EP3969256A1 - Mehrschichtstruktur zum transport oder zur speicherung von wasserstoff - Google Patents
Mehrschichtstruktur zum transport oder zur speicherung von wasserstoffInfo
- Publication number
- EP3969256A1 EP3969256A1 EP21708055.5A EP21708055A EP3969256A1 EP 3969256 A1 EP3969256 A1 EP 3969256A1 EP 21708055 A EP21708055 A EP 21708055A EP 3969256 A1 EP3969256 A1 EP 3969256A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- polyamide
- weight
- multilayer structure
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 118
- 229920002647 polyamide Polymers 0.000 claims abstract description 114
- 239000004952 Polyamide Substances 0.000 claims abstract description 113
- 229920000642 polymer Polymers 0.000 claims abstract description 82
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 57
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 39
- 239000011230 binding agent Substances 0.000 claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 34
- 239000004014 plasticizer Substances 0.000 claims abstract description 30
- 238000007789 sealing Methods 0.000 claims abstract description 30
- 230000004888 barrier function Effects 0.000 claims abstract description 27
- 239000002657 fibrous material Substances 0.000 claims abstract description 18
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 16
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 16
- 230000002787 reinforcement Effects 0.000 claims abstract description 16
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims abstract description 15
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002033 PVDF binder Substances 0.000 claims abstract description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 7
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 3
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 3
- 229920000571 Nylon 11 Polymers 0.000 claims description 71
- 230000003014 reinforcing effect Effects 0.000 claims description 49
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 36
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 36
- 239000004593 Epoxy Substances 0.000 claims description 31
- 238000004078 waterproofing Methods 0.000 claims description 29
- 229920006152 PA1010 Polymers 0.000 claims description 22
- 238000011955 best available control technology Methods 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 13
- 239000003822 epoxy resin Substances 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229920006396 polyamide 1012 Polymers 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 238000010101 extrusion blow moulding Methods 0.000 claims description 5
- 238000009730 filament winding Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000001175 rotational moulding Methods 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229920006125 amorphous polymer Polymers 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims description 2
- 229920006659 PA12 Polymers 0.000 claims 9
- 229920002748 Basalt fiber Polymers 0.000 claims 1
- 229920006177 crystalline aliphatic polyamide Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 273
- 229920000299 Nylon 12 Polymers 0.000 description 41
- 229920001577 copolymer Polymers 0.000 description 27
- 229920000098 polyolefin Polymers 0.000 description 22
- 239000005977 Ethylene Substances 0.000 description 19
- 229920002614 Polyether block amide Polymers 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 229920006345 thermoplastic polyamide Polymers 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000000654 additive Substances 0.000 description 13
- -1 aliphatic diamine Chemical class 0.000 description 13
- 230000035699 permeability Effects 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 12
- 150000004985 diamines Chemical class 0.000 description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000002667 nucleating agent Substances 0.000 description 10
- 239000000565 sealant Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 description 9
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000470 constituent Substances 0.000 description 7
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 239000004416 thermosoftening plastic Substances 0.000 description 6
- 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 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 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
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 230000007717 exclusion Effects 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000012760 heat stabilizer Substances 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 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
- 239000003381 stabilizer Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 229920006114 semi-crystalline semi-aromatic polyamide Polymers 0.000 description 4
- 229920006135 semi-crystalline thermoplastic polymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004634 thermosetting polymer Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229920000305 Nylon 6,10 Polymers 0.000 description 3
- 239000004708 Very-low-density polyethylene Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229920001866 very low density polyethylene Polymers 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 108010021519 haematoporphyrin-bovine serum albumin conjugate Proteins 0.000 description 2
- 229920006017 homo-polyamide Polymers 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- DHRXPBUFQGUINE-UHFFFAOYSA-N n-(2-hydroxypropyl)benzenesulfonamide Chemical compound CC(O)CNS(=O)(=O)C1=CC=CC=C1 DHRXPBUFQGUINE-UHFFFAOYSA-N 0.000 description 2
- OHPZPBNDOVQJMH-UHFFFAOYSA-N n-ethyl-4-methylbenzenesulfonamide Chemical compound CCNS(=O)(=O)C1=CC=C(C)C=C1 OHPZPBNDOVQJMH-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 2
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- 229920006260 polyaryletherketone Polymers 0.000 description 2
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- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
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- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 1
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- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
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- 229920000297 Rayon Polymers 0.000 description 1
- 229920001872 Spider silk Polymers 0.000 description 1
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 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
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
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- 239000011247 coating layer Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
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- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000009792 diffusion process Methods 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
- 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
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002557 mineral fiber Substances 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
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- Y02E60/32—Hydrogen storage
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
- Y02P90/45—Hydrogen technologies in production processes
Definitions
- TITLE MULTI-LAYER STRUCTURE FOR THE TRANSPORT OR STORAGE OF
- the present patent application relates to composite multilayer structures for the transport, distribution or storage of hydrogen, in particular for the distribution or storage of hydrogen, and their manufacturing process.
- Hydrogen tanks are a subject that is currently attracting a lot of interest from many manufacturers, especially in the automotive field.
- One of the goals is to offer vehicles that pollute less and less.
- electric or hybrid vehicles comprising a battery aim to gradually replace thermal vehicles, such as gasoline or diesel vehicles.
- thermal vehicles such as gasoline or diesel vehicles.
- the battery is a relatively complex component of the vehicle.
- the electric vehicle still suffers today from several problems, namely the autonomy of the battery, the use in these rare earth batteries whose resources are not inexhaustible, recharging times much longer than the durations. tank filling, as well as a problem of electricity production in the different countries to be able to recharge the batteries.
- Hydrogen therefore represents an alternative to the electric battery since hydrogen can be transformed into electricity by means of a fuel cell and thus power electric vehicles.
- Hydrogen tanks generally consist of a metal casing (liner or sealing layer) which must prevent the permeation of hydrogen.
- liner or sealing layer One of the types of tanks being considered, called Type IV, is based on a thermoplastic liner around which a composite is wrapped.
- thermoplastic resin liner or sealing sheath
- a reinforcing structure made up of fibers (glass, aramid, carbon). called sheath or reinforcing layer which allow to work at much higher pressures while reducing the mass and avoiding the risk of explosive rupture in the event of severe external attacks.
- the permeability of the liner is indeed a key factor in limiting hydrogen losses from the tank;
- the first generation of type IV tanks used a liner based on high density polyethylene (HDPE).
- HDPE high density polyethylene
- HDPE has the drawback of having too low a melting temperature and high hydrogen permeability, which is a problem with the new thermal withstand requirements and does not allow the filling speed of the tank to be increased. tank.
- PA6 polyamide
- Application US2014 / 008373 describes a lightweight storage cylinder for a high pressure compressed gas, the cylinder having a liner wrapped in a stress layer, the liner comprising: a first inner layer of impact modified polyamide (PA) in contact with gas, an outer thermoplastic layer in contact with the stress layer; and an adhesive tie layer between the first impact modified inner PA layer and the outer thermoplastic layer.
- PA impact modified polyamide
- French application FR2923575 describes a reservoir for storing fluid under high pressure comprising at each of its ends along its axis a nozzle metal end, a liner enveloping said end caps and a structural layer of fiber impregnated with thermosetting resin enveloping said liner.
- WO1 8155491 describes a hydrogen transport component having a three-layer structure, the inner layer of which is a composition consisting of PA11, 15 to 50% of an impact modifier and 1 to 3% of plasticizer or without plasticizer which exhibits hydrogen barrier properties, good flexibility and durability at low temperature.
- this structure is suitable for pipes for transporting hydrogen but not for storing hydrogen.
- the matrix of the composite in order to optimize its mechanical resistance at high temperature and on the other hand the material composing the sealing sheath, in order to optimize its processing temperature.
- the possible modification of the composition of the material composing the sealing sheath, which will be made, must not result in a significant increase in the manufacturing temperature (extrusion-blow molding, injection, rotomoulding, etc.) of this liner, compared to what is practiced today.
- the present invention therefore relates to a multilayer structure intended for the transport, distribution and storage of hydrogen, in particular for the storage of hydrogen, comprising from the inside to the outside a sealing layer (1) and at least one composite reinforcing layer (2), said waterproofing layer comprising from the inside to the outside: a layer (a) consisting of a composition mainly comprising: a thermoplastic polyamide polymer with a short chain and whose Tf , as measured according to ISO 11357-3: 2013, is greater than 160 ° C, in particular greater than 170 ° C, more than 15% and up to 50% of impact modifier, or comprising mainly: a thermoplastic polyamide polymer with long semi-crystalline chain and whose Tm, as measured according to ISO 11357-3: 2013, is greater than 160 ° C, in particular greater than 170 ° C, up to 50% by weight of impact modifier, in particular up to less than 15% by weight of impact modifier, in particular up to 12% by weight of impact modifier relative to the total weight of the composition, up to 3% by weight of plasticizer relative to
- PVDF corresponds to polyvinylidene fluoride.
- EVOH stands for ethylene vinyl alcohol.
- the Tm of the short-chain polyamide thermoplastic polymer is greater than 200 ° C.
- thermoplastic polyamide polymer with a short semi-crystalline chain strongly impact modified or long semi-crystalline chain and comprising a proportion of impact modifier and plasticizer limited above and above.
- a barrier layer for the waterproofing layer, with a different polymer for the matrix of the composite and in particular an epoxy resin or epoxy-based, said composite being wound on the waterproofing layer, made it possible to obtain a structure suitable for transporting, distributing or storing hydrogen and in particular an increase in the maximum temperature of use which can go up to 120 ° C, thus making it possible to increase the filling speed of the tanks.
- multilayer structure should be understood to mean a reservoir comprising or made up of several layers, namely a sealing layer comprising at least three layers and at least one reinforcing layer, in particular a single reinforcing layer.
- the multilayer structure is therefore meant to the exclusion of a pipe or tube.
- the tank can be a tank for the mobile storage of hydrogen, i.e. on a truck for the transport of hydrogen, on a car for the transport of hydrogen and the supply of hydrogen d '' a fuel cell for example, on a train for the supply of hydrogen or on a drone for the supply of hydrogen, but it can also be a stationary storage tank for hydrogen in a station for the distribution of hydrogen to vehicles.
- said short-chain or long-chain thermoplastic polyamide polymer of layer (a) is to the exclusion of a polyether block amide (PEBA).
- PEBA polyether block amide
- Poly ether block amide are copolymers with amide units (Ba1) and polyether units (Ba2), said amide unit (Ba1) corresponding to an aliphatic repeating unit chosen from a unit obtained from at least one amino acid or a unit obtained from at least one lactam, or an XY unit obtained from polycondensation:
- diamine being preferably chosen from a linear or branched aliphatic diamine or a mixture thereof, and
- dicarboxylic acid being preferably chosen from: a linear or branched aliphatic dicacid, or a mixture of these, said diamine and said dicacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms; said polyether units (Ba2) being in particular derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol.
- composition of layer (a) is devoid of nucleating agent.
- Nucleating agents are known to those skilled in the art and refer to a substance which, when incorporated into a polymer, forms nuclei for crystal growth in the molten polymer.
- They can be chosen, for example, from micro talc, carbon black, silica, titanium dioxide and nanoclays.
- said short-chain or long-chain thermoplastic polyamide polymer of layer (a) is to the exclusion of a polyether block amide (PEBA) and said composition of layer (a) is devoid of agent. nucleating.
- PEBA polyether block amide
- said short-chain or long-chain polyamide thermoplastic polymer of layer (b) is to the exclusion of a polyether block amide (PEBA).
- said composition of layer (b) is devoid of nucleating agent
- said short-chain or long-chain thermoplastic polyamide polymer of layer (b) is excluding a polyether block amide (PEBA) and said composition of layer (b) is devoid of agent. nucleating.
- PEBA polyether block amide
- said short-chain or long-chain thermoplastic polyamide polymer of layer (a) and of layer (b) is to the exclusion of a polyether block amide (PEBA).
- PEBA polyether block amide
- said composition of layer (a) and of layer (b) is devoid of nucleating agent.
- said short-chain or long-chain thermoplastic polyamide polymer of layer (a) and of layer (b) is excluding a polyether block amide (PEBA) and said composition of the layer ( a) and layer (b) is devoid of nucleating agent.
- PEBA polyether block amide
- said multilayer structure consists of a waterproofing layer and a reinforcing layer.
- the sealing layer (1) is impermeable to hydrogen at 23 ° C, that is to say that the permeability to hydrogen at 23 ° C is less than 500 cc.mm/m2. 24h. .atm at 23 ° C under 0% relative humidity (RH).
- PA11 is excluded from the composition of layer (a).
- PA11 is excluded from the composition of layer (b).
- PA11 is excluded from the composition of layer (a) and from the composition of layer (b).
- the composite reinforcing layer (s) is (are) wound (s) around the waterproofing layer by means of tapes (or tapes or rovings) of fibers impregnated with polymer which are deposited, for example, by filament winding.
- the polymers are different.
- the polymers of the reinforcing layers are identical, there may be several layers present, but advantageously, only one reinforcing layer is present and which then has at least one complete winding around the waterproofing layer.
- the outermost layer (b) of said sealing layer may or may not adhere to the outermost layer. internal of said composite reinforcement.
- the other composite reinforcement layers may or may not also adhere to each other.
- the other waterproofing layers may or may not adhere to each other.
- only a waterproofing layer and a reinforcing layer are present and do not adhere to each other.
- the reinforcing layer consists of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least one polymer P1j , in particular an epoxy resin or based on epoxy.
- a waterproofing layer and a reinforcing layer are present and do not adhere to each other and the reinforcing layer consists of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising a polymer P1j which is an epoxy resin or epoxy-based.
- epoxy-based throughout the description means that the epoxy represents at least 50% by weight of the matrix.
- Each of said layers (a) and (b) consists of a composition predominantly comprising at least one short-chain semi-crystalline polyamide thermoplastic polymer or a long-chain semi-crystalline polyamide thermoplastic polymer.
- the short chain expression means that the polyamide has a number of carbon atoms per nitrogen atom ranging from 4 to less than 8, in particular from 6 to less than 8.
- the long chain expression means that the polyamide has a number of carbon atoms per nitrogen atom greater than or equal to 8, preferably greater than 9, in particular greater than 10.
- the term “predominantly” means that said at least one polymer is present in more than 50% by weight relative to the total weight of the composition.
- said at least one majority polymer is present at more than 60% by weight, in particular at more than 70% by weight, particularly at more than 80% by weight, more particularly greater than or equal to 90% by weight relative to the total weight of the composition.
- Said composition of layer (a) when the polyamide is long chain can also comprise up to 50% by weight relative to the total weight of the composition of impact modifiers and / or up to 3% by weight of plasticizer and / or up to 5% additives.
- the additives can be selected from another polymer, an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and carbonaceous nanofillers, with the exception of a nucleating agent, in particular the additives are chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and carbonaceous nanofillers, except for a nucleating agent.
- Said other polymer can be another semi-crystalline thermoplastic polymer or a different polymer and in particular an EVOH (Ethylene vinyl alcohol).
- EVOH Ethylene vinyl alcohol
- said composition of layer (a) comprises said thermoplastic polyamide polymer with a predominantly long chain, from 0 to 50% by weight of impact modifier, in particular from 0 to less than 15% of impact modifier, in particular from 0 to 12% of impact modifier, from 0 to 3% of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
- said composition of layer (a) consists of said thermoplastic polyamide polymer with a predominantly long chain, from 0 to 50% by weight of impact modifier, in particular from 0 to less than 15% of impact modifier, in particular from 0 to 12 % impact modifier, 0 to 3% plasticizer and 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
- only one major polymer is present in the sealant layer.
- said composition of layer (a) comprises an impact modifier of 0.1 to 50% by weight, in particular from 0.1 to less than 15% by weight, in particular from 0.1 to 12% by weight of impact modifier relative to the total weight of the composition. In one embodiment, said composition of layer (a) is devoid of plasticizer.
- said composition of layer (a) comprises an impact modifier from 0.1 to 50% by weight, in particular from 0.1 to less than 15% by weight, in particular from 0.1 to 12% by weight. % by weight of impact modifier and said composition of layer (a) is devoid of plasticizer relative to the total weight of the composition.
- said composition of layer (a) comprises an impact modifier from 0.1 to 50% by weight, in particular from 0.1 to less than 15% by weight, and from 0.1 to 1 5% by weight of plasticizer relative to the total weight of the composition.
- Said composition of layer (a) when the polyamide is short chain also comprises more than 15% by weight and up to 50% by weight of impact modifier relative to the total weight of the composition and / or up to 3% by weight. weight of plasticizer and / or up to 5% additives.
- the additives can be selected from another polymer, an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and carbonaceous nanofillers, with the exception of a nucleating agent, in particular the additives are chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and carbonaceous nanofillers, except for a nucleating agent.
- Said other polymer can be another semi-crystalline thermoplastic polymer or a different polymer and in particular an EVOH (Ethylene vinyl alcohol).
- EVOH Ethylene vinyl alcohol
- said composition of layer (a) comprises said predominantly short-chain polyamide thermoplastic polymer, from more than 15% to 50% by weight of impact modifier, in particular from 20% by weight to 50% of impact modifier, in particular of 30% by weight to 40% by weight of impact modifier, from 0 to 3% of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
- said composition of layer (a) consists of said predominantly short-chain thermoplastic polyamide polymer, from more than 15% to 50% by weight of impact modifier, in particular from 20% by weight to 50% of impact modifier, from 0 3% plasticizer and 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
- only one major polymer is present in the sealant layer.
- said composition of layer (a) comprises an impact modifier of more than 15% to 50% by weight of impact modifier, in particular from 20% by weight to 50% of impact modifier, relative to the total weight of the composition.
- said composition of layer (a) is devoid of plasticizer.
- said composition of layer (a) comprises an impact modifier of 0.1 to 50% by weight, in particular from 0.1 to less than 15% by weight, in in particular from 0.1 to 12% by weight of impact modifier and said composition of layer (a) is devoid of plasticizer relative to the total weight of the composition.
- said composition of layer (a) comprises an impact modifier from 0.1 to 50% by weight, in particular from 0.1 to less than 15% by weight, and from 0.1 to 1 5% by weight of plasticizer relative to the total weight of the composition.
- layer (b) it has the same characteristics as detailed above for layer (a) whether it is short-chain polyamide or long-chain polyamide.
- the polyamide of layer (a) and that of layer (b) can be identical or different, in particular they are identical.
- thermoplastic polyamide polymer or semi-crystalline thermoplastic polyamide polymer is understood to mean a material which is generally solid at room temperature, and which softens during an increase in temperature, in particular after passing its glass transition temperature (Tg), and which may present a clear melting on passing of its so-called melting temperature (Tm), and which becomes solid again when the temperature drops below its crystallization temperature.
- Tg, Te and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2: 2013 and 11357-3: 2013 respectively.
- the number-average molecular mass Mn of said semi-crystalline polyamide thermoplastic polymer is preferably in a range from 10,000 to 85,000, in particular from 10,000 to 60,000, preferably from 10,000 to 50,000, even more preferably from 12,000 to 50,000. These Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in m-cresol according to ISO 307: 2007 but by changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20 ° C).
- the polyamide can be a homopolyamide or a copolyamide or a mixture thereof.
- said thermoplastic polymer is a long-chain aliphatic polyamide, that is to say a polyamide having an average number of carbon atoms per nitrogen atom greater than or equal to 8, preferably greater than 9, in particular greater than 10.
- the long chain aliphatic polyamide is chosen from: polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture thereof or a copolyamide thereof, in particular PA11 and PA12.
- polyamide 11 PA11
- PA12 polyamide 12
- PA1012 polyamide 1012
- PA1012 polyamide 1212
- PA1012 polyamide 1212
- PA1012 polyamide 1212
- the long chain aliphatic polyamide is chosen from: polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these- ci or a copolyamide thereof, in particular PA12.
- the long chain aliphatic polyamide is selected from: polyamide 12 (PA12), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these or a copolyamide of those here, in particular PA12.
- said thermoplastic polymer is a short-chain aliphatic polyamide, that is to say a polyamide having a number of carbon atoms per nitrogen atom of from 4 to less than 8, in particular of 6 to less than 8.
- the short-chain aliphatic polyamide is chosen from PA6, PA66 and PA6 / 66.
- soldering elements made of thermoplastic polyamide polymer.
- thermoplastic polyamide polymer it can be used heated blades with or without contact, ultrasound, infrared, application of vibrations, a rotation of one element to be welded against the other or even laser welding.
- the impact modifier can be any impact modifier from the moment when a polymer of lower modulus than that of the resin, exhibiting good adhesion with the matrix, so as to dissipate the cracking energy.
- the impact modifier is advantageously constituted by a polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178 standard and of Tg less than 0 ° C (measured according to the 11357-2 standard at the inflection point of the DSC thermogram ), in particular a polyolefin.
- PEBAs are excluded from the definition of impact modifiers.
- 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.
- the polyolefin has been designated by (B) and functionalized polyolefins (B1) and unfunctionalized polyolefins (B2) have been described below.
- An unfunctionalized polyolefin (B2) is conventionally a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
- alpha olefins or diolefins such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
- LLDPE linear low density polyethylene, or linear low density polyethylene
- VLDPE very low density polyethylene, or very low density polyethylene
- metallocene polyethylene metallocene polyethylene
- ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
- EPR abbreviation of ethylene-propylene-rubber
- EPDM ethylene / propylene / diene
- SEBS 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.
- polyolefins (B2) grafted or co- or ter polymerized with unsaturated epoxides such as glycidyl (meth) acrylate, or with carboxylic acids or the corresponding salts or esters such as (meth) acrylic acid (the latter being able to be totally or partially neutralized by metals such as Zn, etc.) or alternatively by carboxylic acid anhydrides such as maleic anhydride.
- 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 from 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:
- - ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
- EPR abbreviation of ethylene-propylene-rubber
- EPDM ethylene / propylene / diene
- SEBS ethylene-butene / styrene
- SBS styrene / butadiene / styrene
- SIS isoprene / styrene
- SEPS styrene / ethylene-propylene / styrene
- alkyl (meth) acrylate copolymers containing up to 40% by weight of alkyl (meth) acrylate;
- the functionalized polyolefin (B1) can also be chosen from ethylene / propylene copolymers predominantly in propylene grafted with maleic anhydride then condensed with mono-amine 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 vinyl ester of saturated carboxylic acid and (3) anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate.
- (meth) acrylic acid can be salified with Zn or Li.
- alkyl (meth) acrylate in (B1) or (B2) denotes methacrylates and acrylates of C1 to C8 alkyl, and may be chosen from methyl acrylate, ethyl acrylate , n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
- the aforementioned polyolefins (B1) can also be crosslinked by any suitable process or agent (diepoxy, diacid, peroxide, etc.); the term functionalized polyolefin also includes mixtures of the aforementioned polyolefins with a difunctional reagent such as as diacid, dianhydride, diepoxy, etc. capable of reacting with these or mixtures of at least two functionalized polyolefins capable of reacting with each other.
- a difunctional reagent such as as diacid, dianhydride, diepoxy, etc.
- copolymers mentioned above, (B1) and (B2) can be copolymerized in a random or block fashion and have a linear or branched structure.
- the molecular weight, the MFI number, the density of these polyolefins can also vary to a large extent, which will be appreciated by those skilled in the art.
- MFI short for Melt Flow Index, is the melt flow index. It is measured according to standard ASTM 1238.
- the unfunctionalized polyolefins (B2) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and of a comonomer of higher alpha olefinic type. such as butene, hexene, octene or 4-methyl 1-Pentene.
- PPs high density PE, medium density PE, linear low density PE, low density PE, very low density PE.
- polyethylenes are known to those skilled in the art as being produced according to a “radical” process, according to a “Ziegler” type catalysis or, more recently, according to a so-called “metallocene” catalysis.
- the functionalized polyolefins (B1) are chosen from any polymer comprising alpha olefinic units and units bearing polar reactive functions such as epoxy, carboxylic acid or carboxylic acid anhydride functions.
- polymers mention may be made of the ter polymers of ethylene, of alkyl acrylate and of maleic anhydride or of glycidyl methacrylate, such as Lotader® from the Applicant or polyolefins grafted with l.
- maleic anhydride such as Orevac® from the Applicant as well as ter polymers of ethylene, of alkyl acrylate and of (meth) acrylic acid.
- Mention may also be made of homopolymers or copolymers of polypropylene grafted with a carboxylic acid anhydride and then condensed with polyamides or mono-amino polyamide oligomers.
- said constituent composition of said sealant layer or layers is devoid of polyether block amide (PEBA).
- PEBAs are therefore excluded from the impact modifiers.
- said transparent composition is devoid of core-shell particles or “core-shell” core-shell polymers.
- core-shell particle it is necessary to understand a particle of which the first layer forms the core and the second or all of the following layers form the respective shell.
- the core-shell particle can be obtained by a multi-step process comprising at least two steps. Such a method is described for example in documents US2009 / 0149600 or EP0722961. Regarding the plasticizer
- the plasticizer can be a plasticizer commonly used in compositions based on polyamide (s).
- a plasticizer which has good thermal stability so that no fumes are formed during the stages of mixing the various polymers and of processing the composition obtained.
- this plasticizer can be chosen from: benzene sulfonamide derivatives such as n-butyl benzene sulfonamide (BBSA), ortho and para isomers of ethyl toluene sulfonamide (ETSA), N-cyclohexyl toluene sulfonamide and N- (2-hydroxypropyl) benzenesulfonamide (HP-BSA), esters of hydroxybenzoic acids such as 2-ethylhexyl para-hydroxybenzoate
- BBSA n-butyl benzene sulfonamide
- ETSA ethyl toluene sulfonamide
- HP-BSA N- (2-hydroxypropyl) benzenesulfonamide
- esters of hydroxybenzoic acids such as 2-ethylhexyl para-hydroxybenzoate
- EHPB 2-decylhexyl para-hydroxybenzoate
- HDPB 2-decylhexyl para-hydroxybenzoate
- esters or ethers of tetrahydrofurfuryl alcohol such as oligoethyleneoxy-tetrahydrofurfurylalcohol
- esters of citric acid or hydroxymalonic acid such as oligoethylene oxymalonate.
- a preferred plasticizer is n-butyl benzene sulfonamide (BBSA).
- Another more particularly preferred plasticizer is N- (2-hydroxy-propyl) benzene sulfonamide (HP-BSA).
- HP-BSA N- (2-hydroxy-propyl) benzene sulfonamide
- the polymer P1j can be a thermoplastic polymer or a thermosetting polymer.
- One or more composite reinforcement layers may or may be present.
- the term “predominantly” means that said at least one polymer is present in more than 50% by weight relative to the total weight of the composition and of the matrix of the composite.
- said at least one major polymer is present at more than 60% by weight, in particular at more than 70% by weight, particularly at more than 80% by weight, more particularly greater than or equal to 90% by weight, relative to the weight total composition
- Said composition can also comprise impact modifiers and / or additives.
- the additives can be selected from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a plasticizer and a colorant, except for a nucleating agent.
- said composition consists of said thermoplastic polymer P1j predominantly, from 0 to 15% by weight of impact modifier, in particular from 0 to 12% by weight of impact modifier, from 0 to 5% by weight of additives, the sum of constituents of the composition being equal to 100% by weight.
- Said at least one majority polymer of each layer may be identical or different.
- a single major polymer is present at least in the composite reinforcing layer and which does not adhere to the waterproofing layer.
- each reinforcing layer comprises the same type of polymer, in particular an epoxy or epoxy-based resin.
- thermoplastic or thermoplastic polymer
- Tg temperature of glass transition
- Tf melting temperature
- Tg, Te and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2: 2013 and 11357-3: 2013 respectively.
- the number average molecular weight Mn of said thermoplastic polymer is preferably in a range of 10,000 to 40,000, preferably 10,000 to 30,000. These Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in the m-cresol according to ISO 307: 2007 but changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20 ° C).
- polyamides in particular comprising an aromatic and / or cycloaliphatic structure
- copolymers for example polyamide-polyethers, polyesters, copolymers, polyaryletherketones (PAEK), polyetherether ketones (PEEK), polyetherketone ketones (PEKK), polyetherketoneetherketone ketones (PEKEKK), polyimides in particular polyetherimides (PEI) or polyamide-imides (in particular PSU )sulfones, polylsulfones polyarylsulfones such as polyphenyl sulfones
- PAEK polyaryletherketones
- PEEK polyetherether ketones
- PEKK polyetherketone ketones
- PEKEKK polyetherketoneetherketone ketones
- PEI polyetherimides
- PSU polyamide-imides
- PPSU polyethersulfones
- semi-crystalline polymers are more particularly preferred, and in particular polyamides and their semi-crystalline copolymers.
- the polyamide can be a homopolyamide or a copolyamide or a mixture thereof.
- the semi-crystalline polyamides are semi-aromatic polyamides, in particular a semi-aromatic polyamide of formula X / YAr, as described in EP1505099, in particular a semi-aromatic polyamide of formula A / XT in which A is chosen from a unit obtained from an amino acid, a unit obtained from a lactam and a unit corresponding to the formula (diamine in Ca).
- (Cb diacid) with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the unit (Ca diamine) being chosen from aliphatic, linear or branched diamines, cycloaliphatic diamines and alkylaromatic diamines and the unit (Cb diacid) being chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids and aromatic diacids ;
- XT denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid, with x representing the number of carbon atoms of the Cx diamine, x being between 5 and 36, advantageously between 9 and 18, in particular a polyamide of formula A / 5T, A / 6T, A / 9T, A / 10T or A / 11 T, A being as defined above, in particular a polyamide chosen from a PA MPMDT / 6T, one PA11 / 10T, one PA 5T / 10T, one PA 11 / BACT, one PA 11 / 6T / 10T, one PA MXDT / 10T, one PA MPMDT / 10T, one PA BACT / 10T, one PA BACT / 6T, PA BACT / 10T / 6T, one PA 11 / BACT / 6T, PA 11 / MPMDT / 10T, PA 11 / B
- T corresponds to terephthalic acid
- MXD corresponds to m-xylylenediamine
- MPMD corresponds to methylpentamethylene diamine
- BAC corresponds to bis (aminomethyl) cyclohexane.
- Said semi-aromatic polyamides defined above have in particular a Tg greater than or equal to 80 ° C.
- thermosetting polymers are chosen from epoxy or epoxy-based resins, polyesters, vinyl esters and polyurethanes, or a mixture of these, in particular epoxy or epoxy-based resins.
- each composite reinforcing layer consists of a composition comprising the same type of polymer, in particular an epoxy or epoxy-based resin.
- Said composition comprising said polymer P1j may be transparent to radiation suitable for welding.
- the winding of the composite reinforcing layer around the waterproofing layer is carried out in the absence of any subsequent welding.
- the binder can be an adhesive composition as described in EP2098580, that is to say an adhesive composition comprising:
- At least one polyamide noted B having a melting point greater than or equal to 180 ° C and an average number of carbon atoms per nitrogen atom noted CB between 7 and 10, advantageously between 7.5 and 9.5 ;
- At least one polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted CC of between 9 and 18, advantageously between 10 and 18; at least 50% by weight of said composition being formed from one or more polyamides chosen from polyamides A, B and C, the weighted average of the enthalpies of fusion of these polyamides within said composition being greater than 25J / g (DSC), the average number of carbon atoms per nitrogen atom of polyamides A, B and C also satisfying the following strict equation: CA ⁇ CB ⁇ CC.
- the binder can also be, for example, but without being limited to these, a composition based on 50% copolyamide 6/12 (of 70/30 ratio by weight) of Mn 16000, and 50% copolyamide 6/12 (ratio 30/70 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 ( of Mn 30,000, and as defined elsewhere) and of 36% of PA6 (of Mn 28,000) and of 1.2% of organic stabilizers (consisting of 0.8% of Lowinox 44B25 phenol from Great Lakes, of 0.2% of Irgafos phosphite 168 from the company Ciba, 0.2% anti-UV Tinuvin 312 from the company Ciba), a composition based on PA612 (of Mn 29000, and as defined elsewhere) and of 36% of PA6 (of Mn 28000
- barrier layer designates a layer having characteristics of low permeability and good resistance to hydrogen, that is to say that the barrier layer slows down the passage of hydrogen into the other layers of the structure. or even outside the structure.
- the barrier layer is therefore a layer that allows, above all, not to lose too much hydrogen in the atmosphere by diffusion, thus avoiding problems of explosion and ignition.
- barrier materials can be low carbon polyamides, that is to say whose average number of carbon atoms (C) relative to the nitrogen atom (N) is less than 9, preferably semi- crystalline and high-melting point, polyphthalamides and / or also non-polyamide barrier materials such as very crystalline polymers such as the copolymer of ethylene and vinyl alcohol (noted EVOH below), or even fluorinated materials functionalized such as functionalized polyvinylidene fluoride (PVDF), functionalized ethylene-tetrafluoroethylene (ETFE) copolymer, functionalized ethylene, tetrafluoroethylene and hexafluoro-propylene (EFEP) copolymer, polyphenylene sulfide (PPS) ) functionalized, functionalized polynaphthalate (PBN). Yes these polymers are not functionalized, so an intermediate binder layer can be added to ensure good adhesion within the MLT structure.
- PVDF functionalized polyvinylidene fluoride
- the EVOHs are particularly advantageous, in particular the richest in vivnyl alcohol comonomer as well as those modified impact because they make it possible to produce less fragile structures.
- barrier layer means in other words that said barrier layer is very poorly permeable to hydrogen, in particular the permeability to hydrogen at 23 ° C. is less than 75 cc.mm/m2.24h. atm at 23 ° C under 0% relative humidity (RH).
- the permeability can also be expressed in (cc.mm/m 2 .24h.Pa).
- the permeability must then be multiplied by 101325.
- Said multilayer structure therefore comprises a waterproofing layer and at least one composite reinforcing layer which is wrapped around the waterproofing layer and which may or may not adhere to each other.
- said sealing and reinforcing layer do not adhere to each other and consist of compositions which respectively comprise different polymers.
- said different polymers can be of the same type.
- the waterproofing layer consisting of a composition comprising an aliphatic polyamide
- the composite reinforcing layer consists of a composition comprising an aliphatic polyamide different from that of the waterproofing layer (for example PA11 for the layer. sealant and PA12 for the reinforcing layer or vice versa) or the composite reinforcing layer consists of a composition comprising a polyamide which is not aliphatic and which is for example a semi-aromatic polyamide so as to have of a high tg polymer as the matrix of the composite reinforcement.
- the waterproofing layer comprises from the inside to the outside: the layer (a), optionally a binder layer, the barrier layer, optionally a binder layer and the layer (b).
- Binder layers can be the same or different
- the sealant layer comprises from the inside to the outside: the layer (a), the barrier layer, a binder layer and the layer (b).
- the waterproofing layer comprises from the inside to the outside: the layer (a), a binder layer, the barrier layer, optionally a binder layer and the layer (b).
- the waterproofing layer comprises from the inside to the outside: the layer (a), a binder layer, the barrier layer and the layer (b). In one embodiment, the waterproofing layer comprises from the inside to the outside: the layer (a), optionally a binder layer, the barrier layer, a binder layer and the layer (b).
- the sealant layer comprises from the inside to the outside: the layer (a), the barrier layer, a binder layer and the layer (b).
- the sealant layer comprises from the inside to the outside: the layer (a), a binder layer, the barrier layer, a binder layer and the layer (b).
- the sealing layer may comprise one or more other layers, made of a thermoplastic polymer, below the layer (a) and one or more other layers, made of a thermoplastic polymer, above the layer ( b).
- the sealant layer is made from the inside to the outside: the layer (a), the barrier layer, a binder layer and the layer (b).
- the waterproofing layer is made up from the inside to the outside: the layer (a), a binder layer, the barrier layer, optionally a binder layer and the layer (b).
- the waterproofing layer is made from the inside to the outside: the layer (a), a binder layer, the barrier layer and the layer (b).
- the waterproofing layer consists of the interior to the exterior: the layer (a), optionally a binder layer, the barrier layer, a binder layer and the layer (b).
- the sealant layer is made from the inside to the outside: the layer (a), the barrier layer, a binder layer and the layer (b).
- the sealant layer is made up from the inside to the outside: the layer (a), a binder layer, the barrier layer, a binder layer and the layer (b).
- Said multilayer structure can include up to 10 composite reinforcement layers of different types.
- said multilayer structure comprises one, two, three, four, five, six, seven, eight, nine or ten layers of composite reinforcement.
- said multilayer structure comprises one, two, three, four or five composite reinforcement layers.
- said multilayer structure comprises one, two or three composite reinforcement layers.
- compositions which respectively comprise identical polymers consist of compositions which respectively comprise polymers of the same type.
- compositions which respectively comprise different polymers consist of compositions which respectively comprise different polymers.
- said multilayer structure comprises a sealing layer and a plurality of reinforcing layers, said reinforcing layer adjacent to the sealing layer being wrapped around said sealing layer and the other reinforcing layers being wrapped around of the directly adjacent reinforcement layer.
- said multilayer structure comprises a single waterproofing layer and a single composite reinforcing layer, said reinforcing layer being wrapped around said waterproofing layer.
- said polyamide of layers (a) and / or (b) is a short-chain aliphatic polyamide, in particular chosen from PA6, PA66 and PA6 / 66, or long-chain polyamide, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12, and said polymer P1j is an epoxy resin or an epoxy-based resin.
- said polyamide of layers (a) and (b) is a short-chain aliphatic polyamide, in particular chosen from PA6, PA66 and PA6 / 66, or long-chain, in particular chosen from PA1010 , PA 1012, PA 1212,
- PA11 and PA12 in particular PA11 and PA12, and said polymer P1j is an epoxy or epoxy-based resin.
- said polyamide of layer (a) is a short-chain aliphatic polyamide, in particular chosen from PA6, PA66 and PA6 / 66
- said polyamide of layer (b) is an aliphatic polyamide long chain, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12
- said polymer P1j is an epoxy resin or an epoxy-based resin.
- said polyamide of layer (a) is a long-chain aliphatic polyamide, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12, and said polyamide of layer (b) is a short-chain aliphatic polyamide, in particular chosen from PA6, PA66 and PA6 / 66, and said polymer P1j is an epoxy resin or based on epoxy.
- said polyamide of layers (a) and / or (b) is a short-chain aliphatic polyamide, in particular chosen from PA6, PA66 and PA6 / 66, or long-chain polyamide, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12, and said polymer P1j is a long-chain aliphatic polyamide, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12 , or a semi-aromatic polyamide, in particular chosen from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T and BACT / 10T.
- said polyamide of layers (a) and (b) is a short-chain aliphatic polyamide, in particular chosen from PA6, PA66 and PA6 / 66, or long-chain, in particular chosen from PA1010 , PA 1012, PA 1212,
- PA11 and PA12, in particular PA11 and PA12, and said polymer P1j is a long-chain aliphatic polyamide, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12, or a semi-aromatic polyamide, in particular chosen from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T and BACT / 10T.
- said polyamide of layers (a) and (b) is a short-chain aliphatic polyamide, in particular chosen from PA6, PA66 and PA6 / 66, and said polymer P1j is a long-chain aliphatic polyamide. chain, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12, or a semi-aromatic polyamide, in particular chosen from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T and BACT / 10T.
- said polyamide of layers (a) and (b) is a long-chain aliphatic polyamide, in particular chosen from PA1010,
- PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12, and said polymer P1j is a long-chain aliphatic polyamide, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12, or a semi-aromatic polyamide, in particular chosen from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T and BACT / 10T.
- said polyamide of layer (a) is a short-chain aliphatic polyamide, in particular chosen from PA6, PA66 and PA6 / 66
- said polyamide of layer (b) is an aliphatic polyamide long chain, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12
- said polymer P1j is a long chain aliphatic polyamide, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12, or a semi-aromatic polyamide, in particular chosen from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T and BACT / 10T.
- said polyamide of layer (a) is a long-chain aliphatic polyamide, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12
- said polyamide of layer (b) is a short-chain aliphatic polyamide, in particular chosen from PA6, PA66 and PA6 / 66
- said polymer P1j is a long-chain aliphatic polyamide, in particular chosen from PA1010, PA 1012, PA 1212, PA11 and PA12, in particular PA11 and PA12, or a semi-aromatic polyamide, in particular chosen from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T and BACT / 10T.
- each reinforcing layer consists of a composition comprising the same type of polymer P1j, in particular an epoxy resin or an epoxy-based resin.
- the polyamide P1j is identical for all the reinforcing layers.
- said multilayer structure further comprises at least one outer layer made of a continuous fiberglass fibrous material impregnated with a transparent amorphous polymer, said layer being the outermost layer of said multilayer structure.
- Said outer layer is a second but transparent reinforcing layer which makes it possible to put an inscription on the structure.
- constituent fibers of said fibrous material they are in particular fibers of mineral, organic or plant origin.
- said fibrous material can be sized or not sized.
- Said fibrous material can therefore comprise up to 3.5% by weight of an organic material (thermosetting or thermoplastic resin type) called sizing.
- fibers of mineral origin mention may be made of carbon fibers, glass fibers, basalt or basalt-based fibers, silica fibers, or silicon carbide fibers, for example.
- fibers of organic origin mention may be made of fibers based on a thermoplastic or thermosetting polymer, such as semi-aromatic polyamide fibers, aramid fibers or polyolefin fibers, for example.
- they are based on an amorphous thermoplastic polymer and have a glass transition temperature Tg greater than the Tg of the polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is amorphous, or greater than the Tm of the polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is semi-crystalline.
- they are based on a semi-crystalline thermoplastic polymer and have a melting point Tm greater than the Tg of the polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is amorphous, or greater than the Tm. polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is semi-crystalline.
- the organic fibers constituting the fibrous material during impregnation with the thermoplastic matrix of the final composite.
- the fibers of plant origin mention may be made of natural fibers based on flax, hemp, lignin, bamboo, silk, in particular spider silk, sisal, and other cellulose fibers, in particular viscose. These fibers of plant origin can be used pure, treated or else coated with a coating layer, with a view to facilitating the adhesion and the impregnation of the thermoplastic polymer matrix.
- the fibrous material can also be fabric, braided or woven with fibers.
- organic fibers can be mixed with mineral fibers to be pre-impregnated with thermoplastic polymer powder and to form the pre-impregnated fibrous material.
- the rovings of organic fibers can have several grammages. They can also have several geometries.
- the fibers constituting the fibrous material can also be in the form of a mixture of these reinforcing fibers of different geometries. Fibers are continuous fibers.
- the fibrous material is chosen from glass fibers, carbon fibers, basalt or basalt-based fibers, or a mixture of these, in particular carbon fibers.
- It is used as a wick or several wicks.
- the present invention relates to a method of manufacturing a multilayer structure as defined above, characterized in that it comprises a step of preparing the sealing layer by extrusion blow molding, by rotational molding, by injection and / or extrusion.
- said method of manufacturing a multilayer structure comprises a step of filament winding of the reinforcing layer as defined above around the sealing layer as defined above.
- Example 1 Permeability to hydrogen at 23 ° C of PA 11 liners and of a liner of the invention was tested.
- a 2mm sealing layer (liner) having five layers according to the invention constituting a tank of the invention was obtained by extrusion blow molding at a temperature suited to the nature of the various thermoplastic resins used.
- the liner has the following structure: PA11 // binder // EVOH // binder // PA11, the layers having the following respective thicknesses: (900pm // 50pm // 100pm // 50pm // 900pm).
- PA11 is a polyamide 11 of Mn (number molecular mass) 45,000.
- the melting point is 190 ° C., its enthalpy of fusion is 56 kJ / m 2 .
- the binder is a Tieflex S442® marketed by the company Arkema.
- EVOH is a 32% ethylene EVOH, type EVAL FP101B (Eval company)
- a wet filament winding process which consists in winding fibers around the liner, which fibers are previously pre-assembled. -impregnated in a bath of liquid epoxy or a bath based on liquid epoxy. The reservoir is then polymerized in an oven for 2 hours.
- the permeability of a PA11 liner and of a liner of the invention is measured according to a test which consists in sweeping the upper face of a film made of PA11 or made up of the five layers of the invention with the test gas (Hydrogen) and to measure by gas chromatography the flow which diffuses through the film in the lower part, swept by the carrier gas: nitrogen
- the permeability can also be expressed in (cc.mm/m 2 .24h.Pa). The permeability must then be multiplied by 101325.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Reinforced Plastic Materials (AREA)
- Moulding By Coating Moulds (AREA)
- Packages (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR2000818A FR3106648B1 (fr) | 2020-01-28 | 2020-01-28 | Structure multicouche pour le transport ou le stockage de l’hydrogene |
PCT/FR2021/050141 WO2021152255A1 (fr) | 2020-01-28 | 2021-01-26 | Structure multicouche pour le transport ou le stockage de l'hydrogene |
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EP3969256A1 true EP3969256A1 (de) | 2022-03-23 |
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EP21708055.5A Pending EP3969256A1 (de) | 2020-01-28 | 2021-01-26 | Mehrschichtstruktur zum transport oder zur speicherung von wasserstoff |
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US (1) | US20220364678A1 (de) |
EP (1) | EP3969256A1 (de) |
JP (1) | JP2023512009A (de) |
KR (1) | KR20220133961A (de) |
CN (1) | CN115003487A (de) |
CA (1) | CA3163639A1 (de) |
FR (1) | FR3106648B1 (de) |
MX (1) | MX2022008889A (de) |
WO (1) | WO2021152255A1 (de) |
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FR3124428A1 (fr) * | 2021-06-28 | 2022-12-30 | Arkema France | Structure multicouche pour le transport ou le stockage de l’hydrogene |
KR20230049396A (ko) * | 2021-10-06 | 2023-04-13 | 코오롱플라스틱 주식회사 | 폴리아미드 수지 조성물 및 이로 이루어진 성형품 |
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FR2629090B1 (fr) | 1988-03-24 | 1990-11-23 | Atochem | Copolymere greffe a base d'alpha-mono-olefine, son procede de fabrication, son application a la fabrication d'alliages thermoplastiques, alliages thermoplastiques obtenus |
US5526994A (en) * | 1994-12-01 | 1996-06-18 | Essef Corporation | Filament-wound isotensoid pressure vessels having geodesic domes |
US5534594A (en) | 1994-12-05 | 1996-07-09 | Rohm And Haas Company | Preparation of butadiene-based impact modifiers |
FR2858626B1 (fr) | 2003-08-05 | 2005-10-07 | Atofina | Polyamides semi aromatiques souple a faible reprise en humidite |
KR101106406B1 (ko) * | 2003-08-19 | 2012-01-17 | 솔베이 어드밴스트 폴리머스 엘.엘.씨. | 충격 보강된 폴리아미드 필름 |
DE602005022494D1 (de) | 2004-11-22 | 2010-09-02 | Arkema Inc | Schlagzäh modifizierte thermoplastische harzzusammensetzung |
FR2923575A1 (fr) * | 2007-11-13 | 2009-05-15 | Michelin Soc Tech | Reservoir de fluide sous pression, methode et appareil pour la fabrication d'un tel reservoir. |
FR2928152B1 (fr) | 2008-03-03 | 2011-04-01 | Arkema France | Composition adhesive et structure comprenant au moins une couche de ladite composition |
DE112012001543T5 (de) * | 2011-04-01 | 2013-12-24 | Luxfer Canada Limited | Mehrschicht-Auskleidung für eine Hochdruckgasflasche |
HUE053820T2 (hu) | 2016-09-20 | 2021-07-28 | Alcon Inc | Eljárás kontaktlencsék elõállítására rajtuk tartós síkosító bevonatokkal |
CN110325777A (zh) | 2017-02-24 | 2019-10-11 | 株式会社普利司通 | 氢气输送部件 |
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2020
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2021
- 2021-01-26 CN CN202180011519.8A patent/CN115003487A/zh active Pending
- 2021-01-26 CA CA3163639A patent/CA3163639A1/fr active Pending
- 2021-01-26 JP JP2022545849A patent/JP2023512009A/ja active Pending
- 2021-01-26 KR KR1020227029678A patent/KR20220133961A/ko unknown
- 2021-01-26 US US17/620,363 patent/US20220364678A1/en active Pending
- 2021-01-26 WO PCT/FR2021/050141 patent/WO2021152255A1/fr unknown
- 2021-01-26 EP EP21708055.5A patent/EP3969256A1/de active Pending
- 2021-01-26 MX MX2022008889A patent/MX2022008889A/es unknown
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WO2021152255A1 (fr) | 2021-08-05 |
JP2023512009A (ja) | 2023-03-23 |
MX2022008889A (es) | 2022-08-15 |
US20220364678A1 (en) | 2022-11-17 |
FR3106648B1 (fr) | 2022-05-27 |
CN115003487A (zh) | 2022-09-02 |
KR20220133961A (ko) | 2022-10-05 |
CA3163639A1 (fr) | 2021-08-05 |
FR3106648A1 (fr) | 2021-07-30 |
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