CN100460458C - 含有丙烯腈丁二烯橡胶弹性体组合物和氟塑料阻透层的软管构造 - Google Patents
含有丙烯腈丁二烯橡胶弹性体组合物和氟塑料阻透层的软管构造 Download PDFInfo
- Publication number
- CN100460458C CN100460458C CNB2005101298004A CN200510129800A CN100460458C CN 100460458 C CN100460458 C CN 100460458C CN B2005101298004 A CNB2005101298004 A CN B2005101298004A CN 200510129800 A CN200510129800 A CN 200510129800A CN 100460458 C CN100460458 C CN 100460458C
- Authority
- CN
- China
- Prior art keywords
- phosphonium
- flexible pipe
- acrylonitrile
- weight
- layer
- 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.)
- Expired - Fee Related
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 56
- 230000004888 barrier function Effects 0.000 title description 42
- 239000000203 mixture Substances 0.000 title description 34
- 229920002313 fluoropolymer Polymers 0.000 title description 16
- 239000000806 elastomer Substances 0.000 title description 6
- 238000010276 construction Methods 0.000 title description 3
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 91
- 239000005060 rubber Substances 0.000 claims abstract description 50
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000001409 amidines Chemical class 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 16
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 11
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 41
- 239000012964 benzotriazole Substances 0.000 claims description 29
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 28
- 229920006029 tetra-polymer Polymers 0.000 claims description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 5
- 229920001774 Perfluoroether Polymers 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- 229920001169 thermoplastic Polymers 0.000 abstract description 10
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 8
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 abstract 1
- 150000004714 phosphonium salts Chemical class 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 12
- 239000000370 acceptor Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 9
- -1 benzotriazole trioctylphosphine Chemical compound 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 6
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 description 6
- 239000004811 fluoropolymer Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 4
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 4
- 239000004808 2-ethylhexylester Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- PGZIKUPSQINGKT-UHFFFAOYSA-N dialuminum;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O PGZIKUPSQINGKT-UHFFFAOYSA-N 0.000 description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 4
- 229960001545 hydrotalcite Drugs 0.000 description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- KNXVOGGZOFOROK-UHFFFAOYSA-N trimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane Chemical compound [Mg+2].[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O KNXVOGGZOFOROK-UHFFFAOYSA-N 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 241000863032 Trieres Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 150000003463 sulfur Chemical class 0.000 description 3
- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical compound N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- LOUICXNAWQPGSU-UHFFFAOYSA-N 2,2,3,3-tetrafluorooxirane Chemical compound FC1(F)OC1(F)F LOUICXNAWQPGSU-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 229920013647 Krynac Polymers 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 2
