CN1243762C - 橡胶粘合促进剂 - Google Patents
橡胶粘合促进剂 Download PDFInfo
- Publication number
- CN1243762C CN1243762C CNB988120070A CN98812007A CN1243762C CN 1243762 C CN1243762 C CN 1243762C CN B988120070 A CNB988120070 A CN B988120070A CN 98812007 A CN98812007 A CN 98812007A CN 1243762 C CN1243762 C CN 1243762C
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- Prior art keywords
- acid
- organometallics
- rubber
- residue
- metal
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 22
- 239000002318 adhesion promoter Substances 0.000 title abstract 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910001369 Brass Inorganic materials 0.000 claims abstract description 6
- 239000010951 brass Substances 0.000 claims abstract description 6
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 5
- 239000010959 steel Substances 0.000 claims abstract description 5
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- 229910052719 titanium Inorganic materials 0.000 claims abstract 2
- 125000002524 organometallic group Chemical group 0.000 claims description 20
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- -1 aryloxy carboxylic acid Chemical class 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000004513 sizing Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 2
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 claims description 2
- SXERGJJQSKIUIC-UHFFFAOYSA-N 2-Phenoxypropionic acid Chemical compound OC(=O)C(C)OC1=CC=CC=C1 SXERGJJQSKIUIC-UHFFFAOYSA-N 0.000 claims description 2
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 2
- UEDBHEFYEKZZBA-UHFFFAOYSA-N ac1np5zy Chemical compound C1=CC=[C+]=C[CH]1 UEDBHEFYEKZZBA-UHFFFAOYSA-N 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- NQBWNECTZUOWID-QSYVVUFSSA-N cinnamyl cinnamate Chemical compound C=1C=CC=CC=1\C=C/C(=O)OC\C=C\C1=CC=CC=C1 NQBWNECTZUOWID-QSYVVUFSSA-N 0.000 claims description 2
- 229920006270 hydrocarbon resin Polymers 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 2
- 239000004200 microcrystalline wax Substances 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 239000010734 process oil Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 claims 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims 1
- 229960004889 salicylic acid Drugs 0.000 claims 1
- 239000004636 vulcanized rubber Substances 0.000 claims 1
