Composition of acrylonitrile-butadiene-styrene material

Abstract

Composition of acrylonitrile-butadiene-styrene material. The present invention relates to a composition comprising: - an acrylonitrile-butadiene-styrene polymer or a derivative of an acrylonitrile-butadiene-styrene polymer, - a high-temperature-resistant additive selected from a terpolymer of an N-substituted maleimide monomer, a vinyl monomer, and an unsaturated dicarboxylic acid anhydride monomer, and a polyalphamethylstyrene, and mixtures thereof, - at least one impact-modifying additive, and - at least one antioxidant additive. Figure for abstract: None

Description

Title of the invention: Acrylonitrile-butadiene-styrene material composition

[0001] The present invention relates to an acrylonitrile-butadiene-styrene material composition comprising various additives. The present invention also relates to a method for preparing such a composition. The present invention also relates to the use of such a composition for manufacturing a part. The present invention also relates to a part comprising such a composition.

[0002] Plastic products are generally formed from virgin plastics (also called native materials). For example, acrylonitrile butadiene styrene (known by the acronym ABS) is a plastic material used in many everyday applications: toys, consumer goods, telephones, household appliances, and, in particular, interior parts of motor vehicles. Although this material inherently possesses interesting properties of impact resistance and hardness, it is known to add one or more additives to produce different grades with specific properties. However, there is always a need to improve and / or modulate these performance characteristics depending on the intended application.

[0003] There is therefore a need for acrylonitrile-butadiene-styrene materials exhibiting both good impact resistance and good thermal resistance.

[0004] In addition, societal expectations regarding environmental preservation and resource reduction are increasingly strong, and it is therefore necessary to develop new materials obtained from recycled materials, in particular from recycled ABS.

[0005] The disadvantage of using recycled ABS is that its performance is generally degraded compared to that of the corresponding virgin ABS, particularly its impact resistance and thermal resistance. Furthermore, the future use of recycled ABS is not necessarily identical to its past use, which implies that the properties of the recycled polymer must be modified / adapted for this new use.

[0006] There is a need for recycled acrylonitrile-butadiene-styrene materials exhibiting good performance, particularly thermal and mechanical, similar to or superior to the performance of native acrylonitrile-butadiene-styrene materials.

[0007] An objective of the present invention is to provide an acrylonitrile-butadiene-styrene material composition, in particular recycled acrylonitrile-butadiene-styrene material, exhibiting good thermal resistance and resistance to shocks.

[0008] In particular, an objective of the present invention is to provide an acrylonitrile-butadiene-styrene material composition, in particular recycled acrylonitrile-butadiene-styrene material, having a flexural modulus value greater than or equal to 2150 MPa, preferably greater than or equal to 2300 MPa.

[0009] Another particular objective of the invention is to provide an acrylonitrile-butadiene-styrene material composition, in particular recycled acrylonitrile-butadiene-styrene material, having an IZOD impact resistance value greater than or equal to 9 kJ / m2, preferably greater than or equal to 10 kJ / m2.

[0010] Another particular objective of the invention is to provide an acrylonitrile-butadiene-styrene material composition, in particular recycled acrylonitrile-butadiene-styrene material, having a load deflection temperature value greater than or equal to 95°C, preferably greater than or equal to 99°C, or a Vicat point greater than or equal to 94°C, preferably greater than or equal to 97°C.

[0011] Yet another objective of the invention is to provide an acrylonitrile-butadiene-styrene material composition, in particular recycled acrylonitrile-butadiene-styrene material, which has both a flexural modulus value greater than or equal to 2150 MPa, preferably greater than or equal to 2300 MPa, an IZOD impact resistance value greater than or equal to 9 kJ / m2, preferably greater than or equal to 10 kJ / m2, and a load deflection temperature value greater than or equal to 95 °C, preferably greater than or equal to 99 °C, or a Vicat point greater than or equal to 94 °C, preferably greater than or equal to 97 °C.

[0012] The present invention therefore relates to a composition comprising:

[0013] - an acrylonitrile-butadiene-styrene polymer or an acrylonitrile- polymer derivative butadiene-styrene,

[0014] - a high thermal resistance additive selected from a terpolymer of a monomer N-substituted maleimide, a vinyl monomer and an unsaturated dicarboxylic acid anhydride monomer; and polyalphamethylstyrene, and mixtures thereof,

[0015] - at least one impact modifying additive, and

[0016] - at least one antioxidant additive.

[0017] Preferably, in the composition according to the invention, the mass content of high thermal resistance additive varies from 15% to 35%, preferably from 18% to 30%, advantageously from 20% to 25% by mass relative to the total mass of the composition.

[0018] Preferably, in the composition according to the invention, the total mass content of impact modifier additive varies from 8% to 35%, preferably from 10% to 25%, preferably from 12% to 20%, advantageously from 13% to 18% by mass relative to the total mass of the composition.

[0019] Preferably, in the composition according to the invention, the ratio between the content total mass content of impact modifier additive and mass content of high thermal resistance additive varies from 0.3 to 2.0, preferably from 0.4 to 1.5, preferably from 0.5 to 1.2, more preferably from 0.6 to 1.0, advantageously from 0.65 to 0.85.

[0020] Preferably, in the composition according to the invention, the content of acrylonitrile-butadiene-styrene polymer or of acrylonitrile-butadiene-styrene polymer derivative varies from 40% to 75%, preferably from 50% to 70%, more preferably from 55% to 65%, advantageously from 60% to 65% by mass relative to the total mass of the composition.

[0021] Preferably, the composition according to the invention is characterized by a flexural modulus at 23°C of a value greater than or equal to 1800 MPa, preferably greater than or equal to 2000 MPa, more preferably greater than or equal to 2300 MPa, more preferably between 2000 MPa and 2800 MPa, advantageously between 2200 MPa and 2500 MPa, advantageously between 2300 and 2500 MPa.

[0022] The value of the flexural modulus of the composition according to the invention is determined according to ISO 178 (2019 version).

[0023] Preferably, the composition according to the invention is characterized by an IZOD impact resistance of a value greater than or equal to 7.5 kJ / m2, preferably greater than or equal to 8.0 kJ / m2, more preferably greater than or equal to 9.8 kJ / m2, more preferably between 8.5 and 16 kJ / m2, more preferably between 9.0 and 15 kJ / m2, advantageously between 9.8 and 12.5 kJ / m2.

[0024] The IZOD impact resistance value of the composition according to the invention corresponds to the IZOD impact resistance notched at 23 °C determined according to ISO 180 of 2019.

[0025] Preferably, the composition according to the invention is characterized by a load bending temperature (LBT) of a value greater than or equal to 95°C, preferably greater than or equal to 96°C, preferably greater than or equal to 97°C, more preferably greater than or equal to 98°C, and even more preferably greater than or equal to 99°C. The value of the load bending temperature may preferably be between 95°C and 103°C, advantageously between 97°C and 101°C.

[0026] The value of the deflection temperature under load of the composition according to the invention is determined according to ISO 75-2A (2013 version).

[0027] Preferably, the composition according to the invention is characterized by a Vicat softening point of a value greater than or equal to 94°C, preferably greater than or equal to 97°C, preferably greater than or equal to 99°C, more preferably greater than or equal to 100°C, and more preferably still greater than or equal to 103°C. The value of the Vicat softening point may preferably be between between 94°C and 110°C, advantageously between 101°C and 105°C.