- 229940031826 phenolate Drugs 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical group C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKJADYKTJJGKDX-UHFFFAOYSA-N Butyl pentanoate Chemical compound CCCCOC(=O)CCCC OKJADYKTJJGKDX-UHFFFAOYSA-N 0.000 description 1
- AKQRHVUPISQYDC-UHFFFAOYSA-N CCCCP.C(C=C1)=CC2=C1N=NN2 Chemical compound CCCCP.C(C=C1)=CC2=C1N=NN2 AKQRHVUPISQYDC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- ZHZOWLCXBBOSBP-UHFFFAOYSA-N N1CCOCC1.N1CCOCC1.[S] Chemical class N1CCOCC1.N1CCOCC1.[S] ZHZOWLCXBBOSBP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- LFABKIZAWMMODX-UHFFFAOYSA-N SC=1SC2=C(N1)C=CC=C2.NC2=CC=CC=C2.C(CCC)=O Chemical compound SC=1SC2=C(N1)C=CC=C2.NC2=CC=CC=C2.C(CCC)=O LFABKIZAWMMODX-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 229950004288 tosilate Drugs 0.000 description 1
- NAXVGLGYVHLSAR-UHFFFAOYSA-N tributyl(3-methoxypropyl)phosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCOC NAXVGLGYVHLSAR-UHFFFAOYSA-N 0.000 description 1
- QRCJOCOSPZMDJY-UHFFFAOYSA-N valnoctamide Chemical compound CCC(C)C(CC)C(N)=O QRCJOCOSPZMDJY-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/045—Hoses, i.e. flexible pipes made of rubber or flexible plastics with four or more layers without reinforcement
-
- 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
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber 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
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
-
- 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
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
-
- 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
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
-
- 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
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- 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
- B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/026—Knitted fabric
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
- B32B2262/0269—Aromatic polyamide fibres
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/04—Cellulosic plastic fibres, e.g. rayon
-
- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
-
- 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
- B32B2274/00—Thermoplastic elastomer material
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
-
- 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
- B32B2597/00—Tubular articles, e.g. hoses, pipes
-
- 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
- B32B2605/00—Vehicles
- B32B2605/08—Cars
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Laminated Bodies (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
公开的是一种包含直接相互接触的第一层与第二层的软管；第一层包含从四氟乙烯、六氟丙烯、偏二氟乙烯、和全氟乙烯醚衍生的一种热塑性四元共聚物；第二层包含100重量份丙烯腈丁二烯橡胶(NBR)，所述丙烯腈橡胶包含约20～约65wt%结合丙烯腈；每100重量份NBR约3～约20重量份至少一种酸受体；每100重量份NBR约1～约10重量份至少一种有机鏻盐；和每100重量份NBR约0.25～约10重量份至少一种脒。
Description
技术领域
本发明涉及含有NBR弹性体组合物和氟塑料阻透层的软管。
发明背景
目前用于汽车用途的燃料软管的主要部分是一种多层结构。该软管的最内管状层是由一种意在将流体保持在该软管中的弹性体材料形成的。位于最内层与外弹性体被覆层之间的是一个阻透层。在其它燃料软管中，该阻透层是最内管状层(称为单板软管)，而该弹性体材料位于这样的阻透层外侧。已经使用了很多阻透层；然而，该阻透层中使用的很多这样的化合物并不粘附到最内管状层中使用的惯常弹性体材料上。作为这个问题的结果，业内技术人员惯常在最内层与阻透层之间使用一个对最内层与阻透层中使用的弹性体都兼容的层。具体地说，高度不可渗透的热塑性聚合物阻透层与弹性体最内层之间的粘合一直是有问题的。因此，理想的是有一种在高度不可渗透热塑性聚合物阻透层与弹性体层之间有优异粘合力的软管。