- 239000010941 cobalt Substances 0.000 abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010703 silicon Substances 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 abstract 1
- 150000002902 organometallic compounds Chemical class 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 5
- 235000019260 propionic acid Nutrition 0.000 description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-M benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-M 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- TZWGXFOSKIHUPW-UHFFFAOYSA-L cobalt(2+);propanoate Chemical compound [Co+2].CCC([O-])=O.CCC([O-])=O TZWGXFOSKIHUPW-UHFFFAOYSA-L 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- COKKIDKKSICZHR-UHFFFAOYSA-N 1,1'-biphenyl;silicon Chemical compound [Si].C1=CC=CC=C1C1=CC=CC=C1 COKKIDKKSICZHR-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- QRMMMWOSHHVOCJ-UHFFFAOYSA-N 2,2-dimethylheptanoic acid Chemical compound CCCCCC(C)(C)C(O)=O QRMMMWOSHHVOCJ-UHFFFAOYSA-N 0.000 description 1
- LLMLGZUZTFMXSA-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobenzenethiol Chemical compound SC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl LLMLGZUZTFMXSA-UHFFFAOYSA-N 0.000 description 1
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 1
- ZWQBZEFLFSFEOS-UHFFFAOYSA-N 3,5-ditert-butyl-2-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=C(O)C(C(C)(C)C)=C1 ZWQBZEFLFSFEOS-UHFFFAOYSA-N 0.000 description 1
- HMMSZUQCCUWXRA-UHFFFAOYSA-N 4,4-dimethyl valeric acid Chemical compound CC(C)(C)CCC(O)=O HMMSZUQCCUWXRA-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- AAOISIQFPPAFQO-UHFFFAOYSA-N 7:0(6Me,6Me) Chemical compound CC(C)(C)CCCCC(O)=O AAOISIQFPPAFQO-UHFFFAOYSA-N 0.000 description 1
- 101100149706 Arabidopsis thaliana SMR10 gene Proteins 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- BAZMYXGARXYAEQ-UHFFFAOYSA-N alpha-ethyl valeric acid Chemical compound CCCC(CC)C(O)=O BAZMYXGARXYAEQ-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- YCIVSJFIXXVSRH-UHFFFAOYSA-N amino-methyl-phenylsilicon Chemical compound C[Si](N)C1=CC=CC=C1 YCIVSJFIXXVSRH-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HZEIHKAVLOJHDG-UHFFFAOYSA-N boranylidynecobalt Chemical compound [Co]#B HZEIHKAVLOJHDG-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008380 degradant Substances 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- ASTNLROMDNGJLS-UHFFFAOYSA-N hot-7 Chemical compound CCCSC1=CC(OC)=C(CCNO)C=C1OC ASTNLROMDNGJLS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- RHHHGLCTQKINES-UHFFFAOYSA-M sodium;5-amino-2-methoxy-4-sulfobenzenesulfonate Chemical compound [Na+].COC1=CC(S(O)(=O)=O)=C(N)C=C1S([O-])(=O)=O RHHHGLCTQKINES-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical compound N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
