WO2023281222A1 - Structure tubulaire monocouche ou multicouche a base de polyamide recycle - Google Patents
Structure tubulaire monocouche ou multicouche a base de polyamide recycle Download PDFInfo
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- WO2023281222A1 WO2023281222A1 PCT/FR2022/051363 FR2022051363W WO2023281222A1 WO 2023281222 A1 WO2023281222 A1 WO 2023281222A1 FR 2022051363 W FR2022051363 W FR 2022051363W WO 2023281222 A1 WO2023281222 A1 WO 2023281222A1
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- WIPO (PCT)
- Prior art keywords
- layer
- weight
- composition
- tube
- tubular structure
- Prior art date
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- 239000002356 single layer Substances 0.000 title claims abstract description 112
- 229920002647 polyamide Polymers 0.000 title claims abstract description 67
- 239000004952 Polyamide Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 197
- 239000012530 fluid Substances 0.000 claims abstract description 82
- 229920006177 crystalline aliphatic polyamide Polymers 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 60
- 239000000654 additive Substances 0.000 claims abstract description 41
- 238000000227 grinding Methods 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 20
- 150000002825 nitriles Chemical group 0.000 claims abstract description 20
- 239000000446 fuel Substances 0.000 claims abstract description 19
- 239000003225 biodiesel Substances 0.000 claims abstract description 17
- 239000003921 oil Substances 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000003570 air Substances 0.000 claims abstract description 12
- 239000002826 coolant Substances 0.000 claims abstract description 12
- 150000001336 alkenes Chemical group 0.000 claims abstract description 7
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 256
- 239000003502 gasoline Substances 0.000 claims description 84
- 239000004609 Impact Modifier Substances 0.000 claims description 76
- 229910052757 nitrogen Inorganic materials 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 38
- 239000004014 plasticizer Substances 0.000 claims description 32
- 229920000098 polyolefin Polymers 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 230000001476 alcoholic effect Effects 0.000 claims description 28
- -1 gasoline Chemical compound 0.000 claims description 27
- 229920006659 PA12 Polymers 0.000 claims description 23
- 238000001125 extrusion Methods 0.000 claims description 22
- 150000003140 primary amides Chemical class 0.000 claims description 22
- 239000000470 constituent Substances 0.000 claims description 21
- 238000003860 storage Methods 0.000 claims description 19
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 13
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- 150000001408 amides Chemical group 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000284 extract Substances 0.000 claims description 9
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 9
- 238000007872 degassing Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000009423 ventilation Methods 0.000 claims description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- 150000003949 imides Chemical class 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
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- 238000002360 preparation method Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 14
- 150000001732 carboxylic acid derivatives Chemical group 0.000 abstract description 9
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000008188 pellet Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 125000005462 imide group Chemical group 0.000 abstract 1
- 125000001749 primary amide group Chemical group 0.000 abstract 1
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- 150000004985 diamines Chemical class 0.000 description 24
- 239000003381 stabilizer Substances 0.000 description 22
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 21
- 238000006068 polycondensation reaction Methods 0.000 description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 18
- 150000003334 secondary amides Chemical class 0.000 description 18
- 229920006114 semi-crystalline semi-aromatic polyamide Polymers 0.000 description 18
- 239000005977 Ethylene Substances 0.000 description 17
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 12
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 12
- 150000001413 amino acids Chemical class 0.000 description 11
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 11
- 150000003951 lactams Chemical class 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 10
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 10
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 10
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 9
- 230000035939 shock Effects 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000004953 Aliphatic polyamide Substances 0.000 description 8
- 229920003231 aliphatic polyamide Polymers 0.000 description 8
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 7
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 206010011906 Death Diseases 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 6
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 5
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- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 5
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- YIMHRDBSVCPJOV-UHFFFAOYSA-N n'-(2-ethoxyphenyl)-n-(2-ethylphenyl)oxamide Chemical compound CCOC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1CC YIMHRDBSVCPJOV-UHFFFAOYSA-N 0.000 description 5
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- DWHXNKJKNIHNOI-UHFFFAOYSA-N 10-azaniumylundecanoate Chemical compound CC(N)CCCCCCCCC(O)=O DWHXNKJKNIHNOI-UHFFFAOYSA-N 0.000 description 1
- GNHLOUIICBHQIT-UHFFFAOYSA-N 11-(heptylamino)undecanoic acid Chemical compound CCCCCCCNCCCCCCCCCCC(O)=O GNHLOUIICBHQIT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 1
- 102100020895 Ammonium transporter Rh type A Human genes 0.000 description 1
- 101100301844 Arabidopsis thaliana RH50 gene Proteins 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 101150107345 Rhag gene Proteins 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000008331 benzenesulfonamides Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- LJOSESICVCVVCK-UHFFFAOYSA-N docosane-1,1-diamine Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)N LJOSESICVCVVCK-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920006017 homo-polyamide Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- FCGASPQFBJKTRO-UHFFFAOYSA-N n-cyclohexyl-1-phenylmethanesulfonamide Chemical compound C1CCCCC1NS(=O)(=O)CC1=CC=CC=C1 FCGASPQFBJKTRO-UHFFFAOYSA-N 0.000 description 1
- OHPZPBNDOVQJMH-UHFFFAOYSA-N n-ethyl-4-methylbenzenesulfonamide Chemical compound CCNS(=O)(=O)C1=CC=C(C)C=C1 OHPZPBNDOVQJMH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- IJRVDOPVQJSPRP-UHFFFAOYSA-N octan-4-yl prop-2-enoate Chemical compound CCCCC(CCC)OC(=O)C=C IJRVDOPVQJSPRP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004525 petroleum distillation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical class OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
-
- 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
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
-
- 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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
- B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
-
- 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
- B32B2597/00—Tubular articles, e.g. hoses, pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- DESCRIPTION TITLE SINGLE-LAYER OR MULTI-LAYER TUBULAR STRUCTURE BASED ON RECYCLED POLYAMIDE
- the present invention relates to a composition obtained from used polyamide pipes from motor vehicles, single-layer or multi-layer tubular structures comprising at least one layer consisting of said composition and their method of manufacture.
- An end-of-life motor vehicle (ELV) contains many toxic and polluting products (liquid or solid): engine oil, battery, air conditioning fluid, explosive elements of airbags, etc. Treated in poor conditions, this waste can lead to soil and water pollution, as well as accidents. ELVs are therefore considered hazardous waste.
- a large number of vehicle components can be recovered and recycled, in the form of second-hand spare parts or raw materials.
- Parts intended for reuse (headlights, indicators, engine, radiator, starter, bonnet, fenders, doors, etc.) are dismantled and stored for resale.
- Non-recyclable carcasses and parts (ferrous and non-ferrous metals, plastics, glass, rubber, etc.) are separated and crushed for recycling or landfill.
- European Directive 2000/53/EC on end-of-life vehicles has set a reuse and recovery rate of 95% by weight per vehicle from 2015. There must therefore be only 5% of final waste left, that is to say waste which is not likely to be treated under the technical and economic conditions of the moment and which will be incinerated or evacuated to specific storage centres.
- These pipes can be single-layer and/or multi-layer tubular structures, in particular based on polyamide(s), just as the tanks can be single-layer and/or multi-layer structures, in particular based on polyamide(s).
- the various pipes present in it are generally very or too degraded to be able to be reused such as, in the form of a tube, without risk or without this leading to use properties. too degraded.
- the tubes, in particular under the engine cover are placed in a severe thermo-oxidative environment due to the heat given off by the engine which can typically reach 150° C. and the presence of air and therefore of oxygen. Each increase in temperature of 10° C.
- the reuse, without modification, of the tubes taken from end-of-life cars is not envisaged for the following reasons:
- the analysis of the end-of-life tubes showed that they had stiffened compared to a new tube : the end-of-life tube has a higher threshold stress (loss of additives, and crystallization induced by the working environment).
- This stiffening is a problem because the tube risks being damaged during disassembly and assembly on a new vehicle (tubes particularly stressed during feathering).
- the tubes at the end of their life have also been thermoformed during their installation in the new vehicle to fit exactly into the vehicle model, a model which will probably no longer be produced 10 to 15 years after the sale of the said vehicle.
- a tank has a specific shape adapted to each vehicle model which changes regularly.
- the present invention therefore relates to a composition
- a composition comprising: (a) 30% to 99.8% by weight, in particular 50 to 99.8% by weight, of recycled material originating from a tube and/or from a monolayer tank and/or or used multilayer that originally carried or contained motor vehicle fluids, in particular air, oil, water, urea solution, glycol-based coolant, or fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen, said tube and/or said tank consisting of a composition which mainly comprises at least one polyamide, said monolayer and/or multilayer tube and/or said used reservoir(s) having been ground into granules and the fluid residues present in said tube and/or reservoir having been totally or partially extracted, before or after grinding of said tube and/or reservoir, (b) up to 70%, in particular up to to 50% of a semi-crystalline aliphatic polyamide, (c) up to 45% by weight of at least one impact modifier, in particular from 1 to
- said single-layer and/or multi-layer tube and/or said used tank(s) is (are) only ground into granules, excluding grinding followed by recompounding with or without reformulation.
- Said single-layer and/or multi-layer tube and/or said used tank(s) are therefore excluding any single-layer and/or multi-layer tube and/or virgin tank, i.e. never having transported or contained a motor vehicle fluid even if its intended purpose is said transportation of fluids for motor vehicles. This therefore excludes de facto any single-layer and/or multi-layer pipe manufacturing scrap and/or reservoir for the transport or storage of motor vehicle fluids.
- said composition of said tube and/or said reservoir is excluding polyphenylene sulfide (PPS).
- the expression "motor vehicle” means any vehicle with a thermal, electric or hybrid engine fitted with wheels or tracks, excluding a flying vehicle.
- the motor vehicle can be two-wheeled, three-wheeled, four-wheeled or tracked. It is for example chosen from an electric bicycle, a moped, a motorcycle, a side car, a car, a van, a tractor, a truck, a bus, a coach, a snowmobile, a half-track, a bulldozer, a snow groomer and an assault tank. In particular, it is chosen from a car, a van, a truck, a bus and a coach. In particular, it is chosen from a car, a van, a truck, a bus and a heat engine coach.
- the absorption band from 1700 to 1740cm -1 corresponds to an imide, that of 1680 to 1720 cm -1 to the carbonyl of the carboxylic acid and that of 3580 to 3670 cm-1 corresponds to the alcohol function of the carboxylic acid.
- the absorption band from 3580 to 3670 cm-1 corresponds to the free alcohol function.
- the amide function is characterized on the one hand by a couple of absorption bands from 3100 to 3500 cm-1 and from 1560 to 1640 cm-1 which corresponds to the NH group of the amide and on the other hand by the band of absorption of 1650 to 1700 cm-1 which corresponds to the carbonyl group of the amide. Infrared allows the detection of the presence or absence of said new species resulting from oxidation mechanisms.
- the quantification of said new species resulting from oxidation mechanisms is carried out by proton NMR in dichloromethane-d2, by adding HFIP (hexafluoroisopropanol) to solubilize the polyamide.
- HFIP hexafluoroisopropanol
- 20 mg of polymer can be dissolved in 0.7 mL of solvent with an HFIP/CD2Cl2 ratio of 1/3.
- Some of the functions mentioned below can for example be observed in 13C NMR.
- the line at 36 ppm corresponds to the CH2 in ⁇ of the primary amide
- that at 34 ppm corresponds to the CH2 in ⁇ of the carboxylic acid.
- These species can be quantified by integrating the area under the lines and comparing them to the area under the 37.1 ppm line corresponding to the secondary amide.
- the lines corresponding to the carbonyl groups of the primary amide, carboxylic acid and secondary amide functions are observed at 181.2 ppm, 179.6 ppm and 177.4 ppm respectively.
- the line at 16.7 ppm corresponds to the CH2 in ⁇ of the nitrile group.
- the formamide moiety gives a chemical shift at 163.0 ppm and 166.3 ppm.
- Other functions mentioned above can be observed in proton NMR (1H NMR) solvent HFIP/CD2Cl2 as described above.
- the line of the CHO groups of the formamides emerges at 7.92 and 8.01 ppm.
- the line corresponding to the CH2 in ⁇ of the primary amides can be observed at 2.30 ppm.
- the 0.9 ppm line corresponds to the CH3 groups of the CH3-(CH2)n type.
- the line at 2.40 ppm corresponds to the CH2 in ⁇ of the nitrile function. Similar to what is described for carbon NMR, the ratios of new functions with respect to secondary amides can be determined by integrating the area under the lines and comparing them to the area under the line corresponding to CH2 at ⁇ secondary amide (2.20 ppm).
- the inventors have therefore surprisingly found that the use of at least 30% by weight, in particular at least 50% by weight, of recycled material based on partially oxidized polyamides and originating from a tube and/or from a single-layer and/or multi-layer tank used and only ground, the fluid residues present in said tube and/or tank having been totally or partially extracted, before or after grinding of said tube and/or tank, with a semi-crystalline aliphatic polyamide , and optionally an additive, allowed the constitution of a composition which can then be transformed into a tube or a tank whose mechanical properties are equivalent to those of a tube or a tank made from non-recycled and non-used material, i.e. a new tube or tank.
- said single-layer and/or multi-layer tube and/or said used reservoir(s) means that said single-layer and/or multi-layer tube and/or said reservoir initially fitted to a motor vehicle and were used to transport or store a motor vehicle fluid during the life of the motor vehicle.
- the expression "the fluid residues present in the said tube and/or reservoir having been totally or partially extracted, before or after grinding of the said tube and/or reservoir” means that the said tube and/or reservoir has undergone a treatment making it possible to eliminate partially or totally said fluid.
- said tube and/or reservoir has transported air, it is for example an “air brake” pipe used for braking the vehicle.
- composition comprising the constituents a) + b) + c) + d) + e).
- said fluid designates fuels, in particular gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
- gasoline designates a mixture of hydrocarbons resulting from the distillation of petroleum to which additives or alcohols such as methanol and ethanol may be added, alcohols being able to be major components in certain cases.
- alcoholic gasoline designates a gasoline in which methanol or ethanol has been added. It also designates an E95 type gasoline which does not contain any petroleum distillation product.
- the expression “based on polyamide” means at least 50% by weight of polyamide in the layer.
- the semi-crystalline aliphatic polyamide used in b) may contain impact modifiers, and/or plasticizers and/or additives.
- the oxidation reactions or oxidation mechanisms correspond to an oxidation in particular of the amide functions and/or of methylene to alpha ( ⁇ ) of said amide functions.
- the used tube and/or the used tank to be reused or in other words to be recycled (monolayer and/or multilayer both for the tube and for the tank) is therefore removed from the motor vehicle, in particular from the automobile, and undergoes grinding .
- it only undergoes grinding, excluding grinding followed by recompounding with or without reformulation.
- Such recompounding is conventionally carried out by introducing the ground material at least once into an extruder, in particular of the co-rotating twin-screw type, or of the co-kneader type (Buss), where the ground material is remixed by melting, with or without addition of at least one compound chosen from a semi-crystalline aliphatic polyamide, of recycled origin or not, at least one impact modifier, a plasticizer, an additive and antistatic fillers.
- the molten material comes out of the extruder in rods which are cooled and cut into granules which will then be introduced into an extruder for the manufacture of the monolayer or multilayer tubular structure.
- the fluid residues present in said tube and/or reservoir are totally or partially extracted, before or after grinding of said tube and/or reservoir.
- said molar ratio of the functions resulting from oxidation reactions is comprised from 1/10,000 to 1/20.
- the concentrations can be measured by proton or carbon NMR in dichloromethane-d2, by adding HFIP (hexafluoroisopropanol) to solubilize the polyamide.
- said molar ratio of the imide functions is comprised from 1/1000 to 1/20, in particular from 1/500 to 1/20, in particular from 1/200 to 1/50.
- said molar ratio of the carboxylic acid functions is comprised from 1/5000 to 1/20, in particular from 1/3000 to 1/50 very advantageously comprised from 1/500 to 1/15.
- said molar ratio of the alcohol functions is comprised from 1/1000 to 1/20 and advantageously comprised from 1/1000 to 1/25 very advantageously comprised from 1/200 to 1/50.
- said molar ratio of the primary amide functions is comprised from 1/2000 to 1/20 and advantageously comprised from 1/1000 to 1/100 very advantageously comprised from 1/1000 to 1/500.
- said molar ratio of the nitrile functions is comprised from 1/1000 to 1/20 and advantageously comprised from 1/500 to 1/15 very advantageously comprised from 1/100 to 1/10.
- said molar ratio of the methyl functions at the end of the chain is comprised from 1/5000 to 1/50 and advantageously comprised from 1/2000 to 1/100 very advantageously comprised from 1/1000 to 1/200.
- said ratio of said functions is calculated according to the integration of the peak of the secondary amide.
- composition consists of at most 99.8% recycled material
- a polyamide identical or different
- an impact modifier and/or a plasticizer and/or optionally an additive.
- This can be done by dry mixing (mixture of recycled ground material and virgin granules formulated or not and/or optionally the additive) or by compounding, advantageously by dry mixing. This dry mix is then introduced into the extruder during the manufacture of the single-layer or multi-layer tubular structure or else.
- polyamide denotes both a homopolyamide and a copolyamide.
- polyamides within the meaning of the invention throughout the description denotes polyamides which have a melting temperature (Tm) and an enthalpy of fusion ⁇ H > 25 J/g, in particular > 40 J/g, in particular > 45J/g, as well as a glass transition temperature (Tg) as determined by DSC according to ISO 11357-1:2016 and ISO 11357-2 and 3:2013, at a heating rate of 20K/min.
- Tm melting temperature
- Tg glass transition temperature
- Said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one lactam, or from the polycondensation of at least one amino acid, or from the polycondensation of at least one diamine X with at least one dicarboxylic acid Y.
- said at least one lactam can be chosen from a C6 to C18 lactam, preferably C10 at C18, more preferably at C10 to C12.
- a C6 to C18 lactam is in particular caprolactam, decanolactam, undecanolactam, and lauryllactam.
- said at least one aliphatic semi-crystalline polyamide When said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one lactam, it can therefore comprise a single lactam or several lactams.
- said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of a single lactam and said lactam is chosen from lauryllactam and undecanolactam, advantageously lauryllactam.
- said at least one amino acid may be chosen from a C6 to C18 amino acid, preferably C10 to C18, more preferably C10 at C12.
- a C6 to C18 amino acid is in particular 6-aminohexanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid as well as its derivatives, in particular N-heptyl-11-aminoundecanoic acid.
- said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one amino acid, it can therefore comprise a single amino acid or several amino acids.
- said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one diamine X at C4-C36, preferentially C5-C18, preferentially C5-C12, more preferentially C10-C12, with at least one diacid Y at C4-C36, preferably C6-C18, preferably C6-C12, more preferably C10-C12, then said at least one diamine at X is an aliphatic diamine and said at least one diacid Y is an aliphatic diacid.
- the diamine can be linear or branched. Advantageously, it is linear.
- Said at least one C4-C36 diamine X may in particular be chosen from 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine and 1 ,18- octadecamethylenediamine, octadecenediamine, eicosanediamine, docosanediamine and diamines obtained from fatty acids.
- said at least one diamine X is C5-C18 and chosen from 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine and 1,18-octadecamethylenediamine.
- said at least one C5 to C12 diamine X is chosen in particular from 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9- nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine.
- said at least one C6 to C12 diamine X is chosen in particular from 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8- octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine.
- the diamine X used is C10 to C12, in particular chosen from 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine.
- Said at least one C4 to C36 dicarboxylic acid Y may be chosen from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and diacids obtained from fatty acids.
- the diacid can be linear or branched. Advantageously, it is linear.
- said at least one dicarboxylic acid Y is C6 to C18 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid.
- said at least one dicarboxylic acid Y is C6 to C12 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid.
- said at least one dicarboxylic acid Y is C10 to C12 and is chosen from sebacic acid, undecanedioic acid, dodecanedioic acid.
- said aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one diamine X with at least one dicarboxylic acid Y, it can therefore comprise a single diamine or several diamines and a single dicarboxylic acid or several dicarboxylic acids.
- said semi-crystalline aliphatic polyamide is obtained from the polycondensation of a single diamine X with a single dicarboxylic acid Y.
- composition of the layer ( 1) comprises at least 50% by weight of at least one aliphatic polyamide relative to the total weight of said composition.
- composition of the layer (1) comprises at least 60% by weight, in particular at least 70% by weight, in particular at least 80% by weight, more particularly at least 90% by weight of at least one aliphatic polyamide relative to the total weight of said composition.
- Said composition of the layer (1) consists of at least 30%, in particular of at least 50% and at most 99.8%, of recycled material originating from a monolayer tube and/or multilayer and/or a reservoir, said tubes and reservoirs being used and having been intended for the transport or storage of fluids for motor vehicles.
- the "at least one majority polyamide" of said composition corresponds in its entirety to what is referred to as "at least 50% of recycled material” or that at least 50% by weight of all the constituents of the composition are of recycled origin coming from monolayer pipe, or from multilayer pipe, or from reservoir or from a mixture of these.
- the recycled material may come from a single-layer and/or multi-layer tube and/or from a single-layer and/or multi-layer tank, said single-layer and/or multi-layer tubes being used and having been intended for the transport of fluid for motor vehicles and/or or the single-layer and/or multi-layer tank being used and having been intended for the storage of fluid for a motor vehicle.
- Said tube or tank is therefore a used tube or a used tank, that is to say that it has been used for at least one year for the transport or storage of the said fluid defined above.
- Said monolayer tube consists of a composition comprising a semi-crystalline aliphatic polyamide and optionally impact modifiers and/or additives and/or plasticizers and/or antistatic fillers.
- Said multilayer tube comprises at least one layer consisting of a composition comprising a semi-crystalline aliphatic polyamide and optionally impact modifiers and/or additives.
- Said reservoir can be monolayer and consists of a composition comprising a semi-crystalline aliphatic polyamide and optionally impact modifiers and/or additives and/or plasticizers and/or antistatic fillers.
- Said reservoir can be multilayer and comprises at least one layer consisting of a composition comprising a semi-crystalline aliphatic polyamide and optionally impact modifiers and/or additives.
- the single-layer tube can also be a mixture of single-layer tubes, that is to say for example two types of single-layer tubes each consisting of a different semi-crystalline aliphatic polyamide, for example a PA11 and a PA12 .
- the multilayer tube can also be a mixture of different types of multilayer tube, provided that at least one of the layers of one of the types of multilayer tube is made of a semi-crystalline aliphatic polyamide.
- the single-layer reservoir can also be a mixture of single-layer reservoirs, that is to say, for example, two types of single-layer tubes each consisting of a different semi-crystalline aliphatic polyamide, for example a PA11 and a PA12.
- the multilayer reservoir can also be a mixture of different types of multilayer reservoir, provided that at least one of the layers of one of the types of multilayer reservoir is made of a semi-crystalline aliphatic polyamide. If the mixed tubes or reservoirs are mutually incompatible, then the addition of a third semi-crystalline aliphatic polyamide denoted B having an average number of carbon atoms per nitrogen atom CB is present to make them compatible.
- the extraction of said fluid residues is carried out by means of washing or ventilation. Washing can be done before or after grinding.
- the washing is carried out using a fluid such as supercritical CO2 or solvents such as methanol, ethanol, in particular methanol, or a mixture of supercritical CO2 and solvent.
- This washing makes it possible in particular to remove fluids that are miscible in methanol, such as fuels, oil, cooling liquids.
- ventilation is carried out by means of an inerted oven or a desiccator.
- the extraction is carried out after grinding by means of a degassing zone in said extruder or by means of another apparatus allowing degassing to be carried out in the molten state.
- the used pipes before or after grinding are cleaned to remove any residual oligomers present in the used pipes.
- Fluids such as fuels during their storage in a tank or their transport in a tube degrade the polymer of the constituent layer of the tube in contact with the fluid and cause the appearance of oligomers which must therefore be cleaned before recycle tubes.
- the oligomers are cleaned by washing with water or by polar solvents such as methanol or ethanol.
- polar solvents such as methanol or ethanol.
- PA 6 and 66 are systematically washed in hot water (around 100 to 120°C) to remove as much caprolactam as possible.
- the oligomers can be distilled.
- Residual fluids can be any fluid originally transported by the single-layer or multi-layer tubing or stored in the reservoir.
- the extraction can also be carried out before or after grinding, for example by placing under vacuum if the fluid residues are volatile.
- said composition consists of: (a) 30% to 99.8% by weight, in particular 50 to 99.8% by weight of recycled material from a tube and/or a tank used monolayer and/or multilayer(s) having initially transported or contained fluids for motor vehicles, in particular air, oil, water, a urea solution, a coolant containing of glycol, or a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen, said tube and/or said tank consisting of a composition which mainly comprises at least one polyamide, said monolayer and/or multilayer tube and/or said used tank(s) having been ground into granules and the fluid residues present in said tube and / or reservoir having been totally or partially extracted, before or after grinding of said tube and/or reservoir, (b) up to 70%, in particular r up to 50% of a semi-crystalline aliphatic polyamide, (c) up to 45% by weight of at least one impact modifier, in particular from 1 to
- said composition consists of: (a) 30% to 99.8% by weight, in particular 50 to 99.8% by weight of recycled material from a tube and/or a used single-layer and/or multi-layer tank(s) having initially transported or contained fluids for motor vehicles, in particular air, oil, water, urea solution, coolant at glycol base, or a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen, said tube and/or the said tank being made of a composition which consists mainly of at least one polyamide, said single-layer and/or multi-layer tube and/or said used tank(s) having been ground into granules and the fluid residues present in said tube and/or reservoir having been totally or partially extracted, before or after grinding of said tube and/or reservoir, (b) up to 70%, in particular up to 50% of a semi-crystalline aliphatic polyamide, (c) up to 45% by weight of at least one impact modifier, in particular from 1 to 45%
- said monolayer and/or multilayer tube and/or said used reservoir(s) is only ground, excluding grinding followed by recompounding with or without reformulation.
- said tube and/or said reservoir consists of a composition which consists of at least one polyamide.
- said composition comprises the constituents a) + b) + c) + d) + e) mentioned above in the following proportions: a) 30% to 87.8% by weight, in particular 50 to 87 .8% by weight of recycled material from a used tube and/or single-layer and/or multi-layer tank(s) having initially transported or contained fluids for motor vehicles, in particular air, oil, water, urea solution, glycol-based coolant, or a fuel such as gasoline, especially alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen, said tube and/or said tank consisting of a composition which mainly comprises at least one polyamide, b) from 10 to 70%, in particular from 10 to 50% of a semi-crystalline aliphatic polyamide, (c) from 1 to 45% by weight of at least one impact modifier, in particular from 2 to 45% by weight of at least one impact modifier, (d) from 1 to 20% by weight of at least one plasticizer , (e) up to
- said composition consists of the constituents a) + b) + c) + d) + e) mentioned above in the following proportions: a) 30% to 87.8% by weight, in particular 50 to 87.8% by weight of recycled material originating from a used tube and/or single-layer and/or multi-layer tank(s) having initially transported or contained fluids for motor vehicles, in particular air, oil, water, urea solution, glycol-based coolant, or fuel such as gasoline, especially alcoholic gasoline, biogasoline, or diesel , in particular bio-diesel, or hydrogen, said tube and/or said tank consisting of a composition which mainly comprises at least one polyamide, b) from 10 to 70%, in particular from 10 to 50 % of a semi-crystalline aliphatic polyamide, (c) from 1 to 45% by weight of at least one impact modifier, in particular from 2 to 45% by weight of at least one impact modifier, (d) from 1 to 20 % by weight of at least one plasticizer,
- said monolayer and/or multilayer tube and/or said used reservoir(s) is only ground, excluding grinding followed by recompounding with or without reformulation.
- said tube and/or said reservoir advantageously consists of a composition which mainly consists of at least one polyamide, in particular it consists of at least one polyamide.
- the present invention relates to a single-layer or multi-layer tubular structure (MLT) intended for the transport of fluids for motor vehicles, in particular air, oil, water, urea solution , a glycol-based cooling liquid, or a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen, comprising at least one layer (1) consisting of a composition as defined above.
- said tubular structure having present during the first storage of gasoline, in particular alcoholic gasoline, at most 0.3 g/m 2 of insoluble extract, advantageously at most 0.2 g/m2.
- said said tubular structure has, during the first storage of gasoline, in particular alcoholic gasoline, 30%, in particular 40%, in particular 50% less insoluble extract than the same tubular structure derived from not recycled.
- the monolayer tubular structure intended for the transport of fluids for a motor vehicle of the invention makes it possible to greatly reduce the proportion of extractables as determined by a test which consists in filling a tubular structure with alcoholic gasoline type FAM-B and heating the whole at 60° C. for 96 hours, then emptying it by filtering the fluid into a beaker.
- the insoluble extracts present during filtration on the filter are weighed after drying and represent less than 0.3 g/m2.
- the soluble extracts are quantified by allowing the filtrate in the beaker to evaporate at room temperature and then by weighing this residue.
- the proportion of soluble extracts is advantageously less than or equal to approximately 15 g/m2 of internal tube surface.
- FAM B alcoholic gasoline is described in DIN 51604-1:1982, DIN 51604-2:1984 and DIN 51604-3:1984. Briefly, alcoholic gasoline FAM A is first prepared with a mixture of 50% Toluene, 30% isooctane, 15% di-isobutylene and 5% ethanol then FAM B is prepared by mixing 84.5% FAM A with 15% methanol and 0.5% water.
- FAB consists of 42.3% toluene, 25.4% isooctane, 12.7% di-isobutylene, 4.2% ethanol, 15% methanol and 0.5% water.
- Said tubular structure has a rate of extractables lower than that of the same tubular structure resulting from non-recycled material, that is to say virgin or original during the first storage of gasoline, in particular alcoholic gasoline and in particular a proportion of insoluble extract lower by 30%, in particular by 40%, in particular by 50% compared to the proportion present in the same tubular structure but resulting from non-recycled or virgin material.
- the layer (1) consists of a composition mainly comprising at least one semi-crystalline aliphatic polyamide, the said composition consisting of at least 30%, in particular of at least 50% of recycled material originating from a single-layer and/or multi-layer tube having been intended for the transport of fluids for motor vehicles and/or from a single-layer and/or multi-layer tank having been intended for the storage of fluids for motor vehicles.
- the composition of the layer (1) being made of recycled material at most 99.8%, it is then necessary to add a polyamide (identical or different) of non-recycled origin to the material to be recycled and this is then done during passage through the extruder during the manufacture of the single-layer or multi-layer tubular structure and/or an additive.
- said composition of the layer (1) comprises: d) from 1 to 20% by weight of at least one plasticizer.
- said composition of the layer (1) comprises: e) from 1 to 0.2% by weight of at least one additive. All the combinations between a), b1), b2), c), d) and e) defined above are possible in this first variant.
- the polyamides denoted A, B and C can be of recycled or non-recycled origin provided that the composition of the layer (1) consists of at least 50% recycled material.
- the Tf of the majority aliphatic semi-crystalline polyamide of layer (1) is ⁇ 225°C, in particular ⁇ 200°C, as determined according to ISO 11357-3: 2013, at a heating rate of 20K/min .
- said composition of the layer (1) is devoid of plasticizer and/or impact modifier.
- said composition of the layer (1) comprises at least one compound chosen from a plasticizer, an impact modifier and an additive, and said recycled material is chosen from a shredded tube.
- said tube is a monolayer tube and/or a multilayer tube.
- the fluid transported by said monolayer and/or multilayer tube or stored in said reservoir is different from that of said multilayer tubular structure (MLT).
- MLT multilayer tubular structure
- the single-layer and/or multi-layer tube has transported a fluid such as air
- said multi-layer tubular structure (MLT) may be intended to transport gasoline or even if the single-layer and/or multi-layer tube transported a fluid such as alcoholic gasoline, said tubular structure (MLT) may be intended to transport diesel.
- the fluid transported by said monolayer and/or multilayer tube or stored in said reservoir is the same as that of said multilayer tubular structure (MLT).
- the recycled material comes from a single-layer tube consisting of a composition comprising only a PA11. It is obvious that said PA11 can be formulated.
- said composition of the layer (1) comprises at least 60% by weight, in particular at least 70% by weight, in particular at least 80% by weight, in particular at least 90% by weight, more particularly at least 95% recycled material without however exceeding 99.8%.
- the recycled material can be mixed with virgin polyamide with additives or with a master batch with a large quantity of additives.
- the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.
- it is only ground, excluding grinding followed by recompounding with or without reformulation.
- said used tube or said tank was intended for the transport or storage of fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
- the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for the transport of fuel such as gasoline, in in particular alcoholic gasoline, biogasoline or diesel, in particular biodiesel.
- said tube or said tank which has been intended for the transport or storage of fluid for a motor vehicle is single-layer, advantageously said tube and said tank are mixed in a range of 5/95 to 95/5 by weight.
- said used tube or tank which has been intended for the transport or storage of fluid for a motor vehicle is ground with extractions of the fluid residues before or after the grounding and the composition of the layer (1) resulting from said recycling consists of a composition as defined for the first variant and the embodiments associated therewith described in the paragraph “Regarding the layer (1)” above.
- the structure is multilayered and comprises at least one layer (2).
- the multilayer tubular structure comprises at least one layer (2) consisting of a composition mainly comprising at least one semi-crystalline, semi-aromatic aliphatic polyamide or a polyolefin,
- said layer (2) consists at least 90% non-recycled material.
- polysemi-crystalline polyamide and “aliphatic” have the same definition as for layer (1). Said at least one aliphatic semi-crystalline polyamide is obtained in the same way as described above for layer (1).
- the semi-aromatic polyamide is as defined below.
- the polyolefin is as defined below for the impact modifier polyolefin.
- said layer (2) consists of a composition mainly comprising at least one semi-crystalline aliphatic polyamide and optionally at least one impact modifier, and when the layer (2) consists of a composition mainly comprising at at least one semi-crystalline aliphatic polyamide which is PA12 and/or PA610 and/or PA612 and/or PA1010 and/or PA 6, then said composition comprises said impact modifier, and said layer (2) consists of at least 90% non-recycled material.
- said layer (2) has no impact modifier.
- the semi-crystalline aliphatic polyamide which is PA12 and/or PA610 and/or PA612 and/or PA1010 and/or PA 6 is excluded from the composition which constitutes layer (2).
- said layer (2) comprises c) from 3 to 45% by weight of at least one impact modifier, in particular from 5 to 20% by weight of at least one impact modifier.
- said composition of the layer (2) comprises: d) from 1 to 20% by weight of at least one plasticizer .
- said composition of the layer (2) comprises: e) from 1 to 0.2% by weight of at least one additive.
- said composition of layer (2) comprises: f) from 1 to 35% of at least one antistatic filler. All the combinations between a), b1), b2), c), d), e) and f) defined above are possible in this first variant.
- the composition of said layer (2) of the first and second variant comprises a PA11, a PA12 or a PA612 and from 3 to 45% by weight of an impact modifier, in particular from 5 to 20% by weight of an impact modifier.
- said layer (2) consists of a composition mainly comprising at least one semi-aromatic polyamide.
- said layer (2) consists of a composition mainly consisting of at least one semi-aromatic polyamide.
- said layer (2) consists of a composition consisting of at least one semi-aromatic polyamide.
- said layer (2) consists of a composition consisting of at least one semi-aromatic polyamide.
- said layer (2) consists of a composition mainly comprising at least one polyolefin.
- said layer (2) consists of a composition mainly consisting of at least one polyolefin.
- said layer (2) consists of a composition consisting of at least one polyolefin.
- the multilayer tubular structure comprises at least one layer (2') consisting of a composition mainly comprising at least one semi-crystalline, semi-aromatic aliphatic polyamide or a polyolefin, said layer (2') consisting of at least 90% non-recycled material.
- the terms “semi-crystalline polyamide” and “aliphatic” have the same definition as for layer (1) or layer (2).
- Said at least one aliphatic semi-crystalline polyamide is obtained in the same way as described above for layer (1) and layer (2).
- said layer (2') is devoid of impact modifier.
- said layer (2') comprises from 3 to 45% by weight of at least one impact modifier, in particular from 5 to 20% by weight of at least one impact modifier .
- said composition of the layer (2') comprises: d) from 1 to 20% by weight of at least one plasticizer ing.
- said composition of the layer (2′) comprises: e) from 1 to 0.2% by weight of at least one additive.
- said composition of the layer (2') comprises: f) from 1 to 35% of at least one antistatic filler.
- the composition of said layer (2') comprises a PA11, a PA12 or a PA612 and from 3 to 45% by weight of at least one impact modifier, in particular from 5 to 20% by weight of at least one shock modifier.
- said layer (2') consists of a composition mainly comprising at least one semi-aromatic polyamide. Said at least one semi-aromatic semi-crystalline polyamide is obtained from the polycondensation of at least one diamine X as defined above, with at least one aromatic dicarboxylic acid or one diamine Xa with a dicarboxylic acid Y such as defined above.
- the aromatic dicarboxylic acid is advantageously chosen from terephthalic acid (denoted T), isophthalic acid (denoted I) and 2,6-naphthalene dicarboxylic acid (denoted N) or mixtures thereof, in particular it is chosen from terephthalic acid (denoted T), isophthalic acid (denoted I) or mixtures thereof.
- the diamine Xa is advantageously an arylamine, which can be chosen from meta-xylylene diamine (MXD, CAS No: 1477-55-0) or para-xylylene diamine (PXD, CAS No: 539-48-0) .
- said semi-aromatic semi-crystalline polyamide is obtained from the polycondensation of at least one diamine X with at least one aromatic dicarboxylic acid, or of at least one diamine Xa with at least one dicarboxylic acid Y, it may therefore comprise a single diamine or several diamines and a single dicarboxylic acid or several dicarboxylic acids.
- said semi-aromatic semi-crystalline polyamide is obtained from the polycondensation of a single diamine X with a single aromatic dicarboxylic acid or from the polycondensation of a single diamine Xa with a single dicarboxylic acid Y.
- said semi-aromatic semi-crystalline polyamide is obtained from the polycondensation of at least one diamine X with at least one dicarboxylic acid chosen from terephthalic acid and isophthalic acid, in particular terephthalic acid, or said semi- -semi-aromatic crystalline is obtained from the polycondensation of at least one diamine Xa with at least one dicarboxylic acid Y.
- said at least one C6 to C12 diamine X is chosen from 1,6-hexamethylenediamine 1 ,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9- nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine and said at least dicarboxylic acid is an acid chosen from terephthalic acid and isophthalic acid, in particular terephthalic acid.
- said at least one diamine Xa is an arylamine chosen from meta-xylylene diamine (MXD, CAS No: 1477-55-0) or para-xylylene diamine (PXD, CAS No: 539-48-0) and said at least one dicarboxylic acid Y is C6 to C18 and is selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassyl, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid.
- MXD meta-xylylene diamine
- PXD para-xylylene diamine
- said at least one dicarboxylic acid Y is C6 to C12 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid.
- Each of these semi-aromatic polyamides can be copolymerized is a lactam or an amino acid to lead to structures such as PA10/10T, PA10/9T, PA 10/12T, PA11/9T, PA11/10T, PA11/12T, PA12/ 9T, PA12/10T and PA12/12T or PA11/MXD6, PA11/MXD10, PA12/MXD6, PA12/MXD10.
- said layer (2') consists of a composition mainly comprising at least one polyolefin.
- the impact modifier is advantageously constituted by a polymer having a flexural modulus of less than 100 MPa measured according to standard ISO 178: 2010, determined at 23° C. with relative humidity: RH50%, and of Tg below 0° C. (measured according to standard 11357-2:2013 at the inflection point of the DSC thermogram, at a heating rate of 20 K/min), in particular a polyolefin.
- the polyolefin of the impact modifier can be functionalized or non-functionalized or be a mixture of at least one functionalized and/or at least one non-functionalized.
- polyolefin has been designated by (B) and functionalized polyolefins (B1) and non-functionalized polyolefins (B2) have been described below.
- a non-functionalized polyolefin (B2) is conventionally a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
- - homopolymers and copolymers of polyethylene in particular LDPE, HDPE, LLDPE (linear low density polyethylene, or linear low density polyethylene), VLDPE (very low density polyethylene, or very low density) and metallocene polyethylene.
- LDPE low density polyethylene
- HDPE linear low density polyethylene
- LLDPE linear low density polyethylene
- VLDPE very low density polyethylene, or very low density
- metallocene polyethylene -the homopolymers or copolymers of propylene.
- ethylene/alpha-olefin copolymers such as ethylene/propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene/propylene/diene (EPDM).
- SEBS styrene/ethylene-butene/styrene
- SBS styrene/butadiene/styrene
- SIS styrene/isoprene/styrene
- SEPS styrene/ethylene-propylene/styrene
- the functionalized polyolefin (B1) can be a polymer of alpha olefins having reactive units (the functionalities); such reactive units are acid, anhydride or epoxy functions.
- reactive units are acid, anhydride or epoxy functions.
- a functionalized polyolefin is, for example, a PE/EPR mixture, the weight ratio of which can vary widely, for example between 40/60 and 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride, according to a degree of grafting for example of 0.01 to 5% by weight.
- the functionalized polyolefin (B1) can be chosen from the following (co)polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is for example from 0.01 to 5% by weight: - PE, PP, copolymers of ethylene with propylene, butene, hexene, or octene containing for example from 35 to 80% by weight of ethylene; - ethylene/alpha-olefin copolymers such as ethylene/propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene/propylene/diene (EPDM).
- SEBS styrene/ethylene-butene/styrene
- SBS styrene/butadiene/styrene
- SIS styrene/isoprene/styrene
- SEPS styrene/ethylene-propylene/styrene
- the functionalized polyolefin (B1) can also be chosen from ethylene/propylene copolymers with a majority of propylene grafted with maleic anhydride then condensed with monoamino polyamide (or a polyamide oligomer) (products described in EP-A-0342066) .
- the functionalized polyolefin (B1) can also be a co- or ter-polymer of at least the following units: (1) ethylene, (2) alkyl (meth)acrylate or saturated carboxylic acid vinyl ester and (3) anhydride such as maleic anhydride or (meth)acrylic acid or epoxy such as glycidyl (meth)acrylate.
- the ethylene preferably represents at least 60% by weight and in which the ter monomer (the function) represents, for example, from 0.1 to 10% by weight of the copolymer: - ethylene/alkyl (meth)acrylate/(meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymers; - ethylene/vinyl acetate/maleic anhydride or glycidyl methacrylate copolymers; - ethylene/vinyl acetate or alkyl (meth)acrylate/(meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymers.
- the (meth)acrylic acid can be salified with Zn or Li.
- alkyl (meth)acrylate in (B1) or (B2) denotes alkyl methacrylates and C1 to C8, and can be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate, l cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
- the aforementioned polyolefins (B1) can also be crosslinked by any appropriate process or agent (diepoxy, diacid, peroxide, etc.); the term functionalized polyolefin also includes mixtures of the aforementioned polyolefins with a difunctional reagent such as diacid, dianhydride, diepoxy, etc. capable of reacting with these or mixtures of at least two functionalized polyolefins capable of reacting with one another.
- the copolymers mentioned above, (B1) and (B2) can be randomly or block copolymerized and have a linear or branched structure.
- the molecular weight, the MFI index, the density of these polyolefins can also vary to a large extent, which those skilled in the art will appreciate.
- MFI short for Melt Flow Index, is the Melt Flow Index. It is measured according to the ASTM 1238 standard.
- the non-functionalized polyolefins (B2) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and of a comonomer of the higher alpha olefinic type. such as butene, hexene, octene or 4-methyl 1-pentene.
- the functionalized polyolefins (B1) are chosen from any polymer comprising alpha olefin units and units carrying polar reactive functions such as epoxy, carboxylic acid or carboxylic acid anhydride functions.
- ter-polymers of ethylene, alkyl acrylate and maleic anhydride or glycidyl methacrylate such as the Applicant's Lotader® or polyolefins grafted with maleic anhydride such as the Applicant's Orevac® as well as ter polymers of ethylene, alkyl acrylate and (meth)acrylic acid.
- the additives optionally used in the compositions of the invention are the conventional additives used in polyamides well known to those skilled in the art and are described in particular in EP 2098580.
- they are chosen from a catalyst, a antioxidant, heat stabilizer, UV absorber, light stabilizer, lubricant, inorganic filler, flame retardant, nucleating agent and colorant, reinforcing fibers, wax and mixtures thereof.
- the term “catalyst” designates a polycondensation catalyst such as an inorganic or organic acid.
- the proportion by weight of catalyst is comprised from approximately 50 ppm to approximately 5000 ppm, in particular from approximately 100 to approximately 3000 ppm relative to the total weight of the composition.
- the catalyst is chosen from phosphoric acid (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof.
- the stabilizer can be a UV stabilizer, an organic stabilizer or more generally a combination of organic stabilizers, such as a phenol-type antioxidant (for example of the type of that of irganox® 245 or 1098 or 1010 of the company Ciba-BASF), a phosphite-type antioxidant (for example irgafos® 126 and irgafos® 168 from the company Ciba-BASF) and even possibly other stabilizers such as a HALS, which means Hindered Amine Light Stabilizer or light stabilizer of the hindered amine type (for example Tinuvin® 770 from the company Ciba-BASF), an anti-UV (for example Tinuvin® 312 from the Ciba company) or a phosphorus-based stabilizer.
- antioxidants of the amine type such as Naugard® 445 from the company Crompton or alternatively polyfunctional stabilizers such as Nylostab® S-EED from the company Clariant.
- This stabilizer can also be an inorganic stabilizer, such as a copper-based stabilizer.
- inorganic stabilizers mention may be made of copper halides and acetates. Incidentally, one can possibly consider other metals such as silver, but these are known to be less effective.
- copper-based compounds are typically associated with alkali metal halides, particularly potassium.
- the plasticizers are, by way of example, the plasticizers are chosen from benzene sulfonamide derivatives, such as n-butyl benzene sulfonamide (BBSA); ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide; hydroxybenzoic acid esters, such as ethyl-2-hexyl parahydroxybenzoate and decyl-2-hexyl parahydroxybenzoate; tetrahydrofurfuryl alcohol esters or ethers, such as oligoethyleneoxytetrahydrofurfuryl alcohol; and esters of citric acid or hydroxy-malonic acid, such as oligoethyleneoxy malonate.
- BBSA n-butyl benzene sulfonamide
- the additives when they are present in the composition are advantageously present from 1 to 20% by weight, in particular from 5 to 15% by weight, in particular from 5 to 12% by weight.
- the antistatic fillers are for example chosen from carbon black, graphite, carbon fibers, carbon nanotubes, in particular carbon black and carbon nanotubes.
- said layer (1) is located between a layer (2) and a layer (2').
- said layer (2') is the layer in contact with the transported fluid.
- said layer (2') is as defined for layer (2), and preferably layers (2) and (2') are identical.
- layers (2) and (2') are different, only layer 2' can contain anti-static fillers.
- said layer (2') is as defined for layer (2) means that the compositions of layer (2) and of layer (2') may be identical or different. When they are different, they may differ by the polyamide or the proportion of polyamide or by one of the other constituents of the composition.
- the composition of said layer (2) comprises a PA11, a PA12 or a PA612 and the recycled material comes from a single-layer tube and/or a tank consisting of a composition comprising only a PA11, in particular the composition of the layer (1) consists of at most 99.8% recycled material.
- the composition of said layer (2) comprises a PA11, a PA12 or a PA612, the recycled material comes from a single-layer tube and/or a tank consisting of a composition comprising only a PA11, in particular the composition of the layer (1) consists of at most 99.8% recycled material and the composition of said layer (2') comprises a PA11, a PA12 or a PA612.
- the composition of said layer (2) comprises a PA11, a PA12 or a PA612 and from 3 to 45% by weight of at least one impact modifier, in particular from 5 to 20% by weight of at least one shock and the recycled material comes from a single-layer tube and/or a tank consisting of a composition comprising only a PA11, in particular the composition of the layer (1) consists of at most 99.8% of material recycled.
- the composition of said layer (2) comprises a PA11, a PA12 or a PA612 and from 3 to 45% by weight of at least one impact modifier, in particular from 5 to 20% by weight of at least one shock and the recycled material comes from a single-layer tube and/or a tank consisting of a composition comprising only a PA11, in particular the composition of the layer (1) consists of at most 99.8% of material recycled material and the composition of said layer (2') comprises a PA11, a PA12 or a PA612 and from 3 to 45% by weight of at least one impact modifier, in particular from 5 to 20% by weight of at least one shock modifier.
- the compositions of the layer (2) and of the layer (2') are identical and therefore the layers (2) and (2') are of course identical, that is to say that both the polyamide that the other constituents of the composition are identical in nature and proportion and that and that the thickness of the two layers (2) and (2') is identical.
- the layer (2') is then a layer (2).
- the latter consists of three layers (2)//(1)//(2'),
- this consists of three layers (2)/ /(1)///(2).
- at least one binder layer (3) is present, said layer (3) being located between layer (2) and layer (1) and/or between layer (1) and layer ( 2').
- the latter In a second variant of the multilayer tubular structure (MLT), the latter consists of four layers (2)//binder (3) //(1)//(2'), in particular (2)//binder (3) //(1)//(2). In a third variant of the multilayer tubular structure (MLT), the latter consists of four layers (2)//(1)// binder (3) // (2'), in particular (2)//( 1)// binder (3) // (2). In a fourth variant of the multilayer tubular structure (MLT), the latter consists of five layers (2)// binder (3) //(1)// binder (3) //(2'), in particular (2)// binder (3) //(1)// binder (3) //(2). In this fourth variant, the two layers of binder (3) can be identical or different, in particular they are identical.
- At least one layer of EVOH is present, said layer (3) being located between layer (1) and layer (2').
- the multilayer tubular structure (MLT) then consists of four layers (2)//(1)// EVOH // (2'), in particular (2)//(1)/// EVOH // (2).
- said layer (1) represents at least 10%, in particular at least 30%, in particular at least 50% of the total thickness of said multilayer tubular structure (MLT).
- said layer (1) represents at least 60%, in particular at least 70%, of the total thickness of said multilayer tubular structure (MLT).
- said composition of said layer (1) is devoid of polyamides denoted A and B and said composition of said layer (2) comprises polyamides chosen from those denoted E, F and a mixture thereof.
- said composition of said layer (1) comprises polyamides chosen from those denoted A, B and a mixture thereof, and said composition of said layer (2) is free of polyamides denoted E and F.
- said composition of said layer (1) comprises polyamides chosen from those denoted A, B and a mixture thereof
- said composition of said layer (2) comprises polyamides chosen from those denoted E , F and a mixture thereof.
- said composition of said layer (1) is devoid of polyamides denoted A and B and said composition of said layer (2) is devoid of polyamides denoted E and F.
- the layer (1) comes from a single-layer recycled tube or a single-layer recycled tank or a mixture of the two.
- the layer (1) comes from a single-layer recycled tube or from a single-layer recycled tank or from a mixture of the two and only said composition of said layer (1) comprises at least one shock modifier.
- the layer (1) comes from a single-layer recycled tube or from a single-layer recycled tank or from a mixture of the two and said composition of said layer (1) as well as said compositions of the layer (2) and the layer (2') comprise at least one impact modifier.
- the layer (1) comes from a multilayer recycled tube or from a multilayer recycled tank or from a mixture of the two.
- the layer (1) comes from a multilayer recycled tube or from a multilayer recycled tank or from a mixture of the two and only said composition of said layer (1) comprises at least one shock modifier.
- the layer (1) comes from a monolayer recycled tube or from a multilayer recycled tank or from a mixture of the two.
- the layer (1) comes from a multilayer recycled tube or from a monolayer recycled tank or from a mixture of the two.
- the layer (1) comes from a multilayer recycled tube and the said composition of the said layer (1) as well as the said compositions of the layer (2) and of the layer (2') comprise at least one impact modifier.
- said multilayer tubular (MLT) is intended for the transport of fluids chosen from a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
- a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
- the binder is described in particular in patents EP1452307 and EP1162061, EP1216826, EP0428833 and EP3299165. It is implicit that the layers (2) and (1) or (1) and (2') adhere to each other.
- the binder layer is intended to be interposed between two layers which do not or hardly adhere to each other.
- the binder can be, for example, but without being limited thereto, a composition based on 50% copolyamide 6/12 (ratio 70/30 by mass) of Mn 16000, and 50% copolyamide 6/12 ( of 30/70 ratio by mass) of Mn 16000, a composition based on PP (polypropylene) grafted with maleic anhydride, known under the name of Admer QF551A from the company Mitsui, a composition based on PA610 (from Mn 30000, and as defined elsewhere) and from 36% of PA6 (from Mn 28000) and 1.2% organic stabilizers (consisting of 0.8% Lowinox 44B25 phenol from the Great Lakes company, 0.2% Irgafos 168 phosphite from the Ciba company, 0.2% Tinuvin 312 anti-UV from the Ciba company), a composition based on PA612 (from Mn 29000, and as defined elsewhere) and 36% PA6 (from Mn 28000, and as defined elsewhere)
- the present invention relates to a method for preparing a tubular structure as defined above, characterized in that it comprises the extrusion of at least one layer (1) consisting of at least 50 % of recycled material as defined above, after sampling used pipes on a motor vehicle, in an extruder optionally provided with a degassing zone.
- All the embodiments of the layer (1) described above in the paragraph “concerning the layer (1)” can be used for the method detailed in this part.
- the used pipes are ground into pellets after removal.
- the fluid residues have been totally or partially extracted from the used pipes before or after grinding.
- the extraction is carried out by means of washing or ventilation.
- the washing is carried out using a solvent, in particular methanol.
- the ventilation is carried out by means of an inerted oven.
- the extraction is carried out after grinding by means of a degassing zone in said extruder.
- the used pipes before or after grinding are cleaned to remove any residual oligomers present in the used pipes.
- said method comprises the following steps: 1) sampling a used monolayer and/or multilayer tube and/or a used tank on a motor vehicle, 2) optionally cleaning the oligomers present, 3) optionally extraction of fluid residues, 4) grinding of said tubes and/or said reservoir, 5) extraction of fluid residues if this was not carried out in step 3), 6) extrusion in the form of a tubular structure monolayer or multilayer of said tubes and/or of said crushed reservoir.
- the present invention relates to the use of a used tube and/or single-layer and/or multi-layer tank having initially transported or contained fluids for a motor vehicle, as defined above, for the preparation of a single-layer and/or multi-layer tubular structure intended for the transport of motor vehicle fluids, in particular air, oil, water, a urea solution, a coolant based on of glycol, or a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen as defined above, said monolayer and/or multilayer tube and/or said used tank(s) having been ground into granules and the fluid residues present in said tube and/or tank having been totally or partially extracted, before or after grinding of said tube and / or tank and said said tubular structure having during the first r storage of gasoline, in particular alcoholic gasoline, less than 0.3 g/m 2 of insoluble extract.
- a used tube and/or single-layer and/or multi-layer tank having initially transported or contained fluids
- Figure 1 shows the Fourier Transform Infrared (FTIR) analysis in attenuated total reflectance (ATR) mode of a crushed PA 11 PL VHU gasoline line (solid gray line), and compared to a gasoline line PA 11 PL made from 100% virgin material (solid black line).
- FTIR Fourier Transform Infrared
- FIG. 2 shows the CH2CO zones of the different secondary amide, primary amide and carboxylic acid functions in C13 NMR in a solvent mixture with an HFIP/CD2Cl2 ratio of 1/3.
- Top spectrum PA 11 PL ground ELV gasoline line and bottom spectrum PA 11 PL gasoline line based on 100% virgin material.
- Compositions of the invention Monolayer tubes of the invention: The tubes are 8*1mm in size
- Preparation of the monolayer structures (tubes) are produced by extrusion.
- a Maillefer industrial extrusion line is used. This line includes a single-screw extrusion extruder equipped with a screw with a screw profile suitable for polyamides.
- the extrusion line comprises: a die-punch assembly, located at the end of the extrusion head; the internal diameter of the die and the external diameter of the punch are chosen according to the structure to be made and the materials of which it is made, as well as the dimensions of the tube and the line speed; a vacuum tank with an adjustable vacuum level. In this tank circulates water maintained at 20°C in general, a gauge is inserted in the front of this tank allowing to conform the tube in its final dimensions.
- the diameter of the gauge is adapted to the dimensions of the tube to be produced, typically from 8.1 to 10 mm for a tube with an external diameter of 8 mm and a thickness of 1 mm; a cooling tank in which water is kept at around 20°C, allowing the tube to be cooled along the route from the head to the draw bench; a diameter gauge; a draw bench.
- the tubes which meet the characteristics described in the present patent application, were taken, after stabilization of the extrusion parameters, the dimensions of the tubes objectives no longer evolving over time.
- the diameter is controlled by a laser diameter gauge installed at the end of the line.
- Line speed is typically 20m/min. It generally varies between 5 and 100m/min.
- the screw speed of the extruders depends on the thickness and diameter of the tube as known to those skilled in the art.
- the temperatures of the extruders and the tools (head and connection) must be adjusted so as to be sufficiently higher than the melting temperature of the compositions under consideration, so that they remain in the molten state, thus avoiding they solidify and block the machine.
- a durability (resistance to thermo-oxidative aging) that can be described as “acceptable”, which corresponds to > 50h of half-life (and ⁇ 100h)
- - a durability (resistance to thermo-oxidative aging) that we can qualify as “bad”, which corresponds to ⁇ 50h In the case where a half-life figure is given to show nuances, this figure is rounded off by 25h increments, to take significant figures into account, linked to the accuracy of the assessment.
- PA 11 PL ground VHU gasoline line are chips from gasoline lines collected on VHU having a molar ratio of primary amide functions to secondary amide functions of 0.02, a molar ratio of nitrile functions of 0.05, a ratio molar of methyl functions of 0.004.
- PA 12 PL ground VHU gasoline line are chips from gasoline lines collected on VHU having a molar ratio of primary amide functions to secondary amide functions of 0.02, a molar ratio of nitrile functions of 0.05, a ratio molar of methyl functions of 0.004.
- PA11 PL ground VHU tank are fuel tank shavings collected on VHU with a molar ratio of primary amide functions to secondary amide functions of 0.01, a molar ratio of nitrile functions of 0.02, a ratio molar of methyl functions of 0.002.
- PA12 PL ground VHU tank are fuel tank shavings collected on VHU with a molar ratio of primary amide functions to secondary amide functions of 0.01, a molar ratio of nitrile functions of 0.02, a ratio molar of methyl functions of 0.002.
- PA11PL crushed VHU air transport line are brake pipe shavings collected on VHU having a molar ratio of primary amide functions compared to secondary amide functions of 0.04, a molar ratio of nitrile functions of 0.1 , a molar ratio of methyl functions of 0.01.
- PA12PL crushed VHU air transport line are brake pipe shavings collected on VHU having a molar ratio of primary amide functions compared to secondary amide functions of 0.03, a molar ratio of nitrile functions of 0.09, a molar ratio of methyl functions of 0.008.
- PA610PL crushed VHU air transport line are brake pipe shavings collected on VHU having a molar ratio of primary amide functions to secondary amide functions of 0.02, a molar ratio of nitrile functions of 0.07 , a molar ratio of methyl functions of 0.010.
- PA612PL crushed ELV air transport line are brake pipe shavings collected on ELV with a molar ratio of primary amide functions to secondary amide functions of 0.03, a molar ratio of nitrile functions of 0.08 , a molar ratio of methyl functions of 0.009.
- PA610PL ground VHU gasoline line are chips from gasoline lines collected on VHU having a molar ratio of primary amide functions to secondary amide functions of 0.01, a molar ratio of nitrile functions of 0.03, a molar ratio of 0.001 methyls.
- PA612PL ground VHU gasoline line are chips from gasoline lines collected on VHU having a molar ratio of primary amide functions to secondary amide functions of 0.01, a molar ratio of nitrile functions of 0.04, a molar ratio of 0.002 methyls.
- PA610 PL ground VHU tank are fuel tank shavings collected on VHU with a molar ratio of primary amide functions to secondary amide functions of 0.009, a molar ratio of nitrile functions of 0.01, a molar ratio of methyl functions of 0.001.
- PA612 PL ground VHU tank are fuel tank shavings collected on VHU with a molar ratio of primary amide functions to secondary amide functions of 0.008, a molar ratio of nitrile functions of 0.02, a molar ratio of methyl functions of 0.001. The molar ratio is determined as defined in the text above.
- Multilayer tubes of the invention The layers are described from the outside to the inside, followed by their respective thicknesses indicated in the form of %; the tubes are of dimension 8*1mm
- the extrusion line comprises: a die-punch assembly, located at the end of the coextrusion head; the internal diameter of the die and the external diameter of the punch are chosen according to the structure to be made and the materials of which it is made, as well as the dimensions of the tube and the line speed; a vacuum tank with an adjustable vacuum level. In this tank circulates water maintained at 20°C in general, in which is immersed a gauge allowing to conform the tube in its final dimensions.
- the diameter of the gauge is adapted to the dimensions of the tube to be produced, typically from 8.5 to 10 mm for a tube with an external diameter of 8 mm and a thickness of 1 mm; a succession of cooling tanks in which water is kept at around 20°C, allowing the tube to be cooled along the route from the head to the draw bench; a diameter gauge; a draw bench.
- the 5-extruder configuration is used to produce tubes ranging from 2 layers to 5 layers (and also single-layer tubes). In the case of structures whose number of layers is less than 5, several extruders are then fed with the same material.
- the extruded materials Before the tests, in order to ensure the best tube properties and good extrusion quality, it is checked that the extruded materials have a residual moisture content before extrusion of less than 0.08%. Otherwise, an additional stage of drying the material is carried out before the tests, generally in a vacuum dryer, for 1 night at 80°C.
- the tubes which meet the characteristics described in this patent application, were sampled, after stabilization of the extrusion parameters, the dimensions of the targeted tubes no longer changing over time.
- the diameter is controlled by a laser diameter gauge installed at the end of the line. Line speed is typically 20m/min. It generally varies between 5 and 100m/min.
- the screw speed of the extruders depends on the thickness of the layer and the diameter of the screw as is known to those skilled in the art.
- “Virgin monolayer petrol line” is a virgin monolayer petrol line of dimension 8*1mm composed of PA11 PL
- Single-layer petrol line from VHU is a single-layer petrol line of dimension 8*1mm composed of PA11 PL collected on an end-of-life motor vehicle (VHU)
- “Virgin three-layer petrol line” is a virgin three-layer petrol line of dimension 8 *1mm interior>PA11NX2// PA610 PL // PA11NX2 ⁇ exterior having the following thickness distributions: 15%/70%/15%
- “Three-layer gasoline line from VHU” is a three-layer gasoline line from VHU of dimension 8* 1mm interior>PA11NX2// PA610 PL // PA11NX2 ⁇ exterior having the following thickness distributions: 15%/70%/15%
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KR1020247003663A KR20240032898A (ko) | 2021-07-09 | 2022-07-07 | 재생 폴리아미드를 기반으로 한 단층 또는 다층 관형 구조체 |
EP22754115.8A EP4367185A1 (fr) | 2021-07-09 | 2022-07-07 | Structure tubulaire monocouche ou multicouche a base de polyamide recycle |
CN202280048297.1A CN117616085A (zh) | 2021-07-09 | 2022-07-07 | 基于回收的聚酰胺的单层或多层管状结构体 |
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FR2107457A FR3125052A1 (fr) | 2021-07-09 | 2021-07-09 | Structure tubulaire monocouche ou multicouche a base de polyamide recycle |
FRFR2107457 | 2021-07-09 |
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WO2023281222A1 true WO2023281222A1 (fr) | 2023-01-12 |
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PCT/FR2022/051363 WO2023281222A1 (fr) | 2021-07-09 | 2022-07-07 | Structure tubulaire monocouche ou multicouche a base de polyamide recycle |
Country Status (5)
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EP (1) | EP4367185A1 (fr) |
KR (1) | KR20240032898A (fr) |
CN (1) | CN117616085A (fr) |
FR (1) | FR3125052A1 (fr) |
WO (1) | WO2023281222A1 (fr) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0342066A1 (fr) | 1988-03-24 | 1989-11-15 | Elf Atochem S.A. | Copolymère greffé à base d'alpha-mono-oléfine, son procédé de fabrication, son application à la fabrication d'alliages thermoplastiques, alliages thermoplastiques obtenus |
EP0428833A2 (fr) | 1989-11-20 | 1991-05-29 | Technoflow Tube-Systems GmbH | Conduite pour automobiles en matière plastique fabriquée par coextrusion |
EP1162061A1 (fr) | 2000-06-09 | 2001-12-12 | EMS-Chemie AG | Stratifiés thermoplastiques |
EP1216826A2 (fr) | 2000-12-21 | 2002-06-26 | Degussa AG | Film multicouche avec une couche d'EVOH |
JP2003042351A (ja) * | 2001-07-25 | 2003-02-13 | Toyoda Gosei Co Ltd | 多層管状体のリサイクル方法 |
EP1452307A1 (fr) | 2003-02-28 | 2004-09-01 | EMS-Chemie AG | Laminé thermoplastique et multi-couche sous forme de corps creux |
EP2098580A1 (fr) | 2008-03-03 | 2009-09-09 | Arkema France | Composition adhésive et structure comprenant au moins une couche de ladite composition. |
US20140333002A1 (en) * | 2009-10-07 | 2014-11-13 | Arkema Inc. | Melt processable composition from recycled multi-layer articles containing a fluoropolymer layer |
EP3299165A1 (fr) | 2016-09-21 | 2018-03-28 | Evonik Degussa GmbH | Corps creux multicouches tres resistant au lavage |
-
2021
- 2021-07-09 FR FR2107457A patent/FR3125052A1/fr active Pending
-
2022
- 2022-07-07 WO PCT/FR2022/051363 patent/WO2023281222A1/fr active Application Filing
- 2022-07-07 KR KR1020247003663A patent/KR20240032898A/ko unknown
- 2022-07-07 EP EP22754115.8A patent/EP4367185A1/fr active Pending
- 2022-07-07 CN CN202280048297.1A patent/CN117616085A/zh active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0342066A1 (fr) | 1988-03-24 | 1989-11-15 | Elf Atochem S.A. | Copolymère greffé à base d'alpha-mono-oléfine, son procédé de fabrication, son application à la fabrication d'alliages thermoplastiques, alliages thermoplastiques obtenus |
EP0428833A2 (fr) | 1989-11-20 | 1991-05-29 | Technoflow Tube-Systems GmbH | Conduite pour automobiles en matière plastique fabriquée par coextrusion |
EP1162061A1 (fr) | 2000-06-09 | 2001-12-12 | EMS-Chemie AG | Stratifiés thermoplastiques |
EP1216826A2 (fr) | 2000-12-21 | 2002-06-26 | Degussa AG | Film multicouche avec une couche d'EVOH |
US20040265527A1 (en) * | 2000-12-21 | 2004-12-30 | Degusa Ag | Composite having two or more layers, including an EVOH layer |
JP2003042351A (ja) * | 2001-07-25 | 2003-02-13 | Toyoda Gosei Co Ltd | 多層管状体のリサイクル方法 |
EP1452307A1 (fr) | 2003-02-28 | 2004-09-01 | EMS-Chemie AG | Laminé thermoplastique et multi-couche sous forme de corps creux |
EP2098580A1 (fr) | 2008-03-03 | 2009-09-09 | Arkema France | Composition adhésive et structure comprenant au moins une couche de ladite composition. |
US20140333002A1 (en) * | 2009-10-07 | 2014-11-13 | Arkema Inc. | Melt processable composition from recycled multi-layer articles containing a fluoropolymer layer |
EP3299165A1 (fr) | 2016-09-21 | 2018-03-28 | Evonik Degussa GmbH | Corps creux multicouches tres resistant au lavage |
Also Published As
Publication number | Publication date |
---|---|
EP4367185A1 (fr) | 2024-05-15 |
FR3125052A1 (fr) | 2023-01-13 |
KR20240032898A (ko) | 2024-03-12 |
CN117616085A (zh) | 2024-02-27 |
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