发明内容
公开的是一种包含直接相互接触的第一层与第二层的软管；第一层包含从四氟乙烯、六氟丙烯、偏二氟乙烯、和全氟乙烯醚衍生的一种热塑性四元共聚物；第二层包含
100重量份丙烯腈-丁二烯橡胶(NBR)，所述丙烯腈橡胶包含约20～约65wt％结合丙烯腈；
每100重量份NBR约3～约20重量份至少一种酸受体；
每100重量份NBR约1～约10重量份至少一种有机鏻盐；和
每100重量份NBR约0.25～约10重量份至少一种脒。
附图简述
图1是一种按照本发明的软管的透视图。
图2是一种按照本发明的软管的透视图。
具体实施方式
公开的是一种包含直接相互接触的第一层与第二层的软管；第一层包含从四氟乙烯、六氟丙烯、偏二氟乙烯、和全氟乙烯醚衍生的一种热塑性四元共聚物；第二层包含
100重量份丙烯腈-丁二烯橡胶(NBR)，所述丙烯腈-丁二烯橡胶包含约20～约65wt％结合丙烯腈；
每100重量份丙烯腈-丁二烯橡胶约3～约20重量份至少一种酸受体；
每100重量份丙烯腈-丁二烯橡胶约1～约10重量份至少一种苯并三唑有机鏻；和
每100重量份丙烯腈-丁二烯橡胶约0.25～约10重量份至少一种脒。
本发明的软管包含一层NBR橡胶组合物和一层从四氟乙烯、六氟丙烯、偏二氟乙烯、和全氟乙烯醚衍生的热塑性四元共聚物，这两层是直接相互接触的。当生产一种诸如图1中所示的软管时，该NBR层可以是内芯层(1)。该四元共聚物层可以是阻透层(3)。稍后会描述该四元共聚物层是内芯(1)而且是单板阻透层且层(3)为NBR橡胶组合物的实施方案。
可以使用各种丙烯腈-丁二烯橡胶(NBR)。例如，门尼粘度(M/L1+4100℃)和丙烯腈含量可以因该软管的用途而异。NBR的适当实例可以有低达约20～高达约110的门尼粘度。适用NBR的结合丙烯腈含量范围可以从低达约20wt％到高达约65wt％。适用NBR是ZeonChemical公司作为Nipol例如Nipol 35-5、Nipol DN4555、Nipol DN003等和拜耳公司作为KRYNAC例如DRYNAC 4560 C、KRYNAC 34E80销售的。在一种实施方案中，该NBR可以包含约30～约40wt％的结合丙烯腈(ACN)。在另一种实施方案中，该NBR可以包含至少41wt％的结合丙烯腈(ACN)。在另一种实施方案中，该NBR可以是一种包含至少45wt％结合丙烯腈(ACN)的高腈NBR。
该NBR橡胶组合物包含至少一种有机鏻盐，在一种实施方案中，该有机鏻盐可以选自下列组成的一组：含有1～20个碳原子的烷基取代基团的季鏻盐。在一种实施方案中，该有机鏻盐包括卤化有机鏻例如氯化四丁基鏻、氯化烯丙基三丁基鏻、溴化四丁基鏻、氯化三丁基(甲氧基丙基)鏻、氯化苄基三苯基鏻、和氯化苄基三辛基鏻。在另一种实施方案中，该有机鏻盐可以选自有苯并三唑阴离子的季鏻盐，包括例如苯并三唑有机鏻，例如苯并三唑四丁基鏻和苯并三唑三辛基乙基鏻。在一种实施方案中，该有机鏻盐是苯并三唑四正丁基鏻，可作为ZE0NET PB购自Zeon Chemicals公司。可以使用的有机鏻盐的数量是能在该软管的第一层与第二层之间给予粘合力所必需的量。在一种实施方案中，该NBR组合物包含约1～约10phr有机鏻盐。在另一种实施方案中，该NBR组合物包含约2～约7phr有机鏻盐。
在一种实施方案中，该有机鏻盐包含苯并三唑有机鏻，且实质上不包括卤化有机鏻。所谓实质上不包括卤化有机鏻，系指该NBR组合物包括的卤化有机鏻数量不会足以提高第一层对第二层的粘合力。在一种实施方案中，该有机鏻盐包含不到1phr卤化有机鏻。在另一种实施方案中，该有机鏻盐包含不到0.25phr卤化有机鏻盐。
该NBR橡胶组合物包含至少一种。在一种实施方案中，该脒包括1，8-二氮杂双环[5.4.0]十一碳烯-7(DBU)和1，5-二氮杂双环[4.3.0]壬烯-5(DBN)及其盐。DBU盐的实例包括1，8-二氮杂双环[5.4.0]十一碳烯-7的碳酸盐、长链脂肪酸盐、羧酸盐、芳香族磺酸盐或羧酸盐、苯酚盐、硫醇盐等。典型实例是DBU-碳酸盐、DBU-硬脂酸盐、DBU-萘甲酸盐、DBU-对羟基苯甲酸盐、DBU-对甲苯磺酸盐等。也包括的是1，8-二氮杂双环[5.4.0]十一碳烯-7的无取代或有取代苯酚盐。此类化合物的实施包括1，8-二氮杂双环[5.4.0]十一碳烯-7的苯酚盐、1，8-二氮杂双环[5.4.0]十一碳烯-7的甲苯酚盐、1，8-二氮杂双环[5.4.0]十一碳烯-7的间苯二酚盐、和1，8-二氮杂双环[5.4.0]十一碳烯-7的氢醌盐。1，8-二氮杂双环[5.4.0]十一碳烯-7的一种无取代苯酚盐是Mitsui & Co(Canada)以Accelerator P152的商品名销售的。可用的脒的数量是在该软管第一层与第二层之间给出粘合力所必需的数量。在一种实施方案中，该NBR组合物包含约0.25～约10phr脒。在另一种实施方案中，该NBR组合物包含约0.5～约3phr脒。
在一种实施方案中，该NBR组合物中存在的有机鏻盐的重量至少等于所存在脒的重量。在另一种实施方案中，该NBR组合物中存在的有机鏻盐的重量大于所存在脒的重量。在一种实施方案中，该NBR组合物中所存在的有机鏻盐与脒的重量比范围为约1～约10。在另一种实施方案中，该NBR组合物中所存在的有机鏻盐与脒的重量比范围为约1.1～约7。在另一种实施方案中，该NBR组合物中所存在的有机鏻盐与脒的重量比范围为约1.5～约3。
该NBR橡胶组合物包含至少一种酸受体。适用的酸受体包括但不限于氧化镁、氢氧化钙、铅黄、二代亚磷酸铅、氧化钙、和氧化锌，水滑石或铝酸三钙六水合物Ca3Al2O·6H2O。水滑石包括但不限于下式所描述的材料:Mg(1-x)Alx(OH)2(CO3)x/2·nH2O；0.25<x<0.33。合成水滑石可以包括x在所给出范围内的各种化合物的混合物。水滑石的合成形式可从若干个来源得到，包括Kyowa Chemical Industry Co.Ltd.的DHT-4A2
和Alcamizer
，Sud-Chemie AG的Sorbacid
911，CibaSpecialty Chemicals的Hycite
713。在一种实施方案中，该酸受体包括氢氧化钙。
酸受体是以每100重量份弹性体约3～约20重量份酸受体，换言之，3～约20phr(份/100份橡胶)的范围存在于该橡胶组合物中的。在一种实施例方案中，酸受体是以约5～约15phr的范围存在的。
该软管中使用的橡胶组合物可以是用硫磺、紫外线硫化或过氧化物硫化系统交联的。可以使用的众所周知过氧化物类别包括过氧化二酰基、过氧酯、过氧化二烷基和过氧缩酮。具体实例包括过氧化二枯基、4，4-二(叔丁过氧基)戊酸正丁酯、1，1-二(叔丁过氧基)-3，3，5-三甲基环己烷、1，1-二(叔丁过氧基)环己烷、1，1-二(叔戊基)环己烷、3，3-二(叔丁过氧基)丁酸乙酯、3，3-二(叔戊过氧基)丁酸乙酯、2，5-二甲基-2，5-二(叔丁过氧基)己烷、过氧化叔丁基·枯基、α，α’-二(叔丁过氧基)二异丙苯、过氧化二叔丁基、2，5-二甲基-2，5-二(叔丁过氧基)己炔-3、过苯甲酸叔丁酯、4-甲基-4-叔丁过氧基-2-戊酮及其混合物。在一种实施方案中，过氧化物是α，α’-二(叔丁过氧基)二异丙苯。过氧化物的典型数量范围是1～12phr(以过氧化物的有效份额为基准)。在一种实施方案中，过氧化物的数量范围为1～8phr。