包含3个或4个钴或镍原子以及脂族和芳族羧酸残基的金属有机化合物可用作粘合促进剂,每个钴或镍原子都通过氧原子与铝、硅或钛原子相连,促进镀有黄铜膜的钢与硫化橡胶的粘合。
Description
本发明涉及金属有机化合物、含有它们的组合物及其用途。
包含3个,每个都通过氧原子与硼或磷原子相连的二价金属(例如钴),还包含与金属键合的脂肪族单羧酸残基的化合物是已知的。这样的已知化合物已经被用作橡胶贴胶胶料的添加剂以改善橡胶与金属的粘合。
以易于使用的形式,特别是它们本身不粘或不稠的形式提供它们。
本发明提供新的化合物,这些化合物不仅具有上述已知化合物的优点,而且与已知的含钴化合物相比,还改善了橡胶与镀有黄铜膜的钢帘线之间的粘合力,在蒸汽和盐老化的条件下也能保持这种粘合力。
根据本发明,提供了用于促进橡胶与金属之间粘合的下列平均化学式的金属有机化合物:
X(OMA’p)m(OMB’q)n
其中:
M是Co或Ni,优选为Co(II);
A’是含有7-15个碳原子的脂族羧酸残基(通式R1COO);
B’是含有7-15个碳原子的芳族羧酸残基(通式RCOO)或含有8-15个碳原子的芳氧基取代的脂族或芳族羧酸;
p和q独立地为0.5-1.5,优选为1.0;
m+n=x,其中x是X的化合价,m/n典型地为0.67-9.0,优选为1.5-4.0;
典型地,n为0.2-(x-1),优选为0.5-3,特别优选为0.5-1.4。
当X为烷基和/或芳基取代的硅时,烷基优选为含有1-4个碳原子的烷基,特别为甲基,而芳基优选为苯基。典型的例子包括甲基硅、二甲基硅、二苯基硅和甲基苯基硅。
脂族羧酸(A’H)优选为单羧酸,例如正庚酸、2,2-二甲基戊酸、2-乙基戊酸、4,4-二甲基戊酸、正辛酸、2,2-二甲基己酸、2-乙基己酸、4,4-二甲基己酸、2,4,4-三甲基戊酸、正壬酸、2,2-二甲基庚酸、6,6-二甲基庚酸、3,5,5-三甲基己酸、正癸酸、2,2-二甲基辛酸、7,7-二甲基辛酸、正十一碳烷酸、异十一碳烷酸、C0-3烷基取代的正庚酸(cekanoic)或者已知作为新癸酸的2,2,2-三烷基乙酸的混合物。
芳族羧酸(B’-H)例如可以为苯甲酸、烷基,烷氧基,氨基,卤素,硫代或羟基取代的苯甲酸例如2-、3-或4-甲基苯甲酸、水杨酸、3,5-二异丙基水杨酸、3,5-二叔丁基水杨酸、邻氨基苯甲酸或4-氯苯甲酸、邻苯二甲酸、对苯二甲酸、肉桂酸或含有共轭环体系的更复杂的芳香酸。当B’-H是芳氧基取代的酸时,优选为苯氧基取代的脂族酸或芳香酸,特别为苯氧基乙酸和苯氧基丙酸。
金属有机化合物可以与周期表的第IA或IIA族元素(即碱金属或碱土金属)的硼酸盐缔合。所说的硼酸盐的浓度最高可以达到金属有机化合物的20%重量。合适的硼酸盐包括硼酸钠、硼酸钾、硼酸钙和硼酸镁。
金属有机化合物还可以与微晶石蜡和/或操作油、和/或烃树脂、和/或间苯二酚/甲醛树脂缔合。
新的金属有机化合物可以作为粘合促进剂掺入含有橡胶和常用的橡胶配混成分的橡胶贴胶胶料中。所述橡胶可以用镀有黄铜膜的钢来强化然后硫化。金属有机化合物典型地占橡胶重量的0.2-2%重量,典型地,金属有机化合物提供大约占橡胶重量0.224%重量的钴金属。
本发明的金属有机化合物可以这样制备:按照要求的比例一起加热(1)产生上述A’和B’残基的酸A’H和B’H、(2)钴或镍源如它们的氧化物、氢氧化物或碳酸盐、(3)低级醇例如正丁醇的铝酸酯、硅酸酯或钛酸酯、和(4)能与所说的酯中存在的低级醇残基形成挥发性酯的酸(例如乙酸或丙酸)的混合物,蒸去所说的挥发性酯,优选在减压下蒸去所说的挥发性酯。在加入酯(3)之前必须预先使所有的酸(1)和(4)与金属源(2)反应。反应温度典型地在50-250℃的范围。
通过下列实施例来说明本发明。实施例1-4描述新的金属有机化合物的制备。
实施例1
在机械搅拌下,把新癸酸丙酸钴(891g)的溶剂油溶液加热到50℃,加入丙酸(44g)和苯甲酸(72.5g)。搅拌反应物质10分钟,加入氢氧化钴(57g)。把反应混合物缓慢加热到195℃,通过真空蒸馏蒸去水(24g)和溶剂油(446g)。在170℃下向反应混合物中加入甲基三乙氧基硅烷(126.1g),反应在回流下进行4小时,然后当反应温度升高到220℃时,通过真空蒸馏蒸去丙酸乙酯。
产物(540g)为硬而脆的蓝色固体,其平均化学式为:
MeSi[OCo(新癸酸根)1.0]2.16[OCo(苯甲酸根)1.0]0.84,含有22.9%(w/w)的钴。
实施例2
在搅拌下,把9.8%新癸酸丙酸钴(817g)溶液,钴在溶剂油中计,加热到40℃,加入丙酸(44g)和苯甲酸(71.8g)。向反应物中加入氢氧化钴(55.4g)。把反应混合物加热到190℃,通过真空蒸馏蒸去水和溶剂油(总重量415g)。
缓慢加入加入三异丙醇铝(132g),把反应物加热到190℃,蒸去形成的丙酸异丙酯。
把反应温度缓慢升高到240℃,通过真空蒸馏蒸去剩余的酯,总共收集到159g丙酸异丙酯。
产物(533g)为硬而脆的蓝色固体,其平均化学式为:
