CN1177540A - Multi-layer structure containing one binder and one layer of polyketone - Google Patents
Multi-layer structure containing one binder and one layer of polyketone Download PDFInfo
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- CN1177540A CN1177540A CN 97117129 CN97117129A CN1177540A CN 1177540 A CN1177540 A CN 1177540A CN 97117129 CN97117129 CN 97117129 CN 97117129 A CN97117129 A CN 97117129A CN 1177540 A CN1177540 A CN 1177540A
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- copolymer
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- ethene
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- 229920001470 polyketone Polymers 0.000 title claims abstract description 20
- 239000011230 binding agent Substances 0.000 title abstract 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229920001577 copolymer Polymers 0.000 claims abstract description 48
- -1 polyethylene Polymers 0.000 claims abstract description 25
- 239000005977 Ethylene Substances 0.000 claims abstract description 21
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000004593 Epoxy Substances 0.000 claims abstract description 8
- 229920001971 elastomer Polymers 0.000 claims abstract description 6
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 23
- 229920000098 polyolefin Polymers 0.000 claims description 19
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 13
- 229920000800 acrylic rubber Polymers 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 229960004424 carbon dioxide Drugs 0.000 claims description 6
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 abstract description 10
- 229920000573 polyethylene Polymers 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 30
- 239000000203 mixture Substances 0.000 description 19
- 150000002148 esters Chemical class 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 229940117958 vinyl acetate Drugs 0.000 description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 12
- 150000002118 epoxides Chemical class 0.000 description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 229920013640 amorphous poly alpha olefin Polymers 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QYYZXEPEVBXNNA-QGZVFWFLSA-N (1R)-2-acetyl-N-[4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)phenyl]-5-methylsulfonyl-1,3-dihydroisoindole-1-carboxamide Chemical compound C(C)(=O)N1[C@H](C2=CC=C(C=C2C1)S(=O)(=O)C)C(=O)NC1=CC=C(C=C1)C(C(F)(F)F)(C(F)(F)F)O QYYZXEPEVBXNNA-QGZVFWFLSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- RIVJYLGQARVCBI-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;cumene Chemical compound CC(C)C1=CC=CC=C1.CC(C)(C)OOC(C)(C)C RIVJYLGQARVCBI-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
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JBTKRORASQFRHQ-UHFFFAOYSA-N cumene ethene Chemical compound C1(=CC=CC=C1)C(C)C.C=C JBTKRORASQFRHQ-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a multilayer structure comprising a layer of a binder either containing a hydroxyl function or containing an epoxy function or alternatively consisting of an ethylene/alkyl (meth)acrylate copolymer and, directly attached thereto, a layer of polyketone.The structure may also comprise, on the binder side and directly attached thereto, either a layer of thermoplastic polymer such as polyethylene or a layer of rubber or a metal layer.The invention is useful for manufacturing packaging, bottles or pipes.
Description
The present invention relates to a kind of sandwich construction that one deck bond and one deck directly connect polyketone thereon that comprises.The polymer of this bond or a kind of hydroxy functional groups, or a kind of polymer that contains epoxy functionality, or the copolymer of a kind of ethene and (methyl) alkyl acrylate.The present invention also relates to for example polyethylene (F) of thermoplastic polymer that said structure and one deck directly be connected in this bond one side, one deck rubber, or substitute layer of metal.
Therefore, the invention provides a kind of bond so that the polyketone layer with or a metal level, perhaps a thermoplastic layer or rubber layer are bonding.Structure of the present invention is for making soft or hard packing for example sachet or bottle, or for making pipe, is suitable for.These products can be used the manufacturings of coextrusion, lamination or coextrusion blow moulding.This polyketone is the wire alternate copolymer of carbonoxide and at least a unsaturated monomer.
The multilayer thing of being made up of one deck polyketone and one deck polyolefin has been described in the WO95/09212 application; Bond between this is two-layer is the graft reaction product of polyolefin and maleic anhydride or diamines.
United States Patent (USP) 5,369,70 have described similar bond.The manufacture process of the bond of prior art can cause crosslinked, and this makes their purposes complicated, and particularly melt index (MI) (MFI) can make coextrusion no longer can carry out.