自由基交联反应期间可以存在一种活性助剂。活性助剂是单官能的和多官能的不饱和有机化合物，是与自由基引发剂配合使用来达到改善的硫化性能的。代表性实例包括有机丙烯酸酯、有机甲基丙烯酸酯、二乙烯酯、二乙烯基苯、联马来酰亚胺、氰脲酸三烯丙酯、多烷基醚和酯、α，β-不饱和有机酸的金属盐及其混合物。在一种实施方案中，该活性助剂是可作为SR533购自Sartomer公司的异氰脲酸三烯丙酯。在另一种实施方案中，该活性助剂是N，N’-间苯二马来酰亚胺，可作为SR525购自Sartomer公司或作为HVA-2购自DuPont-Dow公司.
该活性助剂可以一系列水平存在于该NBR胶料中。在一种实施方案中，该活性助剂是以0.1～15phr范围内的数量存在的。在另一种实施方案中，该活性助剂是以1～10phr范围内的数量存在的。
该软管中使用的橡胶组合物可以用硫磺硫化剂硫化。适用硫磺硫化剂的实例包括元素硫(游离硫)或给硫型硫化剂，例如二硫化胺、聚合物多硫化物或硫磺烯烃加合物。在一种实施方案中，该硫磺硫化剂当使用时是元素硫。该硫磺硫化剂的数量将因该涂层中的其余组分和所使用的硫磺硫化剂的特定类型而异。在一种实施方案中，硫磺硫化剂的数量范围为约0.1～约8phr。在另一种实施方案中，该硫磺硫化剂的数量范围为约1.0～约3phr。
可以使用促进剂来控制该橡胶组合物硫化所需要的时间和/或温度。如业内技术人员所知道的，可以使用单一促进剂，其存在数范围为约0.2～约3.0phr。替而代之，可以使用2种或更多种促进剂的组合，该组合由一般以较大数量(0.3～约3.0phr)使用的主促进剂和一般以较小数量(0.05～约1.50phr)使用的副促进剂组成，以期活化和改善该胶料的性能。这些促进剂的组合已知能对最终性能产生协同效应，而且略优于由任意一种促进剂单独使用所产生的效果。延迟作用促进剂也已知可以使用，它们不受正常加工温度影响，而且能在通常硫化温度产生令人满意的硫化。适用的促进剂类型包括胺、二硫化物、胍、硫脲、噻唑、秋兰姆、亚磺酰胺、二硫代氨基甲酸盐和黄原酸酯。适用的具体化合物的实例包括二乙基二硫代氨基甲酸锌、4，4’-二硫二吗啉、N，N-二甲基-S-叔丁基亚磺酰二硫代氨基甲酸酯、二硫化四甲基秋兰姆、二硫化2，2’-二苯并噻唑基、丁醛苯胺巯基苯并噻唑、N-氧二亚乙基-2-苯并噻唑亚磺酰胺。在一种实施方案中，该促进剂是一种亚磺酰胺。
通常使用一种作为防焦剂已知的配混材料。邻苯二甲酸酐、水杨酸、乙酸钠、和N-环己基硫代邻苯二甲酰亚胺是已知的防焦剂。防焦剂的使用量范围一般是约0.1～0.5phr。
惯常炭黑也可以存在于该橡胶组合物中。在一种实施方案中，炭黑的用量范围为5～250phr。在另一种实施方案中，炭黑的用量范围为20～100phr。可以使用的炭黑的代表性实例包括但不限于那些因其如下ASTM名称而知名者：N110，N121，N242，N293，N299，N315，N326，N330，N332，N339，N343，N347，N351，N358，N375，N550，N582，N630，N624，N650，N660，N683，N754，N762，N907，N908，N990，N991，及其混合物。
业内技术人员容易理解的是，该橡胶组合物会用橡胶配混业内普遍知道的方法配混，例如使各种组分橡胶与各种常用添加剂材料例如硫化助剂和加工添加剂例如油、树脂包括增粘树脂和增塑剂、填料、颜料、脂肪酸、蜡、抗氧化剂和抗臭氧化剂。以上提到的添加剂加以选择并以惯常数量使用。
增粘树脂当使用时的典型数量包含约0.5～约10phr、通常约1～约5phr。加工助剂的典型数量包含约1～约50phr。这样的加工助剂可以包括，例如，聚乙二醇、环烷类和/或链烷类加工油。抗氧化剂的典型数量包含约1～约5phr。代表性抗氧化剂是三甲基二氢喹啉。可以包括硬脂酸在内的脂肪酸当使用时的典型数量包含约0.5～约3phr。蜡的典型数量包含约1～约5phr。通常使用微晶蜡和加洛巴蜡。增塑剂当使用时的典型数量包含1～100phr。此类增塑剂的代表性实例包括癸二酸二辛酯、氯代链烷烃等。
可以添加各种非炭黑填料和/或增强剂，以提高本发明软管制造用橡胶组合物的强度和完整性。增强剂的一个实例是二氧化硅。二氧化硅在该橡胶组合物中的使用量可以是约0～80份。在一种实施方案中，以100重量份橡胶为基准，二氧化硅的使用量是约10～20重量份。
该橡胶组合物的混合可以用橡胶混炼业内技术人员已知的方法完成。例如，各组份可以用一个阶段混合、但典型地用至少2个阶段混合，即至少一个非生产性阶段随后一个生产性混炼阶段。最终硫化剂典型地在惯常称为“生产性”混炼阶段的最终阶段混炼，其中该混炼典型地在低于前面的非生产性混炼阶段的混炼温度的温度或极限温度混炼。
在一种实施方案中，该橡胶组合物的硫化是在约150℃～190℃范围内的温度和至少75psig的压力进行的。在另一种实施方案中，该硫化是在约160℃～180℃范围内的温度和至少75psig的压力进行的。后硫化可以包括压力和温度的逐渐降低。硫化可以用业内已知的任何一种方法例如水蒸汽高压釜、加热压机等进行。
参照图1，内芯层(1)可以有以上所述NBR橡胶组合物，且阻透层(3)有与第二层直接相互接触的热塑性四元共聚物。
按照另一种实施方案，四元共聚物的阻透层或单板层(1)可以是内芯层，且NBR橡胶层(3)与第一层直接相互接触。
该NBR橡胶层可以用业内技术人员已知的挤塑方法形成。此层的厚度，无论作为内芯层(1)还是层(3)，都是重要的，因为过薄的壁厚或过厚的壁厚都会产生最终软管复合材料的挠曲性或扭结问题或偶合兼容性问题。相信，无论由橡胶还是阻透层制成，内芯层(1)的内直径均应在3mm～100mm的范围内。在一种实施方案中，该内芯层的内直径将在4mm～75mm范围内。当该内芯层由该橡胶组合物制成时，在一种实施方案中，内芯层(1)的壁厚应当在0.1mm～8.0mm的范围内，而在另一种实施方案中，该范围是0.5mm～4.0mm。当该内芯层由阻透层化合物制成时，内芯层(1)的壁厚应在0.02～0.76mm范围内。
本发明的一个优点是NBR橡胶组合物层是与本发明中使用的四元共聚物阻透层直接相互接触的、因而可以直接粘附于其上。因此，不牺牲该橡胶组合物层与该阻透层之间的粘合力，就可以利用该四元共聚物阻透层的优异渗透阻力。
本发明中使用的阻透层(1)或(3)是从一种会在本文中稍后更充分描述的氟热塑性塑料衍生的。这个阻透层(1)或(3)的厚度是重要的，因为过薄的壁厚或过厚的壁厚都会产生挠曲性或扭结问题或所希望的阻透层性能。一般地说，阻透层(1)或(3)的厚度将在约0.1mm～约1mm范围内。替而代之，阻透层(1)或(3)的厚度将在约0.15mm～0.5mm范围内。
可以是阻透层(3)或单板阻透层(1)的阻透层包括从四氟乙烯、六氟丙烯、偏二氟乙烯、和全氟乙烯醚衍生物的一种四元共聚物。在一种实施方案中，该四元共聚物是全文列为本文参考文献的美国专利NO.6,489,420中公开的。如其中所公开的，适用的热塑性四元共聚物是从下列成份衍生的：i)四氟乙烯，ii)偏二氟乙烯，iii)式CF2＝CFRf的至少一种烯键不饱和单体，式中Rf是一种1～8个碳原子的全氟烷基或全氟烷氧基，和iv)式CF2＝CF-(OCF2CF(Rf))aOR’f的全氟乙烯醚，式中Rf同(iii)中所述，R’f是1～8、较好1～3个碳原子的全氟脂肪族基团、较好全氟烷基或全氟烷氧基，a有0～3的值.在一种实施方案中，适用的热塑性四元共聚物包含(i)40～80wt％(替而代之，45～76wt％)四氟乙烯，(ii)10～30wt％(替而代之，12～25wt％)偏二氟乙烯，(iii)5～40wt％(替而代之，10～30wt％)式CF2＝CFRf共聚单体，和(iv)0.1～15wt％(替而代之，1～10wt％)式CF2＝CF-(OCF2CF(Rf))aOR’f的全氟乙烯醚。
在一种替代实施方案中，该热塑性四元共聚物含有从TFE、VDF、HFP和全氟乙烯醚衍生的共聚单元，其中“a”的值是0、1或2。
在一种替代实施方案中，该热塑性四元共聚物含有从TFE、VDF、HFP和式PPVE1或PPVE2的全氟乙烯醚衍生物的共聚单元：