Al[OCo(新癸酸根)1.0]2.1[OCo(苯甲酸根)1.0]0.9,含有20.8%(w/w)的钴。
实施例3
在机械搅拌下,把新癸酸(294g)、丙酸(188g)、苯甲酸(88g)和甲苯(200g)加入反应瓶中,加热到50℃。加入氢氧化钴(233g),把温度升高到90℃,得到一种流动的蓝色液体。进一步通过迪安-斯脱克水分测定仪(Dean-Stark装置)加热除去反应中的水,把反应温度升高到190℃,在真空下除去最后的痕量溶剂,得到91g水和206g甲苯。向160℃的反应物中缓慢加入钛酸四丁基酯(205g),在160℃的回流温度下维持反应3小时。通过加热到230℃真空蒸馏除去丙酸丁酯(240g)。
产物(624g)为硬而脆的蓝色固体,其平均化学式为:
Ti[OCo(新癸酸根)1.0]2.8[OCo(苯甲酸根)1.0]1.2,含有22.5%(w/w)的钴。
实施例4
把新癸酸(193g)、苯甲酸(62g)和甲苯(420g)加入带有机械搅拌的反应瓶中,加入氢氧化钴(156g)和丙酸(130g)。
把温度缓慢升高到120℃,得到一种粘稠的的蓝色液体。通过迪安-斯脱克水分测定仪除去反应中的水,进一步在180℃和真空下通过加热蒸馏除去剩余的甲苯。向反应物中缓慢加入原硅酸四乙基酯(85g),在145℃的回流温度下维持反应2小时,然后通过真空蒸馏达到最终反应温度230℃而除去丙酸乙酯(136g)。
产物(416g)为硬而脆的蓝色固体,其平均化学式为:
Si[OCo(新癸酸根)1.0]2.75[OCo(苯甲酸根)1.0]1.25,含有22.8%(w/w)的钴。
本发明的橡胶贴胶胶料含有橡胶和一种或多种常用的橡胶配混成分例如色料、填料、增量剂、促进剂、抗氧化剂、硫化剂等以及作为粘合促进剂的本发明的金属有机化合物。橡胶贴胶胶料按照下列配方配制:
重量份
天然橡胶SMR10 100
胶溶剂(硫代苯酚12)a) 0.05
MAF碳黑N-326 57
氧化锌 8
抗降解剂(6PPD)b) 2.0
促进剂DCBSc) 0.7
不溶性硫 4.0
a)五氯硫代苯酚的锌盐
b)N-(1,3-二甲基丁基)-N’-苯基-对苯二胺
c)N,N-二环己基-2-苯并噻唑基亚磺酰胺。
使用上述的橡胶贴胶胶料和下述的粘合促进剂制备可硫化的组合物。在一个15升的实验室用密闭式混合器中,边搅拌边把粘合促进剂加入贴胶胶料中,在实验室用Z-型辊炼机压片。把所有的组合物硫化到T90,然后在153℃硫化8分钟。
使用基于ASTM D2229(埋置长度为10mm)的改良的静态拉板试验进行粘合力试验。使用从Bekaert得到的结构为2+2=X 0.25的典型的镀有黄铜膜的钢制轮胎帘线,每根线的黄铜膜中铜的平均含量为63.5%。粘合力值用牛顿/10mm表示,结果列于表1中。
老化条件
蒸汽 16小时 @ 121℃
湿度 7天 @ 70℃ 95%RH
热 7天 @ 85℃
盐 7天 @ R.T., 3.6%w/w氯化钠的水溶液
上表中的结果表明,含有本发明的金属有机化合物的橡胶贴胶胶料实质上具有比已知的新癸酸硼化合物更好的橡胶-金属粘合力。这种改善在蒸汽老化的条件下特别显著。另外,新的金属有机化合物在低于相应的新癸酸硼的用量的情况下具有等同的效能。
在一种实施方式中,把金属化合物沉积到载体上,例如从化合物的油溶液中沉积到载体上。载体典型地为硅石或第IA或IIA族金属的硅酸盐,例如硅酸钠、硅酸钾、硅酸镁或硅酸钙。
表1.粘合力试验结果
化合物 | 每100份橡胶贴胶胶料中Co的添加量 | 粘合力试验条件 | ||||
未老化的 | 热老化的 | 湿度老化的 | 蒸汽老化的 | 盐老化的 | ||
对照 | 0.000 | 19.8 | 21.8 | 22.2 | 28.8 | 20.6 |
新癸酸硼钴(ManobondC22.5) | 0.2240.1500.100 | 37.240.239.1 | 35.733.037.4 | 33.839.336.4 | 15.427.237.2 | 33.233.025.1 |
实施例1 | 0.2240.1500.100 | 38.244.437.4 | 38.337.438.6 | 39.237.832.1 | 31.438.939.7 | 36.142.133.9 |
实施例2 | 0.2240.1500.100 | 42.440.943.9 | 40.738.536.8 | 37.936.237.3 | 32.736.840.5 | 40.037.433.8 |
实施例3 | 0.2240.1500.100 | 44.244.039.3 | 42.439.540.7 | 44.539.437.6 | 36.538.637.6 | 34.737.433.7 |
实施例4 | 0.2240.1500.100 | 40.738.043.7 | 37.537.435.8 | 39.231.037.7 | 25.136.242.5 | 37.730.934.6 |
Claims (11)
1.下列平均化学式的金属有机化合物:
X(OMA’p)m(OMB’q)n
其中:
X是Al、Ti、Zr或Si、烷基-或芳基-Si或者二烷基-、二芳基-或烷芳基-Si;
M是Co或Ni;
A’是含有7-15个碳原子的脂族羧酸的残基;
B’是含有7-15个碳原子的芳族羧酸的残基或含有8-15个碳原子的脂族或芳族芳氧基羧酸;
p和q独立地为0.5-1.5;
m+n=x,其中x是X的化合价,m/n为0.67至9.0且n为0.2至(x-1)。
2.权利要求1的金属有机化合物,其中M是Co(II)。
3.权利要求1或2的金属有机化合物,其中B’是苯甲酸、2-、3-或4-甲基苯甲酸、水杨酸、3,5-二异丙基水杨酸、3,5-二叔丁基水杨酸、邻氨基苯甲酸、肉桂酸、苯氧基乙酸或苯氧基丙酸的残基。
