CN1245457A - Laminate structures for fuel containers - Google Patents
Laminate structures for fuel containers Download PDFInfo
- Publication number
- CN1245457A CN1245457A CN97181182A CN97181182A CN1245457A CN 1245457 A CN1245457 A CN 1245457A CN 97181182 A CN97181182 A CN 97181182A CN 97181182 A CN97181182 A CN 97181182A CN 1245457 A CN1245457 A CN 1245457A
- Authority
- CN
- China
- Prior art keywords
- layer
- blend
- fuel
- talan
- alkyl
- 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
- 239000000446 fuel Substances 0.000 title claims abstract description 116
- 239000000203 mixture Substances 0.000 claims abstract description 91
- 229920000642 polymer Polymers 0.000 claims abstract description 51
- 229920000098 polyolefin Polymers 0.000 claims abstract description 50
- 239000010410 layer Substances 0.000 claims description 140
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 75
- -1 polybutylene terephthalate Polymers 0.000 claims description 64
- 238000010276 construction Methods 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 46
- 229920001903 high density polyethylene Polymers 0.000 claims description 39
- 239000004700 high-density polyethylene Substances 0.000 claims description 38
- 229920000728 polyester Polymers 0.000 claims description 38
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 37
- 229920000573 polyethylene Polymers 0.000 claims description 36
- 239000004698 Polyethylene Substances 0.000 claims description 34
- 229920006324 polyoxymethylene Polymers 0.000 claims description 28
- 239000000945 filler Substances 0.000 claims description 25
- 239000010445 mica Substances 0.000 claims description 25
- 229910052618 mica group Inorganic materials 0.000 claims description 25
- 229920001971 elastomer Polymers 0.000 claims description 22
- 239000000806 elastomer Substances 0.000 claims description 22
- 229920000570 polyether Polymers 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 19
- 239000004927 clay Substances 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000013047 polymeric layer Substances 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- XHLATTBMSGXSFT-UHFFFAOYSA-N 4-propoxycarbonylbenzoic acid Chemical compound CCCOC(=O)C1=CC=C(C(O)=O)C=C1 XHLATTBMSGXSFT-UHFFFAOYSA-N 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- BKIKRRUKWYJTEU-UHFFFAOYSA-N propane terephthalic acid Chemical compound CCC.OC(=O)c1ccc(cc1)C(O)=O BKIKRRUKWYJTEU-UHFFFAOYSA-N 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 238000010998 test method Methods 0.000 claims description 6
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 230000035699 permeability Effects 0.000 abstract description 9
- 230000004888 barrier function Effects 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000003487 anti-permeability effect Effects 0.000 description 6
- 229920003345 Elvax® Polymers 0.000 description 5
- 238000000748 compression moulding Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000005977 Ethylene Substances 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
- 238000007664 blowing Methods 0.000 description 4
- 239000002828 fuel tank Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 235000012222 talc Nutrition 0.000 description 4
- 238000003856 thermoforming Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000001746 injection moulding 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
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 2
- CTIKAHQFRQTTAY-UHFFFAOYSA-N fluoro(trimethyl)silane Chemical compound C[Si](C)(C)F CTIKAHQFRQTTAY-UHFFFAOYSA-N 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- LCJHLOJKAAQLQW-UHFFFAOYSA-N acetic acid;ethane Chemical compound CC.CC(O)=O LCJHLOJKAAQLQW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940038553 attane Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010423 industrial mineral Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- PZRHRDRVRGEVNW-UHFFFAOYSA-N milrinone Chemical compound N1C(=O)C(C#N)=CC(C=2C=CN=CC=2)=C1C PZRHRDRVRGEVNW-UHFFFAOYSA-N 0.000 description 1
- 229960003574 milrinone Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
- B32B2323/043—HDPE, i.e. high density polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2369/00—Polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2371/00—Polyethers, e.g. PEEK, i.e. polyether-etherketone; PEK, i.e. polyetherketone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
A multilayer laminate structure comprising (A) one or more layers of a polyolefin or a blend of two or more different polyolefins; and (B) one or more layers of a fuel barrier polymer or blends thereof, the fuel barrier polymer or blends thereof having a Fuel CM15 permeability of 45 g-mil/m<2>-day or less, based on a layer thickness of 1 mil, when measured at 40 DEG C and under ambient pressure conditions of 700 to 760 torr; and optionally (C) a tie layer interposed between a polyolefin layer and an adjacent fuel barrier layer; and/or optionally (D) a regrind layer interposed between a tie layer and a polyolefin layer.
Description
The present invention relates to the multilayer structure made that the mixture gasoline of alcoholic compound (as contain) to vehicle fuel (as gasoline) and hydrocarbon and oxygen-containing organic compound has impermeability (anti-permeability performance).
US5,443,874 have described by comprising a special polyethylene layer, the fuel tank that the layer laminates of the adhesive phase that an impervious barrier of making by polyester, as ethylene glycol terephthalate and is made by modified poly ethylene is made.Yet the oxidized significantly fuel swelling of PET, oxidation material especially wherein are alcohol, during as methyl alcohol, are a kind of impervious materials of oxygenated fuel of difference therefore.Ethylene/vinyl base alcohol (EVOH), as Eval
TMThe F product of company (a kind of Eval) is used as the impervious material of fuel at present when producing fuel tank.Yet known as auto industry, Eval F is that the oxygenated fuel of alcohol (as methyl alcohol) can't provide enough impermeabilities to oxidation material wherein.In addition, the known Eval F of packaging industry is to moisture-sensitive, in being exposed to moisture after, it is much higher that oxygen, carbon dioxide, steam and VOC penetrate the speed of film of this material.
US5,443,766 have described and have comprised a PEN internal layer and the outer field laminated vessel of a PETG.This structure is too expensive for fuel tank applications.
People are desirable to provide the container of a kind of multilayer structure made with the mixture that is used to make vehicle fuel and hydrocarbon and oxygen-containing organic compound, and this structure does not have the above-mentioned shortcoming of prior art constructions body.
First aspect, the present invention is a kind of multilayer structure made, comprising:
(A) one or more layers polyolefin or two or more different polyolefinic blends; With
(B) the impervious polymer of one or more layers fuel or its blend, the impervious polymer choosing of this fuel
From:
(1) contain alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit,
(2) contain alpha-alkyl-1, the polyester of 2-talan construction unit,
(3) contain alpha-alkyl-1, the Merlon of 2-talan construction unit,
(4) contain alpha-alkyl-1, the polyester of 2-talan construction unit-altogether-Merlon,
(5) polyacetals,
(6) (1), (2), (3), (4), (5) and/or thermoplastic polyester, and/or flexibilizer and/or have high slenderness ratio filler blend and
(7) (a) polybutylene terephthalate (PBT) (PBT), (b) PETG (PET), and/or (c) flexibilizer and/or (d) have the blend of the filler of high slenderness ratio; With, alternatively
(C) place tack coat between the impervious layer of polyolefin layer and adjacent fuel; And/or alternatively
(D) place the reuse bed of material between tack coat and the polyolefin layer.