Bond of the present invention is much simple; It can be:
-or contain the thermoplastic polymer of at least one hydroxy functional group, the latter can be the polymer of hydroxy functional groups, each polymer all contains the polymeric blends of at least one hydroxy functional group, or contain the polymer and the another kind of mixture of polymers of at least one hydroxy functional group or the mixture of any other combination.
-or contain the thermoplastic polymer of at least one epoxy functionality, the latter can be the polymer that contains epoxy functionality, each polymer all contains the polymeric blends of at least one epoxy functionality, or contain polymer and the another kind of mixture of polymers that at least one epoxy functional closes, or the mixture of any other combination.
-contain the thermoplastic polymer of ethylene unit and at least one (methyl) acrylic acid alkyl ester units.
Bond as for hydroxy functional groups, hydroxy functional group is by polymerisation or by one or more proper monomer in the grafting, or by the appropriate functional group that is present in the polymer is carried out chemical modification, or can provide the product of at least one hydroxy functional group and oneself functionalized polymer or a kind of functionalized polymeric to react by usefulness, and be connected in the polymer.
Process rule according to solid-state, molten state or solution carries out various reactions (polymerisation, graft reaction or modification).
Hydroxy functional group normally by trifunctional acrylate monomer such as HEA or HEMA (hydroxy-ethyl acrylate or hydroxyethyl methacrylate) but or the alcohols that has polymerizable or a grafted functional group (as vinyl) for example vinylphenol provide.These monomers also can have not too reacting with hydroxy functional group or nonreactive functional group such as acid amides or amine of other.
Hydroxy functional group also can be by the appropriate functional group that is present in the polymer, utilize suitable reaction for example vinyl alkylation functional group catalyzing hydrolysis and make.
In polymer, also can have other monomers, as one or more alkene (ethene, propylene, butylene, hexene, octene, the 4-methylpentene, vinyl norbornene, or the like), alkyl acrylate or alkyl methacrylate, or vinyl alkyl.These monomers can exist jointly.
Products obtained therefrom can use separately, or as using with mixture of polymers, its polymer itself can contain or not contain hydroxy functional group.When the situation of mixture,, may need to use additive or other polymer for guaranteeing the good mixing and the excellent compatibility of polymer.
Also can be from the polymer (this functional group provides by for example copolymerization or grafting) that has carboxylic acid or carboxylic acid anhydrides functional group so that with glycol ethylene glycol or with PTMEG such as polyethylene glycol for example, polypropylene glycol or polytetramethylene glycol this functional group that neutralizes.
Beneficial is that providing the polymer of hydroxy functional group by grafting is polyolefin.And have the monomer of monomer polymerization that hydroxy functional group maybe can change the group of hydroxy functional group into and be preferably alkene.The polymer of band carboxylic acid or carboxylic acid anhydrides functional group is that polyolefin also is good.
The term polyolefin is interpreted as referring to:
The homopolymers of-ethene or propylene;
The copolymer of-ethene and vinylacetate;
The copolymer of-ethene and at least a (methyl) alkyl acrylate.Alkyl in (methyl) alkyl acrylate has and is up to 10 carbon atoms, and can be straight chain, branching or ring-type.For explanation (methyl) alkyl acrylate, should note n-butyl acrylate, methyl acrylate, isobutyl acrylate, 2-EHA, cyclohexyl acrylate, methyl methacrylate, and EMA.In these (methyl) acrylate, ethyl acrylate, methyl acrylate, n-butyl acrylate and methyl methacrylate are preferred.
The copolymer of-ethene and butylene or ethene and hexene,
-amorphous poly-alpha-olefines (APAOs).Preferably use by ethene propylene, the APAOs that butylene or hexene obtain.The ethene that butene content is high, propylene, butylene copolymer, or high ethene, propylene, the butylene copolymer of propylene content, the perhaps homopolymers of butylene or copolymer.
It is superior using ethene/(methyl) alkyl acrylate copolymer.
Therefore, the bond of hydroxy functional groups can be ethene/(methyl) acrylate/hydroxyethyl methacrylate copolymer for example, ethylene/vinyl acetate/(methyl) hydroxy-ethyl acrylate copolymer, or with ethene/(methyl) alkyl acrylate or the ethyl/vinyl acetate co-polymer of (methyl) hydroxy-ethyl acrylate grafting.
PHEMA or poly hydroxy ethyl acrylate are always not thermoplastic.Therefore, with them and other mixed with polymers so that this resin has thermoplasticity is good.Because this resin is thermoplastic, so it for example carries out coextrusion and be converted into film by order easily.
Even it is thermoplastic containing the polymer of at least one hydroxy functional group, also it may be mixed with other thermoplastic polymer.
As can mentioning with the example of mixed with polymers with hydroxy functional group:
-polyethylene, polypropylene,
The salt and the ester of-ethene and at least a being selected from (i) unsaturated carboxylic acid, the (ii) vinyl acetate of saturated carboxylic acid, the (iii) copolymer of alpha-olefin, to (iii) monomer, it can be by grafting or copolymerization for (i);
-styrene/ethylene-butylene/styrene (SEBS) block copolymer;
-styrene/butadiene/styrene (SBS) block copolymer;
-styrene/isoprene/styrene (SIS) block copolymer.
The composition of this mixture, co-monomer content, the hydroxy functional group number and the structure of polymer are considered required bond properties and serviceability and are optimized.
May need in resin, to add compatilizer to promote the uniformity of resin.These products are known; They are functionalised polyolefins for example, for example ethene and at least a being selected from (i) unsaturated carboxylic acid, their salt and their ester; (ii) unsaturated dicarboxylic, their salt, their ester, their half ester and their acid anhydrides, the (iii) vinyl acetate of saturated carboxylic acid; The (iv) copolymer of the product of alpha-olefin can be by grafting or by copolymerization concerning the monomer of (i)-(iv).
As the example of the thermoplastic resin that contains at least one hydroxy functional group, can mention:
The mixture of-following each thing
Ethylene/vinyl alcohol (EVOH) copolymer or poly hydroxy ethyl acrylate;
And at least aly be selected from following product
Ethene and at least a being selected from (i) unsaturated carboxylic acid, their salt and their ester; (ii) unsaturated dicarboxylic, their salt, their ester, their half ester and their acid anhydrides; The (iii) copolymer of the product of the vinyl acetate of saturated carboxylic acid can be by grafting or by copolymerization concerning (i)-(iii) monomer;
Polyethylene, the copolymer of ethene and alpha-olefin;
The mixture of-following each thing:
The copolymer of polyethylene or ethene and esters of unsaturated carboxylic acids, or the copolymer of ethene and saturated carboxylic acid vinyl acetate;
The copolymer of polyethylene or ethene and alpha-olefin;
One or another kind of or the two quilt (methyl) hydroxy-ethyl acrylate difference or grafting simultaneously in these polymer;
-the ethylene/vinyl acetate copolymer of hydrolysis partially or completely also can contain (methyl) alkyl acrylate concerning these copolymers.
Use following resin to be good:
The mixture of-following each thing:
Ethene/(methyl) alkyl acrylate copolymer; EVOH
Ethene/(methyl) alkyl acrylate/maleic anhydride or (methyl) glycidyl acrylate copolymer;
The mixture of-following each thing:
Ethene/(methyl) alkyl acrylate copolymer;
·EVOH
Linear low density of polyethylene with maleic anhydride graft.
EPR (ethylene-propylene) elastomer;
The mixture of-following each thing:
Ethene/(methyl) alkyl acrylate copolymer;
Poly-((methyl) hydroxy-ethyl acrylate);
The mixture of-following each thing:
Ethene/(methyl) alkyl acrylate copolymer,
Ethylene/alpha-olefin copolymer;
A kind of, another kind of in these copolymers or the two are by with (methyl) hydroxy-ethyl acrylate respectively or grafting simultaneously.
One ethylene/vinyl acetate/vinyl alcohol/(methyl) alkyl acrylate copolymer.
As an example, the thickness of this bond film is between 5-50 μ m.
This polyolefin under molten condition can be by grafting in the presence of free-radical initiator.
Graft reaction feeds in the feeding funnel in single screw rod of pelletized polyolefin for example or the double screw extruder and carries out; At first section of extruder, polyolefin is heated fusing, and at second section, reactant is delivered in the polyolefinic fused mass.
Free-radical initiator can be selected from peroxide, and peracid is crossed ester and peroxide acetal.Their consumption is with respect to being 0.01%-0.5% weight by the polyolefin of grafting.
As an example, can mention:
-dicumyl peroxide (DICUP),
-2,5-dimethyl-2,5-di-t-butyl hexane peroxide (DHBP),
-α, α ' (di-tert-butyl peroxide isopropyl) benzene (Y1490).
Preferably before for example liquid being injected the molten state polyolefin, free-radical initiator is dissolved in by in the product of grafting with measuring pump.
The preferred long enough of reactant introduction segment, temperature is enough low, and is low as far as possible with the thermal decomposition of the fine dispersion that guarantees reactant and free-radical initiator.
Real graft reaction occurs in the 3rd section of extruder, and temperature is to be suitable for guaranteeing that free-radical initiator decomposes fully; Before melt leaves extruder head, an exhaust section is provided, in this section, decomposition of initiator product and unreacted graft product are by exhaust under the vacuum for example.
In the exit of extruder, the polyolefin of own grafting after with chilled air cools with for example bar-shaped being recovered of grain.
Grafting is generally 0.1%-5% with respect to the weight ratio of own graft polymers, is preferably 0.15%-2.5%.
As for the bond that contains epoxy functionality, this functional group can import by grafting or copolymerization.About grafting, this can carry out on any thermoplastic polymer, but is good on polyolefin.The polyolefin of having mentioned above can be used for the grafting hydroxy functional group.
Use ethene/(methyl) alkyl acrylate copolymer to be good.
The unsaturated epoxide example that can mention especially has ethylene oxidic ester and ether, glycidyl itoconate, vinyl glycidyl ether, allyl glycidyl ether and VCH monoxide.
Alicyclic ring ethylene oxidic ester and ether also can be mentioned 2-cyclohexene 1-glycidol ether, carboxylic acid cyclohexene-4, the 5-2-glycidyl ester, carboxylic acid cyclohexene-4-ethylene oxidic ester, carboxylic acid 5-ENB-2-methyl-2-ethylene oxidic ester, and dicarboxylic acids bridge dicyclo (2,2,1)-and 5-heptene-2, the 3-2-glycidyl ester.
In these unsaturated epoxides, glycidyl acrylate and GMA are the most particularly preferred.
For unsaturated epoxide is grafted on the polyolefin, can use the identical method used with grafting hydroxy functional groups monomer.
As for the copolymer with own copolymerization epoxy-functional, they are copolymers of unsaturated epoxide and any other monomer, if this monomer can copolymerization with unsaturated epoxide.Preferably these comonomers are alkene, (methyl) alkyl acrylate and saturated carboxylic acid vinyl acetate.
The bond that contains own copolymerization epoxy-functional is that the copolymer of ethene and at least one unsaturated epoxide is good.
For ethene and these copolymers of at least one unsaturated epoxide, this epoxides can be selected from and the identical gang of this class bond of polyolefin with the unsaturated epoxide grafting above-mentioned.The copolymer of this ethene and at least a unsaturated epoxide also can comprise (methyl) alkyl acrylate or vinylacetate, and this (methyl) alkyl acrylate can be selected from and the identical gang of comonomer that also can contain with the monomer-grafted polyolefin of hydroxy functional groups above-mentioned.The example of the copolymer of ethene and at least a unsaturated epoxide can be mentioned ethene, (methyl) alkyl acrylate and glycidyl methacrylate copolymer, it contains 2-10% weight, the GMA of preferred 6-8% weight and the ethene of at least 50% weight.
As for the thermoplastic polymer that contains ethylene unit and at least a (methyl) acrylic acid alkyl ester units, can mention by ethene/(methyl) alkyl acrylate copolymer and forming.And mention in the polyolefinic in the above general description of this copolymer.Use comprises 20-40% weight, and the copolymer of (methyl) acrylate of preferred 25-38% weight is good.Their melt index (MI) (MFI) can for example be between the 1-500.
These copolymers can with poly homopolymers, the copolymer of ethene and at least a alpha-olefin, amorphous poly-alpha-olefines, the copolymer of ethene and vinylacetate, and SEBS, the mixture of SBS or SIS block copolymer uses.
The mixture that use is made up of at least two kinds of bonds of the present invention should not constitute deviating from the scope of the invention.
Polyketone is the polymer that in fact every mole of unsaturated monomer is comprised one mole of carbonoxide.Alpha-olefin or its substitutive derivative of the optional self-contained 2-12 carbon atom of this monomer.It can be selected from also that styrene or it are replaced by alkyl and derivative, for example methyl styrene, ethyl styrene and cumene ethene.
Preferably, polyketone is the copolymer of ethene and carbonoxide, or the copolymer of ethene, propylene and carbonoxide.
When polyketone is an ethene, during the copolymer of second monomer and carbonoxide, second monomer of each unit is had at least 2 ethylene unit, be preferably the 10-100 unit.
This polyketone can be with following general formula:
-(CO one CH
2-CH
2-)
x-(CO one A-)
yA represents to contain the unsaturated monomer of at least three carbon atoms among the-Shi, and ratio x/y is at least 2.
Unit-(CO-CH
2-CH
2-) and-(CO-A-)-random distribution in the polyketone chain.
Number-average molecular weight can be 1000-200,000, be preferably 20,000-90,000 (measuring) with gel permeation chromatography.Its fusing point can be 175-300 ℃, is generally 200-270 ℃.
The synthetic method of these polyketone has been described in United States Patent (USP) 4843144,4880903 and 3694412.
The polyketone layer can be any thickness.
(F) Ceng thermoplasticity thing can be a polyolefin, particularly above-mentioned those, polyamide, fluoropolymer polymer, or polyester for example PET or PBT.
(F) also can be rubber, for example EPDM (ethylene/propylene/diene), NBR (nitrile/butadiene) or HNBR (hydrogenated nitrile/butadiene).
The present invention is specially adapted to (F) layer by polyethylene or polypropylene (homopolymers or copolymer) system.
Polyolefinic layer is a polyethylene layer for example, polypropylene layer, or ethylene copolymer ethylene/propene for example, ethylene/butylene, ethylene/hexene, ethylene/octene, or the layer of ethylene/propene/butylene, or the copolymer of the product of ethene and at least a ester that is selected from saturated carboxylic acid vinyl acetate and unsaturated carboxylic acid and salt.This one deck can contain other polymer except polyolefin, also compatilizer can be arranged.It also can contain polyolefinic mixture.
Metal level can be the paper tinsel or the film of metal, and this metal is an aluminium for example, iron, and copper, tin or nickel perhaps contain two kinds of alloys as its Main Ingredients and Appearance in these metals at least.The thickness of film or paper tinsel can be about 0.01-0.2mm.Before being pressed onto bonding agent layer of the present invention on it, the common practice is the grease of removing on the layer on surface of metal.
Bond of the present invention, (F) Ceng polyketone, thermoplasticity thing and rubber can contain useful additives for example plasticizer, antioxidant and UV resistant agent.
Structure of the present invention is according to lamination, and coextrusion is extruded the current techique of a lamination and stratification and made.
Structure of the present invention also can contain other layer; For example, another layer of bond of the present invention can be used on the polyketone, is another (F) layer subsequently, and they are following structures in other words:
(F)/bond/polyketone of the present invention/bond of the present invention/(F)
Embodiment
Used product is as follows:
EPCO: carbon monoxide with olefin hydrocarbon alternate copolymer, its fusing point are equivalent to 204 ℃, and the melt index (MI) that records under 240 ℃ and 5kg load is equivalent to 44 grams/10 minutes.
Lotader 1: ethylene/ethyl acrylate/glycidyl methacrylate copolymer, its weight ratio are 66.9/25.5/7.6, MFI be 6 (190 ℃, 2.16kg).
Lotader 2: ethylene/ethyl acrylate/glycidyl methacrylate copolymer, its weight ratio are 71/27/2, and MFI is 6.
Lotader 3: ethylene/ethyl acrylate/copolymer-maleic anhydride, its weight ratio are 91.5/5/3.5, and MFI is 5.
Lotryl 1: ethylene/methyl acrylate copolymer, contain the acrylate of 29% weight, and MFI is 3.
Lotryl 2: ethylene/butylacrylate copolymer, contain the acrylate of 35% weight, and MFI is 40.
Lotryl 3: ethylene/butylacrylate copolymer, contain the acrylate of 35% weight, and MFI is 320.
Orevac 1: the polypropylene of maleic anhydride graft contains 1%MAH.
Orevac 2: the polyethylene of maleic anhydride graft, contain 0.4%MAH, and MFI is 1.
Make the thick EPCO of 50 μ m) film of (polyketone).
By following assembling form various products are heat sealed on the above-mentioned film:
EPCO (50 μ m)/bond (200 μ m)/EPCO (50 μ m)
Hydraulic pressure with 350 crust carried out heat-seal operation 1 minute under 220 ℃.
Peel off method at the bond properties of measuring under 200 millimeters/minute the speed between bond film and the EPCO film with T.
Obtained following peel strength:
| Product | Peel strength N/15mm |
| Lotader?1 | Not delamination |
| Lotader?2 | Not delamination |
| Lotader?3 | ???????1 |
| Lotryl?1 | Not delamination |
| Lotryl 1 with 12% hydroxy-ethyl acrylate grafting | Not delamination |
| Lotryl?2 | ???????2 |
| Lotryl 2 with 1.8% hydroxy-ethyl acrylate grafting | ??????17 |
| Lotryl?3 | ??????5.2 |
| Lotryl 3 with 3% hydroxy-ethyl acrylate grafting | ???????7 |
| Orevac?1 | ??????0.1 |
| Orevac?2 | ???????1 |
Claims (7)
1, sandwich construction, it comprises:
One deck bond, it is selected from:
-contain the thermoplastic polymer of at least one hydroxy functional group;
-contain the thermoplastic polymer of at least one epoxy functionality;
-contain the thermoplastic polymer of ethylene unit and at least one (methyl) acrylic acid alkyl ester units,
Reach one deck polyketone that directly connects thereon.
2, according to the structure of claim 1, thermoplastic polymer layer (F) wherein, rubber layer or substitute metal level directly are connected in a side of bond.
3, according to the structure of claim 1 or 2, wherein bond is the polyolefin with the unsaturated monomer grafting that contains at least one hydroxy functional group.
4, according to the structure of claim 3, wherein bond is ethene/(methyl) alkyl acrylate copolymer with the grafting of (methyl) hydroxy-ethyl acrylate.
5, according to the structure of claim 1 or 2, wherein bond is ethene/(methyl) alkyl acrylate/(methyl) glycidyl acrylate copolymer.
6, according to any structure of aforementioned claim, wherein polyketone is the linear alternate copolymer of carbonoxide and at least a unsaturated monomer, and these monomers are selected from alpha-olefin and substitutive derivative thereof, perhaps styrene and use alkyl-substituted derivatives.
7, according to any structure of aforementioned claim, wherein (F) layer is Alathon or copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97117129 CN1177540A (en) | 1996-07-05 | 1997-07-05 | Multi-layer structure containing one binder and one layer of polyketone |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9608418 | 1996-07-05 | ||
| CN 97117129 CN1177540A (en) | 1996-07-05 | 1997-07-05 | Multi-layer structure containing one binder and one layer of polyketone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1177540A true CN1177540A (en) | 1998-04-01 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97117129 Pending CN1177540A (en) | 1996-07-05 | 1997-07-05 | Multi-layer structure containing one binder and one layer of polyketone |
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| Country | Link |
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| CN (1) | CN1177540A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290392A (en) * | 2015-12-15 | 2018-07-17 | 三井化学株式会社 | Laminated body and its manufacturing method and bonding composition |
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1997
- 1997-07-05 CN CN 97117129 patent/CN1177540A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290392A (en) * | 2015-12-15 | 2018-07-17 | 三井化学株式会社 | Laminated body and its manufacturing method and bonding composition |
| CN108290392B (en) * | 2015-12-15 | 2020-10-16 | 三井化学株式会社 | Laminate, method for producing same, and adhesive composition |
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