrigerators which are predominantly made of styrene polymers and styrene copolymers (also referred to all-styrenics fridges in the following), which are for example (i) based mainly on (i) SAN and/or ABS or (ii) based mainly on general purpose polystyrene (GPPS) and/or high impact polystyrene (HIPS) and/or styrene/butadiene (block) copolymers.
  • GPPS general purpose polystyrene
  • HIPS high impact polystyrene
  • suitable fridge components ready for recycling are (for example, further components possible):
  • refrigerator liner ABS, optionally with 1 or more cap layers or co-extrusion layers made of ABS, and/or of SAN and/or of polystyrene, compatibilized with suitable compatibilizer, for example styrene/butadiene copolymers;
  • thermal insulation parts made of ABS and/or SAN, extruded or as bead foam
  • refrigerator liner HIPS or HIPS/GPPS, optionally with 1 or more cap layers or co-extru- sion layers made of GPPS, and/or GPPS/HIPS and/or GPPS/SBC and/or of polystyrene, optionally compatibilized with suitable compatibilizer;
  • thermal insulation parts made of HIPS and/or GPPS, extruded or as bead foam.
  • a further application example includes automotive interior parts, such as consoles, dashboard carriers, knobs, decorative parts, covers, all of the afore-mentioned applications comprising (or consisting of) foamed and/or non-foamed moldings made fully or partly of recycled ABS, optionally including polymers selected from the group consisting of polycarbonate (PC), poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (SAN), styrene-butadiene copolymer (SBC), high impact polystyrene (HIPS), N-phenylmaleimide copolymers, thermoplastic polyurethanes, and virgin ABS and/or SAN (non-recycled).
  • PC polycarbonate
  • PMMA poly(methyl methacrylate)
  • SAN poly(styrene-co-acrylonitrile)
  • SBC styrene-butadiene copolymer
  • HIPS high impact polystyrene
  • a further application example includes parts for electric/electronical applications, such as housing for tools, kitchen appliance housing, housing and/or parts for vacuum cleaners, coffee machine parts, edge bands, decorative covers, all of the afore-mentioned applications comprising (or consisting of) foamed and/or non-foamed moldings made fully or partly of recycled ABS, optionally including polymers selected from the group consisting of polycarbonate (PC), poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (SAN), styrene-methyl methacrylate copolymers, styrene-butadiene copolymer (SBC), high impact polystyrene (HIPS), N- phenylmaleimide copolymers, thermoplastic polyurethanes, and virgin ABS (non-recycled).
  • PC polycarbonate
  • PMMA poly(methyl methacrylate)
  • SAN poly(styrene-co-acrylonitrile)
  • a further application example includes toys and/or parts of toys, all of the afore-mentioned applications comprising (or consisting of) foamed and/or non-foamed moldings made fully or partly of recycled ABS, optionally including polymers selected from the group consisting of polycarbonate (PC), poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (SAN), styrene-butadiene copolymer (SBC), high impact polystyrene (HIPS), N-phenylmaleimide copolymers, thermoplastic polyurethanes, virgin ABS and/or SAN (non-recycled).
  • PC polycarbonate
  • PMMA poly(methyl methacrylate)
  • SAN poly(styrene-co-acrylonitrile)
  • SBC styrene-butadiene copolymer
  • HIPS high impact polystyrene
  • thermoplastic polyurethanes virgin ABS and/or
  • a further application example includes healthcare applications and/or parts of healthcare applications, such as housings, carriers for diagnostics/analytics, infusion sets, all of the aforementioned applications comprising (or consisting of) foamed and/or non-foamed moldings made fully or partly of recycled ABS, optionally including polymers selected from the group consisting of polycarbonate (PC), poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylo- nitrile) (SAN), styrene-butadiene copolymer (SBC), high impact polystyrene (HIPS), N-phe- nylmaleimide copolymers, and virgin ABS and/or SAN (non-recycled).
  • PC polycarbonate
  • PMMA poly(methyl methacrylate)
  • SAN poly(styrene-co-acrylo- nitrile)
  • SBC styrene-butadiene copolymer
  • HIPS high impact polyst
  • a further application example includes healthcare applications and/or parts of healthcare applications, such as housings, carriers for diagnostics/analytics, infusion sets, all of the aforementioned applications comprising (or consisting of) foamed and/or non-foamed moldings made fully or partly of recycled HIPS and/or GPPS, optionally including polymers selected from the group consisting of styrene-butadiene copolymer (SBC), styrene-methyl methacrylate copolymers, and virgin HIPS and/or GPPS (non-recycled).
  • SBC styrene-butadiene copolymer
  • styrene-methyl methacrylate copolymers styrene-methyl methacrylate copolymers
  • virgin HIPS and/or GPPS non-recycled
  • a further application example includes single layer and/or multilayer laminates or coextruded films and/or sheets, containing recycled layers, all of the afore-mentioned applications comprising (or consisting of) foamed and/or non-foamed moldings made fully or partly of recycled ABS, optionally including polymers selected from the group consisting of polycarbonate (PC), poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (SAN), styrene-butadiene copolymer (SBC), high impact polystyrene (HIPS), N-phenylmaleimide copolymers, thermoplastic polyurethanes, and virgin ABS and/or SAN (non-recycled).
  • PC polycarbonate
  • PMMA poly(methyl methacrylate)
  • SAN poly(styrene-co-acrylonitrile)
  • SBC styrene-butadiene copolymer
  • HIPS high impact polys
  • a further application example includes single layer and/or multilayer laminates or coextruded films and/or sheets (for example used in food packaging), containing recycled layers, all of the afore-mentioned applications comprising (or consisting of) foamed and/or non-foamed moldings made fully or partly of recycled polystyrene (e.g. HIPS and/or GPPS), optionally including polymers selected from the group consisting of styrene-butadiene copolymer (SBC), styrenemethyl methacrylate copolymers, and virgin HIPS and/or GPPS (non-recycled).
  • SBC styrene-butadiene copolymer
  • SBC styrenemethyl methacrylate copolymers
  • virgin HIPS and/or GPPS virgin HIPS and/or GPPS
  • the invention also relates to a component of a refrigerating device or a freezing device, in particular for a refrigerator or a freezer, automotive interior parts, electric/electronical applications, toys, healthcare applications and/or parts of healthcare applications, single layer and/or multilayer laminates or coextruded films and/or sheets, and other industrial applications requiring a combination of impact resistance and stiffness, using or comprising the vinylaromatic polymer composite article according to the invention.
  • SAN-1 Acrylonitrile-styrene copolymer comprising 67 wt.-% styrene and 33 wt.-% acrylonitrile and having a viscosity number VN of 60 determined according to DIN 53726.

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Abstract

La présente invention concerne un article composite en polymère vinylaromatique comprenant au moins deux segments comprenant des compositions de polymère vinylaromatique, dont chacune comprend au moins un (co)polymère vinylaromatique, les pourcentages de motifs structuraux dérivés de monomères vinylaromatiques dans chaque (co)polymère vinylaromatique différant les uns des autres de moins de 25 % en poids. L'article composite en polymère vinylaromatique se caractérise par une tendance réduite au délaminage et une aptitude améliorée au recyclage. L'invention concerne en outre un procédé de production de l'article composite en polymère vinylaromatique et l'utilisation de l'article composite en polymère vinylaromatique obtenu en tant que composant de dispositifs de réfrigération ou de congélation.
PCT/EP2024/071859 2023-08-03 2024-08-01 Article composite en polymère vinylaromatique recyclable et son procédé de production Pending WO2025027149A1 (fr)

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