4.权利要求1-3的任何一个的金属有机化合物,其中A’是新癸酸、异十一烷酸、C0-3烷基取代的正庚酸或2-乙基己酸的残基。
5.权利要求1的金属有机化合物,其中m/n为1.5-4.0。
6.与周期表的第IA或IIA族金属的硼酸盐缔合的权利要求1-5的任何一个的金属有机化合物,所述硼酸盐的最高浓度为所述金属有机化合物的20%重量。
7.与微晶石蜡、操作油或烃树脂或间苯二酸/甲醛树脂缔合的权利要求1-5的任何一个的金属有机化合物。
8.负载在硅石或第IA或IIA族金属的硅酸盐上的权利要求1-5的任何一个的金属有机化合物。
9.包含橡胶和作为粘合促进剂的至少一种权利要求1-5的任何一个的金属有机化合物的橡胶贴胶胶料。
10.权利要求9的橡胶贴胶胶料,含有占橡胶重量0.2-2.0%重量的所述金属有机化合物。
11.用镀有黄铜膜的钢强化的硫化橡胶,包含至少一种权利要求1-5的任何一个的金属有机化合物作为粘合促进剂。
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1998
- 1998-10-09 RU RU2000111471/04A patent/RU2218344C2/ru not_active IP Right Cessation
- 1998-10-09 ID IDW20000658A patent/ID24179A/id unknown
- 1998-10-09 WO PCT/GB1998/003069 patent/WO1999019336A1/en active IP Right Grant
- 1998-10-09 AT AT98946623T patent/ATE248847T1/de not_active IP Right Cessation
- 1998-10-09 EP EP98946623A patent/EP1023303B1/en not_active Expired - Lifetime
- 1998-10-09 CA CA002305626A patent/CA2305626C/en not_active Expired - Fee Related
- 1998-10-09 BR BR9812758-6A patent/BR9812758A/pt not_active Application Discontinuation
- 1998-10-09 CN CNB988120070A patent/CN1243762C/zh not_active Expired - Fee Related
- 1998-10-09 JP JP2000515907A patent/JP4287590B2/ja not_active Expired - Fee Related
- 1998-10-09 KR KR1020007003661A patent/KR100572688B1/ko not_active IP Right Cessation
- 1998-10-09 AU AU93618/98A patent/AU746070B2/en not_active Ceased
- 1998-10-09 DE DE69817849T patent/DE69817849T2/de not_active Expired - Fee Related
- 1998-10-09 PT PT98946623T patent/PT1023303E/pt unknown
- 1998-10-09 ES ES98946623T patent/ES2205549T3/es not_active Expired - Lifetime
- 1998-10-09 US US09/529,129 patent/US6353047B1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
RU2218344C2 (ru) | 2003-12-10 |
DE69817849D1 (de) | 2003-10-09 |
EP1023303B1 (en) | 2003-09-03 |
JP4287590B2 (ja) | 2009-07-01 |
DE69817849T2 (de) | 2004-08-19 |
EP1023303A1 (en) | 2000-08-02 |
AU746070B2 (en) | 2002-04-11 |
JP2001519435A (ja) | 2001-10-23 |
WO1999019336A1 (en) | 1999-04-22 |
CN1281461A (zh) | 2001-01-24 |
ES2205549T3 (es) | 2004-05-01 |
ID24179A (id) | 2000-07-13 |
US6353047B1 (en) | 2002-03-05 |
AU9361898A (en) | 1999-05-03 |
KR100572688B1 (ko) | 2006-04-24 |
CA2305626C (en) | 2008-02-19 |
KR20010030938A (ko) | 2001-04-16 |
BR9812758A (pt) | 2000-08-29 |
CA2305626A1 (en) | 1999-04-22 |
PT1023303E (pt) | 2003-12-31 |
ATE248847T1 (de) | 2003-09-15 |
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