[0028] The Vicat softening point value of the composition according to the invention is determined according to ISO 306 (2013 version).

[0029] Acrylonitrile-butadiene-styrene (ABS) polymer and derivatives

[0030] The composition according to the invention comprises an acrylonitrile-butadiene-styrene polymer or a derivative of an acrylonitrile-butadiene-styrene polymer.

[0031] According to the invention, an acrylonitrile-butadiene-styrene polymer derivative is a copolymer in which an aromatic vinyl monomer and a vinyl cyanide monomer are grafted to a rubbery polymer.

[0032] The rubber copolymer is preferably selected from the group consisting of diene-based rubbers such as polybutadiene, polystyrene-butadiene, and polyacrylonitrile-butadiene; saturated rubbers obtained by hydrogenation of diene-based rubbers; acrylic rubbers such as C1-C8 alkyl acrylate, polybutyl acrylate, and ethylhexyl acrylate; isoprene rubbers; chloroprene rubbers; ethylene-propylene rubbers (EPM); and ethylene-propylene-diene monomer rubbers (EPDM). Preferably, the rubber polymer is selected from among the diene-based rubbers, and more preferably polybutadiene.

[0033] The rubbery polymer content preferably ranges from 5 to 30% by weight relative to the total weight of the acrylonitrile-butadiene-styrene polymer derivative

[0034] The aromatic vinyl monomer is preferably chosen from the group consisting of styrene, α-methylstyrene, γ-methylstyrene, β-methylstyrene, ethylstyrene, hydroxystyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibro-mostyrene and vinylnaphthalene, and is preferably styrene.

[0035] The aromatic vinyl compound content preferably ranges from 35 to 80% by weight relative to the total weight of the acrylonitrile-butadiene-styrene polymer derivative.

[0036] The vinyl cyanide monomer is preferably chosen from saturated nitriles such as acrylonitrile and unsaturated nitriles such as methacrylonitrile and rethacrylonitrile, and is preferably acrylonitrile.

[0037] The vinyl cyanide compound content preferably ranges from 15 to 35% by weight relative to the total weight of the acrylonitrile-butadiene-styrene polymer derivative.

[0038] Preferably, the composition according to the invention comprises an acrylonitrile-butadiene-styrene polymer.

[0039] According to the invention, an acrylonitrile-butadiene-styrene polymer is a polymer obtained by grafting, preferably by emulsion grafting, acrylonitrile and styrene onto polybutadiene, by dispersing an acrylonitrile-butadiene copolymer in an acrylonitrile-styrene copolymer matrix, or by bulk polymerization of acrylonitrile and styrene in the presence of polybutadiene. Preferably, the polymer Acrylonitrile-butadiene-styrene is a resin in which a styrene-acrylonitrile copolymer is grafted to a polybutadiene.

[0040] It generally comprises 15% to 35% by weight of acrylonitrile, 5% to 30% by weight of butadiene and 35% to 80% by weight of styrene, relative to the total weight of the acrylonitrile-butadiene-styrene polymer.

[0041] Preferably, the acrylonitrile-butadiene-styrene polymer has a number-average molar mass Mn of between 50,000 and 75,000 g / mol.

[0042] The acrylonitrile-butadiene-styrene polymer has an average molar mass in mass between 100,000 and 150,000 g / mol.

[0043] Preferably, the acrylonitrile-butadiene-styrene polymer has a number-average molar mass Mn of between 50,000 and 75,000 g / mol, and a mass-average molar mass of between 100,000 and 150,000 g / mol.

[0044] According to a particular embodiment, the acrylonitrile-butadiene-styrene polymer or the acrylonitrile-butadiene-styrene polymer derivative is recycled.

[0045] By recycled polymer, we mean a post-consumer polymer, that is, one that has already been used in the manufacture of an object. In contrast, a virgin (or native) polymer is a polymer obtained through a polymerization process that prepares it from one or more monomers. There are also post-industrial polymers, which refer to plastic waste generated by manufacturers of the consumer products mentioned above. Finally, post-production polymers are waste generated by producers of plastic materials. The thermomechanical properties of post-production polymers are much closer to those of virgin polymers than to those of post-consumer or post-industrial polymers.Indeed, a post-consumer polymer has been subjected to shocks and / or temperature variations and / or UV radiation, and its thermomechanical properties are diminished compared to those of a virgin polymer or a post-production polymer. A post-industrial polymer also exhibits modified properties compared to a virgin polymer insofar as it has undergone transformation steps.

[0046] A recycled acrylonitrile-butadiene-styrene polymer according to the invention is a post-consumer acrylonitrile-butadiene-styrene polymer or a post-industrial acrylonitrile-butadiene-styrene polymer, preferably post-consumer.

[0047] Typically, a post-consumer acrylonitrile-butadiene-styrene polymer has a flexural modulus value less than or equal to 2700 MPa, preferably less than or equal to 2550 MPa, preferably ranging from 2200 MPa to 2700 MPa, preferably ranging from 2300 to 2550 MPa, and / or an IZOD impact resistance value less than or equal to 12 kJ / m², preferably less than or equal to 8 kJ / m², preferably ranging from 6 to 12 kJ / m², preferably ranging from 6.5 to 8 kJ / m², and / or a deflection temperature value under load less than or equal to 91°C, preferably between 85°C and 91°C.

[0048] The recycled acrylonitrile-butadiene-styrene polymer is obtained after collecting consumer products containing acrylonitrile-butadiene-styrene polymer, grinding these products, separating the ground materials containing acrylonitrile-butadiene-styrene polymer and melting these ground materials.

[0049] Terpolymer of an N-substituted maleimide monomer, a vinyl monomer, and an unsaturated dicarboxylic acid anhydride monomer; polyalphamethylstyrene and mixtures thereof

[0050] The composition according to the invention may include a high thermal resistance additive comprising a terpolymer of an N-substituted maleimide monomer, a vinyl monomer and an unsaturated dicarboxylic acid monomer (referred to as terpolymer P in the following description).

[0051] The N-substituted maleimide monomer is preferably chosen from the group consisting of N-alkylmaleimides, such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide, and N-arylmaleimides, such as N-phenylmaleimide, N-methylphenylmaleimide, and N-chlorophenylmaleimide. Preferably, the N-substituted maleimide monomer is N-phenylmaleimide.

[0052] The content of N-substituted maleimide monomer preferably ranges from 45 to 55% by weight relative to the total weight of the terpolymer P.

[0053] The vinyl monomer is preferably chosen from the group consisting of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methylstyrene and α-methyl-p-methylstyrene. Preferably, the vinyl monomer is styrene.

[0054] The vinyl monomer content preferably ranges from 40 to 50% by weight relative to the total weight of the terpolymer P.

[0055] The unsaturated dicarboxylic acid anhydride monomer is preferably chosen from maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride. Preferably, the unsaturated dicarboxylic acid anhydride monomer is maleic anhydride.

[0056] The content of unsaturated dicarboxylic acid anhydride monomer preferably ranges from 5 to 10% by weight relative to the total weight of the terpolymer P.

