CA2276009A1 - Laminate structures for fuel containers - Google Patents
Laminate structures for fuel containers Download PDFInfo
- Publication number
- CA2276009A1 CA2276009A1 CA002276009A CA2276009A CA2276009A1 CA 2276009 A1 CA2276009 A1 CA 2276009A1 CA 002276009 A CA002276009 A CA 002276009A CA 2276009 A CA2276009 A CA 2276009A CA 2276009 A1 CA2276009 A1 CA 2276009A1
- Authority
- CA
- Canada
- Prior art keywords
- layer
- moiety
- alkylstilbene
- alpha
- blend
- 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.)
- Abandoned
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 112
- 239000000203 mixture Substances 0.000 claims abstract description 85
- 230000004888 barrier function Effects 0.000 claims abstract description 83
- 229920000098 polyolefin Polymers 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- 230000035699 permeability Effects 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 226
- -1 poly(butylene terephthalate) Polymers 0.000 claims description 71
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 55
- 239000012745 toughening agent Substances 0.000 claims description 50
- 229920000573 polyethylene Polymers 0.000 claims description 37
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 37
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 37
- 239000004698 Polyethylene Substances 0.000 claims description 35
- 229920001903 high density polyethylene Polymers 0.000 claims description 28
- 239000004700 high-density polyethylene Substances 0.000 claims description 28
- 229920000728 polyester Polymers 0.000 claims description 28
- 229920006324 polyoxymethylene Polymers 0.000 claims description 28
- 229930182556 Polyacetal Natural products 0.000 claims description 26
- 239000000945 filler Substances 0.000 claims description 23
- 239000010445 mica Substances 0.000 claims description 22
- 229910052618 mica group Inorganic materials 0.000 claims description 22
- 229920001971 elastomer Polymers 0.000 claims description 20
- 239000000806 elastomer Substances 0.000 claims description 20
- 239000004417 polycarbonate Substances 0.000 claims description 19
- 229920000515 polycarbonate Polymers 0.000 claims description 19
- 229920000570 polyether Polymers 0.000 claims description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 17
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012792 core layer Substances 0.000 claims description 10
- 229920001169 thermoplastic Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 6
- 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
- 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
- 239000004743 Polypropylene Substances 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000003348 petrochemical agent Substances 0.000 description 5
- 229920003345 Elvax® Polymers 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000002828 fuel tank Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 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
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000001125 extrusion Methods 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
- 239000010423 industrial mineral Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 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
- FAIFRACTBXWXGY-JTTXIWGLSA-N COc1ccc2C[C@H]3N(C)CC[C@@]45[C@@H](Oc1c24)[C@@]1(OC)C=C[C@@]35C[C@@H]1[C@](C)(O)CCc1ccccc1 Chemical compound COc1ccc2C[C@H]3N(C)CC[C@@]45[C@@H](Oc1c24)[C@@]1(OC)C=C[C@@]35C[C@@H]1[C@](C)(O)CCc1ccccc1 FAIFRACTBXWXGY-JTTXIWGLSA-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
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 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
- 239000011354 acetal resin Substances 0.000 description 1
- 150000007513 acids Chemical class 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
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 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
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 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
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QYFRTHZXAGSYGT-UHFFFAOYSA-L hexaaluminum dipotassium dioxosilane oxygen(2-) difluoride hydrate Chemical compound O.[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O QYFRTHZXAGSYGT-UHFFFAOYSA-L 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000002648 laminated material Substances 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical group C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007493 shaping process Methods 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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/m2-day or less, based on a layer thickness of 1 mil, when measured at 40 ~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
WO 98!29245 PCTIUS97/23835 LAMINATE STRUCTURES FOR FUEL CONTAINERS
This invention relates to multilayer laminate structures having barrier properties (permeation preventing properties) with respect to vehicle fuels (such as gasoline) and mixtures of hydrocarbons with oxygen-containing organic compounds {such as gasoline containing alcohol compounds).
Fuel tanks made of a multilayer laminate material comprising a layer of a particular polyethylene, a barrier layer made of a polyester, such as polyethylene terephthalate (PET), and an adhesive layer made of a modified polyethylene are described in U.S. Patent 5,443,874. However, PET is swelled significantly by oxygenated fuels, especially fuels in which the oxygenate is an alcohol such as methanol, and therefore, is a poor barrier to oxygenated fuels. Ethylene vinyl alcohols (EVOH), such as EvaITM F, a product of Eval Co., are currently used as fuel barriers in the manufacture of fuel tanks. However, Eval F, as known in the automotive industry, does not provide adequate barrier properties toward oxygenated fuels in which the oxygenate is an alcohol, such as methanol. In addition, Eval F is known to the packaging industry to be moisture sensitive, which, after exposure to moisture, possesses a substantially higher rate of permeation of oxygen) carbon dioxide, water vapor, and volatile organic compounds through films of this material.
Multilayer containers comprising an inner layer of polyethylene naphthalenedicarboxylate) and an outer layer of polyethylene terephthalate) are described in U.S. Patent 5,443,766. This structure) is too expensive for the fuel tank application.
It would be desirable to provide a multilayer laminate structure for making containers for vehicle fuels and mixtures of hydrocarbons with oxygen-containing organic compounds which do not have the above disadvantages of the prior art structures.
In a first aspect, the present invention is 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 selected from:
(1 ) a hydroxy-functionalized polyether containing an a-alkylstilbene moiety, (2) a polyester containing an a-alkylstilbene moiety, SUBSTITUTE SHEET ( rule 26 ) (3) a polycarbonate containing an a-alkylstilbene moiety, ( 4 ) polyester-co-carbonate containing an a-aikylstilbene moiety, (5) polyacetal, (6) blends of (1 ), (2), (3), {4), (5), and/or a thermoplastic polyester, and/or a toughening agent and/or a filler having a high aspect ratio, and (7) a blend of (a) poly(butylene terephthalate) (PBT), (b) polyethylene terephthalate){PET), and/or (c) a toughening agent and/or {d) a filler having a high aspect ratio; 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.
In a second aspect, the present invention is a multiiayer laminate structure comprising:
(A) an outer layer of a polyolefin or a blend of two or more different poiyolefins;
and (B) an inner layer of a fuel barrier polymer or blends thereof, the fuel barrier polymer or blends thereof having a Fuel CM15 permeability of 45 g-mil/m2-day or less, based on a layer thickness of 1 mil, when measured at 40°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.
in a third aspect, the present invention is a multilayer laminate structure comprising:
(A) an inner layer of a fuel barrier polymer, and/or (B) an outer layer of a fuel barrier polymer, the fuel barrier polymer selected from:
(1 ) a hydroxy-functionalized polyether containing an a-alkylstilbene moiety, SUBSTITUTE SHEET ( rule 26 ) (2) a polyester containing an a-alkylstilbene moiety (3) a polycarbonate containing an a-alkylstilbene moiety, (4) a polyester-co-carbonate containing an a-aikylstilbene moiety) (5) poly{ethylene-2,6-naphthalenedicarboxylate) (PEN), (6) poly(butylene-2,6-naphthalenedicarboxyiate) (PBN), (7) poly(butylene terephthalate) (PBT), (8) poly(propane terephthalate) (PPT), (9) polyacetal, and (10) blends of (1 )) (2), (3), (4), (5), (6), (7), (8), and/or (9), and/or PET, and/or a toughening agent and/or a filler having a high aspect ratio; and (C) a core layer of a polyolefin or a blend of two or more different polyolefins;
and optionally (D) a tie layer interposed between a polyolefin layer and an adjacent fuel barrier layer; and/or optionally (E) a regrind layer interposed between a tie layer and a polyolefin layer.
In a fourth aspect) the present invention is a multilayer laminate structure comprising:
(A) an inner layer and an outer layer of a polyolefin or a blend of two or more different poiyolefins, (B) a core layer of a fuel barrier polymer consisting of a blend of EVOH and a filler having a high aspect ratio; 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.
In a fifth aspect, the present invention is a process for preparing the multilayer laminate structures of the first, second, third and fourth aspects, which comprises coextruding the layers defined in each of said aspects.
When formed into a container, the inner layer of the multilayer laminate structure is the layer which comes in contact with the fuel placed inside the container.
SUBSTITUTE SHEET ( rule 26 ) As used herein, the term "Fuel CM15" refers to a test fuel mixture consisting of 42.5 volume percent toluene, 42.5 volume percent isooctane and 15 volume percent methanol.
The multilayer laminate structure of the present invention can be used wherever very good fuel resistance and hydrolytic stability is desired. Hence, the multilayer laminate structure can be used as a container, such as a fuel tank for any vehicle, for example, a jet aircraft, an automobile, truck) lawn and garden applications; marine applications; and storage tanks or bottles for chemicals. The laminate structure can also be used as tubing for the transfer of fuel or chemicals.
By the term "polyolefin" is meant a polymer or copolymer of ethylene, that is, a polymer derived solely from ethylene, or ethylene and one or more monomers copolymerizable therewith. Such polymers (including raw materials, their proportions, polymerization temperatures, catalysts and other conditions) are well-known in the art and reference is made thereto for the purpose of this invention. Additional comonomers which can be polymerized with ethylene include olefin monomers having from 3 to 12 carbon atoms, ethylenically unsaturated carboxylic acids (both mono- and difunctional) and derivatives of such acids such as esters (for example., alkyl acryiates) and anhydrides; monovinylidene aromatics and monovinylidene aromatics substituted with a moiety other than halogen such as styrene and methylstyrene; and carbon monoxide. Exemplary monomers which can be polymerized with ethylene include 1-octene, acrylic acid, methacryiic acid, vinyl acetate and malefic anhydride.