Second aspect, the present invention is a multilayer structure made, comprising:
(A) polyolefin or two or more different polyolefinic blend skins; With
(B) the impervious polymer of fuel or its blend internal layer, the impervious polymer of fuel or its blend
Fuel CM15 penetrating power, be 1 mil based on the thickness of layer, press at 40 ℃, environment
The power condition is that test is 45g-mil/m under 700 to 760 torrs
2-sky or lower; Alternatively
(C) place tack coat between the impervious layer of polyolefin layer and adjacent fuel, and/or alternatively
(D) place the reuse bed of material between tack coat and the polyolefin layer.
The third aspect, the present invention is a multilayer structure made, comprising:
(A) the impervious polymer inner layer of fuel, and/or
(B) the impervious polymeric outer layer of fuel,
The impervious polymer of fuel is selected from:
(1) contain alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit,
(2) contain alpha-alkyl-1, the polyester of 2-talan construction unit,
(3) contain alpha-alkyl-1, the Merlon of 2-talan construction unit,
(4) contain alpha-alkyl-1, the polyester of 2-talan construction unit-altogether-Merlon,
(5) gather 2,6-(ethylene naphthalate) (PEN),
(6) gather 2,6-naphthalenedicarboxylic acid butanediol ester (PBN),
(7) polybutylene terephthalate (PBT) (PBT),
(8) poly terephthalic acid propyl ester (poly (propane terephthalate)) (PPT),
(9) polyacetals and
(10) (1), (2), (3), (4), (5), (6), (7), (8) and/or (9), and/or PET, and/or flexibilizer and/or have high slenderness ratio filler blend and
(C) polyolefin or two or more different polyolefinic blend sandwich layers; Alternatively
(D) place tack coat between the impervious layer of polyolefin layer and adjacent fuel; And/or alternatively
(E) place the reuse bed of material between tack coat and the polyolefin layer.
Fourth aspect, the present invention is a multilayer structure made, comprising:
(A) polyolefin or two or more different polyolefinic blend internal layers and skin; With
(B) by EVOH with have an impervious polymer of fuel of the blend that the filler of high slenderness ratio forms
Sandwich layer and alternatively
(C) place tack coat between the impervious layer of polyolefin layer and adjacent fuel, and/or alternatively
(D) place the reuse bed of material between tack coat and the polyolefin layer.
The 5th aspect, the present invention is the method for a preparation first, second, third and the multilayer structure made of fourth aspect, comprises that co-extrusion is at described those layers that define in aspect each.
When making container, the internal layer of multilayer structure made is and the contacted layer of fuel that is placed in the container.
Term used herein " Fuel CM15 " is meant the test fuel mixture that the methyl alcohol of the isooctane of a kind of toluene by 42.5 percentage volumes, 42.5 percentage volumes and 15 percentage volumes is formed.Multilayer structure made of the present invention can be used for the place of extraordinary fuel resistance of any needs and water-resistant stability.Therefore, multilayer structure made can be used as container, as the fuel tank of any vehicles such as jet plane, automobile, truck, meadow and garden articles for use; The ocean articles for use; With storage tank or chemical reagent bottle.Laminate structures also can be as the pipeline of transfer the fuel or chemical reagent.
Term " polyolefin " is meant the polymer or the copolymer of ethene, that is to say, just the polymer of derived from ethylene or ethene and one or more can with the polymer of monomers of its copolymerization.These polymer (comprising raw material, their ratio, polymerization temperature, catalyst and other conditions) are well known in the art, are incorporated herein by reference for the purposes of the present invention.Other can comprise the olefinic monomer that contains 3～12 carbon atoms with the comonomer of vinyl polymerization, and ethylenically unsaturated carboxylic acids (simple function with dual functional) and these sour derivatives are as ester (as alkyl acrylate) and acid anhydrides; Monovinylidene aromatic compounds and the monovinylidene aromatic compounds such as styrene and the methyl styrene that replace with the substituting group that is not halogen; And carbon monoxide.Can comprise 1-octene, acrylic acid, methacrylic acid, vinyl acetate and maleic anhydride with the monomer of the illustrative of ethylene copolymer.
Can be used for the polyolefin that is used for preparing multilayer structure made of the present invention and comprise polypropylene, polyethylene and its copolymer and blend, and ethylene-propylene-diene terpolymer.The LLDPE (LLDPE) that preferred polyolefin is polypropylene, linear high-density polyethylene (HDPE), non-homogeneous branching is as DOWLEX
TMThe ultralow linear density polyethylene (ULDPE) of polyvinyl resin (trade mark of Dow Chemical), non-homogeneous branching is as ATTANE
TMULDPE (trade mark of Dow Chemical); Linear ethylene/the alpha olefin copolymer such as the TAFMER of even branching
TM(trade mark of Mitsui petrochemistry Co., Ltd) and EXACT
TM(trade mark of Exxon chemical company); The substantial linear ethylene/alpha-olefin polymer of even branching such as the AFFINITY of polyolefin elastomer
TM(trade mark of Dow Chemical) and ENGAGE (trade mark of DuPont Dow Elastomers L.L.C), these elastomers can be by US5, disclosed method preparation in 272,236 and 5,278,272; And the ethene polymers of high-pressure free radical polymerization and copolymer such as low density polyethylene (LDPE) (LDPE), ethylene-acrylic acid (EAA) copolymer such as PRIMACOR
TM(trade mark of Dow Chemical) and ethane-acetic acid ethyenyl ester (EVA) copolymer such as ESCORENE
TMPolymer (trade mark of Exxon chemical company), and ELVAX
TM(E.I.du Pont de Nemours ﹠amp; Co. a trade mark).Preferred polyolefin is the linearity and the substantial linear ethylene copolymer of even branching, and its density (measuring according to ASTM D-792) is 0.85 to 0.99g/cm
3, the ratio of weight average molecular weight and number-average molecular weight (Mw/Mn) is 1.5 to 3.0, actual measurement melt index (MI) (press ASTMD-1238 and measure (190/2.16)) is that 100g/10min, its I10/I2 are 6 to 20 (pressing ASTM D-1238 (190/10) measures).
Generally speaking, the density of high density polyethylene (HDPE) (HDPE) is at least about every cubic centimetre of (g/cc) (ASTM method of testing D-1505) of 0.94 gram.HDPE adopts the technology similar to the preparation method of LLDPE widely to produce.These technology are at US2, and 825,721; 2,993,876; In 3,250,825 and 4,204,050 description is arranged.The density that is used for preferred HDPE of the present invention is 0.94 to 0.99g/cc, and melt index (MI) is 0.01 to 35 gram/10 minutes, and D-1238 measures with the ASTM method of testing.
Can be used for the FuelCM15 penetrating power that is used to prepare the impervious polymer of fuel of multilayer structure made of the present invention, is 1 mil based on the thickness of layer, and at 40 ℃, ambient pressure conditions is that test is 45g-mil/m under 700 to 760 torrs
2-sky or lower.
The impervious polymer of these fuel comprises hydroxy-functionalized polyether, Merlon, polyester or the polyestercarbonate of the construction unit that contains the following formula representative
Wherein, R is methyl, ethyl or propyl group.
Be preferred for the alpha-alkyl-1 that contains of the present invention, the hydroxy-functionalized polyether of 2-talan construction unit is the following formula representative:
Wherein R is methyl, ethyl or propyl group, and n is from 10 to 1000 integer.
Contain alpha-alkyl-1, the hydroxy-functionalized polyether of 2-talan is to adopt following method preparation: (a) make inertia dihydroxy-alpha-alkyl-1 that replace or non-replacement, 2-talan and inertia dihydroxy-alpha-alkyl-1 that replace or non-replacement, the diglycidyl ether reaction of 2-talan.US5 has described this polymer in 686,551.
That uses among preferred the present invention contains alpha-alkyl-1, and Merlon, polyester or the polyestercarbonate of 2-talan construction unit contain the repetitive of following formula:
Wherein, R is the divalence nuclear of difunctionality aromatic diols in each case independently; X is selected from:
-C (O)-,-C (O)-R
1-C (O)-, or its mixture; R
1Be the divalence nuclear of aromatic dicarboxylic acid in each case independently.
US5, described in 614,599 use among the present invention contain alpha-alkyl-1, Merlon, polyester or the polyestercarbonate of 2-talan construction unit.
Fuel CM15 penetrating power is 1 mil based on the thickness of layer, is that test is 45g-mil/m under 700 to 760 torrs at 40 ℃, ambient pressure conditions
2-day or lower thermoplastic polyester and blend thereof and polyacetals also can be used among the present invention.
Preferably contain terephthalic acid (TPA) construction unit or 2, the thermoplastic polyester of 6-naphthalenedicarboxylic acid construction unit.
The example that can be used for thermoplastic polyester of the present invention comprises poly-2,6-naphthalenedicarboxylic acid butanediol ester (PBN), poly-2,6-(ethylene naphthalate) (PEN), PETG (PET), poly terephthalic acid propyl ester (PPT), polybutylene terephthalate (PBT) (PBT), and composition thereof.Surprisingly, we find PBT, though be the impervious material of fuel that can only accept reluctantly when using separately, with PET (being the poor especially impervious material of fuel when using separately) blend after become the good especially impervious material of fuel.
PEN and PBN and their preparation method (being included in specific monomer used when forming them, their ratio, polymerization temperature, catalyst and other conditions) are well known in the art, are incorporated herein by reference for the purposes of the present invention.In order to illustrate rather than to limit, quoted US5 especially, 102,705.PPT can obtain from shell chemical company, and PET, PBT and polyacetals can have been bought.
Filler with high slenderness ratio also can with the impervious polyblend of fuel.We have found that the filler with high slenderness ratio significantly improves the fuel anti-permeability performance of the impervious polymer of fuel, but the filler with low slenderness ratio but can not.Term used herein " high slenderness ratio " is meant that the ratio of the thickness of the length of platelet or width and platelet is 10 to 1000.Generally speaking, the length of platelet and width are separately all between 10 to 1000nm.
Can be used for the filler with high slenderness ratio of the present invention and include but not limited to mica and montmorillonitic clay.
Also can be with flexibilizer and the impervious polyblend of fuel.Can be used for flexibilizer of the present invention and comprise a kind of elastomer that is called Paraloid (a kind of product of Rohm and Haas) that can buy, this elastomer has butyl acrylate or butadiene rubber shape core and polymethyl methacrylate duricrust, and a kind of polyethylene elastomer body of maleic anhydride graft (ENGAGE -g-MA, a kind of product of DuPont DowElastomers L.L.C.).US5 has described the polyethylene elastomer body of maleic anhydride graft in 686,551.
Flexibilizer and filler can adopt conventional melt-processed method to join in the impervious polymer of fuel, also can adopt the technology of mixing of doing to thermally sensitive polymeric.
Can be used for tack coat of the present invention, also be called adhesive phase usually, by adhesive material, make as the modified poly ethylene elastomer.Preferred this adhesive material is the polyethylene or the polypropylene of maleic anhydride graft, as ADMER
TM(trade mark of Mitsui Petrochemicals) adhesive resin or ethylene-vinyl acetate copolymer resin such as ELVAX
TM(trade mark of Du Pont).
Each polymer that forms multilayer structure made of the present invention can contain the various additives that its amount can the desirable performance of sharp ground impact polymer.The example of these additives comprises antioxidant, ultra-violet absorber, hot-working stabilizing agent, colouring agent, lubricant, fire retardant, anti-impact modifier, plasticizer, antistatic additive, pigment and nucleator, and filler such as zeolite, talcum and calcium carbonate.The method of sneaking into these additives is unimportant.These additives can add before the preparation multilayer structure made easily.If polymer is with the solid form preparation, these additives can join in the polymer melt before making multilayer structure made and go.
Moulding and use the method for multilayer structure making (as these of above-mentioned narration) can produce a certain amount of leftover pieces inevitably.Consider from economic angle, wish to use these leftover pieces in useful mode.Usually these leftover pieces worn into particle or powder and fusion alternatively, knead and be shaped to piller.These powderies, the leftover pieces that grind granular or the ball shape can add as in the moulding multilayer one or more layers a construction unit of raw material or the raw material of the layer made by leftover pieces fully basically as another layer of moulding.Therefore, multilayer structure made of the present invention can also comprise polyolefin polymer layer, the impervious polymeric layer of fuel and the reuse bed of material of adhesive polymer layer (leftover pieces that grind) alternatively.
The design thickness of each layer depends on many factors in the laminate structures, the used specific composition of each layer in time length that comprise the purposes of being planned, be stored in material in the container, stores before using and the laminate structures.
Usually, the gross thickness of laminate structures is 10 to 750 mils, preferred 100 to 500 mils; Wherein the thickness of the impervious polymeric layer of fuel is 0.1 to 50 mil, preferred 0.5 to 25 mil; The thickness of polyethylene layer is 9.9 to 749.9 mils, preferred 9.9 to 499.5 mils; Alternatively, the thickness of tack coat is 0.1 to 20 mil, preferred 0.1 to 5 mil; Alternatively, by the impervious polymer of fuel, polyethylene and alternatively the returns layer thickness formed of the mixture of binding material be 1 to 375 mil, preferred 5 to 250 mils.
In first kind of configuration of each layer, multilayer structure made of the present invention comprises the impervious polymer inner layer of (A) fuel, this polymer is selected from: (1) contains alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit, (2) contain alpha-alkyl-1, the polyester of 2-talan construction unit, Merlon or polyester-altogether-Merlon, (3) polyacetals, (4) PEN, PBN, PPT, or PBT, (5) PEN, PET, PPT, any two or more blend of PBN and PBT, (6) (a) polyacetals, PEN, PPT, PBN or PBT and (b) blend of flexibilizer A or flexibilizer B, (7) (a) PEN, PET, PBN, any two or more and (b) blend of flexibilizer A or flexibilizer B of PPT and PBT, (8) (a) polyacetals, PEN, PPT, PBN or PBT and (b) blend of mica or montmorillonitic clay, (9) (a) PEN, PET, PBN, any two or more and (b) blend of mica or montmorillonitic clay of PPT and PBT, (10) (a) polyacetals, PEN, PPT, PBN or PBT, (b) flexibilizer A or flexibilizer B and (c) blend of mica or montmorillonitic clay, (11) are PEN (a), PET, PBN, PPT and PBT any two or more, (b) flexibilizer A or flexibilizer B and (c) blend of mica or montmorillonitic clay; (B) HDPE skin; (C) place modified poly ethylene elastomer tack coat between impervious polymeric layer of fuel and the HDPE layer; (D) places the reuse bed of material that comprises layer (A), (B) and blend (C) between tack coat and the outer layer of polyethene alternatively, wherein flexibilizer A is a kind of polyethylene elastomer body of maleic anhydride graft, can obtain from DuPontDow Elastomers L.L.C., be called ENGAGE -g-MA, flexibilizer B is a kind of elastomer, this elastomer has butyl acrylate or soft core of butadiene and duricrust, can buy from Rohm and Haas, be called Paraloid , mica is high slenderness ratio inert filler, the product of a kind of FranklinIndustrial Minerals.
Preferred internal layer accounts for 0.1～25% of container weight, and skin accounts for 5.0～99.89% of container weight.Tack coat between impervious polymeric layer of fuel and the polyethylene layer accounts for 0.01～10% of container weight.The optional reuse bed of material between tack coat and the skin accounts for 5～60% of container weight.
Second kind of configuration of each of multilayer structure made of the present invention layer is identical with first kind of configuration, and just the impervious layer of fuel is a skin and the HDPE layer is an internal layer.
In the third configuration, multilayer structure made of the present invention comprises impervious polymer inner layer of (A) fuel and skin, this polymer is selected from: (1) contains alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit, (2) contain alpha-alkyl-1, the polyester of 2-talan construction unit, Merlon or polyester-altogether-Merlon, (3) polyacetals, (4) PEN, PBN, PPT, or PBT, (5) PEN, PET, PPT, any two or more blend of PBN and PBT, (6) (a) polyacetals, PEN, PPT, PBN or PBT and (b) blend of flexibilizer A or flexibilizer B, (7) (a) PEN, PET, PBN, any two or more and (b) blend of flexibilizer A or flexibilizer B of PPT and PBT, (8) (a) polyacetals, PEN, PPT, PBN or PBT and (b) blend of mica or montmorillonitic clay, (9) (a) PEN, PET, PBN, any two or more and (b) blend of mica or montmorillonitic clay of PPT and PBT, (10) (a) polyacetals, PEN, PPT, PBN or PBT, (b) flexibilizer A or flexibilizer B and (c) blend of mica or montmorillonitic clay, (11) are PEN (a), PET, PBN, PPT and PBT any two or more, (b) flexibilizer A or flexibilizer B and (c) blend of mica or montmorillonitic clay; (B) HDPE sandwich layer; (C) place modified poly ethylene elastomer tack coat between impervious polymeric layer of fuel and the HDPE layer; (D) places the reuse bed of material that comprises layer (A), (B) and blend (C) between tack coat and the outer layer polyethylene layer alternatively, and wherein flexibilizer A and B are as defined above.
Preferred internal layer and skin account for 0.1～25% of container weight separately, and sandwich layer accounts for 5.0～99.78% of container weight.Tack coat between impervious polymeric layer of fuel and the polyethylene layer accounts for 0.01～10% of container weight.The optional reuse bed of material between tack coat and the sandwich layer accounts for 5～60% of container weight.
In the 4th kind of configuration, multilayer structure made of the present invention comprises (A) polyethylene inner layer, (B) the impervious core polymer layer of fuel, this polymer is selected from: (1) contains alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit, (2) contain alpha-alkyl-1, the polyester of 2-talan construction unit, Merlon or polyester-altogether-Merlon, (3) polyacetals, (4) (a) PEN, PET, PBN, any two or more and (b) blend of flexibilizer A or flexibilizer B of PPT and PBT, (5) (a) PEN, PET, PBN, any two or more and (b) blend of mica or montmorillonitic clay of PPT and PBT, the blend of (6) EVOH and mica or montmorillonitic clay; (C) outer layer of polyethene; (D) places the modified poly ethylene elastomer tack coat between the impervious polymeric layer of fuel and HDPE internal layer and the skin alternatively; (E) places the reuse bed of material that comprises layer (A), (B), (C) and blend (D) between tack coat and the outer layer polyethylene layer alternatively, and wherein flexibilizer A and B are as defined above.
Preferred internal layer and outer 5～60% of the container weight that accounts for together; The impervious polymeric layer of fuel accounts for 0.1～25% of container weight; Tack coat between impervious polymeric layer of fuel and the polyethylene layer accounts for 0.01～10% of container weight, and the optional reuse bed of material between tack coat and the outer layer polyethylene layer accounts for 5～60% of container weight.
Multilayer structure made of the present invention can adopt conventional extruding technology such as feed block coextrusion technology, expect road die head co-extrusion or The combined use more, also can be by laminating production, the layer of wherein controlling oneself bonds together by heating and pressurization, and these conventional extruding technologies are that purpose of the present invention is incorporated herein by reference.The volume (thickness) of each layer can be controlled when extruding separately.Therefore, can control the gross thickness of multilayer structure making to produce the film or the sheet material of predetermined thickness.
Laminate structures of the present invention can adopt conventional thermoplastic molding's technology, as compression moulding, injection moulding, stratiform injection moulding, blowing, extrusion molding, calendering and thermoforming, is processed into goods.Typical thermoforming technology comprises thermoplastic sheets is heated to its softening point, adopts different moulds and/or vacuum or air pressure pressing aid or formpiston pressing aid formed sheet at forming station then.Other thermoforming technology comprises solid phase pressure forming (SPPF) and so-called scrap less forming process (SFP).For the purposes of the present invention, thermoforming technology of being quoted or thermoformable structure will comprise SPPF and SFP.In process, the molecule of polymer can be orientated by methods known in the art.US5,382,693 have described a kind of this method.(Plastics EngineeringHandbook of the Society of the Plastics Industry, Inc.) the 4th edition, p.113-115,182-183 has also described method for alignment to the plastic processing handbook of association of Plastics Industry Company.The goods of moulding comprise container thus, moulded component and pipeline.The example of these goods comprise flexible and rigid container as be used for storing chemicals and fuel, comprise the oxygenated fuel that wherein contains alcohol as methyl alcohol or ethanol case or bottle, and be used for transporting chemicals and fuel, comprise and wherein contain the pipeline of alcohol as the oxygenated fuel of methyl alcohol or ethanol.
When being shaped to container or pipeline, the internal layer of multilayer structure made of the present invention is to be placed on contacted that one deck of container or insides of pipes and fuel.Therefore, in the configuration of each layer of aforesaid multilayer structure made, the impervious polymeric layer of multilayer structure made fuel is to be placed on contacted that one deck of container or insides of pipes and fuel, and/or that one deck in container or the pipeline outside, or be clipped in polyethylene and that one deck between tack coat and/or the reuse bed of material alternatively.
Embodiment given below should not be construed as its scope that limits for the present invention is described.Except as otherwise noted, all umber and percentage are all by weight.
Embodiment
Be material and method of testing used among the embodiment below.
Material
PBT: polybutylene terephthalate (PBT), a kind of commercially available polyester.
PEN: gather-2,6-(ethylene naphthalate), a kind of commercially available polyester.
PET: PETG, a kind of commercially available polyester.
Polyacetals: a kind of commercially available urea formaldehyde.Be a kind of polyformaldehyde thermoplastic polymer, cause formaldehyde+CH by ion
2Polymerization is to obtain-O-CH
2-O-CH
2=CH
2The linear molecule of-type.
ENGAGE -g-MA: the ethene polymers of the substantial linear of graft modification, DuPont DowElastomers L.L.C. are produced, and US5 has description in 346,963.
Mica: Himod 270 wet-milling muscovites, a kind of commercially available high slenderness ratio inert filler; The product of Franklin Industrial Minerals.
Eval F: by the monomer weight ratio is the EVOH that the vinyl alcohol of 32% ethene and 68% is made; The product of Eval company.
Contain Alpha-Methyl-1, the hydroxy-functionalized polyether of 2-talan construction unit, by the following formula representative:
Contain Alpha-Methyl-1, the Merlon of 2-talan construction unit, by the following formula representative:
HDPE: high density polyethylene (HDPE).
Admer
TMNF 500A: a kind of modified poly ethylene elastomeric adhesive, the product of MitsuiPetrochemicals.
Admer
TMSF 700: a kind of modified poly ethylene elastomeric adhesive, the product of MitsuiPetrochemicals.
Admer
TMSF 710: a kind of modified poly ethylene elastomeric adhesive, the product of MitsuiPetrochemicals.
Elvax 260: a kind of EVAc, and as the adhesive of HDPE, the product of E.I.Du Pont Company.
Test fuel Fuel CM15: a kind of toluene, the mixture that the methyl alcohol of the isooctane of 42.5 percentage volumes and 15 percentage volumes is formed by 42.5 percentage volumes.
Method of testing
The fuel absorption test
The compression molding parts of weighing in advance were immersed under 40 to 41 ℃ among the Fuel CM15 14 days.From fuel, take out parts, blow away remaining liquid with high wind.Weigh calculates weightening finish percentage once more.
Permeability test
Adopt the permeability of 40 to 41 ℃ of following Fuel CM15 of following method test.With the test film of a compression moulding, cast film extrusion or blowing, 4 inches of diameters discoid, thick 1～100 mil is contained between two test cabinets.With chamber in Fuel CM15 (95ml) adding, making flow velocity is that the helium flow of about 10ml/min is crossed down the chamber.Brought into the sparge ring of a gas-chromatography (GC) from test cabinet behind the impervious film of fuel infiltrate.Under CF, the content in the sparge ring is expelled to 140 ℃, uses 25m, the 0.53mm ID of the helium flow of 10ml/min as carrier gas, Chrompack PoraplotU type front end capillaceous.GC separates, discerns and quantize to penetrate the fuel component of sample film according to the time of staying.Be stored in the computer to do further analysis from the time of on-test and the composition and the amount that penetrate component.
Embodiment 1
Prepare several single-interval test samples by compression moulding or injection moulding.Estimate the fuel absorbing state of these samples (as described in Table I).The results are shown in Table I.The fuel absorptivity is the good impervious material that 2wt.% or lower sample are considered to contain pure fuel.
Table I
| Sample | Resin or blend | Weightening finish percentage |
| ?1 | Alpha-Methyl-1, the hydroxy-functionalized polyether of 2-talan | ?2.0 |
| ?2 | Alpha-Methyl-1, the Merlon of 2-talan | ?0.7 |
| ?3 | ?HDPE | ?7.8 |
| ?4 | ?Eval?F | ?2.8 |
| ?5 | ?PBT | ?3.0 |
| ?6 | Polyacetals | ?3.0 |
| ?7 | ?PET | ?15.1 |
Data in the last table show that HDPE, Eval F, PET, PBT and polyacetals do not have good fuel anti-permeability performance when using separately.The fuel absorptivity of PBT and polyacetals is 3wt.%, is counted as the impervious material of inadequate receptible fuel for containing Aalcohols fuel, and Eval F also is.
Embodiment 2
Prepare several monofilm specimen (as described in Table II) by compression moulding.Estimate the Fuel CM15 permeability of these samples.The results are shown in Table II.
Table II
| Resin or blend | Permeability * g-mil/m 2-day | |
| ?8 | ?PBT | 24 |
| ?9 | 85/15PBT/ mica blend | 6.8 |
| ?10 | 75/25PBT/ mica blend | 4.2 |
| ?11 | 75/25PBT/ talcum blend | 27.4 |
| ?12 | 37.5/37.5/25PBT/PET/ mica blend | 3.0 |
| ?13 | ?Eval?F | 50 |
| ?14 | 75/25 Eval F/ mica blend | 7.3 |
| ?15 | 75/25 Eval F/ talcum blend | 45.7 |
* to be normalized to the thickness of total body be that 1 mil, 41 ℃, environmental pressure are measured down to permeability.
As shown in Table II, general filler, as talcum has just improved the fuel anti-permeability performances of material at most to a certain extent, these materials, has only inadequate acceptable fuel anti-permeability performance as PBT and Eval F when not filled.Yet, have the filler of high slenderness ratio, as mica, but improved the fuel anti-permeability performance of these same compounds greatly.
Embodiment 3
Several 3 press mold samples have layer by layer been prepared by flat film co-extrusion or the co-extrusion blow moulding of squeezing.These laminate structures contain the impervious material layer of a fuel, a high-density polyethylene layer and be in a tack coat between impervious material layer of fuel and the polyethylene layer.In the several samples with flat crowded film co-extrusion method preparation, impervious layer and tack coat account for about 10% and 5% of structure gross thickness respectively.In co-extrusion blow-molded plastic body, impervious layer and tack coat account for about 24% and 5% of structure gross thickness respectively.The remaining thickness of these structures is polyethylene layers.Test the fuel C M15 permeability of these films, the impervious material layer of fuel directly contacts with fuel.The osmotic value of these structures is based on the gross thickness of these structures.Test result is shown in Table III.
Table III
| Sample | Impervious material | Tack coat | The preparation method | Permeability * g-mil/m 2-day |
| ?16 | 50/50 PBT/PEN blend | ?Admer ?NF-500 | The flat film co-extrusion that squeezes | 44 |
| ?17 | 50/50 PBT/PEN blend | ?Admer ?SF-710 | The flat film co-extrusion that squeezes | 55 |
| ?18 | 50/50 PBT/PEN blend | ?Elvax ?260 | The flat film co-extrusion that squeezes | 66 |
| ?19 | ?PBT | ?Admer ?NF-500 | The flat film co-extrusion that squeezes | 104 |
| ?20 | ?PBT | ?Admer ?SF-700A | The flat film co-extrusion that squeezes | 102 |
| ?21 | ?PBT | ?Admer ?SF-710A | The flat film co-extrusion that squeezes | 77 |
| ?22 | ?PBT | ?Elvax ?260 | The flat film co-extrusion that squeezes | 80 |
| ?23 | ?PBT | ?Admer ?SF-700A | Co-extrusion blowing | 53 |
| ?24 | ?HDPE | ?Admer ?SF-700A | Co-extrusion blowing | 2670 |
* to be normalized to the thickness of total body be that 1 mil, 41 ℃, environmental pressure are measured down to permeability.
As shown in Table III, contain PBT or 50/50PBT/PEN have the 3-tier architecture of tack coat body between 2 hdpe layers and the polyethylene layer than similar containing as the osmotic value of the laminate structures of impervious material low 25 to 60 times of osmotic value.
Claims (23)
1. multilayer structure made comprises:
(A) one or more layers polyolefin or two or more different polyolefinic blends; With
(B) the impervious polymer of one or more layers fuel or its blend, the impervious polymer choosing of this fuel
From:
(1) contain alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit,
(2) contain alpha-alkyl-1, the polyester of 2-talan construction unit,
(3) contain alpha-alkyl-1, the Merlon of 2-talan construction unit,
(4) contain alpha-alkyl-1, the polyester of 2-talan construction unit-altogether-Merlon,
(5) polyacetals,
(6) (1), (2), (3), (4), (5) and/or thermoplastic polyester, and/or flexibilizer and/or have high slenderness ratio filler blend and
(7) comprise (a) polybutylene terephthalate (PBT) (PBT), (b) PETG (PET) and/or (c) flexibilizer and/or (d) have the blend of the filler of high slenderness ratio; With, alternatively
(C) place tack coat between the impervious layer of polyolefin layer and adjacent fuel; And/or alternatively
(D) place the reuse bed of material between tack coat and the polyolefin layer.
2. laminate structures as claimed in claim 1, hydroxy-functionalized polyether wherein are the following formula representatives:
Wherein R is methyl, ethyl or propyl group, and n is from 10 to 1000 integer.
3. laminate structures as claimed in claim 1, Merlon wherein, polyester or polyester-common-Merlon contains the construction unit of following formula representative:
Wherein, R is methyl, ethyl or propyl group.
4. laminate structures as claimed in claim 1, polyolefin wherein is a high density polyethylene (HDPE).
5. laminate structures as claimed in claim 4, the density of high density polyethylene (HDPE) wherein are 0.94 to 0.99g/cc, and melt index (MI) is 0.01 to 35 gram/minute, and D-1238 measures with the ASTM method of testing.
6. laminate structures as claimed in claim 1, tack coat wherein are polyethylene or the polypropylene or the vinyl-vinyl acetate copolymers of maleic anhydride graft.
7. two-layer laminate structures comprises:
(A) the impervious polymer inner layer of fuel, the impervious polymer of this fuel is selected from:
(1) contain alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit,
(2) contain alpha-alkyl-1, the polyester of 2-talan construction unit,
(3) contain alpha-alkyl-1, the Merlon of 2-talan construction unit,
(4) contain alpha-alkyl-1, the polyester of 2-talan construction unit-altogether-Merlon,
(5) poly terephthalic acid propyl ester (poly (propane terephthalate)) (PPT),
(6) gather 2,6-(ethylene naphthalate) (PEN),
(7) gather 2,6-naphthalenedicarboxylic acid butanediol ester (PBN),
(8) polybutylene terephthalate (PBT) (PBT),
(9) polyacetals
(10) (1), (2), (3), (4), (5), (6), (7), (8) and/or (9), and/or PET, and/or flexibilizer and/or have the blend of the filler of high slenderness ratio; With
(B) polyolefin or two or more different polyolefinic blend layers; Alternatively
(C) place tack coat between the impervious layer of polyolefin layer and adjacent fuel; And/or alternatively
(D) place the reuse bed of material between tack coat and the polyolefin layer.
8. laminate structures as claimed in claim 7, hydroxy-functionalized polyether wherein are the following formula representatives:
Wherein R is methyl, ethyl or propyl group, and n is from 10 to 1000 integer.
9. laminate structures as claimed in claim 7, Merlon wherein, polyester or polyester-common-Merlon contains the construction unit of following formula representative:
Wherein, R is methyl, ethyl or propyl group.
10. laminate structures as claimed in claim 7, polyolefin wherein is a high density polyethylene (HDPE).
11. laminate structures as claimed in claim 10, the density of high density polyethylene (HDPE) wherein are 0.94 to 0.99g/cc, melt index (MI) is 0.01 to 35 gram/minute, and D-1238 measures with the ASTM method of testing.
12. laminate structures as claimed in claim 7, tack coat wherein are polyethylene or the polypropylene or the vinyl-vinyl acetate copolymer of maleic anhydride graft.
13. a multilayer structure made comprises:
(A) the impervious polymer inner layer of fuel,
(B) the impervious polymeric outer layer of fuel,
The impervious polymer of fuel is selected from:
(1) contain alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit,
(2) contain alpha-alkyl-1, the polyester of 2-talan construction unit,
(3) contain alpha-alkyl-1, the Merlon of 2-talan construction unit,
(4) contain alpha-alkyl-1, the polyester of 2-talan construction unit-altogether-Merlon,
(5) poly terephthalic acid propyl ester (poly (propane terephthalate)) (PPT)
(6) gather 2,6-(ethylene naphthalate) (PEN),
(7) gather 2,6-naphthalenedicarboxylic acid butanediol ester (PBN),
(8) polybutylene terephthalate (PBT) (PBT),
(9) polyacetals and
(10) (1), (2), (3), (4), (5), (6), (7), (8) and/or (9), and/or PET, and/or flexibilizer and/or have the blend of the filler of high slenderness ratio; With
(C) polyolefin or two or more different polyolefinic blend sandwich layers; Alternatively
(D) place tack coat between the impervious layer of polyolefin layer and adjacent fuel; And/or alternatively
(E) place the reuse bed of material between tack coat and the polyolefin layer.
14. a multilayer structure made comprises:
(A) polyolefin or two or more different polyolefinic blend skins; With
(B) the impervious polymer of fuel or its blend internal layer, the Fuel CM15 penetrating power of the impervious polymer of fuel or its blend is 1 mil based on the thickness of layer, is that test is 45g-mil/m under 700 to 760 torrs at 40 ℃, ambient pressure conditions
2-sky or lower; Alternatively
(C) place tack coat between the impervious layer of polyolefin layer and adjacent fuel, and/or alternatively
(D) place the reuse bed of material between tack coat and the polyolefin layer.
15. a multilayer structure made comprises:
(A) polyolefin or two or more different polyolefinic blend internal layers;
(B) sandwich layer of the EVOH and the blend of filler with high slenderness ratio,
(C) polyolefin or two or more different polyolefinic blend skins; Alternatively
(D) place tack coat between the impervious layer of polyolefin layer and adjacent fuel, and/or alternatively
(E) place the reuse bed of material between tack coat and the polyolefin layer.
16. a multilayer structure made comprises
(A) the impervious polymer inner layer of fuel, this polymer is selected from:
(1) contain alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit,
(2) contain alpha-alkyl-1, the polyester of 2-talan construction unit,
(3) contain alpha-alkyl-1, the Merlon of 2-talan construction unit,
(4) contain alpha-alkyl-1, the polyester of 2-talan construction unit-altogether-Merlon,
(5) polyacetals,
(6) poly terephthalic acid propyl ester (poly (propane terephthalate)) (PPT),
(7) gather 2,6-(ethylene naphthalate) (PEN),
(8) gather 2,6-naphthalenedicarboxylic acid butanediol ester (PBN),
(9) polybutylene terephthalate (PBT) (PBT),
(10) PEN, PET, PBN, PPT, or any two or more blend of PBT,
(11) (a) PEN, PPT, PBN or PBT and (b) blend of flexibilizer A or flexibilizer B,
(12) (a) any two or more and (b) blend of flexibilizer A or flexibilizer B of PEN, PET, PBN, PPT and PBT,
(13) (a) polyacetals, PEN, PPT, PBN or PBT and (b) blend of mica or montmorillonitic clay,
(14) (a) any two or more and (b) blend of mica or montmorillonitic clay of PEN, PET, PBN, PPT and PBT,
(15) (a) polyacetals, PEN, PPT, PBN or PBT, (b) flexibilizer A or flexibilizer B and (c) mica or montmorillonitic clay blend and
(16) (a) PEN, PET, PBN, PPT and PBT any two or more, (b) flexibilizer A or flexibilizer B and (c) blend of mica or montmorillonitic clay;
(B) high density polyethylene (HDPE) skin;
(C) place modified poly ethylene elastomer tack coat between impervious polymeric layer of fuel and the high-density polyethylene layer; Alternatively
(D) place the reuse bed of material that comprises layer (A), (B) and blend (C) between tack coat and the high density polyethylene (HDPE) skin;
Wherein flexibilizer A is a kind of polyethylene elastomer body of maleic anhydride graft, and flexibilizer B is a kind of elastomer, and this elastomer has butyl acrylate or butadiene rubber shape core and polymethyl methacrylate duricrust, and mica is high slenderness ratio inert filler.
17. a multilayer structure made comprises:
(A) polyolefin internal layer;
(B) the impervious core polymer layer of fuel, this polymer is selected from:
(1) contain alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit,
(2) contain alpha-alkyl-1, the polyester of 2-talan construction unit
(3) contain alpha-alkyl-1, the Merlon of 2-talan construction unit,
(4) contain alpha-alkyl-1, the polyester of 2-talan construction unit-altogether-Merlon,
(5) polyacetals,
(6) (a) (1), (2), (3), (4), or (5) and PEN, PET, PBN, PPT, or the blend of PBT,
(7) (a) any two or more and (b) blend of flexibilizer A or flexibilizer B of PEN, PET, PPT, PBN or PBT, and/or (c) mica or montmorillonitic clay blend and
(C) high density polyethylene (HDPE) skin;
(D) place modified poly ethylene elastomer tack coat between impervious polymeric layer of fuel and the high-density polyethylene layer; Alternatively
(E) place the reuse bed of material that comprises layer (A), (B), (C) and blend (D) between tack coat and the high density polyethylene (HDPE) skin;
Wherein flexibilizer A is a kind of polyethylene elastomer body of maleic anhydride graft, and flexibilizer B is a kind of elastomer, and this elastomer has butyl acrylate or butadiene rubber shape core and polymethyl methacrylate duricrust, and mica is high slenderness ratio inert filler.
18. a method for preparing multilayer structure made comprises co-extrusion:
(A) one or more layers polyolefin or two or more different polyolefinic blends; With
(B) the impervious polymer of one or more layers fuel or its blend, the impervious polymer choosing of this fuel
From:
(1) contain alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit,
(2) contain alpha-alkyl-1, the polyester of 2-talan construction unit,
(3) contain alpha-alkyl-1, the Merlon of 2-talan construction unit,
(4) contain alpha-alkyl-1, the polyester of 2-talan construction unit-altogether-Merlon,
(5) polyacetals,
(6) (1), (2), (3), (4), (5) and/or thermoplastic polyester, and/or flexibilizer and/or have high slenderness ratio filler blend and
(7) comprise (a) polybutylene terephthalate (PBT), (b) PETG, and/or (c) flexibilizer, and/or (d) have the blend of the filler of high slenderness ratio; With, alternatively
(C) place tack coat between the impervious layer of polyolefin layer and adjacent fuel; And/or alternatively
(D) place the reuse bed of material between tack coat and the polyolefin layer.
19. a method for preparing multilayer structure made comprises co-extrusion:
(A) the impervious polymer inner layer of fuel and
(B) the impervious polymeric outer layer of fuel,
The impervious polymer of fuel is selected from:
(1) contain alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit,
(2) contain alpha-alkyl-1, the polyester of 2-talan construction unit,
(3) contain alpha-alkyl-1, the Merlon of 2-talan construction unit,
(4) contain alpha-alkyl-1, the polyester of 2-talan construction unit-altogether-Merlon,
(5) poly terephthalic acid propyl ester (poly (propane terephthalate)) (PPT)
(6) gather 2,6-(ethylene naphthalate) (PEN),
(7) gather 2,6-naphthalenedicarboxylic acid butanediol ester (PBN),
(8) polybutylene terephthalate (PBT) (PBT),
(9) polyacetals and
(10) (2), (3), (4), (5), (6), (7), (8) and/or (9), and/or PET, and/or flexibilizer, and/or have the blend of the filler of high slenderness ratio; With
(C) polyolefin or two or more different polyolefinic blend sandwich layers; Alternatively
(D) place tack coat between the impervious layer of polyolefin layer and adjacent fuel; And/or alternatively
(E) place the reuse bed of material between tack coat and the polyolefin layer.
20. a method for preparing two-layer laminate structures comprises co-extrusion:
(A) the impervious polymer inner layer of fuel, the impervious polymer of this fuel is selected from:
(1) contain alpha-alkyl-1, the polyethers of the hydroxy-functional of 2-talan construction unit,
(2) contain alpha-alkyl-1, the polyester of 2-talan construction unit,
(3) contain alpha-alkyl-1, the Merlon of 2-talan construction unit,
(4) contain alpha-alkyl-1, the polyester of 2-talan construction unit-altogether-Merlon,
(5) poly terephthalic acid propyl ester (poly (propane terephthalate)) (PPT),
(6) gather 2,6-(ethylene naphthalate) (PEN),
(7) gather 2,6-naphthalenedicarboxylic acid butanediol ester (PBN),
(8) polybutylene terephthalate (PBT) (PBT),
(9) polyacetals
(10) (2), (3), (4), (5), (6), (7), (8) and/or (9), and/or PET, and/or flexibilizer and/or have the blend of the filler of high slenderness ratio; With
(C) polyolefin or two or more different polyolefinic blend layers; Alternatively
(D) place tack coat between the impervious layer of polyolefin layer and adjacent fuel; And/or alternatively
(E) place the reuse bed of material between tack coat and the polyolefin layer.
21. comprise the container or the pipeline of the laminate structures of claim 7, wherein internal layer forms container or side opposite, the outer outer surface that forms container or pipeline.
22. comprise the container or the pipeline of the laminate structures of claim 14, wherein internal layer forms container or side opposite, the outer outer surface that forms container or pipeline.
23. comprise the container or the pipeline of the laminate structures of claim 16, wherein internal layer forms container or side opposite, the outer outer surface that forms container or pipeline.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3461396P | 1996-12-31 | 1996-12-31 | |
| US60/034,613 | 1996-12-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1245457A true CN1245457A (en) | 2000-02-23 |
Family
ID=21877508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97181182A Pending CN1245457A (en) | 1996-12-31 | 1997-12-22 | Laminate structures for fuel containers |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0949996A2 (en) |
| JP (1) | JP2001522320A (en) |
| KR (1) | KR20000062401A (en) |
| CN (1) | CN1245457A (en) |
| AR (1) | AR011325A1 (en) |
| BR (1) | BR9713804A (en) |
| CA (1) | CA2276009A1 (en) |
| TW (1) | TW364878B (en) |
| WO (1) | WO1998029245A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100394094C (en) * | 2004-10-20 | 2008-06-11 | 日产自动车株式会社 | Multi-layer resinous tube and multi-layer resinous container |
| CN101193742B (en) * | 2005-06-14 | 2010-10-13 | 巴斯福股份公司 | Multiple component moulded body comprising polyester layers |
| CN101233180B (en) * | 2004-08-06 | 2012-03-07 | 法商Bic公司 | Fuel supplies for fuel cells |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19803134A1 (en) * | 1998-01-28 | 1999-07-29 | Basf Ag | Multi-layer plastic composite material with a barrier layer made of polybutylene terephthalate |
| BE1012224A6 (en) * | 1998-10-08 | 2000-07-04 | Solvay | Hollow thermoplastic multilayer material and method for manufacturing. |
| JP2000154890A (en) | 1998-11-18 | 2000-06-06 | Tokai Rubber Ind Ltd | Tube for fuel pipe |
| DE19951670A1 (en) * | 1999-10-27 | 2001-05-03 | Ticona Gmbh | Weldable components made of polyacetal |
| US20020122926A1 (en) * | 2001-03-05 | 2002-09-05 | Goodson Raymond L. | Laminated article and method of making same |
| US7008700B1 (en) | 2001-03-05 | 2006-03-07 | 3-Form | Architectural laminate panel with embedded compressible objects and methods for making the same |
| FR2840848B1 (en) * | 2002-06-13 | 2004-10-15 | Inst Francais Du Petrole | MULTILAYER STRUCTURE WITH CONTROLLED PERMEABILITY |
| DE10251333A1 (en) * | 2002-11-05 | 2004-05-19 | Ticona Gmbh | Composite including polyacetal and polyolefin shaped parts useful for preparation of structural parts contacting fuels, especially fuel-feed units, valves, tanks, or tank filler caps, gear wheels, guide rollers, drive parts |
| US7183005B2 (en) | 2004-08-20 | 2007-02-27 | Exxonmobil Chemical Patents Inc. | Impact strength improvement of regrind |
| US20060046017A1 (en) | 2004-09-01 | 2006-03-02 | 3Form | Architectural glass panels with embedded objects and methods for making the same |
| EP2150407A4 (en) | 2007-05-08 | 2013-03-06 | Hunter Douglas Ind Switzerland | Multivariate color system with texture application |
| USD691289S1 (en) | 2012-09-05 | 2013-10-08 | 3Form, Inc. | Panel with cut and aligned thatch interlayer |
| JP6870293B2 (en) * | 2016-11-21 | 2021-05-12 | 三菱ケミカル株式会社 | Fuel container |
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|---|---|---|---|---|
| US3255781A (en) * | 1963-11-27 | 1966-06-14 | Du Pont | Polyoxymethylene pipe structure coated with a layer of polyethylene |
| JPS55121058A (en) * | 1979-03-14 | 1980-09-17 | Mitsui Petrochemical Ind | Multilayer laminated structure |
| JPH0751343B2 (en) * | 1988-10-17 | 1995-06-05 | 日本石油化学株式会社 | Hollow container |
| DE4025219A1 (en) * | 1990-08-09 | 1992-02-13 | Hoechst Ag | THERMOPLASTIC POLYOXYMETHYLENE SHAPING MATERIAL WITH HIGH TOUGHNESS AND THEIR USE |
| JPH04224385A (en) * | 1990-12-21 | 1992-08-13 | Tokai Rubber Ind Ltd | Tube for fuel piping |
| JP3067891B2 (en) * | 1992-04-21 | 2000-07-24 | 宇部興産株式会社 | Multilayer fuel tubes for automobiles |
| DE4214383C2 (en) * | 1992-04-30 | 1996-08-14 | Inventa Ag | Coextruded multilayer polymer tube |
| US5443874A (en) * | 1993-05-24 | 1995-08-22 | Mitsubishi Petrochemical Co., Ltd. | Hollow multi-layer molding |
| DE69431579T2 (en) * | 1993-08-03 | 2003-03-27 | Nitta Moore Co., Osaka | Fuel transport tube |
| EP0638749B1 (en) * | 1993-08-09 | 1998-06-17 | Victaulic Plc | Improvements in or relating to pipes |
| JPH07126483A (en) * | 1993-11-04 | 1995-05-16 | Polyplastics Co | Polyacetal resin composition |
| JPH07195496A (en) * | 1993-12-28 | 1995-08-01 | Polyplastics Co | Hollow molded product made of polyacetal resin |
| US5451624A (en) * | 1994-02-15 | 1995-09-19 | Rohm And Haas Company | Stabilized modifier and impact modified thermoplastics |
| JPH0885174A (en) * | 1994-09-19 | 1996-04-02 | Mitsubishi Chem Corp | Multilayer hollow molded form |
| FR2731497B1 (en) * | 1995-03-10 | 1997-04-30 | Atochem Elf Sa | TUBE FOR TRANSPORTING DRINKING WATER |
| CA2175609C (en) * | 1995-05-12 | 2004-06-22 | Hata, Nobuhiko | Fuel tank |
| FR2736987B1 (en) * | 1995-07-20 | 1997-09-26 | Hutchinson | FUEL TRANSPORT HOSE |
-
1997
- 1997-12-22 CN CN97181182A patent/CN1245457A/en active Pending
- 1997-12-22 KR KR1019997005994A patent/KR20000062401A/en not_active Application Discontinuation
- 1997-12-22 CA CA002276009A patent/CA2276009A1/en not_active Abandoned
- 1997-12-22 EP EP97954623A patent/EP0949996A2/en not_active Withdrawn
- 1997-12-22 WO PCT/US1997/023835 patent/WO1998029245A2/en not_active Application Discontinuation
- 1997-12-22 BR BR9713804-5A patent/BR9713804A/en not_active Application Discontinuation
- 1997-12-22 JP JP53019298A patent/JP2001522320A/en active Pending
- 1997-12-30 AR ARP970106257A patent/AR011325A1/en not_active Application Discontinuation
-
1998
- 1998-01-22 TW TW087100866A patent/TW364878B/en active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101233180B (en) * | 2004-08-06 | 2012-03-07 | 法商Bic公司 | Fuel supplies for fuel cells |
| CN100394094C (en) * | 2004-10-20 | 2008-06-11 | 日产自动车株式会社 | Multi-layer resinous tube and multi-layer resinous container |
| CN101193742B (en) * | 2005-06-14 | 2010-10-13 | 巴斯福股份公司 | Multiple component moulded body comprising polyester layers |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998029245A3 (en) | 1998-12-23 |
| TW364878B (en) | 1999-07-21 |
| AR011325A1 (en) | 2000-08-16 |
| JP2001522320A (en) | 2001-11-13 |
| BR9713804A (en) | 2000-01-25 |
| WO1998029245A2 (en) | 1998-07-09 |
| EP0949996A2 (en) | 1999-10-20 |
| CA2276009A1 (en) | 1998-07-09 |
| KR20000062401A (en) | 2000-10-25 |
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