CF2＝CFOCF2CF2CF3 PPVE1
在一种实施方案中，可以用来形成本发明软管的阻透层的热塑性四元共聚物可在商品名THV×815G之下购自Dyneon Company。
该软管可以包括一个外被覆层(5)。这个外被覆层(5)可以从一种弹性体材料制成。当希望一种弹性体被覆层时，被覆层(5)可以挤塑在下层(3)上，或如以下所讨论的，在各种其它任选层上。可以用来形成本发明软管的被覆层(5)的弹性体包括业内技术人员已知的那些，例如氯磺化聚乙烯、氯化聚乙烯、丙烯腈-丁二烯橡胶/PVC共混物、表氯醇、乙烯/丙烯/二烯三元共聚物(EPDM)、聚氯丁二烯、EVA、乙烯-丙烯酸弹性体AEM、和乙烯-乙酸乙烯酯共聚物(EVM)。弹性体被覆层(5)的厚度显然取决于该软管的所希望性能和所使用的弹性。在一种实施方案中，弹性体被覆层(5)的厚度范围为约0.1mm～约10mm。在另一种实施方案中，该被覆层的厚度范围为0.5mm～2.5mm。
虽然以上讨论了本发明所必需的基本层，但本发明的软管可以有任选的特色。例如，当生产一种如图2中所示有内NBR芯层(10)和四元共聚物阻透层(12)的软管时，在阻透层(12)外侧配置的可以是一层(14)另一种聚合物。这样的聚合物可以有与内芯层(10)相同的组成。在另一种实施方案中，在层(14)中使用的、与阻透层(12)形成界面的聚合物可以有不同的聚合物。与阻透层(12)形成界面的层(14)的厚度范围可以因所选择的聚合物而异.在一种实施方案中，层(14)的厚度范围将是约0.25mm～约1.5mm。在另一种实施方案中，层(14)的厚度范围将是约0.50mm～约1.0mm。
本发明的另一个任选特征是可以加在与阻透层(12)形成界面的层(14)上面的增强层(16)。此类增强层(16)是业内技术人员已知的，而且可以由螺旋线、针织纱或编织纱组成。这样的增强层可以从聚酯、尼龙、嫘萦或芳香族聚酰胺帘线衍生。该增强层(16)可以在足够的张力下螺旋式地缠绕在下层上，以改善该软管结构的强度。增强层(16)可以以这样的角度螺旋式缠绕，使得该软管的挠曲不会导致塌陷或扭结。可以使用相对于该软管中心线而言0～89.9°等角度。在一种实施方案中，该螺旋缠绕可以使用54°73’或更小的中性角。
在一种实施方案中，内层(10)是从一种包含NBR的NBR组合物制成的，该NBR包含41wt％以上结合的丙烯腈(ACN)。叠加在该内层上的阻透层(12)包含以上所述四元共聚物。叠加在阻透层(12)上的摩擦层(14)是从一种包含NBR的NBR组合物制成的，该NBR包含30～40wt％结合的丙烯腈。该软管可以进一步任选地包括增强层(16)和被覆层(18)。
按照一种实施方案，内芯层(10)充当一个包含上述四元共聚物的阻透层，下一层(12)由NBR组合物制成，下一层(14)省略，增强层(16)直接挨着橡胶层(12)，随后外被覆层(18)。
如以上提到的，弹性体被覆层(18)是外层。
该NBR层可以用业内技术人员已知的挤塑方法形成。这一层无论作为最内层1或10还是下一层3或12的厚度都是重要的，因为过薄的壁厚或过厚的壁厚都会产生最终软管复合材料的挠曲性或扭结问题或偶合兼容性问题。在一种实施方案中，最内层1或10无论从NBR还是四元共聚物制成，其内直径均应在3mm～100mm范围内。在一种实施方案中，该最内层的内直径将在4mm～75mm范围内。当最内层由NBR组合物制成时，该最内层的壁厚应在0.1mm～8mm范围内。替而代之，该最内层的壁厚将在0.5mm～4mm范围内。当该最内层由阻透层化合物制成时，该最内层的壁厚应在0.1～1mm范围内。
下列实施例是为说明本发明而提供的，而无意限制本发明。
实施例1
制备含有一种有50％结合丙烯腈的NBR的NBR橡胶组合物，并评估其对适合用来作为软管阻透层的热塑性氟聚合物的粘合。该橡胶组合物中使用的配方列于表1和3中，数量均以重量份给出。样品1～4是对照组，样品5～9代表本发明。每种橡胶组合物的样品都与一个THV×815G热塑性氟聚合物层一起制作，在一台加热压机上在340℉以100psig的汽球压力硫化25分钟，随后用10分钟时间逐渐冷却，给出适合于粘合力测试的样品。然后，用一台Instron试验机按照ASTMD 413-98测试该样品中NBR组合物对THV×815G的粘合力。粘合力试验的结果列于表2和4中。
表1
样品号9 1 2 3 4 5
NBR，50％ ACN1 100 100 100 100 100
酸受体2 12 12 12 12 12
眯3 0 0 0 2 2
氯化有机鏻4 0 5 0 0 5
苯并三唑有机鏻5 0 0 5 0 0
过氧化物6 4 6 6 6 6
活性助剂7 1 1 1 1 1
活性助剂8 1 1 1 1 0
1.Nipol DN003，有50wt％结合丙烯腈的丙烯腈-丁二烯橡胶
2.Ca(OH)2
3.DBU，1，8-二氮杂双环[5.4.0]十一碳烯-7
4.FX-5166，氯化烯丙基三丁基鏻
5.Zeonet PB，苯并三唑四正丁基鏻
6.Varox 802 40KE，二(叔丁过氧基)二异丙苯，40％载于KE粘土上
7.HVA-2，N，N’-间苯二马来酰亚胺
8.SR533，异氰脲酸三烯丙酯
9.所有样品都包括下列成分(phr)：Zeon B-210 Resin，18.5；N-550 Black，60.5；邻苯二甲酸二丁酯，9；TOTM，5；Plastha11 203DBEA，7；Mistron Vapor，5；Degussa Si69，0.5；Wingstay 100，1；TMQ，2；Nipol 1312/HiSi，7
表2
对THV×815G氟塑料的粘合力
样品号 1 2 3 4 5
眯 0 0 0 2 2
氯化有机鏻 0 5 0 0 5
苯并三唑有机鏻 0 0 5 0 0
平均粘合力，lbf 1 1 18.2 1 5
界面上的橡胶撕裂，％ 0 0 100 0 0
表3
样品号8 3 4 6 7 8 9
NBR，50％ ACN1 100 100 100 100 100 100
酸受体2 12 12 12 12 12 12
眯3 0 2 2 2 2 2
苯并三唑有机鏻4 5 0 2 3 4 5
过氧化物5 6 6 6 6 6 6
活性助剂6 1 1 1 1 1 1
活性助剂7 0 1 1 0 0 0
1.Nipol DN003，有50wt％结合丙烯腈的丙烯腈-丁二烯橡胶
2.Ca(OH)2
3.DBU，1，8-二氮杂双环[5.4.0]十一碳烯-7
4.Zeonet PB，苯并三唑四正丁基鏻
5.Varox 802 40KE，二(叔丁过氧基)二异丙苯，40％载于KE粘土上
6.HVA-2，N，N’-间苯二马来酰亚胺
7.SR533，异氰脲酸三烯丙酯
8.所有样品都包括下列成分(phr)：Zeon B-210 Resin，18.5；N-550 Black，60.5；邻苯二甲酸二丁酯，9；TOTM，5；Plastha11 203DBEA，7；Mistron Vapor，5；Degussa Si69，0.5；Wingstay 100，1；TMQ，2；Nipol 1312/HiSi1，7
表4
对THV×815G氟塑料的粘合力
样品号 3 4 6 7 8 9
眯 0 2 2 2 2 2
苯并三唑有机鏻 5 0 2 3 4 5
平均粘合力，lbf 18.2 1 7.4 24.3 26.3 27.4
界面上的橡胶撕裂，％ 100 0 10 100 100 100
令人惊讶和出乎意料的是，氯化有机鏻FX-5166的使用并没有导致NBR组合物对氟塑料四元共聚物THV×815G的可接受粘合。脒和苯并三唑有机鏻的组合(样品6～9)导致该高腈NBR与氟塑料四元共聚物THV×815G之间的优异粘合。
实施例2