Polyolefins which can be employed in the practice of the present invention for preparing the multilayer laminate structure include polypropylene, polyethylene, and copolymers and blends thereof, as well as ethylene-propylene-diene terpolymers. Preferred poiyolefins are polypropylene, linear high density polyethylene (HDPE), heterogeneousiy-branched linear low density polyethylene (LLDPE) such as DOWLEXT""
polyethylene resin (a trademark of The Dow Chemical Company), heterogeneously branched ultra low linear density polyethylene (ULDPE) such as ATTANET"~ ULDPE (a trademark of The Dow Chemical Company); homogeneously-branched) linear ethylene/a-olefin copolymers such as TAFMERT""
(a trademark of Mitsui Petrochemicals Company Limited) and EXACTT"" (a trademark of Exxon Chemical Company); homogeneously branched, substantially linear ethylene/a-olefin polymers such as AFFINITYT"~ (a trademark of The Dow Chemical Company) and ENGAGES (a trademark DuPont Dow Elastomers L.L. C) of poiyolefin elastomers, which can be prepared as disclosed in U.S. Patents 5,272,236 and 5,278,272; and high pressure, free radical polymerized ethylene polymers and copolymers such as low density polyethylene (LDPE), ethylene-acrylic SUBSTITUTE SHEET { rule 26 ) WO 98!29245 PCT/US97I23835 acid (EAA) copolymers such as PRIMACORT"" (trademark of The Dow Chemical Company), and ethylene-vinyl acetate (EVA) copolymers such as ESCORENET"" polymers (a trademark of Exxon Chemical Company), and ELVAXT"" (a trademark of E.I. du Pont de Nemours & Co.).
The more preferred polyolefins are the homogeneously-branched linear and substantially linear ethylene copolymers with a density (measured in accordance with ASTM D-792) of 0.85 to 0.99 g/cm3, a weight average molecular weight to number average molecular weight ratio (MwlMn) from 1.5 to 3.0, a measured melt index (measured in accordance with ASTM D-(190/2.16)) of 0.01 to 100 g/10 min, and an 110/12 of 6 to 20 (measured in accordance with ASTM D-1238 (190/10)).
In general, high density polyethylene (HDPE) has a density of at feast about 0.94 grams per cubic centimeter (g/cc) (ASTM Test Method D-1505). HDPE is commonly produced using techniques similar to the preparation of linear low density polyethyienes. Such techniques are described in U.S. Patents 2,825,721; 2,993,876; 3,250,825 and 4,204,050. The preferred HDPE employed in the practice of the present invention has a density of from 0.94 to 0.99 g/cc and a melt index of from 0.01 to 35 grams per 10 minutes as determined by ASTM
Test Method D-1238.
Fuel barrier polymers which can be employed in the practice of the present invention for preparing the multilayer laminate structure have a Fuel CM15 permeability of 45 g-mil/m2-day or less, based on a layer thickness of 1 mil) when measured at 40°C and under ambient pressure conditions of 700 to 760 torr.
These fuel barrier polymers include hydroxy-functionalized polyethers, polycarbonates, polyesters or potyestercarbonates containing a moiety represented by the structu re _ R
/
O-wherein R is methyl, ethyl or propyl.
Preferably, the hydroxy-functionafized polyether containing an a-alkylstilbene moiety employed in the practice of the present invention is represented by the structure:
SUBSTITUTE SHEET ( rule 26 ) R
OH
-, n wherein R is methyl, ethyl or propyl and n is an integer from 10 to 1000.
The hydroxy-functionalized polyether containing an a-alkylstilbene moiety is prepared by (a) reacting an inertly-substituted or unsubstituted dihydroxy-a-alkyistilbene with the digiycidyl ether of an inertly-substituted or unsubstituted dihydroxy-a-alkylstilbene. This polymer is described in U.S. Patent 5,686,551.
Preferably, the polycarbonate, polyester) or polyestercarbonate containing the a-alkylstilbene moiety employed in the practice of the present invention comprises repeat units of the formula:
1o fR-o-x-of wherein R independently in each occurrence is the divalent nucleus of a difunctional aromatic diol; X is selected from:
-C(O)-, -C(O)-R1-C(O)-, or a mixture thereof; and R1 independently in each occurrence is the divalent nucleus of an aromatic dicarboxylic acid.
The polycarbonate, polyester, and polyestercarbonate containing the a-alkylstilbene moiety employed in the practice of the present invention are described in U.S.
Patent 5,614,599.
Thermoplastic polyesters and blends thereof, and polyacetal which have a Fuel CM15 permeability of 45 g-mil/m2-day or less, based on a layer thickness of 1 mil, when measured at 40°C and under ambient pressure conditions of 700 to 760 torn can also be employed as fuel barrier polymers in the practice of the present invention.
Preferably, the thermoplastic polyesters contain a terephthalate moiety or a 2,6-naphthalenedicarboxylate moiety.
Examples of thermoplastic polyesters which can be employed in the practice of the present invention include poly(butylene-2,6-naphthalenedicarboxyiate) (PBN), poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), polyethylene terephthalate) (PET), poly(propane terephthalate) (PPT), poly(butylene terephthalate) (PBT), and mixtures thereof.
Surprisingly, it has been found that PBT, while only a marginally acceptable fuel barrier material SUBSTITUTE SHEET ( rule 26 ) 42474A ,.
alone) becomes an exceptional fuel barrier material when blended with PET, which alone is a very poor fuel barrier material.
PEN and PBN and methods for their preparation (including the specific monomers employed in their formation, their proportions, polymerization temperatures, catalysts and other conditions) are known in the art and reference is made thereto for the purposes of this invention. For purposes of illustration and not limitation, reference is particularly made to U.S. Patent 5,102,705. PPT is available from Shell Chemical. PET, PBT, and polyacetal are commercially available.
Fillers having high aspect ratios can also be blended with the fuel barrier polymers. It has been found that fillers having a high aspect ratio significantly improve the fuel barrier properties of the fuel barrier polymer, while those that have low aspect ratios do not. As used herein, the term "high aspect ratio" refers to the ratio of the length or width of the platelet to the depth of the platelet which is 10 to 1000. Overall the length and width of the platelets are, each individually, from 10 to 1000 nm.
Fillers having high aspect ratios which can be employed in the practice of the present invention include, but are not limited to Mica and montmorillonite clay.
Toughening agents can also be blended with the fuel barrier polymer.
Toughening agents which can be employed in the practice of the present invention include an elastomer commercially available as Paraloid0) (a product of Rohm and Haas) and having a rubbery core of butyl acrylate or butadiene and a hard shell of polymethyl methacrylate) and a malefic anhydride grafted polyethylene elastomer (ENGAGED-g-MA, a product of DuPont Dow Elastomers L.L.C. ). The elastomers having a rubbery core of butyl acrylate or butadiene and a hard shell of polymethyl methacrylate are described in EP-A-0 470 618 and U.S. Patent 5,256,733.
The toughening agents and fillers may be incorporated into the fuel barrier polymers by using conventional melt processing, as well as dry blending techniques for thermally sensitive polymers.
The tie layer, also commonly referred to as an adhesive layer, which can be employed in the practice of the present invention is made of an adhesive material, such as a modified polyethylene elastomer. Preferably, the adhesive material is a malefic anhydride grafted polyethylene or polypropylene such as ADMERT"" (trademark of Mitsui Petrochemicals) adhesive resin or ethylene-vinyl acetate copolymer resins such as ELVAX'''~' (trademark of DuPont).
_7_ A~iE~dDED SHEE r Each of the polymers forming the layers of the multilayer laminate structure of the present invention may contain various additives in an amount that does not adversely affect the desired properties of the polymers, Examples of such additives include antioxidants, ultraviolet light absorbers, thermal processing stabilizers, colorants, lubricants, flame retardants, impact modifiers, plasticizers, antistatic agents, pigments, and nucleating agents and filters, such as zeolite, talc, and calcium carbonate. The method of incorporating the additives is not critical. The additives can conveniently be added to the polymer prior to preparing the multilayer laminate structure. If the polymer is prepared in solid form, the additives can be added to the melt prior to preparing the multilayer laminate structure.
Processes for forming and using multilayer structures such as those described above inherently produce a certain amount of scrap material. From an economic standpoint, it is desirable to employ this scrap material in a useful manner. Generally, the scrap material is ground into particles or powder and) optionally, melted, kneaded and formed into pellets. The ground scrap material, in the form of powder, particles or pellets, may be added either as a part of the material forming one or more of the plurality of layers or as a material for forming an additional layer substantially completely made of the scrap material. Thus, the multilayer laminate structure of the present invention can comprise a further layer of a regrind (ground scrap) of the polyolefin polymer layer, the fuel barrier polymer layer and, optionally) the adhesive polymer layer.
The designed thickness of each layer in the laminate structure is dependent on a number of factors including the intended use, materials stored in the container, the length of storage prior to use, and the specific composition employed in each layer of the laminate.
In general, the laminate structure will have a total thickness of from 10 to mils) preferably from 100 to 500 mils; with the thickness of the fuel barrier polymer layers) being from 0.1 to 50 mils, preferably from 0.5 to 25 mils; the thickness of the polyethylene iayer(s) being from 9.9 to 749.9 mils, preferably from 9.9 to 499.5 mils;
optionally, the thickness of the tie iayer(s) being from 0.1 to 20 mils, preferably from 0.1 to 5 mils;
and optionally, a regrind layer consisting of a blend of the fuel barrier polymer, polyethylene, and optionally, a tie material, from 1 to 375 mils, and preferably from 5 to 250 mils.
In a first configuration of layers, the multilayer laminate structure of the present invention comprises (A) an inner layer of a fuel barrier polymer selected from: (1 ) a hydroxy-functionaiized poiyether containing an a-alkylstilbene moiety, (2) a polyester, polycarbonate or polyester-co-carbonate containing an a-alkylstilbene moiety, (3) polyacetal, (4) PEN, PBN, _g_ SUBSTITUTE SHEET ( rule 26 ) PPT, or PBT, (5) a blend of any two or more of PEN, PET) PPT, PBN, and PBT, (6) a blend of (a) polyacetal) PEN, PPT, PBN) or PBT and (b) toughening agent A or toughening agent B, (7) a blend of (a) any two or more of PEN) PET, PBN, PPT, and PBT, and (b) toughening agent A
or toughening agent B, (8) a blend of (a) polyacetal, PEN, PPT, PBN, or PBT, and (b) Mica or a montmorillonite clay, (9) a blend of (a) any two or more of PEN, PET, PPT, PBN, and PBT, and (b) Mica or a montmorillonite clay) (10) a blend of (a) polyacetal, PEN, PBN, PPT, or PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay, and (11 ) a blend of (a) any 2 or more of PEN) PET, PPT, PBN, and PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay; (B) an outer layer of HDPE; (C) a tie layer of a modified polyethylene elastomer interposed between the fuel barrier polymer and the HDPE layer; and, optionally (D) a regrind layer comprising a blend of layers (A), (B), and (C) interposed between the tie layer and the outer polyethylene layer, wherein toughening agent A is a malefic anhydride-grafted polyethylene elastomer, available from DuPont Dow Elastomers L.L.C, as Engage0-g-MA, toughening agent B is an elastomer having a rubbery core (butyl acrylate or butadiene) and a hard shell, commercially available from Rohm and Haas as Paraloid~, and Mica is a high-aspect ratio inert filler, a product of Franklin Industrial Minerals.
