# US 12,109,786 B2 · Multilayer structure based on recycled polyamide > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,109,786 B2 - Document ID: US12109786B2 - Status: Granted - Kind: B2 - Application number: 17/999,127 - Filed: 2021-05-18 - Published: 2023-06-22 - Granted: 2024-10-08 - Earliest claimed: 2020-05-19 - Assignees: Arkema France - Applicants: Arkema France - Inventors: Thibaut Montanari; Bertrand Verbauwhede; Thierry Vasselin; Pierre Nidercorn - Web page: https://patentgrep.com/patent/US12109786B2 ## CPC - B32B 27/08: of synthetic resin - C08L 77/00: Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain (of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08); Compositions of derivatives of such polymers - B32B 1/08: Tubular products - B32B 27/18: characterised by the use of special additives - B32B 27/34: comprising polyamides - C08K 5/13: Phenols; Phenolates - C08K 5/435: Sulfonamides - C08K 5/526: with hydroxyaryl compounds - C08L 77/02: Polyamides derived from omega-amino carboxylic acids or from lactams thereof (C08L77/10 takes precedence) - C08L 77/06: Polyamides derived from polyamines and polycarboxylic acids (C08L77/10 takes precedence) - C08L 77/10: Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids - B32B 2250/03: 3 layers - B32B 2250/24: All layers being polymeric - B32B 2272/00: Resin or rubber layer comprising scrap, waste or recycling material - B32B 2307/558: Impact strength, toughness - B32B 2307/704: Crystalline - B32B 2307/7265: Non-permeable - B32B 2597/00: Tubular articles, e.g. hoses, pipes - B32B 2605/08: Cars - C08K 5/0016: {Plasticisers} - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) ## Abstract A multilayer tubular structure for transporting fluids for a motor vehicle, the structure including at least three layers: at least one layer having a composition predominantly including at least one semi-crystalline aliphatic polyamide, the composition having at least 50% of recycled material from a single-layer and/or multilayer tube that has been intended for transporting fluids for a motor vehicle, the tube having a composition which predominantly includes at least one polyamide, at least one layer having a composition predominantly including at least semi-crystalline aliphatic polyamide and optionally at least one impact modifier, and when the layer has a composition predominantly including at least one semi-crystalline aliphatic polyamide that is PA12 and/or PA612 and/or PA1010, then the composition includes the impact modifier, and at least one barrier layer, the layer and the barrier layer each having at least 90% of non-recycled material. ## Claims ### Claim 1 A multilayer tubular structure for transporting fluids for a motor vehicle, the structure comprising at least three layers: at least one layer (1) consisting of a composition comprising at least 50% by weight of at least one semi-crystalline aliphatic polyamide, said composition consisting of at least 50% of recycled material from a single layer and/or multilayer tube that initially transported fluids for a motor vehicle, wherein a sum of constituents of the composition is equal to 100%, said tube consisting of a composition that comprises at least 50% by weight of at least one polyamide, at least one layer (2) consisting of a composition comprising at least 50% by weight of at least one semi-crystalline aliphatic polyamide and optionally at least one impact modifier, and when the layer (2) consists of a composition comprising at least 50% by weight of at least one semi-crystalline aliphatic polyamide that is PA12 and/or PA612 and/or PA1010, then said composition comprises said impact modifier, and at least one barrier layer, said layer (2) and the barrier layer each consisting of at least 90% of non-recycled material. ### Claim 2 (depends on 1) The multilayer tubular structure according to claim 1, wherein said layer (1) is located between a layer (2) and a barrier layer. ### Claim 3 (depends on 1) The multilayer tubular structure according to claim 1, wherein the barrier layer is the layer in contact with the fluid. ### Claim 4 (depends on 1) The multilayer tubular structure according to claim 1, wherein said layer (1) represents at least 10% of the total thickness of said multilayer tubular structure. ### Claim 5 (depends on 1) The multilayer tubular structure according to claim 1, wherein said layer (1) consists of a composition comprising: at least 50% by weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted CC comprised from 6 to 18; from 0 to 25% by weight of at least one semi-crystalline aliphatic polyamide denoted B and having an average number of carbon atoms per nitrogen atom denoted CB=Cc−1; from 0 to 25% by weight of a semi-crystalline aliphatic polyamide denoted A having an average number of carbon atoms per nitrogen atom denoted CA=CB−1; from 0 to 45% by weight of at least one impact modifier, from 0 to 20% by weight of at least one plasticizer, from 0 to 2% by weight of at least one additive, the sum of the constituents being equal to 100%. ### Claim 6 (depends on 1) The multilayer tubular structure according to claim 1, wherein the fluid transported by said single layer and/or multilayer tube is the same as that of said multilayer tubular structure. ### Claim 7 (depends on 1) The multilayer tubular structure according to claim 1, wherein the fluid transported by said single layer and/or multilayer tube is different to that of said multilayer tubular structure. ### Claim 8 (depends on 1) The multilayer tubular structure according to claim 1, wherein the Tf of the predominant