制备含有一种有45％结合丙烯腈的NBR的NBR橡胶组合物，并评估其对一种适合用来作为软管阻透层的热塑性氟聚合物的粘合力。该橡胶组合物中使用的配方列于表5中，其数量均以重量份给出。样品10、12和13是对照组，样品11代表本发明的一种实施方案。每一种橡胶组合物的样品都是与一个THV×815G热塑性氟聚合物层一起制作，并在一台加热压机上于340℉以100psig的汽球压力硫化25分钟，随后用10分钟逐渐冷却下来，给出适合于粘合力测试的样品。然后，使用一台Instron试验机按照ASTM D 413-98测试该粘合力样品中NBR组合物对THV×815G的粘合力。粘合力测试的结果列于表6中。
表5
样品号8 10 11 12 13
NBR，45％ ACN1 100 100 100 100
酸受体2 10 10 10 10
眯3 6 6 0 0
苯并三唑有机鏻4 0 2 6 8
过氧化物5 6 6 6 6
活性助剂6 1 1 1 1
活性助剂7 0 0 0 0
1.Nipol DN4555，有45wt％结合丙烯腈的丙烯腈-丁二烯橡胶
2.Ca(OH)2
3.DBU，1，8-二氮杂双环[5.4.0]十一碳烯-7
4.Zeonet PB，苯并三唑四正丁基鏻
5.Varox 802 40KE，二(叔丁过氧基)二异丙苯，40％载于KE粘土上
6.HVA-2，N，N’-间苯二马来酰亚胺
7.SR533，异氰脲酸三烯丙酯
8.所有样品都包括下列成分(phr)：Zeon B-210树脂，18.75；N-550 Black，60；Vulcan XC-72，6；邻苯二甲酸二丁酯，9；TOTM，5；Plastha11 209，7；Mistron Vapor，5；Degussa Si69，0.5；Wingstay100，1；TMQ，2；Nipol 1312/HiSi1，7。
表6
对THV×815G氟塑料的粘合力
样品号 10 11 12 13
眯 6 6 0 0
苯并三唑有机鏻 0 2 6 8
平均粘合力，lbf 2.4 13.8 26.8 22.8
界面上的橡胶撕裂，％ 0 50 100 100
令人惊讶和出乎意料的是，脒 单独使用(实施例10)并没有导致该中腈NBR对氟塑料四元共聚物THV×815G的可接受粘合力。该脒与较少量有机鏻一起使用(实施例11)给出一定粘合力。进而，较高浓度苯并三唑有机鏻单独使用显然没有进一步改善粘合力，而且可能导致降低粘合力(样品12和13)。
实施例3
制备含有一种有35％结合丙烯腈的NBR的NBR橡胶组合物，并评估其对一种适合用来作为软管阻透层的热塑性氟聚合物的粘合力。该橡胶组合物中使用的配方列于表7中，所有数量均以重量份给出。样品14～16是对照组，而样品17代表本发明。每一种橡胶组合物的样品都与一个THV×815G热塑性氟聚合物层一起制作，并在一台加热压机上于340℉以100psig的汽球压力硫化25分钟，随后用10分钟时间逐渐冷却下来，给出适合于粘合力测试的样品。然后，使用一台Instron试验机按照ASTM D 413-98测试该粘合力样品中NBR组合物对THV×815G的粘合力。粘合力测试的结果列于表8中。
表7
样品号7 14 15 16 17
NBR，35％ ACN1 100 100 100 100
酸受体2 8 8 8 8
眯3 0 2 0 2
苯并三唑有机鏻4 0 0 3 3
过氧化物5 1.4 1.4 1.4 1.4
活性助剂6 1 1 1 1
1.Nipol 35-5，有35wt％结合丙烯腈的丙烯腈-丁二烯橡胶
2.Ca(OH)2
3.DBU，1，8-二氮杂双环[5.4.0]十一碳烯-7
4.Zeonet PB，苯并三唑四正丁基鏻
5.Varox 802 40KE，二(叔丁过氧基)二异丙苯，40％载于KE粘土上
6.HVA-2，N，N’-间苯二马来酰亚胺
7.所有样品都包括下列成分(phr)：N-550 Black，64.8；邻苯二甲酸二丁酯，9；TOTM，5.2；Plastha11 209，6.8；Mistron Vapor，5；Degussa Si69/black，1；Oxoflex DPA，2.1
表8
对THV×815G氟塑料的粘合力
样品号 14 15 16 17
眯 0 2 0 2
苯并三唑有机鏻 0 0 3 3
平均粘合力，lbf 1 9.5 1 30.4
界面上的橡胶撕裂，％ 0 0 0 100
令人惊讶和出乎意料的是，脒和苯并三唑有机鏻的组合导致NBR组合物对THV×815G的优异粘合，而无论脒还是苯并三唑有机鏻单独都给出不良的粘合。
Claims (10)
1.一种软管，其特征在于第一层与第二层直接相互接触；第一层包含一种从四氟乙烯、六氟丙烯、偏二氟乙烯、和全氟乙烯醚衍生的热塑性四元共聚物；第二层包含：
100重量份丙烯腈-丁二烯橡胶，所述丙烯腈-丁二烯橡胶包含20～65wt％结合丙烯腈；
每100重量份丙烯腈-丁二烯橡胶3～20重量份至少一种酸受体；
每100重量份丙烯腈-丁二烯橡胶1～10重量份至少一种苯并三唑有机鏻；和
每100重量份丙烯腈-丁二烯橡胶0.25～10重量份至少一种脒。
2.权利要求1的软管，其特征在于该丙烯腈-丁二烯橡胶包含至少41wt％结合丙烯腈。
3.权利要求1的软管，其特征在于该丙烯腈-丁二烯橡胶包含至少45wt％结合丙烯腈。
4.权利要求1的软管，其特征在于该至少一种苯并三唑有机鏻包含苯并三唑四正丁基鏻。
5.权利要求3或4的软管，其特征在于该至少一种苯并三唑有机鏻与该至少一种脒的重量比范围为1.1～7。
6.权利要求3或4的软管，其特征在于该至少一种苯并三唑有机鏻与该至少一种脒的重量比范围为1.5～3。
7.权利要求1的软管，其特征在于该至少一种脒选自1，8-二氮杂双环[5.4.0]十一碳烯-7和1，5-二氮杂双环[4.3.0]壬烯-5及其盐。
8.权利要求1的软管，其特征在于所述至少一种苯并三唑有机鏻包含苯并三唑四正丁基鏻，所述至少一种脒包含1，8-二氮杂双环[5.4.0]十一碳烯-7，且该至少一种苯并三唑有机鏻与该至少一种脒的重量比范围为1.1～7。
9.权利要求1的软管，其特征在于所述热塑性四元共聚物是从下列成分衍生的：(i)四氟乙烯，(ii)偏二氟乙烯，(iii)式CF2＝CFRf的至少一种烯键不饱和单体，式中Rf是一种1～8个碳原子的全氟烷基或全氟烷氧基，和(iv)式CF2＝CF-(OCF2CF(Rf))aOR’f的全氟乙烯醚，式中Rf同(iii)中所述，R’f是1～8个碳原子的全氟脂肪族基团或全氟烷氧基，且a有0～3的值。
10.权利要求9的软管，其中，R’f是1～8个碳原子的全氟烷基。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/009114 | 2004-12-10 | ||
| US11/009,114 US20060127619A1 (en) | 2004-12-10 | 2004-12-10 | Hose construction containing NBR elastomer composition and fluoroplastic barrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1800251A CN1800251A (zh) | 2006-07-12 |
| CN100460458C true CN100460458C (zh) | 2009-02-11 |
Family
ID=35948492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101298004A Expired - Fee Related CN100460458C (zh) | 2004-12-10 | 2005-12-09 | 含有丙烯腈丁二烯橡胶弹性体组合物和氟塑料阻透层的软管构造 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20060127619A1 (zh) |