[0057] Preferably, the terpolymer P has an average molar mass by weight between 70,000 g / mol and 300,000 g / mol and / or a glass transition temperature between 184°C and 197°C.

[0058] Preferably, the terpolymer P is an N-phenyl-maleimide-styrene-maleic anhydride terpolymer.

[0059] The N-phenylmaleimide-styrene-maleic anhydride terpolymer preferably comprises 45 to 55% by weight of N-phenylmaleimide, 40 to 50% by weight of styrene and 5 to 10% by weight of maleic anhydride.

[0060] By way of example, the N-phenylmaleimide-styrene-maleic anhydride terpolymer can be chosen from the commercial N-phenylmaleimide-styrene-maleic anhydride terpolymers available under the reference DENKA® IP MS-CP or DENKA® IP MS-NJP, from the company DENKA. Polyalphamethylstyrene

[0061] The composition according to the invention may include a high heat resistance additive comprising a polyalphamethylstyrene.

[0062] By way of example, the high thermal resistance additive comprising a polyalphamethylstyrene may be the commercial product available under the references ACMA00017077 and ACM9011114 from Alpha Chemistry, or the commercial product available under the reference M-80 from Jiasheng High-Tech Modified Material Co., Ltd. Impact modifier additive

[0063] The composition according to the invention comprises at least one impact modifying additive.

[0064] An impact modifier additive is a chemical compound which, when mixed with a polymer, makes the polymer more impact-resistant. In particular, an impact modifier additive is a polymeric material that improves the impact properties of a polymer, for example, the IZOD notch impact resistance at 23°C, as determined according to ISO 180 (2019 version). This term is also known as "impact modifiers," "impact additives," or "impact modifiers." This term is well known to those skilled in the art.

[0065] Preferably, according to the invention, an impact modifying additive is an additive which enables a polymer comprising 5% by weight of this additive, relative to the total weight of polymer-additive mixture, to exhibit a rate of increase in its impact resistance greater than or equal to 1.2, preferably greater than or equal to 1.5, more preferably greater than or equal to 2.0.

[0066] Thus, preferably, the impact modifier additive makes it possible to increase by at least 10% the IZOD impact resistance of a composition consisting of the recycled polymer and 5% by weight of said impact modifier additive.

[0067] Examples of suitable impact-modifying additives include, for example, grafted polymers, core-shell polymers, and sequenced copolymers. These polymers can be obtained from at least one monomer selected from the group consisting of an alkene, an alkadiene, an arene, and an acrylate.

[0068] Preferably, the impact modifying additive is a copolymer obtained from at least one vinyl monomer.

[0069] By copolymer, we mean a polymer resulting from the copolymerization of at least two or more types of chemically different monomers, called comonomers.

[0070] By vinyl monomer, we mean an organic molecule comprising at least one carbon-carbon double bond. Preferably, the vinyl monomer has the following formula: CH2=CRR', with R and R' being independently chosen from the group consisting of a hydrogen atom, an aromatic group, preferably a phenyl, a hydrocarbon group comprising from 1 to 10 carbon atoms, preferably from 2 to 10 carbon atoms, saturated or unsaturated, further optionally comprising an ester group, a nitrile group, a carboxyl group, an amine group or an amide group.

[0071] Preferably, the impact modifying additive is a copolymer of ethylene and / or styrene, that is to say that at least one of the comonomers of the copolymer is chosen from styrene and ethylene.

[0072] Preferably, the impact modifying additive comprises a copolymer resulting from the copolymerization of at least two monomers selected from the group consisting of a C2-C8 alkene, a C4-C8 diene, a styrenic monomer and an acrylic monomer.

[0073] Preferably, the impact modifying additive comprises a copolymer resulting from the copolymerization of at least two monomers selected from the group consisting of ethylene, butene, styrene, butadiene, acrylonitrile, (m)ethyl (meth)acrylate and butyl (meth)acrylate.

[0074] In some embodiments, the impact-modifying additive is functionalized or grafted. The functionalized or grafted ethylene copolymer may comprise polar compounds, including, for example, an anhydride or epoxy function, preferably cyclic, preferably maleic anhydride or glycidyl (meth)acrylate.

[0075] Preferably, the impact modifier additive is chosen from:

[0076] - copolymers of ethylene and / or butene and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate and (meth)butyl acrylate,

[0077] - modified acrylonitrile-butadiene-styrene copolymers having a level of butadiene greater than or equal to 60% by weight relative to the total weight of the modified acrylonitrile-butadiene-styrene polymer,

[0078] - styrene-ethylene / butene-styrene copolymers grafted with anhydride maleic acid or glycidyl methacrylate,

[0079] - ethylene-butyl acrylate copolymers, possibly grafted by maleic anhydride,

[0080] - styrene-butadiene copolymers, preferably styrene- Block butadiene, preferably multiblock or diblock styrene-butadiene copolymers,

[0081] - styrene-ethylene / butene-styrene copolymers, preferably copolymers styrene-ethylene / butene-styrene block,

[0082] and

[0083] - any one of their mixtures.

[0084] As an example of a styrene-ethylene / butene-styrene copolymer functionalized with maleic anhydride, we can cite the product referenced SEBS-g-MA® from the company Kraton Polymer.

[0085] As an example of styrene-ethylene / butene-styrene copolymers grafted with maleic anhydride, we can cite the product referenced C1010® from the company Kraton Polymer.

[0086] As an example of styrene-ethylene / butene-styrene copolymers grafted with glycidyl methacrylate, we can cite the product referenced 02520 C® from the company Graft polymer.

[0087] As an example of ethylene-butyl acrylate copolymers, we can cite the product Lucofin® 1400PN from the company Lucobit.

[0088] As an example of maleic anhydride grafted ethylene-butyl acrylate copolymers, we can cite the product Lucofin® 1492 MGH from the company Lucobit.

[0089] As an example of a styrene-butadiene copolymer, we can cite the product referenced SBS-C3000® from the company Kraton Polymer or the product referenced DENKA NSBC® from the company DENKA.

[0090] As an example of a styrene-ethylene / butene-styrene copolymer, we can cite the product referenced SBS-C2000® from the company Kraton Polymer.

[0091] Copolymers of ethylene and / or butene and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate and (meth)butyl acrylate

[0092] (M)ethyl means methyl or ethyl group.

[0093] (Meth)acrylate means acrylate or methacrylate.

[0094] Preferably, the copolymer of ethylene and / or butene and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate and butyl (meth)acrylate is a copolymer of ethylene and a polar monomer selected from (m)ethyl acrylate and (m)ethyl methacrylate.

[0095] Preferably, the copolymer of ethylene and / or butene and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate, and (meth)butyl acrylate is a random copolymer. Such a copolymer can be prepared under high pressure from a mixture of ethylene and / or butene and a polar monomer. chosen from (m)ethyl acrylate, (m)ethyl methacrylate and butyl (meth)acrylate in the presence of a radical polymerization initiator.

[0096] The copolymer of ethylene and a polar monomer selected from (m)ethyl acrylate and (m)ethyl methacrylate preferably comprises 5 to 30% by mass, preferably 10% to 30% by mass, preferably still 15% to 31% by mass of polar monomer relative to the total mass of the copolymer, and 70 to 95% by mass of ethylene, preferably 70% to 90% by mass, preferably still 69 to 85% by mass relative to the total mass of the copolymer.