semi-crystalline aliphatic polyamide of the layer is ≤225° C., as determined by DSC according to standard ISO 11357-3:2013, at a heating rate of 20 K/min. ### Claim 9 (depends on 1) The multilayer tubular structure according to claim 1, wherein the predominant semi-crystalline aliphatic polyamide of the layer (1) has a crystallization enthalpy>25 J/g, as determined by DSC according to standard ISO 11357-3:2013 at a heating rate of 20 K/min. ### Claim 10 (depends on 1) The multilayer tubular structure according to claim 1, wherein the multilayer tubular structure consists of three layers with the following structure: (2)//(1)//barrier. ### Claim 11 (depends on 1) The multilayer tubular structure according to claim 1, further comprising a second layer of the at least one layer (2), said second layer of the at least one layer (2) being an innermost layer in contact with the fluid. ### Claim 12 (depends on 11) The multilayer tubular structure according to claim 11, wherein at least one binder layer (3) is present between the barrier layer and the second innermost layer (2) in contact with the fluid, wherein the multilayer tubular structure comprises, from outside to inside, layer (2), layer (1), barrier layer, binder layer (3), and innermost layer (2). ### Claim 13 (depends on 1) The multilayer tubular structure according to claim 1, wherein the recycled material comes from a single layer and/or multilayer tube selected from a crushed single layer and/or multilayer tube, a crushed and recompounded single layer and/or multilayer tube, and a crushed, recompounded and reformulated single layer and/or multilayer tube. ### Claim 14 (depends on 13) The multilayer tubular structure according to claim 13, wherein said composition of the layer (1) is free of plasticizer and/or impact modifier and said recycled material comes from a single layer and/or multilayer tube selected from a crushed single layer and/or multilayer tube, a crushed and recompounded single layer and/or multilayer tube, and a crushed, recompounded and reformulated single layer and/or multilayer tube. ### Claim 15 (depends on 13) The multilayer tubular structure according to claim 13, wherein said composition of the layer (1) comprises at least one compound selected from a plasticizer, an impact modifier and an additive, and said recycled material comes from a single layer and/or multilayer tube selected from a crushed, then recompounded and reformulated single layer and/or multilayer tube. ### Claim 16 (depends on 1) The multilayer tubular structure according to claim 1, wherein the layer (2) consists of a composition comprising: at least 50% by weight of at least one semi-crystalline aliphatic polyamide denoted D having an average number of carbon atoms per nitrogen atom denoted CD comprised from 6 to 18; from 0 to 50% by weight of at least one semi-crystalline aliphatic polyamide denoted E and having an average number of carbon atoms per nitrogen atom denoted CE=CD−1; from 0 to 50% by weight of a semi-crystalline aliphatic polyamide denoted F having an average number of carbon atoms per nitrogen atom denoted CF=CE−1; from 3 to 45% by weight of at least one impact modifier, from 0 to 20% by weight of at least one plasticizer, from 0 to 2% by weight of at least one additive, from 0 to 35% of at least one antistatic filler, the sum of the constituents being equal to 100%. ### Claim 17 (depends on 16) The multilayer tubular structure according to claim 16, wherein said layer (1) consists of a composition comprising: at least 50% by weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted CC comprised from 6 to 18; from 0 to 25% by weight of at least one semi-crystalline aliphatic polyamide denoted B and having an average number of carbon atoms per nitrogen atom denoted CB=Cc−1; from 0 to 25% by weight of a semi-crystalline aliphatic polyamide denoted A having an average number of carbon atoms per nitrogen atom denoted CA=CB−1; from 0 to 45% by weight of at least one impact modifier, from 0 to 20% by weight of at least one plasticizer, from 0 to 2% by weight of at least one additive, the sum of the constituents being equal to 100%, wherein said composition of said layer (1) is free of polyamides denoted A and B and said composition of said layer (2) comprises polyamides selected from those denoted E, F, and a mixture thereof. ### Claim 18 (depends on 16) The multilayer tubular structure according to claim 16, wherein said layer (1) consists of a composition comprising: at least 50% by weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted CC comprised from 6 to 18; from 0 to 25% by weight of at least one semi-crystalline aliphatic polyamide denoted B and having an average number of carbon atoms per nitrogen atom denoted CB=Cc−1; from 0 to 25% by weight of a semi-crystalline aliphatic polyamide denoted A having an average number of carbon atoms per nitrogen atom denoted CA=CB−1; from 0 to 45% by weight of at least one impact modifier, from 0 to 20% by weight of at least one plasticizer, from 0 to 2% by weight of at least one additive, the sum of the constituents being equal to 100%, wherein said composition of said layer (1) comprises polyamides selected from those denoted A, B, and a mixture thereof, and said composition of said layer (2) is free of polyamides denoted E and F. ### Claim 19 (depends on 16) The multilayer tubular structure according to claim 16, wherein the layer (1) comes from a single layer recycled tube. ### Claim 20 (depends on 16) The multilayer tubular structure according to claim 16, wherein the layer comes from a multilayer recycled tube.