| EP (1) | EP1669188B1 (zh) |
| CN (1) | CN100460458C (zh) |
| CA (1) | CA2519541C (zh) |
| DE (1) | DE602005005270T2 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107405886A (zh) * | 2014-12-19 | 2017-11-28 | 威扬斯技术公司 | 低可提取软管 |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8092880B2 (en) * | 2006-03-28 | 2012-01-10 | Tokai Rubber Industries, Ltd. | Fuel hose |
| EP2292687B1 (en) * | 2009-09-03 | 2012-07-25 | Rhein Chemie Rheinau GmbH | Improved vulcanisable guanidine-free mixtures containing ethylene acrylate (AEM), polyacrylate (ACM) and/or hydrogenated acrylnitrile (HNBR)-based rubbers compounds, vulcanisates, prepared by cross-linking this vulcanisable mixtures and their use |
| EP2894380B1 (en) * | 2014-01-10 | 2017-11-22 | ContiTech USA, Inc. | Low permeation curb pump hose |
| DE102016223621A1 (de) | 2016-11-29 | 2018-05-30 | Contitech Schlauch Gmbh | Kautschukmischung, insbesondere für einen Schlauch |
| DE102016223618A1 (de) | 2016-11-29 | 2018-05-30 | Contitech Schlauch Gmbh | Mehrschichtiger flexibler Schlauch |
| KR102422863B1 (ko) * | 2018-03-16 | 2022-07-19 | 미쓰이 가가쿠 가부시키가이샤 | 아크릴로나이트릴·뷰타다이엔 고무 조성물 및 당해 조성물층을 포함하는 적층체 |
| JP2023502379A (ja) * | 2019-11-15 | 2023-01-24 | サン－ゴバン パフォーマンス プラスティックス コーポレイション | 多層管およびその製造方法 |
| JP7364827B1 (ja) | 2023-03-10 | 2023-10-18 | 住友理工株式会社 | 燃料用ホース |
| JP7355966B1 (ja) | 2023-03-10 | 2023-10-03 | 住友理工株式会社 | 燃料用ホース |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066661A (zh) * | 1991-05-15 | 1992-12-02 | 奥西蒙特公司 | 显示优异耐有机碱性能、基于偏二氟乙烯的氟弹性体 |
| CN1136993A (zh) * | 1995-04-24 | 1996-12-04 | 固特异轮胎和橡胶公司 | 含有氟塑料三元共聚物的软管构造 |
| US20030026995A1 (en) * | 2000-06-27 | 2003-02-06 | Dyneon Llc | Novel fluoropolymers with improved characteristics |
| US20040076783A1 (en) * | 2002-10-22 | 2004-04-22 | Andrew Norman | Corrugated liquid and vapor carrying fuel tubes and method |
| EP1484172A1 (en) * | 2003-06-04 | 2004-12-08 | The Goodyear Tire & Rubber Company | Hose construction containing fluoroelastomer composition and fluoroplastic barrier |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482522B1 (en) * | 1997-12-19 | 2002-11-19 | Dyneon Llc | Elastomer compositions for bonding to fluoropolymers |
| US6270901B1 (en) * | 1997-12-19 | 2001-08-07 | Dyneon Llc | Compositions for bonding fluoroplastics |
| US6300446B1 (en) * | 1998-03-31 | 2001-10-09 | Asahi Glass Company, Limited | Fluorine-containing copolymer and composition thereof |
| WO2000052084A1 (en) * | 1999-03-02 | 2000-09-08 | 3M Innovative Properties Company | Compositions for fluoropolymer bonding to non-fluorinated polymers |
| US6261657B1 (en) * | 1999-04-26 | 2001-07-17 | The Goodyear Tire & Rubber Company | Hose construction containing fluoroplastic terpolymers |
| US6682796B2 (en) * | 2000-05-31 | 2004-01-27 | Tokai Rubber Industries, Ltd. | Fuel hose |
| US6686012B1 (en) * | 2000-08-23 | 2004-02-03 | 3M Innovative Properties Company | Multi-layer articles including a fluoroplastic layer |
| DE10320224A1 (de) * | 2003-05-05 | 2004-12-23 | Veritas Ag | Leitung, insbesondere für Tankeinfüllsysteme |
| US20050170117A1 (en) * | 2004-01-31 | 2005-08-04 | Cleveland Rafael L. | Multi-layered hose |
-
2004
- 2004-12-10 US US11/009,114 patent/US20060127619A1/en not_active Abandoned
-
2005
- 2005-09-14 CA CA2519541A patent/CA2519541C/en not_active Expired - Fee Related