[0097] Preferably, the copolymer of ethylene and / or butene and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate and butyl (meth)acrylate is a copolymer of ethylene and methyl acrylate.

[0098] By way of example of a copolymer of ethylene and / or butene and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate and butyl (meth)acrylate, we may cite the commercial ethylene / methylacrylate copolymers available under the reference Lotryl ©29MA03T, from SK Functional Polymer, the Elvaloy® copolymers (AC1125, AC12024 S, AC1330) from Dow, or the EMAC® SP2260, EMAC® SP2403, EMAC® SP2268 products from Westlake.

[0099] Modified acrylonitrile butadiene styrene polymer having a butadiene content greater than or equal to 60% by weight

[0100] Preferably, the modified acrylonitrile butadiene styrene polymer having a butadiene content greater than or equal to 60% by weight comprises a modified acrylonitrile butadiene styrene polymer having a butadiene content ranging from 60% to 80%, preferably ranging from 60% to 65% by mass relative to the total mass of the modified acrylonitrile butadiene styrene polymer.

[0101] This polymer therefore differs in particular from the acrylonitrile-butadiene-styrene polymer described above in that it comprises a higher butadiene content (greater than or equal to 60% by weight).

[0102] As an example of a modified acrylonitrile butadiene styrene polymer having a butadiene content greater than or equal to 60% by mass, we can cite the product referenced KUMHO® HR 181 from the company Korea Kurnho Petrochemical.

[0103] Preferably, the impact modifying additive is chosen from:

[0104] - copolymers of ethylene and / or butene and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate and (meth)butyl acrylate,

[0105] - modified acrylonitrile-butadiene-styrene copolymers having a level of butadiene greater than or equal to 60% by weight relative to the total weight of the modified acrylonitrile-butadiene-styrene polymer,

[0106] - styrene-butadiene copolymers, preferably styrene- block butadiene, preferably multiblock or diblock styrene-butadiene copolymers, and

[0107] - any one of their mixtures,

[0108] in any combination of variants defined above for each of these copolymers.

[0109] According to one embodiment, the impact modifier additive comprises at least a first impact modifier additive and a second impact modifier additive.

[0110] The first impact modifier additive and the second impact modifier additive are different from each other and are preferably each independently an impact modifier additive according to any variant defined above.

[0111] Preferably, the first impact modifying additive and the second impact modifying additive are different from each other and independently chosen from:

[0112] - copolymers of ethylene and / or butene and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate and (meth)butyl acrylate,

[0113] - modified acrylonitrile-butadiene-styrene copolymers having a content of butadiene greater than or equal to 60% by weight relative to the total weight of the modified acrylonitrile-butadiene-styrene polymer,

[0114] - styrene-butadiene copolymers, and

[0115] - any one of their mixtures.

[0116] All variants defined above for each of these copolymers apply.

[0117] Preferably, the ratio between the total mass content of first and second impact modifier additives and the mass content of high thermal resistance additive varies from 0.3 to 2.0, preferably from 0.4 to 1.5, preferably from 0.5 to 1.2, more preferably from 0.6 to 1.0, advantageously from 0.65 to 0.85.

[0118] Preferably, the ratio between the mass content of the second impact modifier additive and the mass content of the first impact modifier additive varies from 0.1 to 12, preferably varies from 0.3 to 8.0, preferably from 0.4 to 6.0, more preferably from 0.5 to 3.0.

[0119] Preferably, the mass content of the first impact modifying additive varies from 2% to 18%, preferably from 3% to 15%, preferably from 4% to 12%, advantageously from 4% to 8% by mass relative to the total mass of the composition.

[0120] Preferably, the mass content of the second impact modifier additive varies from 5% to 25%, preferably from 6% to 20%, preferably from 7% to 16%, advantageously from 8% to 12% by mass relative to the total mass of the composition.

[0121] Preferably, the first impact-modifying additive is selected from copolymers of ethylene and / or butene and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate and butyl (meth)acrylate and the second impact-modifying additive is selected from acrylonitrile- copolymers modified butadiene-styrene having a butadiene content greater than or equal to 60% by weight relative to the total weight of the modified acrylonitrile-butadiene-styrene polymer, or

[0122] the first impact modifying additive is selected from styrene-butadiene copolymers and the second impact modifying additive is selected from ethylene and / or butene copolymers and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate and butyl (meth)acrylate, and modified acrylonitrile-butadiene-styrene copolymers having a butadiene content greater than or equal to 60% by weight relative to the total weight of the modified acrylonitrile-butadiene-styrene polymer.

[0123] Advantageously, the first impact modifying additive is a copolymer of ethylene and (m)ethyl (meth)acrylate, preferably a copolymer of ethylene and methyl acrylate, and the second impact modifying additive is selected from modified acrylonitrile-butadiene-styrene copolymers having a butadiene content greater than or equal to 60% by weight relative to the total weight of the modified acrylonitrile-butadiene-styrene polymer.

[0124] All variants defined above with respect to each of these copolymers apply, as well as all variants concerning the contents of the first and second impact modifier additive. Antioxidant additives

[0125] The composition according to the invention comprises at least one antioxidant additive.

[0126] Preferably, the antioxidant additives are chosen from the group consisting of:

[0127] - bulky phenolic compounds, such as triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-l,3,5-triazine, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), tetrakis(methylene 3,5-di- tert-butyl-hydroxycinnamate)methane, and octadecyl 3,5-di-tert-butylhydroxyhydrocinnamate, preferably N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide),

[0128] - organophosphites, such as tetrakis(2,4-di-tert-butylphenyl) [l,l-biphenyl]-4,4'-diylbisphosphonite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerytritol diphosphite, tris(nonyl phenyl)phosphite and distearyl pentaerythritol diphosphite, preferably is tris(2,4-di-tert-butylphenyl) phosphite.

[0129] Examples of antioxidant additives include the products referenced IRGANOX 1076, IRGANOX 245 and IRGAFOS 168 FF from BASF.

[0130] Preferably, the antioxidant content by mass varies from 0.05% to 1%, preferably from 0.1% to 0.5%, advantageously from 0.15% to 0.25% by mass relative to the total mass of the composition. The composition according to the invention may comprise one antioxidant or a mixture of at least two antioxidants. When the composition comprises at least two antioxidants, the above antioxidant content represents the total antioxidant content.

[0131] Preferably, when the composition comprises at least two antioxidants, it comprises at least one phenolic compound and one organophosphite compound as listed above. Preferably, the mass ratio between the phenolic compound(s) and the organophosphite compound(s) is from 1:1 to 1:4.

[0132] Advantageously, the antioxidant additive of the composition according to the invention comprises a mixture of N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) and tris(2,4-di-tert-butylphenyl) phosphite.

[0133] The present invention also relates to a method for preparing a composition according to the invention, comprising:

[0134] - a step of mixing an acrylonitrile-butadiene-styrene polymer or a derivative of acrylonitrile-butadiene-styrene polymer, of a high thermal resistance additive selected from a terpolymer of an N-substituted maleimide monomer, a vinyl monomer and an unsaturated dicarboxylic acid anhydride monomer, and a polyal-phamethylstyrene, and mixtures thereof, of at least one impact modifier additive, and of at least one antioxidant additive.

[0135] All definitions and preferred embodiments described in the above description apply.

[0136] The mixing step is preferably carried out at a temperature between 235 and 290°C. The mixing step must be carried out using an extruder equipped with a co-rotating twin screw.

[0137] During the injection molding of molded parts, the temperature of the screw-barrel assembly of the injection molding machine must be between 220°C and 250°C at the time of injection. The recommended mold temperature during injection is between 40 and 70°C.

[0138] The present invention also relates to the use of a composition according to the invention for the manufacture of a part, for example a vehicle part, preferably a motor vehicle part.

[0139] The present invention also relates to a method of manufacturing a part, preferably a vehicle part, preferably a motor vehicle part, comprising the molding of a composition according to the invention.

[0140] The present invention also relates to a part, preferably a vehicle part, preferably a motor vehicle part, comprising a composition according to the invention.

[0141] The vehicle part is for example a car taillight, a part under the hood, an interior vehicle part, a passenger compartment part.

[0142] The composition can also be used to manufacture parts in the electrical and electronic fields, for example a telephone box.

[0143] The present invention also relates to a method for improving at least one thermal or mechanical property of a recycled acrylonitrile-butadiene-styrene polymer or a derivative of a recycled acrylonitrile-butadiene-styrene polymer, comprising adding to the recycled acrylonitrile-butadiene-styrene polymer or the derivative of a recycled acrylonitrile-butadiene-styrene polymer a composition comprising:

[0144] - a high thermal resistance additive selected from a terpolymer of a monomer N-substituted maleimide, a vinyl monomer and an unsaturated dicarboxylic acid anhydride monomer, and polyalphamethylstyrene, and mixtures thereof,

[0145] - at least one impact modifying additive, and

[0146] - at least one antioxidant additive.

[0147] All definitions and preferred embodiments described in the above description apply.

[0148] Preferably, the process for improving at least one thermal or mechanical property of a recycled acrylonitrile-butadiene-styrene polymer or a derivative of a recycled acrylonitrile-butadiene-styrene polymer is a process for improving the flexural modulus at 23 °C and / or the IZOD impact strength and / or the temperature of deflection under load and / or the Vicat softening point of the recycled acrylonitrile-butadiene-styrene polymer or the derivative of a recycled acrylonitrile-butadiene-styrene polymer, preferably up to values ​​as defined in this description.

[0149] The present invention also relates to the use of a combination of:

[0150] - a high thermal resistance additive selected from a terpolymer of a monomer N-substituted maleimide, a vinyl monomer and an unsaturated dicarboxylic acid anhydride monomer, and polyalphamethylstyrene, and mixtures thereof,

[0151] - at least one impact modifying additive, and

[0152] - at least one antioxidant additive,

[0153] to improve at least one thermal or mechanical property of a recycled acrylonitrile-butadiene-styrene polymer or a derivative of a recycled acrylonitrile-butadiene-styrene polymer.

[0154] All definitions and preferred embodiments described in the description below above apply.

[0155] Preferably, the use of the combination of additives to improve at least one thermal or mechanical property of a recycled acrylonitrile-butadiene-styrene polymer or of a recycled acrylonitrile-butadiene-styrene polymer derivative improves the flexural modulus at 23 °C and / or the IZOD impact strength and / or the load deflection temperature and / or the Vicat softening point of the recycled acrylonitrile-butadiene-styrene polymer or of the recycled acrylonitrile-butadiene-styrene polymer derivative, preferably up to values ​​as defined in this description.

[0156] The invention will now be described by means of the following non-limiting examples.

[0157] EXAMPLES

[0158] In all the following examples, the compositions were prepared as follows:

[0159] Recycled ABS ground material (also called post-consumer ABS) is mixed mechanically, the high-temperature-resistant additive is added initially. During compounding, the impact-modifying additive(s) and antioxidants are added using metering hoppers.

[0160] In all the following examples, the various thermomechanical properties of the compositions were determined according to the following standards:

[0161] IZOD: ISO 180 (2019 version);

[0162] Bending modulus: ISO 178 (2019 version);

[0163] VICAT: ISO 306 (2013 version) are carried out according to conditions B50 50N;

[0164] HDT: ISO 75-2A (2013 version) carried out under the following conditions: the The test specimens were annealed at 80°C for 4 hours. The weight used for the HDT measurement is 1.8 MPa.

[0165] Example 1: Influence of the quantity and characteristics of the heat-resistant additive

[0166] Initially, several compositions comprising only a heat-resistant additive, in varying concentrations, were prepared. These compositions are therefore not according to the invention, but the determination of the 1TZOD and the HDT of these compositions made it possible to determine a range of heat-resistant additive concentrations that would give the compositions good heat resistance without significantly degrading their mechanical properties.

[0167] Case no. 1: Use of DENKA IP MS-NJP

[0168] In the compositions of Table 1 below, the following materials and additives were used:

[0169] ABS: Recycled ABS EGR0064

[0170] Thermal resistance additive 1: DENKA IP MS-NJP®

[0171] Antioxidant: 0.2% (equi-mass mixture of Irganox 1076® and Irganox 168®)

[0172] Extrusion temperature: 270°C

[0173] Injection temperature: 250°C

[0174] [Tables] Ref. Thermal resistance additive 1 (% mass) Impact modifier additive 1 (% mass) Impact modifier additive 2 (% mass) Notched IZOD 23°C (kJ / m²) Flexural modulus 23°C (MPa) VICAT (°C) HDT (°C) Cl₂O * - - - 7.9 2520 92.5 91 Cl₂O * 20 - - 4.1 2880+30 102 99 Cl₂ * 25 - - 3.7 2935+25 109 103 Cl₂O * 35 - - 3.2 3100+37 115 111

[0175] A thermal resistance additive content of between 20% and 25% by weight provides a good compromise regarding the mechanical and thermal properties of the composition.

[0176] Case #2: Use of the DENKA IP MS-CP

[0177] In the compositions of Table 2 below, the following materials and additives were used:

[0178] ABS: Recycled ABS EGR0064

[0179] Thermal resistance additive 2: DENKA IP MS-CP®

[0180] Antioxidant: 0.2% (equi-mass mixture of Irganox 1076® and Irganox 168®)

[0181] Extrusion temperature: 235°C

[0182] Injection temperature: 220°C

[0183] [Tables2] Ref. Thermal resistance additive 2 (% mass) Impact modifier additive 1 (% mass) Impact modifier additive 2 (% mass) Notched IZOD 23°C (kJ / m²) Flexural modulus 23°C (MPa) VICAT (°C) HDT (°C) Cl-4* - - - 7.9 2520 92.5 91 Cl-5* 5 - - 6.7+0.3 2500+60 - 94.5+0.5 Cl-6* 10 - - 5.6+0.2 2650+22 - 96.6+0.2 Cl-7* 15 - - 5.4+0.1 2660+13 - 98.8+0.3 Cl-8* 20 - - 5+0.1 2800+38 - 100.7 + 0.6

[0184] The use of IP MS-CP increases impact resistance compared to IP MS-NJP, with a lower flexural modulus. The HDT value is higher with this reference: at 20%, 100.7°C + / - 0.6 with IP MS-CP versus 99°C for IP MS-NJP.