Preferably, the inner layer is from 0.1 to 25 weight percent of the container and the outer layer is from 5.0 to 99.89 weight percent of the container. The tie layer between the fuel barrier polymer layer and the polyethylene layer is from 0.01 to 10 weight percent of the container. The optional regrind layer between the tie layer and the outer layer is from 5 to 60 weight percent of the container.
A second configuration of layers of the multilayer laminate structure of the present invention is the same as the first configuration, except the fuel barrier layer is the outer layer and the HDPE layer is the inner layer.
In a third configuration, the multilayer laminate structure of the present invention comprises (A) inner and outer layers of a fuel barrier polymer selected from:
(1 ) a hydroxy-functionalized polyether containing an a-alkylstilbene moiety, (2) a polyester, polycarbonate or polyester-co-carbonate containing an a-alkylstilbene moiety, (3) polyacetal, (4) PEN, PBN, PPT, or PBT, (5) a blend of any two or more of PEN, PET, PPT, PBN, and PBT, (6) a blend of (a) poiyacetal, PEN, PPT, PBN, or PBT, and (b) toughening agent A or toughening agent B, (7) a blend of (a) any two or more of PEN, PET, PPT, PBN, and PBT, and (b) toughening agent A
or toughening agent B, (8) a blend of (a) polyacetal, PEN, PPT, PBN, or PBT, and (b) Mica or a _g_ SUBSTITUTE SHEET { rule 26 ) montmorillonite clay, (9) a blend of (a) any two or more of PEN, PET, PPT) PBN, and PBT, and (b) Mica or a montmorillonite clay, (10) a blend of (a) polyacetal, PEN, PBN, PPT, or PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay, and (11 ) a blend of (a) any 2 or more of PEN, PET, PPT, PBN, and PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay; (B) a core layer of HDPE; (C) a tie layer of a modified polyethylene elastomer interposed between the fuel barrier polymer layers and the HDPE layer; and optionally (D) a regrind layer comprising a blend of layers (A), (B), and (C) interposed between the tie layer and the outer polyethylene layer, wherein toughening agents A and B are as defined previously.
Preferably, the inner and outer layers) each individually, are from 0.1 to 25 weight percent of the container and the core layer is from 5.0 to 99.78 weight percent of the container. The tie layers between the fuel barrier polymer layers and the polyethylene layer is from 0.01 to 10 weight percent of the container. The optional regrind layer between a tie layer and the core layer is from 5 to 60 weight percent of the container.
In a fourth configuration, the multilayer laminate structure of the present invention comprises (A) an inner layer of polyethyiene; (B) a core layer of a fuel barrier polymer selected from: (1 ) a hydroxy-functionalized polyether containing an a-alkylstilbene moiety, (2) a polyester, polycarbonate or polyester-co-carbonate containing an a-alkylstilbene moiety, (3) polyacetal, (4) a blend of (a) any two or more of PEN, PET) PPT, PBN, and PBT, and (b) toughening agent A or toughening agent B, (5) a blend of (a) any two or more of PEN, PET, PPT, PBN, and PBT, and (b) Mica or montmorilfonite clay, and (6) a blend of EVOH and Mica or montmorillonite clay; and (C) an outer layer of a polyethylene; optionally (D) a tie layer of a modified polyethylene elastomer interposed between the fuel barrier polymer layer and the inner and outer HDPE layer; and optionally (E) a regrind layer comprising a blend of layers (A), (B), (C), and (D) interposed between the tie layer and the outer polyethylene layer, wherein toughening agents A and B are as defined previously.
Preferably, the polyethylene inner and outer layers together comprise from 5 to 60 weight percent of the container; the fuel barrier polymer layer comprises from 0.1 to 25 weight percent of the container, the tie layers between the fuel barrier polymer layer and the polyethylene layers comprise from 0.01 to 10 weight percent of the container, and the optional regrind layer between the tie layer and the outer polyethylene layer is from 5 to 60 weight percent of the container.
SUBSTITUTE SHEET ( rule 26 ) The multilayer laminate structure of the present invention can be produced using conventional extrusion techniques such as feedblock coextrusion, multimanifold die coextrusion) or combinations of the two, or may be produced by a laminating procedure whereby self-sustaining lamina are bonded together by applications of heat and pressure and reference is made thereto for the purposes of this invention. The volume (thickness) of each individual layer may be controlled as it is extruded. Thus, the overall thickness of the multilayer structure may be controlled to produce a film or sheet of desired thickness.
The laminate structure of the present invention can be fabricated into articles using conventional thermoplastic fabrication techniques such as compression molding, injection molding, lamellar injection molding, blow molding, extrusion, calendering and thermoforming. A
typical thermoforming process comprises heating a thermoplastic sheet to its softening point and then shaping the sheet at a forming station utilizing various molds and/or vacuum or air pressure assists or plug assists. Other thermoforming techniques include solid phase pressure forming (SPPF) and the so-called scrapiess forming process (SFP). For purposes of this invention, references to thermoforming techniques or thermoformable structures will include SPPF and SFP. During fabrication, the molecules of the polymer can be oriented by methods well known in the art. One such method is described in U.S. Patent 5,382,693.
Orientation is also described in Plastics Engineering Handbook of the Society of the Plastics Industry, Inc., 4th Ed., p. 113-115) 182 and 183. Articles formed therefrom include containers, molded parts) and tubing. Examples of such articles include flexible and rigid containers such as tanks or bottles used for the storage of chemicals and fuels, including oxygenated fuels which contain alcohols such as methanol or ethanol, and tubing used in the transfer of chemicals and fuels, including oxygenated fuels which contain alcohols such as methanol or ethanol.
When formed into a container or tube, the inner layer of the multilayer laminate structure of the present invention is the layer which comes in contact with the fuel that is placed inside the container or tube. Thus, in the previously described configuration of layers of the muitilayer laminate structure, the fuel barrier polymer layer of the multilayer laminate structure is either the layer which comes in contact with the fuel that is placed inside the container or tube, and/or the layer on the outside of the container or tube, or the layer which is sandwiched between layers of polyethylene, and, optionally, tie layers, and/or, regrind layers.
The following working examples are given to illustrate the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and percentages are by weight.
This invention relates to multilayer laminate structures having barrier properties (permeation preventing properties) with respect to vehicle fuels (such as gasoline) and mixtures of hydrocarbons with oxygen-containing organic compounds {such as gasoline containing alcohol compounds).
Fuel tanks made of a multilayer laminate material comprising a layer of a particular polyethylene, a barrier layer made of a polyester, such as polyethylene terephthalate (PET), and an adhesive layer made of a modified polyethylene are described in U.S. Patent 5,443,874. However, PET is swelled significantly by oxygenated fuels, especially fuels in which the oxygenate is an alcohol such as methanol, and therefore, is a poor barrier to oxygenated fuels. Ethylene vinyl alcohols (EVOH), such as EvaITM F, a product of Eval Co., are currently used as fuel barriers in the manufacture of fuel tanks. However, Eval F, as known in the automotive industry, does not provide adequate barrier properties toward oxygenated fuels in which the oxygenate is an alcohol, such as methanol. In addition, Eval F is known to the packaging industry to be moisture sensitive, which, after exposure to moisture, possesses a substantially higher rate of permeation of oxygen) carbon dioxide, water vapor, and volatile organic compounds through films of this material.
Multilayer containers comprising an inner layer of polyethylene naphthalenedicarboxylate) and an outer layer of polyethylene terephthalate) are described in U.S. Patent 5,443,766. This structure) is too expensive for the fuel tank application.
It would be desirable to provide a multilayer laminate structure for making containers for vehicle fuels and mixtures of hydrocarbons with oxygen-containing organic compounds which do not have the above disadvantages of the prior art structures.
In a first aspect, the present invention is 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 selected from:
(1 ) a hydroxy-functionalized polyether containing an a-alkylstilbene moiety, (2) a polyester containing an a-alkylstilbene moiety, SUBSTITUTE SHEET ( rule 26 ) (3) a polycarbonate containing an a-alkylstilbene moiety, ( 4 ) polyester-co-carbonate containing an a-aikylstilbene moiety, (5) polyacetal, (6) blends of (1 ), (2), (3), {4), (5), and/or a thermoplastic polyester, and/or a toughening agent and/or a filler having a high aspect ratio, and (7) a blend of (a) poly(butylene terephthalate) (PBT), (b) polyethylene terephthalate){PET), and/or (c) a toughening agent and/or {d) a filler having a high aspect ratio; 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.
In a second aspect, the present invention is a multiiayer laminate structure comprising:
(A) an outer layer of a polyolefin or a blend of two or more different poiyolefins;
and (B) an inner layer of a fuel barrier polymer or blends thereof, the fuel barrier polymer or blends thereof having a Fuel CM15 permeability of 45 g-mil/m2-day or less, based on a layer thickness of 1 mil, when measured at 40°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.
in a third aspect, the present invention is a multilayer laminate structure comprising:
(A) an inner layer of a fuel barrier polymer, and/or (B) an outer layer of a fuel barrier polymer, the fuel barrier polymer selected from:
(1 ) a hydroxy-functionalized polyether containing an a-alkylstilbene moiety, SUBSTITUTE SHEET ( rule 26 ) (2) a polyester containing an a-alkylstilbene moiety (3) a polycarbonate containing an a-alkylstilbene moiety, (4) a polyester-co-carbonate containing an a-aikylstilbene moiety) (5) poly{ethylene-2,6-naphthalenedicarboxylate) (PEN), (6) poly(butylene-2,6-naphthalenedicarboxyiate) (PBN), (7) poly(butylene terephthalate) (PBT), (8) poly(propane terephthalate) (PPT), (9) polyacetal, and (10) blends of (1 )) (2), (3), (4), (5), (6), (7), (8), and/or (9), and/or PET, and/or a toughening agent and/or a filler having a high aspect ratio; and (C) a core layer of a polyolefin or a blend of two or more different polyolefins;
and optionally (D) a tie layer interposed between a polyolefin layer and an adjacent fuel barrier layer; and/or optionally (E) a regrind layer interposed between a tie layer and a polyolefin layer.
In a fourth aspect) the present invention is a multilayer laminate structure comprising:
(A) an inner layer and an outer layer of a polyolefin or a blend of two or more different poiyolefins, (B) a core layer of a fuel barrier polymer consisting of a blend of EVOH and a filler having a high aspect ratio; 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.
In a fifth aspect, the present invention is a process for preparing the multilayer laminate structures of the first, second, third and fourth aspects, which comprises coextruding the layers defined in each of said aspects.
When formed into a container, the inner layer of the multilayer laminate structure is the layer which comes in contact with the fuel placed inside the container.
SUBSTITUTE SHEET ( rule 26 ) As used herein, the term "Fuel CM15" refers to a test fuel mixture consisting of 42.5 volume percent toluene, 42.5 volume percent isooctane and 15 volume percent methanol.
The multilayer laminate structure of the present invention can be used wherever very good fuel resistance and hydrolytic stability is desired. Hence, the multilayer laminate structure can be used as a container, such as a fuel tank for any vehicle, for example, a jet aircraft, an automobile, truck) lawn and garden applications; marine applications; and storage tanks or bottles for chemicals. The laminate structure can also be used as tubing for the transfer of fuel or chemicals.
By the term "polyolefin" is meant a polymer or copolymer of ethylene, that is, a polymer derived solely from ethylene, or ethylene and one or more monomers copolymerizable therewith. Such polymers (including raw materials, their proportions, polymerization temperatures, catalysts and other conditions) are well-known in the art and reference is made thereto for the purpose of this invention. Additional comonomers which can be polymerized with ethylene include olefin monomers having from 3 to 12 carbon atoms, ethylenically unsaturated carboxylic acids (both mono- and difunctional) and derivatives of such acids such as esters (for example., alkyl acryiates) and anhydrides; monovinylidene aromatics and monovinylidene aromatics substituted with a moiety other than halogen such as styrene and methylstyrene; and carbon monoxide. Exemplary monomers which can be polymerized with ethylene include 1-octene, acrylic acid, methacryiic acid, vinyl acetate and malefic anhydride.
Polyolefins which can be employed in the practice of the present invention for preparing the multilayer laminate structure include polypropylene, polyethylene, and copolymers and blends thereof, as well as ethylene-propylene-diene terpolymers. Preferred poiyolefins are polypropylene, linear high density polyethylene (HDPE), heterogeneousiy-branched linear low density polyethylene (LLDPE) such as DOWLEXT""
polyethylene resin (a trademark of The Dow Chemical Company), heterogeneously branched ultra low linear density polyethylene (ULDPE) such as ATTANET"~ ULDPE (a trademark of The Dow Chemical Company); homogeneously-branched) linear ethylene/a-olefin copolymers such as TAFMERT""
(a trademark of Mitsui Petrochemicals Company Limited) and EXACTT"" (a trademark of Exxon Chemical Company); homogeneously branched, substantially linear ethylene/a-olefin polymers such as AFFINITYT"~ (a trademark of The Dow Chemical Company) and ENGAGES (a trademark DuPont Dow Elastomers L.L. C) of poiyolefin elastomers, which can be prepared as disclosed in U.S. Patents 5,272,236 and 5,278,272; and high pressure, free radical polymerized ethylene polymers and copolymers such as low density polyethylene (LDPE), ethylene-acrylic SUBSTITUTE SHEET { rule 26 ) WO 98!29245 PCT/US97I23835 acid (EAA) copolymers such as PRIMACORT"" (trademark of The Dow Chemical Company), and ethylene-vinyl acetate (EVA) copolymers such as ESCORENET"" polymers (a trademark of Exxon Chemical Company), and ELVAXT"" (a trademark of E.I. du Pont de Nemours & Co.).
The more preferred polyolefins are the homogeneously-branched linear and substantially linear ethylene copolymers with a density (measured in accordance with ASTM D-792) of 0.85 to 0.99 g/cm3, a weight average molecular weight to number average molecular weight ratio (MwlMn) from 1.5 to 3.0, a measured melt index (measured in accordance with ASTM D-(190/2.16)) of 0.01 to 100 g/10 min, and an 110/12 of 6 to 20 (measured in accordance with ASTM D-1238 (190/10)).
In general, high density polyethylene (HDPE) has a density of at feast about 0.94 grams per cubic centimeter (g/cc) (ASTM Test Method D-1505). HDPE is commonly produced using techniques similar to the preparation of linear low density polyethyienes. Such techniques are described in U.S. Patents 2,825,721; 2,993,876; 3,250,825 and 4,204,050. The preferred HDPE employed in the practice of the present invention has a density of from 0.94 to 0.99 g/cc and a melt index of from 0.01 to 35 grams per 10 minutes as determined by ASTM
Test Method D-1238.
Fuel barrier polymers which can be employed in the practice of the present invention for preparing the multilayer laminate structure have a Fuel CM15 permeability of 45 g-mil/m2-day or less, based on a layer thickness of 1 mil) when measured at 40°C and under ambient pressure conditions of 700 to 760 torr.
These fuel barrier polymers include hydroxy-functionalized polyethers, polycarbonates, polyesters or potyestercarbonates containing a moiety represented by the structu re _ R
/
O-wherein R is methyl, ethyl or propyl.
Preferably, the hydroxy-functionafized polyether containing an a-alkylstilbene moiety employed in the practice of the present invention is represented by the structure:
SUBSTITUTE SHEET ( rule 26 ) R
OH
-, n wherein R is methyl, ethyl or propyl and n is an integer from 10 to 1000.
The hydroxy-functionalized polyether containing an a-alkylstilbene moiety is prepared by (a) reacting an inertly-substituted or unsubstituted dihydroxy-a-alkyistilbene with the digiycidyl ether of an inertly-substituted or unsubstituted dihydroxy-a-alkylstilbene. This polymer is described in U.S. Patent 5,686,551.
Preferably, the polycarbonate, polyester) or polyestercarbonate containing the a-alkylstilbene moiety employed in the practice of the present invention comprises repeat units of the formula:
1o fR-o-x-of wherein R independently in each occurrence is the divalent nucleus of a difunctional aromatic diol; X is selected from:
-C(O)-, -C(O)-R1-C(O)-, or a mixture thereof; and R1 independently in each occurrence is the divalent nucleus of an aromatic dicarboxylic acid.
The polycarbonate, polyester, and polyestercarbonate containing the a-alkylstilbene moiety employed in the practice of the present invention are described in U.S.
Patent 5,614,599.
Thermoplastic polyesters and blends thereof, and polyacetal which have a Fuel CM15 permeability of 45 g-mil/m2-day or less, based on a layer thickness of 1 mil, when measured at 40°C and under ambient pressure conditions of 700 to 760 torn can also be employed as fuel barrier polymers in the practice of the present invention.
Preferably, the thermoplastic polyesters contain a terephthalate moiety or a 2,6-naphthalenedicarboxylate moiety.
Examples of thermoplastic polyesters which can be employed in the practice of the present invention include poly(butylene-2,6-naphthalenedicarboxyiate) (PBN), poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), polyethylene terephthalate) (PET), poly(propane terephthalate) (PPT), poly(butylene terephthalate) (PBT), and mixtures thereof.
Surprisingly, it has been found that PBT, while only a marginally acceptable fuel barrier material SUBSTITUTE SHEET ( rule 26 ) 42474A ,.
alone) becomes an exceptional fuel barrier material when blended with PET, which alone is a very poor fuel barrier material.
PEN and PBN and methods for their preparation (including the specific monomers employed in their formation, their proportions, polymerization temperatures, catalysts and other conditions) are known in the art and reference is made thereto for the purposes of this invention. For purposes of illustration and not limitation, reference is particularly made to U.S. Patent 5,102,705. PPT is available from Shell Chemical. PET, PBT, and polyacetal are commercially available.
Fillers having high aspect ratios can also be blended with the fuel barrier polymers. It has been found that fillers having a high aspect ratio significantly improve the fuel barrier properties of the fuel barrier polymer, while those that have low aspect ratios do not. As used herein, the term "high aspect ratio" refers to the ratio of the length or width of the platelet to the depth of the platelet which is 10 to 1000. Overall the length and width of the platelets are, each individually, from 10 to 1000 nm.
Fillers having high aspect ratios which can be employed in the practice of the present invention include, but are not limited to Mica and montmorillonite clay.
Toughening agents can also be blended with the fuel barrier polymer.
Toughening agents which can be employed in the practice of the present invention include an elastomer commercially available as Paraloid0) (a product of Rohm and Haas) and having a rubbery core of butyl acrylate or butadiene and a hard shell of polymethyl methacrylate) and a malefic anhydride grafted polyethylene elastomer (ENGAGED-g-MA, a product of DuPont Dow Elastomers L.L.C. ). The elastomers having a rubbery core of butyl acrylate or butadiene and a hard shell of polymethyl methacrylate are described in EP-A-0 470 618 and U.S. Patent 5,256,733.
The toughening agents and fillers may be incorporated into the fuel barrier polymers by using conventional melt processing, as well as dry blending techniques for thermally sensitive polymers.
The tie layer, also commonly referred to as an adhesive layer, which can be employed in the practice of the present invention is made of an adhesive material, such as a modified polyethylene elastomer. Preferably, the adhesive material is a malefic anhydride grafted polyethylene or polypropylene such as ADMERT"" (trademark of Mitsui Petrochemicals) adhesive resin or ethylene-vinyl acetate copolymer resins such as ELVAX'''~' (trademark of DuPont).
_7_ A~iE~dDED SHEE r Each of the polymers forming the layers of the multilayer laminate structure of the present invention may contain various additives in an amount that does not adversely affect the desired properties of the polymers, Examples of such additives include antioxidants, ultraviolet light absorbers, thermal processing stabilizers, colorants, lubricants, flame retardants, impact modifiers, plasticizers, antistatic agents, pigments, and nucleating agents and filters, such as zeolite, talc, and calcium carbonate. The method of incorporating the additives is not critical. The additives can conveniently be added to the polymer prior to preparing the multilayer laminate structure. If the polymer is prepared in solid form, the additives can be added to the melt prior to preparing the multilayer laminate structure.
Processes for forming and using multilayer structures such as those described above inherently produce a certain amount of scrap material. From an economic standpoint, it is desirable to employ this scrap material in a useful manner. Generally, the scrap material is ground into particles or powder and) optionally, melted, kneaded and formed into pellets. The ground scrap material, in the form of powder, particles or pellets, may be added either as a part of the material forming one or more of the plurality of layers or as a material for forming an additional layer substantially completely made of the scrap material. Thus, the multilayer laminate structure of the present invention can comprise a further layer of a regrind (ground scrap) of the polyolefin polymer layer, the fuel barrier polymer layer and, optionally) the adhesive polymer layer.
The designed thickness of each layer in the laminate structure is dependent on a number of factors including the intended use, materials stored in the container, the length of storage prior to use, and the specific composition employed in each layer of the laminate.
In general, the laminate structure will have a total thickness of from 10 to mils) preferably from 100 to 500 mils; with the thickness of the fuel barrier polymer layers) being from 0.1 to 50 mils, preferably from 0.5 to 25 mils; the thickness of the polyethylene iayer(s) being from 9.9 to 749.9 mils, preferably from 9.9 to 499.5 mils;
optionally, the thickness of the tie iayer(s) being from 0.1 to 20 mils, preferably from 0.1 to 5 mils;
and optionally, a regrind layer consisting of a blend of the fuel barrier polymer, polyethylene, and optionally, a tie material, from 1 to 375 mils, and preferably from 5 to 250 mils.
In a first configuration of layers, the multilayer laminate structure of the present invention comprises (A) an inner layer of a fuel barrier polymer selected from: (1 ) a hydroxy-functionaiized poiyether containing an a-alkylstilbene moiety, (2) a polyester, polycarbonate or polyester-co-carbonate containing an a-alkylstilbene moiety, (3) polyacetal, (4) PEN, PBN, _g_ SUBSTITUTE SHEET ( rule 26 ) PPT, or PBT, (5) a blend of any two or more of PEN, PET) PPT, PBN, and PBT, (6) a blend of (a) polyacetal) PEN, PPT, PBN) or PBT and (b) toughening agent A or toughening agent B, (7) a blend of (a) any two or more of PEN) PET, PBN, PPT, and PBT, and (b) toughening agent A
or toughening agent B, (8) a blend of (a) polyacetal, PEN, PPT, PBN, or PBT, and (b) Mica or a montmorillonite clay, (9) a blend of (a) any two or more of PEN, PET, PPT, PBN, and PBT, and (b) Mica or a montmorillonite clay) (10) a blend of (a) polyacetal, PEN, PBN, PPT, or PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay, and (11 ) a blend of (a) any 2 or more of PEN) PET, PPT, PBN, and PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay; (B) an outer layer of HDPE; (C) a tie layer of a modified polyethylene elastomer interposed between the fuel barrier polymer and the HDPE layer; and, optionally (D) a regrind layer comprising a blend of layers (A), (B), and (C) interposed between the tie layer and the outer polyethylene layer, wherein toughening agent A is a malefic anhydride-grafted polyethylene elastomer, available from DuPont Dow Elastomers L.L.C, as Engage0-g-MA, toughening agent B is an elastomer having a rubbery core (butyl acrylate or butadiene) and a hard shell, commercially available from Rohm and Haas as Paraloid~, and Mica is a high-aspect ratio inert filler, a product of Franklin Industrial Minerals.
Preferably, the inner layer is from 0.1 to 25 weight percent of the container and the outer layer is from 5.0 to 99.89 weight percent of the container. The tie layer between the fuel barrier polymer layer and the polyethylene layer is from 0.01 to 10 weight percent of the container. The optional regrind layer between the tie layer and the outer layer is from 5 to 60 weight percent of the container.
A second configuration of layers of the multilayer laminate structure of the present invention is the same as the first configuration, except the fuel barrier layer is the outer layer and the HDPE layer is the inner layer.
In a third configuration, the multilayer laminate structure of the present invention comprises (A) inner and outer layers of a fuel barrier polymer selected from:
(1 ) a hydroxy-functionalized polyether containing an a-alkylstilbene moiety, (2) a polyester, polycarbonate or polyester-co-carbonate containing an a-alkylstilbene moiety, (3) polyacetal, (4) PEN, PBN, PPT, or PBT, (5) a blend of any two or more of PEN, PET, PPT, PBN, and PBT, (6) a blend of (a) poiyacetal, PEN, PPT, PBN, or PBT, and (b) toughening agent A or toughening agent B, (7) a blend of (a) any two or more of PEN, PET, PPT, PBN, and PBT, and (b) toughening agent A
or toughening agent B, (8) a blend of (a) polyacetal, PEN, PPT, PBN, or PBT, and (b) Mica or a _g_ SUBSTITUTE SHEET { rule 26 ) montmorillonite clay, (9) a blend of (a) any two or more of PEN, PET, PPT) PBN, and PBT, and (b) Mica or a montmorillonite clay, (10) a blend of (a) polyacetal, PEN, PBN, PPT, or PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay, and (11 ) a blend of (a) any 2 or more of PEN, PET, PPT, PBN, and PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay; (B) a core layer of HDPE; (C) a tie layer of a modified polyethylene elastomer interposed between the fuel barrier polymer layers and the HDPE layer; and optionally (D) a regrind layer comprising a blend of layers (A), (B), and (C) interposed between the tie layer and the outer polyethylene layer, wherein toughening agents A and B are as defined previously.
Preferably, the inner and outer layers) each individually, are from 0.1 to 25 weight percent of the container and the core layer is from 5.0 to 99.78 weight percent of the container. The tie layers between the fuel barrier polymer layers and the polyethylene layer is from 0.01 to 10 weight percent of the container. The optional regrind layer between a tie layer and the core layer is from 5 to 60 weight percent of the container.
In a fourth configuration, the multilayer laminate structure of the present invention comprises (A) an inner layer of polyethyiene; (B) a core layer of a fuel barrier polymer selected from: (1 ) a hydroxy-functionalized polyether containing an a-alkylstilbene moiety, (2) a polyester, polycarbonate or polyester-co-carbonate containing an a-alkylstilbene moiety, (3) polyacetal, (4) a blend of (a) any two or more of PEN, PET) PPT, PBN, and PBT, and (b) toughening agent A or toughening agent B, (5) a blend of (a) any two or more of PEN, PET, PPT, PBN, and PBT, and (b) Mica or montmorilfonite clay, and (6) a blend of EVOH and Mica or montmorillonite clay; and (C) an outer layer of a polyethylene; optionally (D) a tie layer of a modified polyethylene elastomer interposed between the fuel barrier polymer layer and the inner and outer HDPE layer; and optionally (E) a regrind layer comprising a blend of layers (A), (B), (C), and (D) interposed between the tie layer and the outer polyethylene layer, wherein toughening agents A and B are as defined previously.
Preferably, the polyethylene inner and outer layers together comprise from 5 to 60 weight percent of the container; the fuel barrier polymer layer comprises from 0.1 to 25 weight percent of the container, the tie layers between the fuel barrier polymer layer and the polyethylene layers comprise from 0.01 to 10 weight percent of the container, and the optional regrind layer between the tie layer and the outer polyethylene layer is from 5 to 60 weight percent of the container.
SUBSTITUTE SHEET ( rule 26 ) The multilayer laminate structure of the present invention can be produced using conventional extrusion techniques such as feedblock coextrusion, multimanifold die coextrusion) or combinations of the two, or may be produced by a laminating procedure whereby self-sustaining lamina are bonded together by applications of heat and pressure and reference is made thereto for the purposes of this invention. The volume (thickness) of each individual layer may be controlled as it is extruded. Thus, the overall thickness of the multilayer structure may be controlled to produce a film or sheet of desired thickness.
The laminate structure of the present invention can be fabricated into articles using conventional thermoplastic fabrication techniques such as compression molding, injection molding, lamellar injection molding, blow molding, extrusion, calendering and thermoforming. A
typical thermoforming process comprises heating a thermoplastic sheet to its softening point and then shaping the sheet at a forming station utilizing various molds and/or vacuum or air pressure assists or plug assists. Other thermoforming techniques include solid phase pressure forming (SPPF) and the so-called scrapiess forming process (SFP). For purposes of this invention, references to thermoforming techniques or thermoformable structures will include SPPF and SFP. During fabrication, the molecules of the polymer can be oriented by methods well known in the art. One such method is described in U.S. Patent 5,382,693.
Orientation is also described in Plastics Engineering Handbook of the Society of the Plastics Industry, Inc., 4th Ed., p. 113-115) 182 and 183. Articles formed therefrom include containers, molded parts) and tubing. Examples of such articles include flexible and rigid containers such as tanks or bottles used for the storage of chemicals and fuels, including oxygenated fuels which contain alcohols such as methanol or ethanol, and tubing used in the transfer of chemicals and fuels, including oxygenated fuels which contain alcohols such as methanol or ethanol.
When formed into a container or tube, the inner layer of the multilayer laminate structure of the present invention is the layer which comes in contact with the fuel that is placed inside the container or tube. Thus, in the previously described configuration of layers of the muitilayer laminate structure, the fuel barrier polymer layer of the multilayer laminate structure is either the layer which comes in contact with the fuel that is placed inside the container or tube, and/or the layer on the outside of the container or tube, or the layer which is sandwiched between layers of polyethylene, and, optionally, tie layers, and/or, regrind layers.
The following working examples are given to illustrate the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and percentages are by weight.
SUBSTITUTE SHEET ( rule 26 ) ,EXAMPLES
The following are the materials and test procedures used in the examples.
Materials:
PBT: Poly(butyiene terephthalate), a commercially available polyester.
PEN: Poly(ethylene-2,6-naphthalenedicarboxylate), a commercially available polyester.
PET: Polyethylene terephthalate), a commercially available polyester.
Polyacetal, a commercially available acetal resin. It is a polyoxymethylene thermoplastic polymer obtained by ionically initiated polymerization of formaldehyde + CH2 to obtain a linear molecule of the type -O-CHZ-O-CHZ CHZ-.
Engage0-g-MA: Graft-modified substantially linear ethylene polymers manufactured by DuPont Dow Elastomers L.L.C. and described in U.S. Patent 5,346,963.
Mica: Himod 270 wet-ground Muscovite mica, a commercially available high-aspect ratio inert filler; a product of Franklin Industrial Minerals.
Eval F: An EVOH resin prepared from a monomer ratio of 32 percent by weight ethylene and 68 percent by weight vinyl alcohol; a product of Eval Co.
Hydroxy-functionalized polyether containing the a-methylstilbene moiety, represented by the structure:
n Polycarbonate containing the a-methylstilbene moiety, represented by the structure:
OCO
n SUBSTITUTE SHEET ( rule 2C ) HDPE: High density polyethylene.
AdmerTM NF 500A: A modified polyethylene elastomeric adhesive, a product of Mitsui Petrochemicals.
AdmerTM SF 700: A modified polyethylene elastomeric adhesive, a product of Mitsui Petrochemicals.
AdmerTM SF 710: A modified polyethylene elastomeric adhesive, a product of Mitsui Petrochemicals.
Elvax 260: An ethylene vinyl acetate copolymer used as an adhesive for HDPE
a product of DuPont.
Test Fuel CM15: A mixture of 42.5 percent by volume toluene, 42.5 percent isooctane and 15 percent methanol.
Test Procedures Fuel Uptake Testing:
Pre-weighed, compression molded parts are immersed in Fuel CM15 for 14 days at 40°C to 41 °C. The parts are removed from the fuel and residual liquid is removed under a strong flow of air. The parts are weighed again and the percent weight gain is calculated.
Permeation Testing:
The permeability of Fuel CM15 is measured at 40°C to 41 °C using the following procedure. A compression molded, cast film extruded, or blow molded test film, in the form of a 4 inch diameter disk with a thickness between 1 and 100 mil, is mounted between the two chambers of the test cell. Fuel CM15 (95 mL) is added to the upper chamber and helium flowing at about 10 mUminute is passed through the lower chamber. As fuel permeates through the barrier film, it is carried from the test cell and into an injector loop of a gas chromatograph (GC). At a specific frequency, the contents of the injector loop are injected onto the front end of a 25 m, 0.53 mm ID, Chrompack Poraplot U capillary column operating at 140°C using a helium flow of 10 mUmin as the carrier gas. The GC
separates, identifies by retention time, and quantifies the fuel components which have permeated through the specimen film. The time since the beginning of the experiment and the identity and amount of the permeated components are stored in a computer file for further analysis.
The following are the materials and test procedures used in the examples.
Materials:
PBT: Poly(butyiene terephthalate), a commercially available polyester.
PEN: Poly(ethylene-2,6-naphthalenedicarboxylate), a commercially available polyester.
PET: Polyethylene terephthalate), a commercially available polyester.
Polyacetal, a commercially available acetal resin. It is a polyoxymethylene thermoplastic polymer obtained by ionically initiated polymerization of formaldehyde + CH2 to obtain a linear molecule of the type -O-CHZ-O-CHZ CHZ-.
Engage0-g-MA: Graft-modified substantially linear ethylene polymers manufactured by DuPont Dow Elastomers L.L.C. and described in U.S. Patent 5,346,963.
Mica: Himod 270 wet-ground Muscovite mica, a commercially available high-aspect ratio inert filler; a product of Franklin Industrial Minerals.
Eval F: An EVOH resin prepared from a monomer ratio of 32 percent by weight ethylene and 68 percent by weight vinyl alcohol; a product of Eval Co.
Hydroxy-functionalized polyether containing the a-methylstilbene moiety, represented by the structure:
n Polycarbonate containing the a-methylstilbene moiety, represented by the structure:
OCO
n SUBSTITUTE SHEET ( rule 2C ) HDPE: High density polyethylene.
AdmerTM NF 500A: A modified polyethylene elastomeric adhesive, a product of Mitsui Petrochemicals.
AdmerTM SF 700: A modified polyethylene elastomeric adhesive, a product of Mitsui Petrochemicals.
AdmerTM SF 710: A modified polyethylene elastomeric adhesive, a product of Mitsui Petrochemicals.
Elvax 260: An ethylene vinyl acetate copolymer used as an adhesive for HDPE
a product of DuPont.
Test Fuel CM15: A mixture of 42.5 percent by volume toluene, 42.5 percent isooctane and 15 percent methanol.
Test Procedures Fuel Uptake Testing:
Pre-weighed, compression molded parts are immersed in Fuel CM15 for 14 days at 40°C to 41 °C. The parts are removed from the fuel and residual liquid is removed under a strong flow of air. The parts are weighed again and the percent weight gain is calculated.
Permeation Testing:
The permeability of Fuel CM15 is measured at 40°C to 41 °C using the following procedure. A compression molded, cast film extruded, or blow molded test film, in the form of a 4 inch diameter disk with a thickness between 1 and 100 mil, is mounted between the two chambers of the test cell. Fuel CM15 (95 mL) is added to the upper chamber and helium flowing at about 10 mUminute is passed through the lower chamber. As fuel permeates through the barrier film, it is carried from the test cell and into an injector loop of a gas chromatograph (GC). At a specific frequency, the contents of the injector loop are injected onto the front end of a 25 m, 0.53 mm ID, Chrompack Poraplot U capillary column operating at 140°C using a helium flow of 10 mUmin as the carrier gas. The GC
separates, identifies by retention time, and quantifies the fuel components which have permeated through the specimen film. The time since the beginning of the experiment and the identity and amount of the permeated components are stored in a computer file for further analysis.
SUBSTITUTE SHEET ( rule 26 ) Exarrtple 1 Several monolayer test specimens were prepared by compression molding or by injection molding. The samples (described in Table I) were evaluated for fuel uptake. The results are shown in Table I. Samples having a fuel uptake of 2 weight percent or less are considered as good barriers to fuels containing alcohols.
TAB I
Sampled Resin or Blend Weight Gain, erg cent 1 hydroxy-functionalized polyether2.0 of a-methylstilbene 2 poiycarbonate of a-methylstilbene0.7 3 HDPE 7.8 4 Eval F 2.8 5 P BT 3.0 6 polyacetal 3.0 7 PET 15.1 The data in the above table indicate that HDPE, Eval F, PET, PBT, and polyacetal do not possess good fuel barrier properties alone. PBT and polyacetal, each having a fuel uptake of 3 weight percent, are considered a marginal fuel barrier material toward fuels containing alcohols, as is Eval F.
Exam Ip a 2 Several monolayer film samples (described in Table I I) were prepared by compression molding. The samples were evaluated for Fuel CM15 permeability.
The results are shown in Table II.
TAB I
Sampled Resin or Blend Weight Gain, erg cent 1 hydroxy-functionalized polyether2.0 of a-methylstilbene 2 poiycarbonate of a-methylstilbene0.7 3 HDPE 7.8 4 Eval F 2.8 5 P BT 3.0 6 polyacetal 3.0 7 PET 15.1 The data in the above table indicate that HDPE, Eval F, PET, PBT, and polyacetal do not possess good fuel barrier properties alone. PBT and polyacetal, each having a fuel uptake of 3 weight percent, are considered a marginal fuel barrier material toward fuels containing alcohols, as is Eval F.
Exam Ip a 2 Several monolayer film samples (described in Table I I) were prepared by compression molding. The samples were evaluated for Fuel CM15 permeability.
The results are shown in Table II.
SUBSTITUTE SHEET ( rule 26 ) T II
Resin or Blend Permeabilit)i*
g-mil/m~-day 9 85/15 PBT/Mica Blend g,g 75/25 PBT/Mica Blend 4.2 11 75/25 PBT/Talc Blend 27.4 12 37.5/37.5/25 PBT/PET/Mica 3.0 Blend 13 Eval F 50 14 75/25 Eval F/Mica Blend 7.3 75/25 Eval F/Talc Blend 45.7 *Permeability normalized to a thickness of 1 mil for the entire structure and measured at 41 °C under ambient pressure.
5 As shown in Table II, common fillers such as talc, at best, only somewhat improved the fuel barrier properties of materials which, unfilled, had marginal fuel barrier properties, such as PBT and Eval F. However, fillers which had high aspect ratios, such as Mica, highly improved the fuel barrier properties of those same compounds.
Example 3 10 Several 3-layer laminate film samples were prepared by cast film coextrusion or by coextrusion blow molding. These laminate structures contained a fuel barrier material layer, a high-density polyethylene layer and a tie layer between the fuel barrier material layer and the polyethylene layer. In the samples prepared by cast film coextrusion, the barrier layer and the tie layer contributed approximately 10 percent and 5 percent, respectively, to the total thickness 15 of the structure. In the coextrusion blow-molded structures, the barrier layer and the tie layer contributed approximately 24 percent and 5 percent, respectively, to the total thickness of the structure. The remaining thickness of these structures was attributed to the polyethylene layer.
These films were tested for fuel CM15 permeability with the barrier material layer in direct contact with the fuel. The permeability values for these structures are based on the total thickness of these structures. The results of this testing are given in Table III.
SUBSTITUTE SHEET ( rule 26 ) Table III
Samples Barrier Material Tie od f Permeability*.
Layer Fabrication a-mil/mz-day 16 50/50 PBT/PEN Admer NF- Cast Film 44 Blend 500 Coextrusion 17 50/50 PBT/PEN Admer SF- Cast Film 55 Blend 710 Coextrusion 18 50/50 PBT/PEN Elvax 260 Cast Film 66 Blend Coextrusion 19 PBT Admer NF- Cast Film 104 500 Coextrusion 20 PBT Admer SF- Cast Film 102 700A Coextrusion 21 PBT Admer SF- Cast Film 710A Coextrusion 22 PBT Elvax 260 Cast Film 80 Coextrusion 23 PBT Admer SF- Coextrusion 53 700A Blow-molding 24 HDPE Admer SF- Coextrusion 2,670 700A Blow-molding *Permeability normalized to a thickness of 1 mil for the entire structure and measured at 41 °C under ambient pressure.
As shown in Table III, the laminate structures containing PBT or 50/50 PBT/PEN
as the barrier material have permeability values which are 25 to 60 times lower than a similar 3 layer structure containing 2 layers of high-density polyethylene and a tie layer between the polyethylene layers.
SUBSTITUTE SHEET ( rule 26 )
Resin or Blend Permeabilit)i*
g-mil/m~-day 9 85/15 PBT/Mica Blend g,g 75/25 PBT/Mica Blend 4.2 11 75/25 PBT/Talc Blend 27.4 12 37.5/37.5/25 PBT/PET/Mica 3.0 Blend 13 Eval F 50 14 75/25 Eval F/Mica Blend 7.3 75/25 Eval F/Talc Blend 45.7 *Permeability normalized to a thickness of 1 mil for the entire structure and measured at 41 °C under ambient pressure.
5 As shown in Table II, common fillers such as talc, at best, only somewhat improved the fuel barrier properties of materials which, unfilled, had marginal fuel barrier properties, such as PBT and Eval F. However, fillers which had high aspect ratios, such as Mica, highly improved the fuel barrier properties of those same compounds.
Example 3 10 Several 3-layer laminate film samples were prepared by cast film coextrusion or by coextrusion blow molding. These laminate structures contained a fuel barrier material layer, a high-density polyethylene layer and a tie layer between the fuel barrier material layer and the polyethylene layer. In the samples prepared by cast film coextrusion, the barrier layer and the tie layer contributed approximately 10 percent and 5 percent, respectively, to the total thickness 15 of the structure. In the coextrusion blow-molded structures, the barrier layer and the tie layer contributed approximately 24 percent and 5 percent, respectively, to the total thickness of the structure. The remaining thickness of these structures was attributed to the polyethylene layer.
These films were tested for fuel CM15 permeability with the barrier material layer in direct contact with the fuel. The permeability values for these structures are based on the total thickness of these structures. The results of this testing are given in Table III.
SUBSTITUTE SHEET ( rule 26 ) Table III
Samples Barrier Material Tie od f Permeability*.
Layer Fabrication a-mil/mz-day 16 50/50 PBT/PEN Admer NF- Cast Film 44 Blend 500 Coextrusion 17 50/50 PBT/PEN Admer SF- Cast Film 55 Blend 710 Coextrusion 18 50/50 PBT/PEN Elvax 260 Cast Film 66 Blend Coextrusion 19 PBT Admer NF- Cast Film 104 500 Coextrusion 20 PBT Admer SF- Cast Film 102 700A Coextrusion 21 PBT Admer SF- Cast Film 710A Coextrusion 22 PBT Elvax 260 Cast Film 80 Coextrusion 23 PBT Admer SF- Coextrusion 53 700A Blow-molding 24 HDPE Admer SF- Coextrusion 2,670 700A Blow-molding *Permeability normalized to a thickness of 1 mil for the entire structure and measured at 41 °C under ambient pressure.
As shown in Table III, the laminate structures containing PBT or 50/50 PBT/PEN
as the barrier material have permeability values which are 25 to 60 times lower than a similar 3 layer structure containing 2 layers of high-density polyethylene and a tie layer between the polyethylene layers.
SUBSTITUTE SHEET ( rule 26 )
Claims (23)
1. 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 selected from:
(1) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) polyacetal, (6) blends of (1), (2), (3), (4), and/or (5), and a thermoplastic polyester and/or a toughening agent and/or a filler having a high aspect ratio, and (7) a blend comprising (a) poly(butylene terephthalate) (PBT), and/or (b) polyethylene terephthalate)(PET) and (c) a toughening agent and/or (d) a filler having a high aspect ratio; 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.
(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 selected from:
(1) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) polyacetal, (6) blends of (1), (2), (3), (4), and/or (5), and a thermoplastic polyester and/or a toughening agent and/or a filler having a high aspect ratio, and (7) a blend comprising (a) poly(butylene terephthalate) (PBT), and/or (b) polyethylene terephthalate)(PET) and (c) a toughening agent and/or (d) a filler having a high aspect ratio; 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.
2. The laminate structure of Claim 1 wherein the hydroxy-functionalized polyether is represented by the structure:
wherein R is methyl, ethyl or propyl and n is an integer from 10 to 1000.
wherein R is methyl, ethyl or propyl and n is an integer from 10 to 1000.
3. The laminate structure of Claim 1 wherein the polycarbonate, polyester or polyester-co-carbonate contains a moiety represented by the structure wherein R is methyl, ethyl or propyl.
4. The laminate structure of Claim 1 wherein the polyolefin is high-density polyethylene.
5. The laminate structure of Claim 4 wherein the high-density polyethylene has a density of from 0.94 to 0.99 g/cc and a melt index of from 0.01 to 35 grams per minute as determined by ASTM Test Method D-1238.
6. The laminate structure of Claim 1 wherein the tie layer is a maleic anhydride grafted polyethylene or polypropylene or an ethylene-vinyl acetate copolymer.
7. A two layer laminate structure comprising:
(A) a layer of a fuel barrier polymer selected from:
(1 ) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) poly(propane terephthalate) (PPT), (6) poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), (7) poly(butylene-2,6-naphthalenedicarboxylate) (PBN), (8) polyacetal, and (9) blends of (1), (2), (3), (4), (5), (6), (7), and/or (8), and PET, and/or a toughening agent and/or a filler having a high aspect ratio; and (B) a layer of a polyolefin or a blend of two or more different polyolefins;
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.
(A) a layer of a fuel barrier polymer selected from:
(1 ) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) poly(propane terephthalate) (PPT), (6) poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), (7) poly(butylene-2,6-naphthalenedicarboxylate) (PBN), (8) polyacetal, and (9) blends of (1), (2), (3), (4), (5), (6), (7), and/or (8), and PET, and/or a toughening agent and/or a filler having a high aspect ratio; and (B) a layer of a polyolefin or a blend of two or more different polyolefins;
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.
8. The laminate structure of Claim 7 wherein the hydroxy-functionalized polyether is represented by the structure:
wherein R is methyl, ethyl or propyl and n is an integer from 10 to 1000.
wherein R is methyl, ethyl or propyl and n is an integer from 10 to 1000.
9. The laminate structure of Claim 7 wherein the polycarbonate, polyester or polyester-co-carbonate contains a moiety represented by the structure wherein R is methyl, ethyl or propyl.
10. The laminate structure of Claim 7 wherein the polyolefin is high-density polyethylene.
11. The laminate structure of Claim 10 wherein the high-density polyethylene has a density of from 0.94 to 0.99 g/cc and a melt index of from 0.01 to 35 grams per minute as determined by ASTM Test Method D-1238.
12. The laminate structure of Claim 7 wherein the tie layer is a maleic anhydride grafted polyethylene or polypropylene or an ethylene-vinyl acetate copolymer.
13. A multilayer laminate structure comprising:
(A) an inner layer of a fuel barrier polymer, (B) an outer layer of a fuel barrier polymer, the fuel barrier polymer being selected from:
(1) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) poly(propane terephthalate) (PPT), (6) poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), (7) poly(butylene-2,6-naphthalenedicarboxylate) (PBN), (8) polyacetal, and (9) blends of (1), (2), (3), (4), (5), (6), (7), and/or (8), and PET, and/or a toughening agent and/or a filler having a high aspect ratio; and (C) a core layer of a polyolefin or a blend of two or more different polyolefins;
and optionally (D) a tie layer interposed between a polyolefin layer and an adjacent fuel barrier layer; and/or optionally (E) a regrind layer interposed between a tie layer and a polyolefin layer.
(A) an inner layer of a fuel barrier polymer, (B) an outer layer of a fuel barrier polymer, the fuel barrier polymer being selected from:
(1) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) poly(propane terephthalate) (PPT), (6) poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), (7) poly(butylene-2,6-naphthalenedicarboxylate) (PBN), (8) polyacetal, and (9) blends of (1), (2), (3), (4), (5), (6), (7), and/or (8), and PET, and/or a toughening agent and/or a filler having a high aspect ratio; and (C) a core layer of a polyolefin or a blend of two or more different polyolefins;
and optionally (D) a tie layer interposed between a polyolefin layer and an adjacent fuel barrier layer; and/or optionally (E) a regrind layer interposed between a tie layer and a polyolefin layer.
14. A multilayer laminate structure comprising (A) an outer layer of a polyolefin or a blend of two or more different polyolefins; and (B) an inner layer of a fuel barrier polymer or blends thereof, the fuel barrier polymer or blends thereof having a Fuel CM15 permeability of 45 g-mil/m2-day or less, based on a layer thickness of 1 mil, when measured at 40°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.
15. A multilayer laminate structure comprising:
(A) an inner layer of a polyolefin or a blend of two or more different polyolefins;
(B) a core layer of a blend of EVOH and a filler having a high aspect ratio;
(C) an outer layer of a polyolefin or a blend of two or more different polyolefins; and optionally (D) a tie layer interposed between a polyolefin layer and an adjacent fuel barrier layer; and/or optionally (E) a regrind layer interposed between a tie layer and a polyolefin layer.
(A) an inner layer of a polyolefin or a blend of two or more different polyolefins;
(B) a core layer of a blend of EVOH and a filler having a high aspect ratio;
(C) an outer layer of a polyolefin or a blend of two or more different polyolefins; and optionally (D) a tie layer interposed between a polyolefin layer and an adjacent fuel barrier layer; and/or optionally (E) a regrind layer interposed between a tie layer and a polyolefin layer.
16. A multilayer laminate structure comprising (A) an inner layer of a fuel barrier polymer selected from:
(1) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) polyacetal, (6) poly(propane terephthalate) (PPT), (7) poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), (8) poly(butylene-2,6-naphthalenedicarboxylate) (PBN), (9) a blend of any two or more of PEN, PET, PPT, PBN, and PBT, (10) a blend of (a) PEN, PBN, PPT, or PBT and (b) toughening agent A or toughening agent B, (11) a blend (a) any two or more of PEN, PET, PPT, PBN and PBT, and (b) toughening agent A or toughening agent B, (12) a blend of (a) polyacetal, PEN, PBN, PPT, or PBT, and (b) Mica or a montmorillonite clay, (13) a blend of (a) any two or more of PEN, PET, PPT, PBN, and PBT, and (b) Mica or a montmorillonite clay, (14) a blend of (a) polyacetal, PEN, PPT, PBN or PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay, and (15) a blend of (a) any 2 or more of PEN, PET, PPT, PBN, and PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay;
(B) an outer layer of high-density polyethylene;
(C) a tie layer of a modified polyethylene elastomer interposed between the fuel barrier polymer and the high-density polyethylene layer; and, optionally (D) a regrind layer comprising a blend of layers (A), (B), and (C) interposed between the tie layer and the outer high-density polyethylene layer;
wherein toughening agent A is a malefic anhydride-grafted polyethylene elastomer, toughening agent B is an elastomer having a rubbery core of butyl acrylate or butadiene and a hard shell of polymethyl methacrylate, and Mica is a high-aspect ratio inert filler.
(1) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) polyacetal, (6) poly(propane terephthalate) (PPT), (7) poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), (8) poly(butylene-2,6-naphthalenedicarboxylate) (PBN), (9) a blend of any two or more of PEN, PET, PPT, PBN, and PBT, (10) a blend of (a) PEN, PBN, PPT, or PBT and (b) toughening agent A or toughening agent B, (11) a blend (a) any two or more of PEN, PET, PPT, PBN and PBT, and (b) toughening agent A or toughening agent B, (12) a blend of (a) polyacetal, PEN, PBN, PPT, or PBT, and (b) Mica or a montmorillonite clay, (13) a blend of (a) any two or more of PEN, PET, PPT, PBN, and PBT, and (b) Mica or a montmorillonite clay, (14) a blend of (a) polyacetal, PEN, PPT, PBN or PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay, and (15) a blend of (a) any 2 or more of PEN, PET, PPT, PBN, and PBT, (b) toughening agent A or toughening agent B, and (c) Mica or a montmorillonite clay;
(B) an outer layer of high-density polyethylene;
(C) a tie layer of a modified polyethylene elastomer interposed between the fuel barrier polymer and the high-density polyethylene layer; and, optionally (D) a regrind layer comprising a blend of layers (A), (B), and (C) interposed between the tie layer and the outer high-density polyethylene layer;
wherein toughening agent A is a malefic anhydride-grafted polyethylene elastomer, toughening agent B is an elastomer having a rubbery core of butyl acrylate or butadiene and a hard shell of polymethyl methacrylate, and Mica is a high-aspect ratio inert filler.
17. A multilayer laminate structure comprising:
(A) an inner layer of polyethylene;
(B) a core layer of a fuel barrier polymer selected from:
(1 ) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) polyacetal, (6) a blend of (a) (1), (2), (3), (4), or (5) and (b) PEN, PET, PBT, PPT, or PBN, and (7) a blend of (a) any two or more of PEN, PET, PPT, PBN, and PBT, and (b) toughening agent A or toughening agent B, and/or (c) Mica or montmorillonite clay; and (C) an outer layer of a high-density polyethylene;
(D) tie layers of a modified polyethylene elastomer interposed between the fuel barrier polymer and the high-density polyethylene layers; and optionally (E) a regrind layer comprising a blend of layers (A), (B), (C), and D
interposed between the tie layer and the outer polyethylene layer;
wherein toughening agent A is a malefic anhydride-grafted polyethylene elastomer, toughening agent B is an elastomer having a rubbery core of butyl acrylate or butadiene and a hard shell of polymethyl methacrylate, and Mica is a high-aspect ratio inert filler.
(A) an inner layer of polyethylene;
(B) a core layer of a fuel barrier polymer selected from:
(1 ) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) polyacetal, (6) a blend of (a) (1), (2), (3), (4), or (5) and (b) PEN, PET, PBT, PPT, or PBN, and (7) a blend of (a) any two or more of PEN, PET, PPT, PBN, and PBT, and (b) toughening agent A or toughening agent B, and/or (c) Mica or montmorillonite clay; and (C) an outer layer of a high-density polyethylene;
(D) tie layers of a modified polyethylene elastomer interposed between the fuel barrier polymer and the high-density polyethylene layers; and optionally (E) a regrind layer comprising a blend of layers (A), (B), (C), and D
interposed between the tie layer and the outer polyethylene layer;
wherein toughening agent A is a malefic anhydride-grafted polyethylene elastomer, toughening agent B is an elastomer having a rubbery core of butyl acrylate or butadiene and a hard shell of polymethyl methacrylate, and Mica is a high-aspect ratio inert filler.
18. A process for preparing a multilayer laminate structure which comprises coextruding:
(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 selected from:
(1) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an.alpha.-alkylstilbene moiety, (4) polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) polyacetal, (6) blends of (1), (2), (3), (4), and/or (5), and a thermoplastic polyester, and/or a toughening agent and/or a filler having a high aspect ratio, and (7) a blend comprising (a) poly(butylene terephthalate), and/or (b) polyethylene terephthalate) and (c) a toughening agent and/or (d) a filler having a high aspect ratio; 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.
(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 selected from:
(1) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an.alpha.-alkylstilbene moiety, (4) polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) polyacetal, (6) blends of (1), (2), (3), (4), and/or (5), and a thermoplastic polyester, and/or a toughening agent and/or a filler having a high aspect ratio, and (7) a blend comprising (a) poly(butylene terephthalate), and/or (b) polyethylene terephthalate) and (c) a toughening agent and/or (d) a filler having a high aspect ratio; 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.
19. A process for preparing a multilayer laminate structure which comprises coextruding:
(A) an inner layer of a fuel barrier polymer, and (B) an outer layer of a fuel barrier polymer, the fuel barrier polymer being selected from:
(1 ) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) poly(propane terephthalate) (PPT), (6) poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), (7) poly(butylene-2,6-naphthalenedicarboxylate) (PBN), (8) polyacetal, and (9) blends of (2), (3), (4), (5), (6), (7), and/or (8), and PET, and/or a toughening agent and/or a filler having a high aspect ratio; and (C) a core layer of a polyolefin or a blend of two or more different polyolefins;
and optionally (D) a tie layer interposed between a polyolefin layer and an adjacent fuel barrier layer; and/or optionally (E) a regrind layer interposed between a tie layer and a polyolefin layer.
(A) an inner layer of a fuel barrier polymer, and (B) an outer layer of a fuel barrier polymer, the fuel barrier polymer being selected from:
(1 ) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) poly(propane terephthalate) (PPT), (6) poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), (7) poly(butylene-2,6-naphthalenedicarboxylate) (PBN), (8) polyacetal, and (9) blends of (2), (3), (4), (5), (6), (7), and/or (8), and PET, and/or a toughening agent and/or a filler having a high aspect ratio; and (C) a core layer of a polyolefin or a blend of two or more different polyolefins;
and optionally (D) a tie layer interposed between a polyolefin layer and an adjacent fuel barrier layer; and/or optionally (E) a regrind layer interposed between a tie layer and a polyolefin layer.
20. A process for preparing a two layer laminate structure which comprises coextruding:
(A) a layer of a fuel barrier polymer selected from:
(1 ) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) poly(propane terephthalate) (PPT), (6) poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), (7) poly(butylene-2,6-naphthalenedicarboxylate) (PBN), (8) polyacetal, and (9) blends of (2), (3), (4), (5), (6), (7), and/or (8), and PET and/or a toughening agent and/or a filler having a high aspect ratio; and (C) a layer of a polyolefin or a blend of two or more different polyolefins;
and optionally (D) a tie layer interposed between a polyolefin layer and an adjacent fuel barrier layer; and/or optionally (E) a regrind layer interposed between a tie layer and a polyolefin layer.
(A) a layer of a fuel barrier polymer selected from:
(1 ) a hydroxy-functionalized polyether containing an .alpha.-alkylstilbene moiety, (2) a polyester containing an .alpha.-alkylstilbene moiety, (3) a polycarbonate containing an .alpha.-alkylstilbene moiety, (4) a polyester-co-carbonate containing an .alpha.-alkylstilbene moiety, (5) poly(propane terephthalate) (PPT), (6) poly(ethylene-2,6-naphthalenedicarboxylate) (PEN), (7) poly(butylene-2,6-naphthalenedicarboxylate) (PBN), (8) polyacetal, and (9) blends of (2), (3), (4), (5), (6), (7), and/or (8), and PET and/or a toughening agent and/or a filler having a high aspect ratio; and (C) a layer of a polyolefin or a blend of two or more different polyolefins;
and optionally (D) a tie layer interposed between a polyolefin layer and an adjacent fuel barrier layer; and/or optionally (E) a regrind layer interposed between a tie layer and a polyolefin layer.
21. A container or tube comprising the laminate structure of Claim 7 wherein the inner layer forms the inside surface of the container or tube and the outer layer forms the outside surface of the container or tube.
22. A container or tube comprising the laminate structure of Claim 14 wherein the inner layer forms the inside surface of the container or tube and the outer layer forms the outside surface of the container or tube.
23. A container or tube comprising the laminate structure of Claim 16 wherein the inner layer forms the inside surface of the container or tube and the outer layer forms the outside surface of the container or tube.
Applications Claiming Priority (3)
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| US3461396P | 1996-12-31 | 1996-12-31 | |
| US60/034,613 | 1996-12-31 | ||
| PCT/US1997/023835 WO1998029245A2 (en) | 1996-12-31 | 1997-12-22 | Laminate structures for fuel containers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2276009A1 true CA2276009A1 (en) | 1998-07-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002276009A Abandoned CA2276009A1 (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) |
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| 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 |
| EP0637509B1 (en) * | 1993-08-03 | 2002-10-23 | Nitta Moore Company | A tube for fuel transportation |
| ATE167558T1 (en) * | 1993-08-09 | 1998-07-15 | Victaulic Plc | IMPROVEMENTS 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 WO PCT/US1997/023835 patent/WO1998029245A2/en not_active Application Discontinuation
- 1997-12-22 CA CA002276009A patent/CA2276009A1/en not_active Abandoned
- 1997-12-22 BR BR9713804-5A patent/BR9713804A/en not_active Application Discontinuation
- 1997-12-22 EP EP97954623A patent/EP0949996A2/en not_active Withdrawn
- 1997-12-22 JP JP53019298A patent/JP2001522320A/en active Pending
- 1997-12-22 KR KR1019997005994A patent/KR20000062401A/en not_active Application Discontinuation
- 1997-12-30 AR ARP970106257A patent/AR011325A1/en not_active Application Discontinuation
-
1998
- 1998-01-22 TW TW087100866A patent/TW364878B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998029245A2 (en) | 1998-07-09 |
| AR011325A1 (en) | 2000-08-16 |
| CN1245457A (en) | 2000-02-23 |
| WO1998029245A3 (en) | 1998-12-23 |
| TW364878B (en) | 1999-07-21 |
| EP0949996A2 (en) | 1999-10-20 |
| BR9713804A (en) | 2000-01-25 |
| KR20000062401A (en) | 2000-10-25 |
| JP2001522320A (en) | 2001-11-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |