EP4096922A1 - Mehrschichtstruktur zum transport oder zur speicherung von wasserstoff - Google Patents
Mehrschichtstruktur zum transport oder zur speicherung von wasserstoffInfo
- Publication number
- EP4096922A1 EP4096922A1 EP21708054.8A EP21708054A EP4096922A1 EP 4096922 A1 EP4096922 A1 EP 4096922A1 EP 21708054 A EP21708054 A EP 21708054A EP 4096922 A1 EP4096922 A1 EP 4096922A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- polymer
- polyamide
- composition
- multilayer structure
- 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 49
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title description 36
- 239000000203 mixture Substances 0.000 claims abstract description 103
- 229920002647 polyamide Polymers 0.000 claims abstract description 96
- 239000004952 Polyamide Substances 0.000 claims abstract description 95
- 229920000642 polymer Polymers 0.000 claims abstract description 82
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 65
- 238000007789 sealing Methods 0.000 claims abstract description 55
- 239000002131 composite material Substances 0.000 claims abstract description 53
- 239000004593 Epoxy Substances 0.000 claims abstract description 39
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 38
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 37
- 239000004014 plasticizer Substances 0.000 claims abstract description 31
- 239000002657 fibrous material Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920002614 Polyether block amide Polymers 0.000 claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- 239000002667 nucleating agent Substances 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 229920000571 Nylon 11 Polymers 0.000 claims description 66
- 239000000835 fiber Substances 0.000 claims description 34
- 238000011955 best available control technology Methods 0.000 claims description 32
- 238000004078 waterproofing Methods 0.000 claims description 32
- 230000002787 reinforcement Effects 0.000 claims description 18
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 13
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 13
- 229920006152 PA1010 Polymers 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 8
- 239000004917 carbon fiber Substances 0.000 claims description 8
- 238000001175 rotational moulding Methods 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920006345 thermoplastic polyamide Polymers 0.000 claims description 7
- 238000009730 filament winding Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000010101 extrusion blow moulding Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229920006125 amorphous polymer Polymers 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims 1
- 230000005923 long-lasting effect Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 176
- 229920000299 Nylon 12 Polymers 0.000 description 32
- 229920001577 copolymer Polymers 0.000 description 23
- 229920000098 polyolefin Polymers 0.000 description 22
- 239000005977 Ethylene Substances 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 16
- 239000000654 additive Substances 0.000 description 16
- 230000035699 permeability Effects 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 13
- 150000004985 diamines Chemical class 0.000 description 11
- 150000002431 hydrogen Chemical class 0.000 description 11
- -1 aliphatic diamine Chemical class 0.000 description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 239000000470 constituent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920002292 Nylon 6 Polymers 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920001903 high density polyethylene Polymers 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- 229920006396 polyamide 1012 Polymers 0.000 description 8
- 239000004700 high-density polyethylene Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000004416 thermosoftening plastic Substances 0.000 description 7
- 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
- 125000001931 aliphatic group Chemical group 0.000 description 6
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 229920006114 semi-crystalline semi-aromatic polyamide Polymers 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 239000004711 α-olefin Substances 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
- 239000002245 particle Substances 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- 229920006135 semi-crystalline thermoplastic polymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 239000004634 thermosetting polymer Substances 0.000 description 4
- 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 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004708 Very-low-density polyethylene Substances 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 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
- 239000003086 colorant Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 239000000314 lubricant 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
- 230000035939 shock Effects 0.000 description 3
- 229920001897 terpolymer 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
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004696 Poly ether ether ketone 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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 238000002474 experimental method Methods 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
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 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
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- 229920006260 polyaryletherketone Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
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- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
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- 239000004814 polyurethane Substances 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
- 239000011342 resin composition Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 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
- 244000198134 Agave sisalana Species 0.000 description 1
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 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
- 229920000339 Marlex Polymers 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
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 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
- 239000002253 acid Substances 0.000 description 1
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- 239000011425 bamboo Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 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
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- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
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- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
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- 239000011487 hemp Substances 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 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
- IJRVDOPVQJSPRP-UHFFFAOYSA-N octan-4-yl prop-2-enoate Chemical compound CCCCC(CCC)OC(=O)C=C IJRVDOPVQJSPRP-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 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
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/01—Applications for fluid transport or storage
- F17C2270/0165—Applications for fluid transport or storage on the road
- F17C2270/0168—Applications for fluid transport or storage on the road by vehicles
- F17C2270/0171—Trucks
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/01—Applications for fluid transport or storage
- F17C2270/0165—Applications for fluid transport or storage on the road
- F17C2270/0184—Fuel cells
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
-
- 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 EP3112421 describes a polyamide resin composition for a molded article intended for high pressure hydrogen, the composition comprising: a polyamide 6 resin (A); and a polyamide resin (B) having a melting point, as determined by DSC, which is not higher than the melting point of the polyamide 6 resin (A) + 20 ° C and a cooling crystallization temperature, such as determined by DSC, which is higher than the cooling crystallization temperature of the polyamide 6 resin (A).
- 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.
- Application EP3222668 describes a polyamide resin composition for a molded article intended for high pressure hydrogen, the composition comprising a polyamide resin (A) comprising a unit derived from hexamethylenediamine and a unit derived from an aliphatic dicarboxylic acid of 8 to 12 carbon atoms and an ethylene / ⁇ -olefin copolymer (B) modified with an unsaturated carboxylic acid and / or a derivative thereof.
- A polyamide resin
- B ethylene / ⁇ -olefin copolymer
- 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
- 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.
- thermoplastic polyamide polymer with a long semi-crystalline chain comprising a proportion of impact modifier and of limited plasticizer, for the sealing layer, with a different polymer for the matrix.
- 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 the transport, distribution or storage of hydrogen and in particular a increase in the maximum temperature of use up to 120 ° C, thus making it possible to increase the speed of filling the tanks.
- multilayer structure is meant a tank comprising or consisting of several layers, namely several sealing layers and several reinforcing layers, or one sealing layer and several reinforcing layers, or several sealing layers and a backing layer or a waterproofing layer and a backing layer.
- the multilayer structure is therefore meant to the exclusion of a pipe or tube.
- 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: - at least one diamine, said 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.
- 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.
- PA6 and PA610 are excluded from said composition.
- said structure being devoid of an outermost layer and adjacent to the outermost layer of composite reinforcement of polyamide polymer means that the structure is devoid of a layer of polyamide polymer situated above the layer. outermost composite reinforcement.
- said multilayer structure consists of two layers, a waterproofing layer and a reinforcing layer.
- the waterproofing layer or layers are the innermost layers compared to the composite reinforcing layers which are the outermost layers.
- 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.
- 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).
- the composite reinforcing layer (s) is (are) wound (s) around the sealing 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 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 P2j , 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 P2j polymer which is an epoxy or epoxy-based resin.
- epoxy-based throughout the description means that the epoxy represents at least 50% by weight of the matrix.
- sealing layer (s) and the thermoplastic polymer P1i One or more sealing 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.
- 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 90% by weight, relative to the total weight of the composition.
- Said composition can also comprise up to 50% by weight relative to the total weight of the composition of impact modifiers and / or a plasticizer and / or 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 comprises said thermoplastic polymer P1i predominantly, 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 1, 5% plasticizer and 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
- said composition consists of said thermoplastic polymer P1i predominantly, 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 1 , 5% plasticizer and 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
- Said at least one majority polymer of each layer may be identical or different.
- a single major polymer is present at least in the sealing layer which does not adhere to the composite reinforcing layer.
- said composition 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 by relative to the total weight of the composition.
- said composition is devoid of plasticizer.
- said composition 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 and said composition is devoid of plasticizer relative to the total weight of the composition.
- said composition 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 modifier. impact and from 0.1 to 1.5% by weight of plasticizer relative to the total weight of the composition.
- said composition is devoid of impact modifier.
- said composition comprises from 0.1 to 1.5% by weight of plasticizer relative to the total weight of the composition and said composition is devoid of impact modifier.
- said composition is devoid of impact modifier and plasticizer.
- said composition comprises said thermoplastic polymer P1i predominantly and from 0 to 5% by weight of additives, in particular from 0.1 to 5% of additives, the sum of the constituents of the composition being equal to 100%.
- said majority thermoplastic polymer P1i is mixed with another polyamide.
- said composition comprises said thermoplastic polymer P1i and from 0 to 5% by weight of additives, in particular from 0.1 to 5% of additives, the sum of the constituents of the composition being equal to 100%.
- said composition consists of said thermoplastic polymer P1i predominantly and from 0 to 5% by weight of additives, in particular from 0.1 to 5% of additives, the sum of the constituents of the composition being equal to 100%.
- said majority thermoplastic polymer P1i is mixed with another polyamide.
- said composition consists of said thermoplastic polymer P1i and from 0 to 5% by weight of additives, in particular from 0.1 to 5% of additives, the sum of the constituents of the composition being equal to 100%.
- thermoplastic or semi-crystalline thermoplastic polymer
- Tg glass transition temperature
- 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 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 8.5, 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 semi-crystalline polyamide thermoplastic polymer is a long-chain semi-crystalline semi-aromatic polyamide, that is to say a polyamide having an average number of carbon atoms per nitrogen atom. greater than 8.5, preferably greater than 9, in particular greater than 10, and a melting temperature of between 240 ° C to less than 280 ° C.
- the long-chain semi-crystalline semi-aromatic polyamide is chosen from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T and BACT / 10T.
- each waterproofing layer consists of a composition comprising the same type of polyamide.
- 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.
- LDPE low density polyethylene
- HDPE high density polyethylene
- 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).
- 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 styrene / 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 abovementioned polyolefins with a difunctional reagent such as diacid, dianhydride, diepoxy, and the like. capable of reacting with these or mixtures of at least two functionalized polyolefins capable of reacting with each other.
- a difunctional reagent such as diacid, dianhydride, diepoxy, and the like.
- 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.
- 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) benzene sulfonamide (HP-BSA), esters of hydroxybenzoic acids such as 2-ethylhexyl para-hydroxybenzoate (EHPB) and 2-decylhexyl para-hydroxybenzoate (HDPB), esters or ethers of tetrahydrofurfuryl alcohol such as oligoethyleneoxy-tetrahydrofurfurylalcohol, and esters of citric acid or of hydroxymalonic acid, such as oligoethylene oxymalonate.
- BBSA n-butyl benzene sulfonamide
- 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 P2j can be a thermoplastic polymer or a thermosetting polymer.
- One or more composite reinforcement layers may or may be present.
- 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 P2j 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 sealing 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, including copolymers, for example polyamide-polyether copolymers, polyesters, polyaryletherketones (PAEKs ), polyetherether ketones (PEEK), polyetherketone ketones (PEKK), polyetherketoneetherketone ketones (PEKEKK), polyimides in particular polyetherimides (PEI) or polyamide-imides, polylsulfones (PSU) in particular polyarylsulfones (PSU) polyphenyl sulfones
- 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 / 6T, PA 11 / MPMDT / 6T, PA 11 /
- T is terephthalic acid
- MXD is m-xylylenediamine
- MPMD is methylpentamethylene diamine
- BAC is 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 resin or an epoxy-based resin.
- Said composition comprising said polymer P2j 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.
- Said multilayer structure therefore comprises at least one 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.
- sealing and reinforcing layers do not adhere to each other and consist of compositions which respectively comprise different polymers.
- said different polymers can be of the same type.
- one of the two composite sealing and reinforcing layers consists of a composition comprising an aliphatic polyamide
- the other 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 a high tg polymer as the matrix of the composite reinforcement.
- Said multilayer structure can include up to 10 waterproofing layers and up to
- said structure is devoid of any binder or adhesive layer, whether between the sealing layers, or between the composite reinforcing layers, or between the outermost sealing layer and the innermost composite reinforcing layer. .
- said multilayer structure is not necessarily symmetrical and that it can therefore include more waterproofing layers than composite layers or vice versa, but there cannot be alternation of layers and of reinforcing layer.
- said multilayer structure comprises one, two, three, four, five, six, seven, eight, nine or ten sealing layers and one, two, three, four, five, six, seven, eight, nine or ten layers composite reinforcement.
- said multilayer structure comprises one, two, three, four or five waterproofing layers and one, two, three, four or five composite reinforcement layers.
- said multilayer structure comprises one, two or three waterproofing layers and one two or three composite reinforcement layers.
- compositions which respectively comprise different polymers consist of compositions which respectively comprise polyamides corresponding to polyamides P1i and an epoxy resin or based on epoxy P2j.
- said multilayer structure comprises a single waterproofing layer and several reinforcing layers, said adjacent reinforcing layer being wrapped around said waterproofing layer and the other reinforcing layers being wrapped around the reinforcing layer. directly adjacent.
- said multilayer structure comprises a single reinforcing layer and several sealing layers, said reinforcing layer being wrapped around said adjacent sealing layer.
- said multilayer structure comprises a single waterproofing layer and a single composite reinforcing layer, said reinforcing layer being wrapped around said waterproofing layer.
- each sealing layer consists of a composition comprising the same type of polymer P1i, in particular a polyamide.
- polystyrene resin By the same type of polymer is meant, for example, a polyamide which can be an identical or different polyamide depending on the layers.
- said polymer P1i is a polyamide and said polymer P2j is an epoxy or epoxy-based resin.
- the polyamide P1i is identical for all the waterproofing layers.
- said polymer P1i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, in particular PA 11 or PA12.
- the polyamide P1i is a long-chain semi-aromatic polyamide, in particular PA 11 / 5T, PA 11 / 6T or PA 11 / 10T.
- the level of 11 must be chosen judiciously so that the Tm of said polymers is less than 280 ° C, preferably 265 ° C.
- each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular an epoxy or epoxy-based resin.
- each sealing layer consists of a composition comprising the same type of polymer P1i, in particular a polyamide and each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular an epoxy resin or an epoxy-based resin.
- said polymer P1 i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, in particular PA 11 or PA12 and said polymer P2j is a semi-aromatic polyamide, in particular chosen from a PA MPMDT / 6T, one PA11 / 10T, one PA 11 / BACT, one PA 5T / 10T, 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 / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T, one PA and 11 / MXDT / 10T.
- PA MPMDT / 6T one PA11 / 10T, one PA 11 / BACT,
- said multilayer structure consists of a single reinforcing layer and a single sealing layer in which said polymer P1 i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212 , PA11, PA12, in particular PA 11 or PA12 and said polymer P2j is a semi-aromatic polyamide, in particular chosen from a PA MPMDT / 6T, a PA11 / 10T, a PA 11 / BACT, a PA 5T / 10T, a 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 / 6T,
- PA 11 / MP M DT / 10T PA 11 / BACT / 10T and a PA 11 / MXDT / 10T.
- said multilayer structure consists of a single reinforcing layer and a single sealing layer in which said polymer P1 i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA12, in particular PA12 and said polymer P2j is a semi-aromatic polyamide, in particular chosen from a PA MPMDT / 6T, a PA PA11 / 10T, a PA 11 / BACT, a PA 5T / 10T and a 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 / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T and a PA 11 / MXDT / 10T.
- the multilayer structure consists of a single reinforcing layer and a single sealing layer in which said polymer P1i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, or semi-aromatic, in particular chosen from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T and BACT / 10T, in particular PA 11 or PA12 and said polymer P2j is an epoxy or epoxy-based resin.
- said polymer P1i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, or semi-aromatic, in particular chosen from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T and BACT / 10T, in particular PA 11 or PA12 and said polymer P2j is an epoxy or epoxy-
- the multilayer structure consists of a single reinforcing layer and a single sealing layer in which said polymer P1 i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA12, or semi-aromatic, in particular chosen from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T and BACT / 10T, in particular PA12 and said polymer P2j is an epoxy or epoxy resin.
- 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.
- Said outer layer in no way corresponds to the layer located above the outermost composite reinforcing layer of polyamide polymer, the structure of which is not mentioned above.
- 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. of the 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 coated with a coating layer, in order to facilitate 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.
- Figure 1 shows the notched Charpy impact at -40 ° C according to ISO 179-1: 2010 of four liners: from left to right PA11, PA12, PA6 and PA66.
- Figure 2 shows the hydrogen permeability at 23 ° C of PA12 and HDPE liners.
- the permeability must then be multiplied by 101325.
- Figure 3 shows the notched Charpy shock at -40 ° C according to ISO 179-1: 2010 for PA11 and PA12 liners: for each group of histograms, PA11 is on the left and PA12 is on the right.
- the first group corresponds to 0% plasticizer, the second group to 7% plasticizer and the last group to 12% plasticizer.
- the tanks are obtained by rotational molding of the sealing layer (liner) at a temperature suited to the nature of the thermoplastic resin used.
- a wet filament winding process is then used which consists in winding fibers around the liner, which fibers are pre-impregnated in an epoxy bath. liquid or a liquid epoxy-based bath.
- the reservoir is then polymerized in an oven for 2 hours.
- thermoplastic resin a fibrous material impregnated with the thermoplastic resin (tape) is used.
- This tape is deposited by filament winding using a robot comprising a 1500W power laser heater at a speed of 12m / min and there is no polymerization step.
- Example 1 Notched Charpy shock at -40 ° C according to ISO 179-1: 2010
- Two long chain liners of PA11 and PA12 and two short chain liners were prepared by rotational molding as above.
- the cold resistance of long-chain liners is much better than that of short-chain liners PA6 and PA66.
- Two long chain liners one in PA11 (Arkema) and the second in PA12 (Arkema) and one liner in HDPE were prepared by rotational molding and the hydrogen permeability at 23 ° C was tested.
- Two liners PA11 and PA12 without plasticizer or comprising 7 or 12% plasticizer (BBSA) relative to the total weight of the composition were prepared by rotational molding.
- the plasticizer has a deleterious cold effect, it weakens the structure and increases the permeability, in particular by 50% with 7% BBSA.
- LT cocktail having the following composition: lotader® 4700 (50%) + lotader® AX8900 (25%) + lucalene® 3110 (25%)) on the permeability to hydrogen of the liner PA12.
- the permeability can also be expressed in (cc.25p / m 2 .24h.Pa).
- the permeability must then be multiplied by 101325.
- Example 5 Type IV hydrogen storage tank, composed of an epoxy composite reinforcement (Tg 120 ° C) T700SC31E carbon fibers (produced by Toray) and a waterproofing layer of PA11.
- the operating temperature is sufficient for rapid filling of the tank, especially in 3 to 5 minutes.
- Type IV hydrogen storage tank composed of an epoxy composite reinforcement (Tg 120 ° C) T700SC31E carbon fibers (produced by Toray) and an HDPE waterproofing layer.
- the operating temperature is too low for rapid filling of the tank, especially in 3 to 5 minutes.
- Example 7 Type IV hydrogen storage tank, composed of a reinforcement of BACT / 10T carbon fiber T700SC31 E composite (produced by Toray) and a waterproofing layer of PA12.
- the BACT / 10T type composition chosen has a melting point, Tm, of 283 ° C, a crystallization temperature, Te, of 250 ° C and a glass transition temperature of 164 ° C.
- Tg, Te and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2: 2013 and 11357-3: 2013 respectively.
- a PA BACT / 10T-based composite exhibits a high Tg matrix, but without having long crosslinking, of the 8h type at 140 ° C.
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FR2000816A FR3106646B1 (fr) | 2020-01-28 | 2020-01-28 | Structure multicouche pour le transport ou le stockage de l’hydrogene |
PCT/FR2021/050139 WO2021152253A1 (fr) | 2020-01-28 | 2021-01-26 | Structure multicouche pour le transport ou le stockage de l'hydrogene |
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EP21708054.8A Pending EP4096922A1 (de) | 2020-01-28 | 2021-01-26 | Mehrschichtstruktur zum transport oder zur speicherung von wasserstoff |
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US (1) | US20230075842A1 (de) |
EP (1) | EP4096922A1 (de) |
JP (1) | JP2023511976A (de) |
KR (1) | KR20220133959A (de) |
CN (1) | CN115023344A (de) |
CA (1) | CA3163652A1 (de) |
FR (1) | FR3106646B1 (de) |
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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 |
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 |
BRPI0413672B1 (pt) * | 2003-08-19 | 2016-03-08 | Solvay Advanced Polymers Llc | película, e, método para fabricar a mesma |
EP1844086B1 (de) | 2004-11-22 | 2010-07-21 | 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. |
WO2012129701A1 (en) * | 2011-04-01 | 2012-10-04 | Dynetek Industries Ltd. | Multilayer liner for a high-pressure gas cylinder |
CN107075251B (zh) * | 2014-11-20 | 2020-07-14 | 东丽株式会社 | 用于与高压氢接触的成型品的聚酰胺树脂组合物及使用了其的成型品 |
US9850380B2 (en) * | 2015-02-27 | 2017-12-26 | Toray Industries, Inc. | Polyamide resin composition for molded article exposed to high-pressure hydrogen and molded article made of the same |
FR3046826B1 (fr) * | 2016-01-15 | 2018-05-25 | Arkema France | Structure tubulaire multicouche possedant une meilleure resistance a l'extraction dans la bio-essence et son utilisation |
FR3048973B1 (fr) * | 2016-03-18 | 2019-11-15 | Arkema France | Compositions rigides et ductiles a froid a base de polyamide pour la preparation d'articles de sport obtenus par injection |
FR3053696B1 (fr) * | 2016-07-11 | 2018-07-06 | Arkema France | Composition de polyamide semi-cristallin de haute temperature de transition vitreuse pour materiau composite, son procede de fabrication et ses utilisations |
WO2018155491A1 (ja) | 2017-02-24 | 2018-08-30 | 株式会社ブリヂストン | 水素輸送部品 |
FR3099409B1 (fr) * | 2019-07-30 | 2021-10-01 | Arkema France | Structure multicouche pour le transport ou le stockage de l’hydrogene |
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- 2021-01-26 WO PCT/FR2021/050139 patent/WO2021152253A1/fr unknown
- 2021-01-26 EP EP21708054.8A patent/EP4096922A1/de active Pending
- 2021-01-26 CA CA3163652A patent/CA3163652A1/fr active Pending
- 2021-01-26 CN CN202180011518.3A patent/CN115023344A/zh active Pending
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CN115023344A (zh) | 2022-09-06 |
FR3106646A1 (fr) | 2021-07-30 |
MX2022008891A (es) | 2022-08-15 |
CA3163652A1 (fr) | 2021-08-05 |
JP2023511976A (ja) | 2023-03-23 |
FR3106646B1 (fr) | 2022-06-24 |
US20230075842A1 (en) | 2023-03-09 |
WO2021152253A1 (fr) | 2021-08-05 |
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