[0185] Example 2: Compositions according to the invention comprising a heat-resistant additive and an impact-modifying additive

[0186] In the compositions of Table 3 below, the following materials and additives were used:

[0187] ABS: Recycled ABS EGR0064

[0188] Thermal resistance additive 1: DENKA IP MS-NJP®

[0189] Thermal resistance additive 2: DENKA IP MS-CP®

[0190] Impact modifier additive 1: Lotryl 29MA03T®

[0191] Impact modifier additive 2: HR-181®

[0192] Impact modifier additive 3: C3000®

[0193] Antioxidant: 0.2% (equi-mass mixture of Irganox 1076® and Irganox 168®)

[0194] Extrusion temperature: 270°C

[0195] Injection temperature: 250°C

[0196] [Tables3] Ref Thermal resistance additive (% mass) Impact modifier additive 1 (% mass) Impact modifier additive 2 (% mass) Impact modifier additive 3 (% mass) Notched IZOD 23°C (kJ / m2) Flexural modulus 23°C (MPa) VICAT (°C) HDT (°C) C2- 0* 0 0 0 - 7.9 - - 91 C2-1 Thermal resistance additive 1 (15%) 8 9.1 + 0.2 2590 + 20 105 95.9 + 0.1 C2- 2 Thermal resistance additive 1 (15%) 10 9.3 + 0.2 2540 + 30 104 95.7 + 0.2 C2- 3 Thermal resistance additive 1 (15%) 12 10.4 + 0.2 2370 + 30 102 95.3 + 0.2 C2- 4 Thermal resistance additive 1 (25%) 24 7 1970 + 19 69.1 + 1.3 101.3 + 0.6 C2- 5 Thermal resistance additive 1 (25%) 24 9.7 2200 + 15 105.3 + 0.6 98.7 + 0.2 C2- 6 Thermal resistance additive - - 15 4.8 + 0.7 2110 + 10 - 99.8 + 0.3 thermal 2 (20%)

[0197] Example 3: Compositions according to the invention comprising a heat-resistant additive and two impact-modifying additives

[0198] In the compositions of Table 4 below, the following materials and additives were used:

[0199] ABS: Recycled ABS EGR0064

[0200] Thermal resistance additive 1: DENKA IP MS-NJP®

[0201] Impact modifier additive 1: Lotryl 29MA03T®

[0202] Impact modifier additive 2: HR-181®

[0203] Antioxidant: 0.2% (equi-mass mixture of Irganox 1076® and Irganox 168®)

[0204] Extrusion temperature: 270°C

[0205] Injection temperature: 250°C

[0206] [Tables4] Ref Thermal resistance additive 1 (% mass) Impact modifier additive 1 (% mass) Impact modifier additive 2 (% mass) Impact modifier additive 2 / Impact modifier additive 1 IZOD notched 23°C (kJ / m2) Flexural modulus 23°C (MPa) VICAT (°C) HDT (°C) C3-1 25 24 - 0 7 1970 + 19 69.1+1.3 101.3 + 0.6 C3-2 25 16 8 0.5 7.7 2180 + 32 94.4+0.6 104 + 0.6 C3-3 25 12 12 1 8.2 2280 + 20 100.2+ 0.7 102+1 C3-4 25 8 16 2 11.3 2060 + 10 103 99 C3-5 25 - 24 - 9.7 2200 + 15 105.3+ 0.6 98.7 + 0.2 C3-6 15 7.5 7.5 1 15.4 + 0.2 2180 + 20 - 96.5 + 0.2 C3-7 20 5 10 2 10.5 2330 + 20 - 99.1 + 0.2 C3-8 20 7.5 7.5 1 10.3 2330 + 20 - 99.1 + 0.2 C3-9 25 5 15 3 12.1+ 0.2 2190 + 20 - 99.7 + 0.1 C3-1 0 25 8 16 2 11.3 2060 - 98.9 + 0.9 C3-1 1 25 7 15 2.1 10.6 2100 - 99.2 + 0.3

[0207] For an equivalent total quantity of impact modifier additive, compositions C3-2, C3-3, and C3-4 exhibit even better mechanical strength than composition C3-1, which contains only one impact modifier additive. Furthermore, for an equivalent total quantity of impact modifier additive, compositions C3-2, C3-3, and C3-4 exhibits an even higher deflection temperature under load than composition C3-5, which includes only one impact modifier additive.

[0208] When the ratio of impact modifier additive 2 to impact modifier additive 1 is greater than or equal to 2, a synergistic effect between the two impact modifier additives is observed. For example, the impact resistance of composition C3-4 according to the invention is even better than that of compositions C3-1 and C3-5, which comprise only one impact modifier additive.

[0209] In the compositions of Table 5 below, the following materials and additives were used:

[0210] ABS: Recycled ABS EGR0064

[0211] Thermal resistance additive 2: DENKA IP MS-CP®

[0212] Impact modifier additive 1: Lotryl 29MA03T®

[0213] Impact modifier additive 2: HR-181®

[0214] Antioxidant: 0.2% (equi-mass mixture of Irganox 1076® and Irganox 168®)

[0215] Extrusion temperature: 235°C

[0216] Injection temperature: 220°C

[0217] [Tables5] Ref. Thermal resistance additive 2 (% mass) Impact modifier additive 1 (% mass) Impact modifier additive 2 (% mass) Impact modifier additive 2 / Impact modifier additive 1 Notched IZOD 23°C (kJ / m²) Flexural modulus 23°C (MPa) HDT (°C) C3-12 15 15 - 0 12.5 + 0.2 2160 + 9 93.6 + 0.6 C3-13 15 11.25 3.75 0.33 14.4 + 0.4 2120 + 32 97.2 + 0.3 C3-14 15 10 5 0.5 14.8 + 0.3 2120 + 10 97.5 + 0.3 C3-15 15 7.5 7.5 1 14.7 + 0.3 2140 + 22 97.4 + 0.6 C3-16 15 5 10 2 13.9 + 0.3 2260 + 14 95.8 + 0.4 C3-17 15 3.75 11.25 3 14.6 + 0.1 2200 + 19 95 + 0.5 C3-18 15 - 15 - 11.6 + 0.2 2310 + 7 94.3 + 0.3

[0218] Regardless of the ratio of impact modifier additive 2 / impact modifier additive 1, a synergistic effect between the two impact modifier additives is observed, with respect to impact resistance and with respect to thermal content.

[0219] In the compositions of Table 6 below, the following materials and additives were used:

[0220] ABS: Recycled ABS EGR0064

[0221] Thermal resistance additive 2: DENKA IP MS-CP®

[0222] Impact modifier additive 1: Lotryl 29MA03T®

[0223] Impact modifier additive 2: HR-181®

[0224] Impact modifier additive 3: C3000®

[0225] Antioxidant: 0.2% (equi-mass mixture of Irganox 1076® and Irganox 168®)

[0226] Extrusion temperature: 235°C

[0227] Injection temperature: 220°C

[0228] [Tableauxô] Ref. Thermal resistance additive 2 (% mass) Impact modifier additive 1 (% mass) Impact modifier additive 2 (% mass) Impact modifier additive 3 (% mass) Ratio of second impact modifier additive / first impact modifier additive IZOD notched 23°C (kJ / m²) Flexural modulus 23°C (MPa) HDT (°C) C3-1 9 20 - - 15 - 4.8 + 0.7 2110 + 10 99.8 + 0.3 C3-2 0 20 10 - 5 2 10.3 + 0.5 2120 + 27 99 + 0.4 C3-2 1 18 - 10 5 2 10.3 + 0.3 2310 + 12 98.1 + 0.3 C3-2 2 20 - 10 5 2 10 + 0.4 2230 + 9 98.9 + 0.4 C3-2 3 20 - 13.3 6.7 2 11 + 0.4 2060 + 2 98.4 + 0.2

[0229] The HR-181® additive gives the formulation a higher flexural modulus of approximately 200MPa than Lotryl29MA03T® and causes a decrease in the HDT value of 1°C.

[0230] Increasing the amount of shock additive increases shock resistance but decreases HDT.

[0231] Example 4: Influence of the ratio between the total quantity of impact modifier additives and the quantity of thermal resistance additive

[0232] In the compositions of Table 7 below, the following materials and additives were used:

[0233] ABS: Recycled ABS EGR0064

[0234] Thermal resistance additive 1: DENKA IP MS-NJP®

[0235] Impact modifier additive 1: Lotryl 29MA03T®

[0236] Impact modifier additive 2: HR-181®

[0237] Antioxidant: 0.2% (equi-mass mixture of Irganox 1076® and Irganox 168®)

[0238] Ratio Impact modifier additive 2 / Impact modifier additive 1 = 2

[0239] Extrusion temperature: 270°C

[0240] Injection temperature: 250°C

[0241] [Tables?] Ref. Thermal resistance additive 1 (% mass) Impact modifier additive 1 (% mass) Impact modifier additive 2 (% mass) Mass ratio (Impact modifier additives) / (Thermal resistance 1) IZOD (kJ / m²) Flexural modulus (MPa) VICA T (°C) HDT (°C) C4-1 22 5.5 11 0.75 10.1 + 0.18 2310 + 21 - 99 + 0.5 C4-2 20 5 10 0.75 10.3 2330 - 99.1 C4-3 25 7.33 14.67 0.88 10.6 2100 - 99.2 + 0.3 C4-4 25 8 16 0.96 11.3 2060+ 10 - C4- 5 20 6.67 13.33 1 10.8 2150 99.6+0.2 97.2+0.2 C4- 6 20 10 20 1.5 15.6 1830 - 96.4

[0242] In the compositions of Table 8 below, the following materials and additives were used:

[0243] ABS: Recycled ABS EGR0064

[0244] Thermal resistance additive 2: DENKA IP MS-CP®

[0245] Antioxidant: 0.2% (equi-mass mixture of Irganox 1076® and Irganox 168®)

[0246] Extrusion temperature: 235°C

[0247] Injection temperature: 220°C

[0248] Ratio Impact modifier additive 2 / Impact modifier additive 1 = 2

[0249] [Tables8] Ref. Thermal resistance additive 2 (% mass) Impact modifier additive 1 (% mass) Impact modifier additive 2 (% mass) Mass ratio (Impact modifier additives) / (Thermal resistance 2) Notched IZOD 23°C (kJ / m²) Flexural modulus 23°C (MPa) HDT (°C) C4-7 21 5 10 0.71 12+0.4 2330+2 0 99.6+0.4 C4-8 17.5 0.86 12.7+0.3 2320+3 8 96.6+0.2 C4-9 15 1 13.9+0.3 2260+1 4 95.8+0.4 C4-1 0 12.5 1.2 15.8+0.4 2190+1 4 95.2+0.2 C4-1 1 10 1.5 17+0.3 2170+1 2 91.6+0.2

[0250] In the compositions of Table 9 below, the following materials and additives were used:

[0251] ABS: Recycled ABS EGR0064

[0252] Thermal resistance additive 2: DENKA IP MS-CP®

[0253] Impact modifier additive 1: Lotryl 29MA03T®

[0254] Impact modifier additive 2: HR-181®

[0255] Antioxidant: 0.2% (equi-mass mixture of Irganox 1076® and Irganox 168®)

[0256] Extrusion temperature: 235°C

[0257] Injection temperature: 220°C

[0258] Ratio Impact modifier additive 2 / Impact modifier additive 1 = 1

[0259] [Tables9] Ref. Thermal resistance additive 2 (% mass) Impact modifier additive 1 (% mass) Impact modifier additive 2 (% mass) Mass ratio (Impact modifier additive) / (Thermal resistance 2) IZOD (kJ / m²) Flexural modulus (MPa) HDT (°C) C4-1 2 15 6 6 0.8 12.1+0.3 2320+2 8 98.9+0.3 C4-1 3 15 7 7 0.93 13.7+0.3 2260+2 5 98.3+0.1 C4-1 4 15 7.5 7.5 1 14.7+0.3 2140+2 2 97.4+0.6 C4-1 5 15 8 8 1.07 14.2 + 0.3 2240 + 1 4 96.9 + 0.4

[0260] The ratio (Impact modifier additives) / (Thermal resistance additive) influences the trade-off between the mechanical strength and impact resistance of the compositions according to the invention. The choice of its value depends on the desired characteristics of the composition.

[0261] Example 5: Other compositions according to the invention

[0262] In the compositions of this example, the following materials and additives were used:

[0263] ABS: Recycled ABS EGR0074

[0264] Impact modifier additive 1: Lotryl 29MA03T®

[0265] Impact modifier additive 2: HR-181®

[0266] Antioxidant: 0.2% (equi-mass mixture of Irganox 1076® and Irganox 168®)

[0267] Ratio Impact modifier additive 2 / Impact modifier additive 1 = 2

[0268] Extrusion temperature: 270°C

[0269] Injection temperature: 250°C

[0270] [TableauxlO] Ref Thermal resistance additive Thermal resistance additive (% mass) Impact modifier additive 1 (% mass) Impact modifier additive 2 (% mass) Mass ratio (impact modifiers) / (thermal resistance) IZO D (kJ / m2) Flexural modulus (MPa) VICA T (°C) HD T (°C) C5-1 * - - - - - 12 2480 94.3 92.5 C5-2 DENKA IP MS-NJP® 20 5 10 0.75 10.4 ±0.2 2330 ± 20 - 95.3 + 0.4 C5-3 DENKA IP MS- CP® 20 5 10 0.75 11.5 ±0.1 2280 ± 30 - 98.5 + 0.5 C5-4 DENKA IP MS- CP® 20 4.33 8.67 0.65 10.9 ±0.6 2380 ± 50 - 97.1 + 1.6 C5-5 DENKA IP MS- CP® 22 5 10 0.75 10.3 ±0.3 2340 ± 24 - 97.3 + 0.9

[0271] These results show that different types of N-phenylmaleimide / styrene / maleic anhydride terpolymers make it possible to obtain compositions according to the invention exhibiting very good thermomechanical properties.

[0272] Example 6: Influence of the origin of recycled ABS

[0273] In the compositions of this example, the following materials and additives were used:

[0274] ABS: Recycled ABS EGR0064, EGR0074, PLS0153 BB36, PLS0163 BB1, PLS0160 BB21, EV4 003 BB1

[0275] Thermal resistance additive 2: DENKA IP MS-CP®

[0276] Impact modifier additive 1: Lotryl 29MA03T®

[0277] Impact modifier additive 2: HR-181®

[0278] Antioxidant: 0.2% (equi-mass mixture of Irganox 1076® and Irganox 168®)

[0279] Extrusion temperature: 235°C

[0280] Injection temperature: 220°C

[0281] In the compositions of this example, the proportions of each additive are fixed. Only the ABS base varies. • % Thermal resistance additive: 21% • % Impact modifier additive 1:5% • % Impact modifier additive 2: 10% • Ratio Impact modifier additive 2 / Impact modifier additive 1=2

[0282] [Tablesll] Properties of recycled ABS (without additives) Composition properties Ref IZOD (kJ / m2) Flexural modulus (MPa) HDT (°C) IZOD (kJ / m2) Flexural modulus (MPa) HDT (°C) EGR0064 7.6+0.2 2520+30 92.5+0.8 10.8+0.4 2350+18 99.3+0.2 EGR0074 12+0.5 2480+34.5 93.5+0.3 11.6+0.2 2320+20 100+0.1 PLS0153 BB36 10.9+0.2 2510+32 94+0.2 10.6+0.4 2350+22 100.5+0.8 PLS0163 BB1 10.4+0.3 2540+29 92.5+0.1 10.4+0.4 2350+32 98.6+0.1 PLS0160 BB21 11.4+0.3 2570+35 92.1+0.3 11.7+0.2 2320+11 98.9+0.7 EV4 003 BB1 9.8+0.3 2540+15 92.5+0.3 11+0.2 2280+45 98.5+0.2

[0283] Depending on the origin of the recycled ABS, its impact resistance and thermal resistance properties can vary significantly. However, the combined addition of a high-temperature additive and an impact modifier additive as defined in this application improves the thermo-mechanical properties of this recycled ABS, regardless of its origin.

Claims

Demands

1. Composition comprising: - an acrylonitrile-butadiene-styrene polymer or an acrylonitrile-butadiene-styrene polymer derivative, - a high thermal resistance additive in the form of a terpolymer of an N-substituted maleimide monomer, a vinyl monomer and an unsaturated dicarboxylic acid anhydride monomer, - at least one first impact modifying additive and one second impact modifying additive, and - at least one antioxidant additive.

2. Composition according to claim 1, wherein the mass content of high thermal resistance additive varies from 15% to 35%, preferably from 18% to 30%, advantageously from 20% to 25% by mass relative to the total mass of the composition.

3. Composition according to claim 1 or 2, wherein the total mass content of impact modifier additives varies from 8% to 35%, preferably from 10% to 25%, preferably from 12% to 20%, advantageously from 13% to 18% by mass relative to the total mass of the composition.

4. A composition according to any one of the preceding claims, wherein the first impact modifying additive and the second impact modifying additive are different from each other and independently selected from: - copolymers of ethylene and / or butene and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate, and (meth)butyl acrylate, - modified acrylonitrile-butadiene-styrene copolymers having a butadiene content greater than or equal to 60% by weight relative to the total weight of the modified acrylonitrile-butadiene-styrene polymer, - styrene-ethylene / butene-styrene copolymers grafted with maleic anhydride or glycidyl methacrylate, - ethylene-butyl acrylate copolymers, optionally grafted with maleic anhydride, - styrene-butadiene copolymers, preferably block styrene-butadiene copolymers,preferably multiblock or diblock styrene-butadiene copolymers, - styrene-ethylene / butene-styrene copolymers, preferably co-, styrene-ethylene / butene-styrene block polymers, and - any of their mixtures.

5. Composition according to any one of the preceding claims, wherein the ratio between the total mass content of first and second impact modifier additives and the mass content of high thermal strength additive varies from 0.3 to 2.0, preferably from 0.4 to 1.5, preferably from 0.5 to 1.2, more preferably from 0.6 to 1.0, advantageously from 0.65 to 0.

85.

6. Composition according to any one of the preceding claims, wherein the ratio between the mass content of the second impact modifier additive and the mass content of the first impact modifier additive varies from 0.1 to 12, preferably varies from 0.3 to 8.0, preferably from 0.4 to 6.0, more preferably from 0.5 to 3.

0.

7. Composition according to any one of the preceding claims, wherein the mass content of first impact modifier additive varies from 2% to 18%, preferably from 3% to 15%, preferably from 4% to 12%, advantageously from 4% to 8% by mass relative to the total mass of the composition.

8. Composition according to any one of the preceding claims, wherein the mass content of the second impact modifier additive varies from 5% to 25%, preferably from 6% to 20%, preferably from 7% to 16%, advantageously from 8% to 12% by mass relative to the total mass of the composition.

9. Composition according to any one of the preceding claims, wherein the first impact modifying additive and the second impact modifying additive are different from each other and independently selected from: - copolymers of ethylene and / or butene and a polar monomer selected from (m)ethyl acrylate, (m)ethyl methacrylate and butyl (meth)acrylate, - modified acrylonitrile-butadiene-styrene copolymers having a butadiene content greater than or equal to 60% by weight relative to the total weight of the modified acrylonitrile-butadiene-styrene polymer, - styrene-butadiene copolymers, and - any mixture thereof.

10. Composition according to any one of the preceding claims, wherein the acrylonitrile-butadiene-styrene polymer or the acrylonitrile-butadiene-styrene polymer derivative is recycled.

11. A process for preparing a composition according to any one of claims 1 to 10, comprising: - a step of mixing an acrylonitrile-butadiene-styrene polymer or an acrylonitrile-butadiene-styrene polymer derivative, a high-temperature additive selected from a terpolymer of an N-substituted maleimide monomer, a vinyl monomer and an unsaturated dicarboxylic acid anhydride monomer, and a polyalphamethylstyrene, and mixtures thereof, at least one impact modifier additive, and at least one antioxidant additive.

12. Use of a composition according to any one of claims 1 to 10, for the manufacture of a part, for example a vehicle part, preferably a motor vehicle part.

13. Part, preferably vehicle part, preferably motor vehicle part, comprising a composition according to any one of claims 1 to 10.

14. A method for improving at least one thermal or mechanical property of a recycled acrylonitrile-butadiene-styrene polymer or a recycled acrylonitrile-butadiene-styrene polymer derivative comprising adding to the recycled acrylonitrile-butadiene-styrene polymer or the recycled acrylonitrile-butadiene-styrene polymer derivative a composition comprising: - a high thermal strength additive selected from a terpolymer of an N-substituted maleimide monomer, a vinyl monomer and an unsaturated dicarboxylic acid anhydride monomer, and a polyal-phamethylstyrene, and mixtures thereof, - at least one impact modifier additive, and - at least one antioxidant additive.

15. Use of a combination of: - a high thermal strength additive selected from a terpolymer of an N-substituted maleimide monomer, a vinyl monomer and an unsaturated dicarboxylic acid anhydride monomer, and a polyal-phamethylstyrene, and mixtures thereof, - at least one impact modifier additive, and - at least one antioxidant additive, to improve at least one thermal or mechanical property of a recycled acrylonitrile-butadiene-styrene polymer or a derivative of a recycled acrylonitrile-butadiene-styrene polymer.