- 2005-12-05 DE DE602005005270T patent/DE602005005270T2/de active Active
- 2005-12-05 EP EP05111697A patent/EP1669188B1/en not_active Expired - Fee Related
- 2005-12-09 CN CNB2005101298004A patent/CN100460458C/zh not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066661A (zh) * | 1991-05-15 | 1992-12-02 | 奥西蒙特公司 | 显示优异耐有机碱性能、基于偏二氟乙烯的氟弹性体 |
| CN1136993A (zh) * | 1995-04-24 | 1996-12-04 | 固特异轮胎和橡胶公司 | 含有氟塑料三元共聚物的软管构造 |
| US20030026995A1 (en) * | 2000-06-27 | 2003-02-06 | Dyneon Llc | Novel fluoropolymers with improved characteristics |
| CN1454222A (zh) * | 2000-06-27 | 2003-11-05 | 德弘公司 | 具有改良特性的新型含氟聚合物 |
| US20040076783A1 (en) * | 2002-10-22 | 2004-04-22 | Andrew Norman | Corrugated liquid and vapor carrying fuel tubes and method |
| EP1484172A1 (en) * | 2003-06-04 | 2004-12-08 | The Goodyear Tire & Rubber Company | Hose construction containing fluoroelastomer composition and fluoroplastic barrier |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107405886A (zh) * | 2014-12-19 | 2017-11-28 | 威扬斯技术公司 | 低可提取软管 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1669188B1 (en) | 2008-03-12 |
| DE602005005270D1 (de) | 2008-04-24 |
| CA2519541C (en) | 2013-04-30 |
| CN1800251A (zh) | 2006-07-12 |
| EP1669188A1 (en) | 2006-06-14 |
| US20060127619A1 (en) | 2006-06-15 |
| DE602005005270T2 (de) | 2009-03-12 |
| CA2519541A1 (en) | 2006-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100460458C (zh) | 含有丙烯腈丁二烯橡胶弹性体组合物和氟塑料阻透层的软管构造 | |
| US10641418B2 (en) | Chemical and gas-resistant, high-pressure, large-bore bonded flexible rubber pipe and method for producing the same | |
| US6166143A (en) | Thermoplastic elastomer composition, hose comprising thermoplastic elastomer composition and process of production thereof | |
| KR101059714B1 (ko) | 냉매 수송용 호스 | |
| US6261657B1 (en) | Hose construction containing fluoroplastic terpolymers | |
| JP2011179003A (ja) | ハイドロタルサイト化合物を有するフルオロエラストマー層を含む燃料管理システム | |
| EP2578391B1 (en) | Refrigerant-transporting hose | |
| US8642149B2 (en) | Hose for transporting refrigerant | |
| US10221306B2 (en) | Rubber composition for hose, and hose | |
| US7029736B2 (en) | Hose construction containing thermoplastic fluoropolymer | |
| JP2008195040A (ja) | 燃料系ゴムホース | |
| US7192646B2 (en) | Hose construction containing fluoroelastomer composition and fluoroplastic barrier | |
| JP2004150457A (ja) | 燃料用ホース | |
| CA2316127C (en) | Hose construction having inner core of hydrogenated nbr | |
| JP4182670B2 (ja) | 加硫接着向上剤、それを用いたエラストマー組成物及び積層体 | |
| TWI756390B (zh) | 積層體及其製造方法 | |
| JP2003278957A (ja) | ホース構造体およびその製法 | |
| US20210130596A1 (en) | High abrasion resistance hose cover | |
| US20220268377A1 (en) | Sustainable industrial hose | |
| JP2004262997A (ja) | 燃料ホース用ゴム組成物およびそれを用いてなる燃料ホース | |
| MXPA00012289A (es) | Construccion de manguera, que tiene nucleo interior de nbr hidrogenado |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: VIYANS TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: GOODYEAR TIRE + RUBBER CO. Effective date: 20090710 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20090710 Address after: ohio Patentee after: Veyance Technologies Inc. Address before: ohio Patentee before: Goodyear Tire & Rubber Co. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090211 Termination date: 20161209 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |