CN1135221C - 壬基化二苯胺 - Google Patents
壬基化二苯胺 Download PDFInfo
- Publication number
- CN1135221C CN1135221C CNB981096557A CN98109655A CN1135221C CN 1135221 C CN1135221 C CN 1135221C CN B981096557 A CNB981096557 A CN B981096557A CN 98109655 A CN98109655 A CN 98109655A CN 1135221 C CN1135221 C CN 1135221C
- Authority
- CN
- China
- Prior art keywords
- area
- mixture
- pentanoic
- acid
- diphenylamine
- 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
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- -1 diphenylamine compound Chemical class 0.000 claims description 63
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 46
- LVZUNTGFCXNQAF-UHFFFAOYSA-N n-nonyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCC)C1=CC=CC=C1 LVZUNTGFCXNQAF-UHFFFAOYSA-N 0.000 claims description 42
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 27
- QVXGKJYMVLJYCL-UHFFFAOYSA-N 2,3-di(nonyl)-N-phenylaniline Chemical compound C(CCCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCCC QVXGKJYMVLJYCL-UHFFFAOYSA-N 0.000 claims description 24
- 239000004927 clay Substances 0.000 claims description 9
- 230000029936 alkylation Effects 0.000 claims description 8
- 238000005804 alkylation reaction Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 11
- 230000000996 additive effect Effects 0.000 abstract description 11
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000000047 product Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 150000002148 esters Chemical class 0.000 description 25
- 239000011541 reaction mixture Substances 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 14
- 230000001939 inductive effect Effects 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229960003742 phenol Drugs 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- 150000003863 ammonium salts Chemical class 0.000 description 7
- 239000012964 benzotriazole Substances 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- 230000002152 alkylating effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 238000001994 activation Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- 229940059574 pentaerithrityl Drugs 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 4
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ICHKVCYUNCKCGL-UHFFFAOYSA-N CN(C)C.OCCCCCCO Chemical compound CN(C)C.OCCCCCCO ICHKVCYUNCKCGL-UHFFFAOYSA-N 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- COVMBDWAODLWIB-UHFFFAOYSA-N n'-(2-hydroxyethyl)oxamide Chemical compound NC(=O)C(=O)NCCO COVMBDWAODLWIB-UHFFFAOYSA-N 0.000 description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 4
- 229950006389 thiodiglycol Drugs 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003822 preparative gas chromatography Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 3
- ZEBMSMUPGIOANU-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methylphosphonic acid Chemical class CC(C)(C)C1=CC(CP(O)(O)=O)=CC(C(C)(C)C)=C1O ZEBMSMUPGIOANU-UHFFFAOYSA-N 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 2
- BVALZCVRLDMXOQ-UHFFFAOYSA-N 1-nitropentane Chemical compound CCCCC[N+]([O-])=O BVALZCVRLDMXOQ-UHFFFAOYSA-N 0.000 description 2
- SLUKQUGVTITNSY-UHFFFAOYSA-N 2,6-di-tert-butyl-4-methoxyphenol Chemical compound COC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SLUKQUGVTITNSY-UHFFFAOYSA-N 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MSGFMKMFGGXSTO-UHFFFAOYSA-N C(C)(C)(C)C=1C=C(C(=CC1O)CN)CCCC Chemical compound C(C)(C)(C)C=1C=C(C(=CC1O)CN)CCCC MSGFMKMFGGXSTO-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 241000534944 Thia Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229940120693 copper naphthenate Drugs 0.000 description 2
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005555 metalworking Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RJDVGKCBHFINOK-UHFFFAOYSA-N tris(2-methylphenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound CC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C RJDVGKCBHFINOK-UHFFFAOYSA-N 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 description 2
- ZIJHTQPOUJBOHK-UHFFFAOYSA-N (3-tert-butyl-4-hydroxy-5-methylphenyl)methylphosphonic acid Chemical class CC1=CC(CP(O)(O)=O)=CC(C(C)(C)C)=C1O ZIJHTQPOUJBOHK-UHFFFAOYSA-N 0.000 description 1
- GCWAFWMUTOXMIT-HWKANZROSA-N (e)-heptadec-2-ene Chemical compound CCCCCCCCCCCCCC\C=C\C GCWAFWMUTOXMIT-HWKANZROSA-N 0.000 description 1
- RAADJDWNEAXLBL-UHFFFAOYSA-N 1,2-di(nonyl)naphthalene Chemical compound C1=CC=CC2=C(CCCCCCCCC)C(CCCCCCCCC)=CC=C21 RAADJDWNEAXLBL-UHFFFAOYSA-N 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical class S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- 150000000182 1,3,5-triazines Chemical class 0.000 description 1
- VDSPRJACLFTGHK-UHFFFAOYSA-N 1-(1-cyclohexyloxybutyl)-4-methylbenzotriazole Chemical compound C1(CCCCC1)OC(CCC)N1N=NC2=C1C=CC=C2C VDSPRJACLFTGHK-UHFFFAOYSA-N 0.000 description 1
- UDAKRDQBQXLJHF-UHFFFAOYSA-N 1-(3-amino-4-hydroxyphenyl)nonan-1-one Chemical compound CCCCCCCCC(=O)C1=CC=C(O)C(N)=C1 UDAKRDQBQXLJHF-UHFFFAOYSA-N 0.000 description 1
- LNZBQIBHNKDRIL-UHFFFAOYSA-N 1-(3-amino-4-hydroxyphenyl)octadecan-1-one Chemical compound CCCCCCCCCCCCCCCCCC(=O)C1=CC=C(O)C(N)=C1 LNZBQIBHNKDRIL-UHFFFAOYSA-N 0.000 description 1
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 1
- DVQDEYTXFHYBNP-UHFFFAOYSA-N 2,5-di(pentan-2-yl)phenol Chemical compound CCCC(C)C1=CC=C(C(C)CCC)C(O)=C1 DVQDEYTXFHYBNP-UHFFFAOYSA-N 0.000 description 1
- FLLRQABPKFCXSO-UHFFFAOYSA-N 2,5-ditert-butyl-4-methoxyphenol Chemical compound COC1=CC(C(C)(C)C)=C(O)C=C1C(C)(C)C FLLRQABPKFCXSO-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- JBYWTKPHBLYYFJ-UHFFFAOYSA-N 2,6-ditert-butyl-4-(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 JBYWTKPHBLYYFJ-UHFFFAOYSA-N 0.000 description 1
- SCXYLTWTWUGEAA-UHFFFAOYSA-N 2,6-ditert-butyl-4-(methoxymethyl)phenol Chemical compound COCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SCXYLTWTWUGEAA-UHFFFAOYSA-N 0.000 description 1
- VMZVBRIIHDRYGK-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VMZVBRIIHDRYGK-UHFFFAOYSA-N 0.000 description 1
- NISAHDHKGPWBEM-UHFFFAOYSA-N 2-(4-nonylphenoxy)acetic acid Chemical group CCCCCCCCCC1=CC=C(OCC(O)=O)C=C1 NISAHDHKGPWBEM-UHFFFAOYSA-N 0.000 description 1
- HOHDYZFUHAZLIT-UHFFFAOYSA-N 2-(aminomethyl)-n-ethylaniline Chemical compound CCNC1=CC=CC=C1CN HOHDYZFUHAZLIT-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UDBQRXOWKPLOHH-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-2-hydroxyphenyl)methyl]propanedioic acid Chemical compound CC(C)(C)C1=CC(CC(C(O)=O)C(O)=O)=C(O)C(C(C)(C)C)=C1 UDBQRXOWKPLOHH-UHFFFAOYSA-N 0.000 description 1
- AYHCRODGWSHDAZ-UHFFFAOYSA-N 2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)methyl]propanedioic acid Chemical compound CC1=CC(CC(C(O)=O)C(O)=O)=CC(C(C)(C)C)=C1O AYHCRODGWSHDAZ-UHFFFAOYSA-N 0.000 description 1
- UIXRDRQSWYSVNK-UHFFFAOYSA-N 2-butyl-4,6-dimethylphenol Chemical compound CCCCC1=CC(C)=CC(C)=C1O UIXRDRQSWYSVNK-UHFFFAOYSA-N 0.000 description 1
- GTLMTHAWEBRMGI-UHFFFAOYSA-N 2-cyclohexyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C2CCCCC2)=C1 GTLMTHAWEBRMGI-UHFFFAOYSA-N 0.000 description 1
- KDHONNUUDHJCID-UHFFFAOYSA-N 2-cyclopentyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C2CCCC2)=C1 KDHONNUUDHJCID-UHFFFAOYSA-N 0.000 description 1
- HLOIHWLCERSJNP-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol nonanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCCC(O)=O.CCCCCCCCC(O)=O.CCCCCCCCC(O)=O HLOIHWLCERSJNP-UHFFFAOYSA-N 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- DBHUTHZPCWZNRW-UHFFFAOYSA-N 3-(3,5-dicyclohexyl-4-hydroxyphenyl)propanoic acid Chemical compound OC=1C(C2CCCCC2)=CC(CCC(=O)O)=CC=1C1CCCCC1 DBHUTHZPCWZNRW-UHFFFAOYSA-N 0.000 description 1
- KMWIPXLIKIAZMT-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanehydrazide Chemical compound CC(C)(C)C1=CC(CCC(=O)NN)=CC(C(C)(C)C)=C1O KMWIPXLIKIAZMT-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 1
- CKRLKUOWTAEKKX-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2h-benzotriazole Chemical compound C1CCCC2=NNN=C21 CKRLKUOWTAEKKX-UHFFFAOYSA-N 0.000 description 1
- BPGUKNRILVZFIA-UHFFFAOYSA-N 4-(2h-benzotriazol-4-ylmethyl)-2h-benzotriazole Chemical compound C=1C=CC=2NN=NC=2C=1CC1=CC=CC2=C1N=NN2 BPGUKNRILVZFIA-UHFFFAOYSA-N 0.000 description 1
- BCZQMWDTKGBZFG-UHFFFAOYSA-N 4-[(4-hydroxy-2,6-dimethylphenyl)disulfanyl]-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1SSC1=C(C)C=C(O)C=C1C BCZQMWDTKGBZFG-UHFFFAOYSA-N 0.000 description 1
- WTWGHNZAQVTLSQ-UHFFFAOYSA-N 4-butyl-2,6-ditert-butylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WTWGHNZAQVTLSQ-UHFFFAOYSA-N 0.000 description 1
- UXMKUNDWNZNECH-UHFFFAOYSA-N 4-methyl-2,6-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC(C)=CC(CCCCCCCCC)=C1O UXMKUNDWNZNECH-UHFFFAOYSA-N 0.000 description 1
- FCQAFXHLHBGGSK-UHFFFAOYSA-N 4-nonyl-n-(4-nonylphenyl)aniline Chemical compound C1=CC(CCCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCCC)C=C1 FCQAFXHLHBGGSK-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical class CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- MYPXYQMABPTFFN-UHFFFAOYSA-N 4-phenoxybenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1OC1=CC=CC=C1 MYPXYQMABPTFFN-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- HQULYFAKUZDRPB-UHFFFAOYSA-N 6-bromo-2-[4-(trifluoromethoxy)phenoxy]-1,3-benzothiazole Chemical group BrC1=CC2=C(N=C(S2)OC2=CC=C(C=C2)OC(F)(F)F)C=C1 HQULYFAKUZDRPB-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- CPUMIQKFVWMTKY-UHFFFAOYSA-N C(C)(C)(C)C=1C(=CC(=C(C1)CCCCC)CN)O Chemical compound C(C)(C)(C)C=1C(=CC(=C(C1)CCCCC)CN)O CPUMIQKFVWMTKY-UHFFFAOYSA-N 0.000 description 1
- RTJUWEUCUSQYAV-UHFFFAOYSA-N C(C)(C)(C)C=1C=C(C=C(C1O)CN)CCC(=O)O Chemical compound C(C)(C)(C)C=1C=C(C=C(C1O)CN)CCC(=O)O RTJUWEUCUSQYAV-UHFFFAOYSA-N 0.000 description 1
- GFMYEVPBEJFZHH-UHFFFAOYSA-N CP(O)(O)O Chemical compound CP(O)(O)O GFMYEVPBEJFZHH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- GZIFEOYASATJEH-UHFFFAOYSA-N D-delta tocopherol Natural products OC1=CC(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000158728 Meliaceae Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical class C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- DRRMRHKHTQRWMB-UHFFFAOYSA-N [3-(2-ethylhexanoyloxy)-2,2-bis(2-ethylhexanoyloxymethyl)propyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC(COC(=O)C(CC)CCCC)(COC(=O)C(CC)CCCC)COC(=O)C(CC)CCCC DRRMRHKHTQRWMB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 229940087168 alpha tocopherol Drugs 0.000 description 1
- 239000010775 animal oil Substances 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
- 229920005601 base polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- SNCZNSNPXMPCGN-UHFFFAOYSA-N butanediamide Chemical compound NC(=O)CCC(N)=O SNCZNSNPXMPCGN-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 235000010389 delta-tocopherol Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- WIYAGHSNPUBKDT-UHFFFAOYSA-N dinonyl hexanedioate Chemical compound CCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCC WIYAGHSNPUBKDT-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
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- NTZXNTYGMRLTSA-UHFFFAOYSA-N dodecyl 2-hydroxyacetate Chemical compound CCCCCCCCCCCCOC(=O)CO NTZXNTYGMRLTSA-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical class CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 235000010382 gamma-tocopherol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical class CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 1
- VDTIMXCBOXBHER-UHFFFAOYSA-N hydroxy-bis(sulfanyl)-sulfanylidene-$l^{5}-phosphane Chemical compound OP(S)(S)=S VDTIMXCBOXBHER-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000013541 low molecular weight contaminant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GXFQBBOZTNQHMW-UHFFFAOYSA-N n'-(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound CC1(C)CC(NCCCCCCN)CC(C)(C)N1 GXFQBBOZTNQHMW-UHFFFAOYSA-N 0.000 description 1
- ZZAMUZWGTXZGKY-UHFFFAOYSA-N n-(6-aminohexyl)-3-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound CC(C)(C)C1=CC(CCC(=O)NCCCCCCN)=CC(C(C)(C)C)=C1O ZZAMUZWGTXZGKY-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- BYYFPVDBAHOLDX-UHFFFAOYSA-N n-dodecyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCCCCC)C1=CC=CC=C1 BYYFPVDBAHOLDX-UHFFFAOYSA-N 0.000 description 1
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 1
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 1
- CDZOGLJOFWFVOZ-UHFFFAOYSA-N n-propylaniline Chemical compound CCCNC1=CC=CC=C1 CDZOGLJOFWFVOZ-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 125000005474 octanoate group Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical class CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- IKXFIBBKEARMLL-UHFFFAOYSA-N triphenoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=S)OC1=CC=CC=C1 IKXFIBBKEARMLL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/55—Diphenylamines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明涉及壬基化二苯胺,特别是二壬基化二苯胺的混合物,以及一种工艺上有利的、通过使用少量的酸性催化剂制备该混合物的方法。该混合物用作稳定易受氧化、热和/或光诱导降解的有机制品的添加剂。
Description
本发明涉及一种壬基化二苯胺的混合物,这一混合物的制备方法,及其作为稳定易受氧化、热和/或光诱导降解的有机制品的添加剂的用途。
在广泛使用于工程的大量有机制品,如润滑剂、传压流体、金属加工液、燃料或聚合物中,为改善其性能要加入添加剂。尤其是需要能有效地抑制那些制品氧化、热和/或光诱导降解,并由此显著提高其使用寿命的添加剂。
美国专利说明书2943112公开了以大量酸性粘土作催化剂并在无机酸的存在下,通过二苯胺与链烯烃反应制备的烷基化二苯胺类抗氧剂。二苯胺与链烯烃如壬烯的烷基化反应形成单和二烷基化的二苯胺混合物。在该方法中,较大量的起始物料,通常有6~12%的二苯胺未反应,这降低了烷基化二苯胺的抗氧化效率,导致淤渣的沉淀,并使得产物具有不期望的毒性。作为将起始物料从产物中蒸馏分离的一种替换选择,建议与另外的链烯烃反应。
法国专利说明书1508785公开了在氯化铝型Friedel-Crafts催化剂的存在下,80%的二壬基二苯胺和15%的壬基二苯胺的混合物的制备,但该混合物仍含有2%的二苯胺(参见实施例2的内容)。该混合物的制备是有缺陷的,因为它被痕量的氯,金属化合物和不期望的副产物,例如N-烷基化的二苯胺和在2-和2′-位置上烷基化的二苯胺所污染,颜色发黑且非常粘。
欧洲专利申请387979公开了二苯胺与8倍过量的三聚丙烯的反应。该方法同样是有缺陷的,因为除大量过量的三聚丙烯外,它还要在大量酸活化的粘土存在下进行。
本发明的目的是制备壬基化二苯胺的混合物,该混合物除壬基二苯胺,例如4-单壬基二苯胺外,含有尽可能大量的二壬基二苯胺,特别是4,4′-二壬基二苯胺,以及尽可能少量的不期望的副产物,例如N-烷基化的二苯胺和在2-和2′-位置上烷基化的二苯胺。
该问题由一非独创的方法解决,该方法包括在基于二苯胺为2.0~25.0重量%的酸性土存在下,并且在无游离质子酸存在下,用过量的壬烯或壬烯异构体的混合物对二苯胺进行烷基化。
本发明涉及壬基化二苯胺的混合物,气相色谱图中该混合物各组份的含量为:a)面积至少为68.0%的二壬基二苯胺;b)面积为20.0~30.0%的壬基二苯胺;c)面积不大于3.5%的三壬基二苯胺;和d)面积不大于1.0%的二苯胺。
优选的混合物是其中在主要组份二壬基二苯胺和共同组份壬基二苯胺中的壬基分别位于二苯胺的4,4′-位和4-位。同样优选的混合物是其中壬基来自于二苯胺和三聚丙烯的反应。
在一优选的实施方案中,本发明涉及气相色谱图中各组份含量如下的混合物:a)面积为70.0~75.0%的二壬基二苯胺;b)面积为25.0~30.0%的壬基二苯胺;c)面积不大于3.5%的三壬基二苯胺;和d)面积不大于1.0%的二苯胺。
在一特别优选的实施方案中,本发明涉及气相色谱图中各组份含量如下的混合物:a)面积为70.0~75.0%的二壬基二苯胺;b)面积为25.0~28.0%的壬基二苯胺;c)面积不大于3.0%的三壬基二苯胺;和d)面积不大于0.8%的二苯胺。
所谓“面积至少为68.0%的二壬基二苯胺”是指优选面积为68.0~78.0%,特别是面积为70.0~75.0%的二壬基二苯胺。
在优选的实施方案中,所谓“面积不大于3.5%的三壬基二苯胺”是指面积为1.0~3.5%,优选面积为1.5~3.5%,同样优选面积为2.0~3.5%,特别是面积为2.5~3.5%的三壬基二苯胺。所谓“面积不大于3.0%的三壬基二苯胺”优选是指面积为1.0~3.0%,优选面积为1.5~3.0%,同样优选面积为2.0~3.0%,特别是面积为2.5~3.0%的三壬基二苯胺。
所谓“面积不大于1.0%的二苯胺”优选是指在气相色谱图中,面积为0.1~1.0%,特别是面积为0.3~0.8%的二苯胺,所谓“面积不大于0.8%的二苯胺”优选是指面积为0.3~0.8%,特别是面积为0.3~0.6%的二苯胺。
本发明还涉及本发明方法的产物,可通过在基于二苯胺为2.0~25.0重量%的酸性土存在下,并且在无质子酸存在下,用过量的壬烯或壬烯异构体的混合物对二苯胺进行烷基化而得到。
本发明还涉及独创方法的产物,40℃下其运动粘度为小于500mm2/秒。
进一步,本发明还涉及壬基化二苯胺混合物的制备方法,气相色谱图中该混合物各组份的含量为:a)面积至少为68.0%的二壬基二苯胺;b)面积为20.0~30.0%的壬基二苯胺;c)面积不大于3.5%的三壬基二苯胺;和d)面积不大于1.0%的二苯胺,该方法包括在基于二苯胺为2.0~25.0重量%的酸性土存在下,并且在无游离质子酸存在下,用过量的壬烯或壬烯异构体的混合物对二苯胺进行烷基化。
优选可获得的产物为在该方法中使用的酸性土为5.0~20.0重量%,特别是5.0~10.0重量%。
适宜的酸性粘土为,例如基于层状硅酸盐的活性催化剂,例如由无机酸如硫酸和/或盐酸活化的蒙脱土,优选其含湿量低于10%,特别是低于5%,例如所谓Fuller型粘土,如在商品名为Fulcat下可得的那些,如20、22B和40型(由硫酸活化的泥质土),商品名为Fulmont(Laporte Industries)的那些,如XMP-4、XMP-3、700C和237型,或者是由Südchemie生产的K5和K10型酸性土(由盐酸活化),KS和KSF型酸性土(由硫酸活化),或KSF0型酸性土(由盐酸和硫酸活化),以及基于膨润土的土,例如Filtrol或Retrol(Engelhard Corp.)型产品。
所谓“在无游离质子酸存在下”是本发明方法的一个特征,它不同于美国专利说明书2943112中公开的方法,反应混合物中不加无机或有机酸。
优选可获得的产物为在该方法中使用三聚丙烯作为壬烯,特别是基于二苯胺使用过量4至10倍摩尔的壬烯。
特别优选可获得的产物为在该方法中使用过量4至8倍,特别是4至6倍摩尔的壬烯,也就是三聚丙烯。
当烷基化在例如120~250℃,特别是150~220℃进行时,得到该方法的产物。
该方法可通过将起始物料和作为催化剂的酸性粘土引入一适宜的反应器中,并加热至特定的温度进行。在另一可选择的不同方法中,三聚丙烯可以在靠后一些的时间点上加入到反应中。优选地,反应的进行无需加入有机溶剂。在二苯胺的含量达到小于1%前,反应时间可以是几小时,特别是5~20小时,二苯胺的含量小于1%可通过取样分析确定。优选地,反应在高压下进行,例如在绝对压力为1~10巴的高压釜内。
在该方法中使用的酸性粘土可通过过滤、离心或倾析从反应混合物中除去,并可再利用。在实际中,它们的用量为5.0~20.0重量%,特别是5.0~10.0重量%。若需要的话,混合物可用常规方式如蒸馏进行提纯。
该方法的产物具有较好的粘度特性。例如用乌类娄德粘度计测得其40℃下的运动粘度较低,小于500mm2/秒(ASTM D 445-94方法,micro-Ubbelohde 2.0-3.0ml,Ubbelohde因子近似为5)。与按法国专利说明书No.1508785,通过用AlCl3反应的方法所得的产物比较,该值较低,并且按上述法国专利的方法所得的产物颜色深,透光率低于本发明方法的产物。
在下述实验报告中,按法国专利说明书F 1508785的实施例2和4制备的组合物和本发明的组合物的比较表明在性能上的明显改进。实验报告I.按法国专利说明书No.1508785的实施例2制备的混合物具有下述组成和性能:·组成(见下述的实施例1对气相色谱分析操作的说明):
面积为1.9%的二苯胺
面积为25.1%的单壬基二苯胺
面积为66.2%的二壬基二苯胺
面积为6.8%的三壬基二苯胺
·黑色产物,在波长为425nm处,其透光率为6.5%
·受氯离子污染:15ppm(由X射线荧光光谱测定)
对1%的上述组合物和99%的含磷量为0.08重量%的合成机油制剂的混合物进行见下述实施例3的试验M 18测试。其诱导期为43分钟,而按实施例1得到的产物诱导期为50分钟。II.按法国专利说明书No.1508785的实施例4制备的混合物具有下述组成和性能:·组成(见下述的实施例1对气相色谱分析操作的说明):
面积为1.1%的二苯胺
面积为19.6%的单壬基二苯胺
面积为71.6%的二壬基二苯胺
面积为7.5%的三壬基二苯胺·黑色产物,在波长为425nm处,其透光率为0.1%·受氯离子污染:15ppm(由X射线荧光光谱测定)
对1%的上述组合物和99%的REOLUBE LPE 602的混合物进行见下述实施例3的试验M 17测试。其诱导期为78分钟;
对1%的上述组合物,1.8%的柴油催化剂(由25%的环烷酸铁溶液,5%的环烷酸铜溶液,它们均来自Strem Chem USA,以及剩余部分为来自Esso的STANCO 150矿物油的混合物组成)和97.2%的REOLUBE LPE602的混合物进行试验M 17测试。其诱导期为73分钟;
对1%的上述组合物,0.5%的硝基戊烷和98.5%的来自FMC的REOLUBE LPE 602的混合物按载荷试验M 17进行测试,其诱导期为69分钟。若对1%的上述组合物和99%的含磷量为0.08%的合成机油制剂的混合物进行试验M 18测试,其诱导期为44分钟。III.已显示的按法国专利说明书No.1508785制备的产物的不利性质归因于其明显偏高的三壬基二苯胺含量。为说明三壬基二苯胺对壬基化二苯胺混合物(单和二壬基二苯胺)的抗氧化作用的不利影响,按与法国专利说明书No.1508785类似的方法制备三壬基二苯胺含量很高的产物。为此,将42.3克二苯胺与5.33克氯化铝和126.2克三聚丙烯混合,并将混合物加热至回流温度,反应2小时。然后将未反应的三聚丙烯通过蒸馏除去。再加入70克新鲜的三聚丙烯。再反应2小时后,冷却至室温并将油状反应混合物用100ml水萃取,直至最后一次的萃取物的pH值为7。然后将未反应的三聚丙烯通过在真空下蒸馏除去,并通过实施例1描述的气相色谱法对反应混合物进行分析。得到下述组成:
面积为0.1%的二苯胺
面积为5.3%的单壬基二苯胺
面积为72.5%的二壬基二苯胺
面积为22.1%的三壬基二苯胺
类似地,将如此制备的产物进行试验M 17测试。在该测试中,测得的诱导期是相当不利的,为56分钟。将三壬基二苯胺含量很高的这种产物进行试验M 18测试。其诱导期为44分钟。
按照本发明的混合物具有显著的抗氧化作用,这可以通过其较好的HPDSC值(高压差示扫描量热)显示,例如对于试验M 17测试(样品在200℃/SX,10巴O2下,1%,在REOLUBE LPE 602中)为79分钟,或对于试验M 18测试(样品在200℃/SX,8巴NOx下,1%,在M251/0.08%P(Shell)中)为50分钟。因此它们可以在广泛用于工程的大量有机制品,如润滑剂、传压流体、金属加工液、燃料或聚合物中,以及基于后者的低分子量组份中用作添加剂。本发明还涉及含稳定剂的组合物,该组合物含有:
α)易受氧化、热和/或光诱导降解的有机制品,和
β)作稳定剂的至少一种稳定混合物,该混合物含如前定义并按本发明方法
制备的二壬基二苯胺作为主要组份。
润滑剂和基于矿物油的操作液,或者是合成润滑剂或操作液,如可用于200℃或更高温度的羧酸酯衍生物形成了一特定类易受不期望的氧化降解的有机制品,对于这种不期望的氧化降解,本发明的混合物是很有价值的稳定剂。
基于要稳定的原料,本发明的混合物的使用浓度可为0.05~10重量%。优选的浓度为0.05~5重量%,特别是0.1~2.5重量%。
以这种方式改进的矿物和合成润滑油、润滑脂、传压流体和弹性体具有优良的抗氧化性能,这明显地表现在由保护的份数体现出来的老化现象的大大减少。如上所述的混合物在润滑油中尤为有利,其中它们具有优良的抗氧化性和抗腐蚀性,而不形成酸或淤渣。
合成润滑油的例子包括基于下述的润滑剂:二元质子酸与一元醇的二元酯,如癸二酸二辛酯或己二酸二壬酯;一元质子酸或这类酸的混合物与三羟甲基丙烷的三元酯,如三羟甲基丙烷三壬酸酯或三辛酸酯,或其混合物;一元质子酸或这类酸的混合物与季戊四醇的四元酯,如四辛酸季戊四醇酯;或一元质子酸或二元质子酸与多元醇的复合酯,如辛酸和癸二酸与三羟甲基丙烷的复合酯,或其混合物。
其它的合成润滑剂对本领域技术人员来说是熟悉的,并描述于例如“Schmiermittel Taschenbuch”(Hüthig-Verlag,Heidelberg,1974)中。它们当中特别适宜的是例如聚α-烯烃,基于酯的润滑剂,磷酸酯,二元醇,多元醇和聚亚烷基二元醇。
适宜的弹性体对本领域技术人员来说是熟悉的。特别适宜的是天然或合成橡胶,例如丁二烯的聚合物或其与苯乙烯或丙烯腈的共聚物,以及异戊二烯或氯丁二烯的聚合物。
另一类待保护的聚合物是通过缩聚形成的,通过添加上述的混合物,它们可以防止被氧化和光诱导降解,其形式既可以是在最终的大分子缩合产物中添加,也可以是在低分子量原料中添加。特别地,这类聚合物包括聚氨酯,它的稳定可通过在例如其原料多元醇中添加二壬基二苯胺来实现。
本发明的混合物也可添加入以纯单体化合物或其混合物形式的天然或合成有机物质中,例如矿物油,动物或植物油,蜡和脂肪,或基于合成酯类(例如邻苯二甲酸酯,己二酸酯,磷酸酯或偏苯三酸酯)的油,蜡和脂肪,以及合成酯类与矿物油以任意所需重量比的混合物,例如用作纺丝制剂,以及其水乳液。
本发明的混合物可加入天然或合成橡胶的天然或合成乳液中,如天然橡胶胶乳或羧基化苯乙烯/丁二烯共聚物胶乳。
此外,含有稳定剂的组合物还可含有其它改进其性能的共添加剂,例如其它的抗氧剂,金属减活剂,防锈剂,粘度指数改进剂/熔点或倾点降低剂,分散剂/洗涤剂和防磨添加剂或极端压力/抗磨添加剂和摩擦改进剂。其它抗氧剂的例子为:1.烷基化一元酚,例如2,6-二叔丁基-4-甲基苯酚,2-丁基-4,6-二甲基苯酚,2,6-二叔丁基-4-乙基苯酚,2,6-二叔丁基-4-正丁基苯酚,2,6-二叔丁基-4-异丁基苯酚,2,6-二环戊基-4-甲基苯酚,2-(α-甲基环己基)-4,6-二甲基苯酚,2,6-二-十八烷基-4-甲基苯酚,2,4,6-三环己基苯酚,2,6-二叔丁基-4-甲氧基甲基苯酚,线性壬基酚或在侧链上支化的壬基酚,例如2,6-二壬基-4-甲基苯酚,2,4-二甲基-6-(1′-甲基-十一烷-1′-基)苯酚,2,4-二甲基-6-(1′-甲基-十七烷-1′-基)苯酚,2,4-二甲基-6-(1′-甲基-十三烷-1′-基)苯酚及其混合物。2.烷硫基甲基苯酚,例如2,4-二辛硫基甲基-6-叔丁基苯酚,2,4-二辛硫基甲基-6-甲基苯酚,2,4-二辛硫基甲基-6-乙基苯酚,2,6-二-十二烷硫基甲基-4-壬基苯酚。3.氢醌和烷基化氢醌,例如2,6-二叔丁基-4-甲氧基苯酚,2,5-二叔丁基-氢醌,2,5-二叔戊基-氢醌,2,6-二苯基-4-十八烷氧基苯酚,2,6-二叔丁基-氢醌,2,5-二叔丁基-4-羟基苯甲醚,3,5-二叔丁基-4-羟基苯甲醚,3,5-二叔丁基-4-羟基苯基-硬脂酸酯,双(3,5-二叔丁基-4-羟基苯基)己二酸酯。4.生育酚,例如α-生育酚,β-生育酚,γ-生育酚,δ-生育酚及其混合物(维生素E)。5.羟基化硫代二苯基醚,例如2,2′-硫代-双(6-叔丁基-4-甲基苯酚),2,2′-硫代-双(4-辛基苯酚),4,4′-硫代-双(6-叔丁基-3-甲基苯酚),4,4′-硫代-双(6-叔丁基-2-甲基苯酚),4,4′-硫代-双(3,6-二仲戊基苯酚),4,4′-双(2,6-二甲基-4-羟基苯基)二硫化物。6.亚烷基双酚,例如2,2′-亚甲基-双(6-叔丁基-4-甲基苯酚),2,2′-亚甲基-双(6-叔丁基-4-乙基苯酚),2,2′-亚甲基-双[4-甲基-6-(α-甲基环己基)苯酚],2,2′-亚甲基-双(4-甲基-6-环己基苯酚),2,2′-亚甲基-双(6-壬基-4-甲基苯酚),2,2′-亚甲基-双(4,6-二叔丁基苯酚),2,2′-亚乙基-双(4,6-二叔丁基苯酚),2,2′-亚乙基-双(6-叔丁基-4-异丁基苯酚),2,2′-亚甲基-双[6-(α-甲基苄基)-4-壬基苯酚],2,2′-亚甲基-双[6-(α,α-二甲基苄基)-4-壬基苯酚],4,4′-亚甲基-双(2,6-二叔丁基苯酚),4,4′-亚甲基-双(6-叔丁基-2-甲基苯酚),1,1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷,2,6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚,1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷,1,1-双(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基巯基丁烷,乙二醇双[3,3-双(3′-叔丁基-4′-羟基苯基)丁酸酯],双(3-叔丁基-4-羟基-5-甲基苯基)双环戊二烯,双[2-(3′-叔丁基-2′-羟基-5′-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二甲酸酯,1,1-双(3,5-二甲基-2-羟基苯基)丁烷,2,2-双(3,5-二叔丁基-4-羟基苯基)丙烷,2,2-双(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷,1,1,5,5-四(5-叔丁基-4-羟基-2-甲基苯基)戊烷。7.O-,N-和S-苄基化合物,例如3,5,3′,5′-四叔丁基-4,4′-二羟基二苄基醚,4-羟基-3,5-二甲基苄基-巯基乙酸十八烷基酯,4-羟基-3,5-二叔丁基苄基-巯基乙酸十三烷基酯,三(3,5-二叔丁基-4-羟基苄基)胺,双(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫代对苯二甲酸酯,双(3,5-二叔丁基-4-羟基苄基)硫化物,3,5-二叔丁基-4-羟基苄基-巯基乙酸异辛基酯。8.羟苄基化丙二酸酯,例如2,2-双(3,5-二叔丁基-2-羟基苄基)丙二酸二-十八烷基酯,2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸二-十八烷基酯,2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸二-十二烷基巯乙基酯,2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸二[4-(1,1,3,3-四甲基丁基)苯基]酯。9.羟基苄基芳族化合物,例如1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯,1,4-双(3,5-二叔丁基-4-羟基苄基)-2,3,5,6-四甲基苯,2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯酚。10.三嗪化合物,例如2,4-二辛基巯基-6-(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氧基)-1,3,5-三嗪,2,4,6-三(3,5-二叔丁基-4-羟基苯氧基)-1,2,3-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯,2,4,6-三(3,5-二叔丁基-4-羟基苯乙基)-1,3,5-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基苯丙酰基)-六氢-1,3,5-三嗪,1,3,5-三(3,5-二环己基-4-羟基苄基)异氰脲酸酯。11.苄基膦酸酯,例如2,5-二叔丁基-4-羟基苄基膦酸二甲基酯,3,5-二叔丁基-4-羟基苄基膦酸二乙基酯,3,5-二叔丁基-4-羟基苄基膦酸二-十八烷基酯,5-叔丁基-4-羟基-3-甲基苄基膦酸二-十八烷基酯,3,5-二叔丁基-4-羟基苄基膦酸单乙酯的钙盐。12.酰氨基酚,例如4-羟基-N-月桂酰苯胺,4-羟基-N-硬脂酰苯胺,N-(3,5-二叔丁基-4-羟基苯基)-氨基甲酸辛酯。13.β-(3,5-二叔丁基-4-羟基苯基)-丙酸与一元醇或多元醇的酯,例如与甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫二甘醇,二甘醇,三甘醇,季戊四醇,三(羟乙基)异氰脲酸酯,N,N′-二(羟乙基)草酸二酰胺,3-硫杂十一烷醇,3-硫杂十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷的酯。14.β-(5-叔丁基-4-羟基-3-甲基苯基)-丙酸与一元醇或多元醇的酯,例如与甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫二甘醇,二甘醇,三甘醇,季戊四醇,三(羟乙基)异氰脲酸酯,N,N′-二(羟乙基)草酸二酰胺,3-硫杂十一烷醇,3-硫杂十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷的酯。15.β-(3,5-二环己基-4-羟基苯基)-丙酸与一元醇或多元醇的酯,例如与甲醇,乙醇,辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫二甘醇,二甘醇,三甘醇,季戊四醇,三(羟乙基)异氰脲酸酯,N,N′-二(羟乙基)草酸二酰胺,3-硫杂十一烷醇,3-硫杂十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷的酯。16.3,5-二叔丁基-4-羟基苯基乙酸与一元醇或多元醇的酯,例如与甲醇,乙醇,辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫二甘醇,二甘醇,三甘醇,季戊四醇,三(羟乙基)异氰脲酸酯,N,N′-二(羟乙基)草酸二酰胺,3-硫杂十一烷醇,3-硫杂十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷的酯。17.β-(3,5-二叔丁基-4-羟基苯基)-丙酸的酰胺,例如N,N′-双(3,5-二叔丁基-4-羟基苯丙酰基)-六亚甲基二胺,N,N′-双(3,5-二叔丁基-4-径基苯丙酰基)-三亚甲基二胺,N,N′-双(3,5-二叔丁基-4-羟基苯丙酰基)-肼。胺类抗氧剂的例子:
N,N′-二异丙基-对苯二胺,N,N′-二仲丁基-对苯二胺,N,N′-双(1,4-二甲基戊基)-对苯二胺,N,N′-双(1-乙基-3-甲基戊基)-对苯二胺,N,N′-双(1-甲基庚基)-对苯二胺,N,N′-二环己基-对苯二胺,N,N′-二苯基-对苯二胺,N,N′-二(萘-2-基)对苯二胺,N-异丙基-N′-苯基-对苯二胺,N-(1,3-二甲基丁基)-N′-苯基-对苯二胺,N-(1-甲基庚基)-N′-苯基-对苯二胺,N-环己基-N′-苯基-对苯二胺,4-(对-甲苯-磺酰氨基)-二苯胺,N,N′-二甲基-N,N′-二仲丁基-对苯二胺,二苯胺,N-烯丙基二苯胺,4-异丙氧基-二苯胺,N-苯基-1-萘胺,N-(4-叔辛基苯基)-1-萘胺,N-苯基-2-萘胺,辛基化二苯胺,例如p,p′-二叔辛基二苯胺,4-正丁氨基苯酚,4-丁酰氨基苯酚,4-壬酰氨基苯酚,4-十二碳酰氨基苯酚,4-十八碳酰氨基苯酚,二(4-甲氧基苯基)胺,2,6-二叔丁基-4-二甲氨基-甲基苯酚,2,4′-二氨基-二苯甲烷,4,4′-二氨基-二苯甲烷,N,N,N′,N′-四甲基-4,4′-二氨基-二苯甲烷,1,2-二[(2-甲基苯基)氨基]乙烷,1,2-二(苯基氨基)丙烷,邻甲苯基二胍,二[4-(1′,3′-二甲基-丁基)-苯基]胺,叔辛基化N-苯基-1-萘胺,单和二烷基化叔丁基-/叔辛基-二苯胺的混合物,单和二烷基化十二烷基二苯胺的混合物,单和二烷基化异丙基-/异己基-二苯胺的混合物,单和二烷基化叔丁基二苯胺的混合物,2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪,吩噻嗪,单和二烷基化叔辛基吩噻嗪的混合物,N-烯丙基吩噻嗪,N,N,N′,N′-四苯基-1,4-二氨基-2-丁烯,N,N-双(2,2,6,6-四甲基-哌啶-4-基)六亚甲基二胺,双(2,2,6,6-四甲基-哌啶-4-基)癸二酸酯,2,2,6,6-四甲基-哌啶-4-酮,2,2,6,6-四甲基-哌啶-4-醇。其它抗氧剂的例子:
脂族或芳族亚磷酸酯,硫代二丙酸或硫代二乙酸的酯,或二硫代氨基甲酸或二硫代磷酸的盐,2,2,12,12-四甲基-5,9-二羟基-3,7,11-三硫杂十三烷,和2,2,15,15-四甲基-5,12-二羟基-3,7,10,14-四硫杂十六烷。金属减活剂的例子,例如对铜的:a)苯并三唑及其衍生物,例如4-或5-烷基苯并三唑(如甲基苯并三唑(tolutriazole))及其衍生物,4,5,6,7-四氢苯并三唑,5,5′-亚甲基双苯并三唑;苯并三唑或甲基苯并三唑如1-[二(2-乙基己基)氨基甲基]-甲基苯并三唑和1-[二(2-乙基己基)氨基甲基]-苯并三唑的Mannich碱;烷氧基烷基苯并三唑,如1-(壬氧基甲基)-苯并三唑,1-(1-丁氧基乙基)-苯并三唑,和1-(1-环己氧基丁基)-甲基苯并三唑。b)1,2,4-三唑及其衍生物,例如3-烷基(或芳基)-1,2,4-三唑,1,2,4-三唑如1-[二(2-乙基己基)氨基甲基]-1,2,4-三唑的Mannich碱;烷氧基烷基-1,2,4-三唑,如1-(1-丁氧基乙基)-1,2,4-三唑;酰化的3-氨基-1,2,4-三唑。c)咪唑衍生物,例如4,4′-亚甲基双(2-十一烷基-5-甲基)咪唑,双[(N-甲基)-咪唑-2-基]甲醇-辛基醚。d)含硫的杂环化合物,例如2-巯基苯并噻唑,2,5-二巯基-1,3,4-噻二唑及其衍生物;3,5-双[二(2-乙基己基)氨基-甲基]-1,3,4-噻二唑啉-2-酮。e)氨基化合物,例如亚水杨基-丙二胺,水杨基氨基胍及其盐。防锈剂的例子:a)有机酸,它们的酯,金属盐,铵盐和酸酐,例如烷基-和链烯基-琥珀酸及其与醇、二元醇或羟基羧酸的部分酯,烷基-和链烯基-琥珀酸的部分酰胺,4-壬基苯氧基乙酸,烷氧基-和烷氧基乙氧基羧酸,如十二烷氧基乙酸,十二烷氧基(乙氧基)-乙酸及其铵盐,N-油酰-肌氨酸,脱水山梨糖醇单油酸酯,环烷酸铅,链烯基琥珀酸酐,如十二碳烯基琥珀酸酐,2-羧甲基-1-十二烷基-3-甲基丙三醇及其铵盐。b)含氮化合物,例如:
I.伯、仲或叔脂族或环脂族胺,及有机和无机酸的铵盐,例如油溶性羧酸烷基铵盐,和1-[N,N-双(2-羟乙基)氨基]-3-(4-壬基苯氧基)丙烷-2-醇。
II.杂环化合物,例如:取代的咪唑啉或噁唑啉,2-十七碳烯基-1-(2-羟乙基)-咪唑啉。c)含磷化合物,例如:
磷酸部分酯或膦酸部分酯的铵盐,二烷基二硫代磷酸锌。d)含硫化合物,例如:
二壬基萘磺酸钡,石油磺酸钙,烷硫基取代的脂族羧酸,脂族2-磺基羧酸的酯及其盐。e)甘油衍生物,例如:
甘油单油酸酯,1-(烷基苯氧基)-3-(2-羟乙基)甘油,1-(烷基苯氧基)-3-(2,3-二羟丙基)甘油,2-羧基烷基-1,3-二烷基甘油。粘度指数改进剂的例子:
聚丙烯酸酯,聚甲基丙烯酸酯,乙烯基吡咯烷酮/甲基丙烯酸酯共聚物,聚乙烯基吡咯烷酮,聚丁烯,烯烃共聚物,苯乙烯/丙烯酸酯共聚物,聚醚。倾点降低剂的例子:
聚甲基丙烯酸酯,烷基化的萘衍生物。分散剂/表面活性剂的例子:
聚丁烯基琥珀酰胺或酰亚胺,聚丁烯基膦酸衍生物,碱式磺酸镁、磺酸钙和磺酸钡,酚盐和水杨酸盐。防磨添加剂的例子:
含硫和/或磷和/或卤素的化合物,例如硫化的烯烃和植物油,二烷基二硫代磷酸锌,烷基化的磷酸三苯酯,磷酸三甲苯酯,氯化石蜡,烷基和芳基二-或三-硫化物,单-和二-烷基磷酸的铵盐,甲基膦酸的铵盐,二乙醇氨基甲基甲苯基三唑,二(2-乙基己基)氨基甲基甲苯基三唑,2,5-二巯基-1,3,4-噻二唑的衍生物,3-[(双-异丙氧基-硫膦基)硫代]丙酸乙酯,硫代磷酸三苯酯,硫代磷酸三(烷基苯基)酯及其混合物(如硫代磷酸三(异壬基苯基)酯),硫代磷酸二苯基-单壬基苯基酯,硫代磷酸异丁基苯基-二苯基酯,3-羟基-1,3-硫磷杂戊环(thiaphosphetan)-3-氧化物的十二烷基铵盐,三硫代磷酸5,5,5-三[乙酸异辛酯(2)],2-巯基苯并噻唑的衍生物如1-[N,N-双(2-乙基己基)氨基甲基]-2-巯基-1H-1,3-苯并噻唑,乙氧基羰基-5-辛基-二硫代氨基甲酸酯。
通过下述实施例进一步说明本发明;温度均为℃:实施例1(高压下的反应)1.1实验装置
所用的高压釜配有带分水器的回流冷凝器,电加热装置,螺旋浆搅拌器,温度记录装置和取样装置。反应可在氮气保护下进行,或事先将高压釜抽空后进行。1.2加料
在高压釜内加入40克二苯胺,并将其在80℃下熔化。然后加入119.5克三聚丙烯(Exxon,USA)和4.0克催化剂FULCAT 22B(Laporte)。1.3反应的进行
将高压釜密封并抽空至压力为20毫巴。搅拌下将高压釜加热至140℃,并保持该温度半小时以除去酸性催化剂土中的水。任意确定反应的起始时间(t=0)并取出第一个样品。
在45分钟内将高压釜加热至205~210℃。210℃下,反应混合物的压力升至绝对压力为3.8巴。温度保持在210℃半小时,然后在1小时内降至156℃。随后,将反应混合物在156℃下再保持6小时。1.4后处理
使反应器内的催化剂沉降1小时,然后通过抽吸沉淀的催化剂粘土上的液体,取出反应混合物。通过孔径为约1~3μm的吸滤器过滤彻底分离掉同时取出的少量粘土。在温度至多270℃以及50毫巴的真空下,在例如理论塔板数为10的塔内,通过真空蒸馏从反应产物中除去起始物料三聚丙烯。提高温度至280~290℃,并进一步将压力降低至17毫巴,可除去未反应的二苯胺。样品(浓度50%,在甲苯中)的透光率为约52.6%(紫外-可见光,425nm处)。1.5气相色谱图
在除去三聚丙烯后,对按实施例1得到的产物以及按法国专利说明书1508785的实施例2得到的混合物进行气相色谱分析。
1.51方法:毛细管-气相色谱(GLC)气相色谱仪 Varian注射方法 直接在柱上注射,Varian Auto Sampler8035注射体积 1微升柱 熔凝硅石,长:15米,截面:0.32毫米固定相 硅油,DB-5,膜厚:0.25微米检测器 FID(灵敏度等级10)积分仪 信号(峰)下的面积;衰减:32积分时间 3~21分钟载气 He:1.5ml/min.;N2:30.0ml/min.;
组份 | 实施例1[%面积] | FR 1508785的实施例2[%面积] |
二苯胺 | 0.3 | 1.1/1.1 |
单壬基二苯胺 | 25.6 | 25.4/25.4 |
二壬基二苯胺 | 71.5 | 67.4/67.7 |
三壬基二苯胺 | 2.6 | 6.1/5.8 |
H2:30.0ml/min.;空气:300.0ml/min.温度 注射器:95℃保持6秒,100℃/min.升至
300℃,300℃下保持21min.;烘箱:
0min.,100℃,10℃/min.升至300℃,300
℃下保持5min.;检测器:300℃测试时间 28min.实施例2(常压下的反应)2.1实验方法
反应不是使用高压釜进行,而是在氮气保护下在一可加热的、配有分水器和回流冷凝器的1000毫升玻璃反应器中进行。此外反应器还配有螺旋桨搅拌器,温度计,取样装置和传热介质的加热装置。2.2加料
在反应器中加入150克二苯胺,并将其在80℃下熔化。然后加入111.9克三聚丙烯(Exxon,USA)和15.0克催化剂FULCAT 22B(Laporte)。2.3反应的进行
将反应混合物以500rev/min(转/分钟)的速率搅拌,开加热至沸点以从酸性催化剂土中除去水。任意确定反应的起始时间(t=0)并取出第一个样品。在随后的两小时内,将反应温度提高至175~180℃。然后,在10小时内计量加入336克壬烯。在该段时间内反应温度降至155~158℃。随后,在回流条件下将反应混合物再保温5小时。与实施例1类似地进行后处理。
在除去三聚丙烯后,在气相色谱图(操作见实施例1)中,混合物含有:
面积为0.7%的二苯胺
面积为25.2%的单壬基二苯胺;
面积为71.5%的二壬基二苯胺
面积为2.6%的三壬基二苯胺。实施例3(应用实施例:热分析测试法)方法
HPDSC:高压差示扫描量热法仪器
使用的仪器是METTLER TA-8000系列(Mettler-Toledo,CH-Greifensee)的DSC27HP。测试原理
DSC:由样品坩埚的热流与参比坩埚的热流的差值测量样品的热流。样品吸热表示吸热反应,例如熔化过程。测试条件(M 17)
将均为钢制品的含有45毫克精制油添加剂混合物的样品坩埚和惰性参比坩埚放置在DSC传感器上。用反应气体氧气将密封室彻底吹几遍,然后在10巴的压力下放置。然后进行加热,加热速率为50℃/min,从室温加热至反应温度200℃。测试条件(M 18)
将均为钢制品的含有45毫克精制油添加剂混合物的样品坩埚和惰性参比坩埚放置在DSC传感器上。用反应气体,混有400ppm氮的氧化物的氧气,将密封室彻底吹几遍,然后在8巴的压力下放置。然后进行加热,加热速率为50℃/min,从室温加热至反应温度200℃。评价
用诱导期作为评价标准。诱导期是氧化反应可见地开始的时间,它由在传感器的基线与反应信号的切线交叉的那一点形成。所用的TA-StationTAS810是基于UNIX操作系统的,使用的评价软件是Mettler GraphwareTA3.00。结果a)1%的按实施例1制备的产物与从FMC,GB购得的油REOLUBE LPE602混合,将该混合物进行试验M 17的测试。测得的诱导期为79分钟。b)1%的按实施例1制备的产物和1.8%的柴油催化剂(由25%的环烷酸铁溶液,5%的环烷酸铜溶液,它们均来自Strem Chem USA,以及剩余部分为来自Esso的STANCO 150矿物油的混合物制成)与从FMC,GBI购得的油REOLUBE LPE 602混合,类似地,将其进行试验M 17的测试。其诱导期为81分钟。c)1%的按实施例1制备的产物,0.5%的硝基戊烷和98.5%的REOLUBELPE 602的混合物在试验M 17的测试条件下,诱导期为73分钟。d)1%的按实施例1制备的产物与99%的基于磷含量为0.08%的合成机油制剂混合,在上述试验M 18的测试条件下,其诱导期为50分钟。实施例5
实验装置,后处理和分析与实施例1类似,但每一个实验的进行均使用不同的反应步骤。对于每一实验,在高压釜中加入40克二苯胺。随后加入重量为m1的三聚丙烯和重量为m2的催化剂FULCAT 22B(Laporte)。将高压釜抽空至20毫巴,并加热至140℃以从催化剂中除去水。然后将高压釜密封,并在15分钟内加热至温度T1。然后开始在t1的时间内,每小时计量加入d1克三聚丙烯。平行地,在t2的时间内,温度保持在T1,并在t3的时间内降至最终温度T2。随后于搅拌下,在t4的时间内,保持反应混合物的温度T2。在反应过程中,最大的压力为绝对压力p1巴。反应结束后,以如实施例1所述的气相色谱法对反应混合物进行分析。不含三聚丙烯的产物组成可参见表1。表中缩写的含义为:DPA=二苯胺,Mono=单壬基二苯胺,Di=二壬基二苯胺,Tri=三壬基二苯胺。百分数表示的是由实施例1所述的气相色谱法测定的面积百分数。表1
*在实验7-10中,前面实验的催化剂留在反应器中,并仅加入通常量一半的催化剂。此外,在这些实验中,重新使用了15克从前面实验再生的三聚丙烯,并补充了15克新鲜的三聚丙烯。实施例6
No. | m1 | m2 | T1 | T2 | p1 | d1 | t1 | t2 | t3 | t4 | DPA | Mono | Di | Tri |
[g] | [g] | [℃] | [℃] | [巴] | [g/h] | [h] | [h] | [h] | [h] | [%] | [%] | [%] | [%] | |
1 | 30 | 4 | 220 | 154 | 3.7 | 0.0 | 0.0 | 1.00 | 1.0 | 4.0 | 1.4 | 31.3 | 65.8 | 1.5 |
2 | 0 | 4 | 213 | 156 | 3.1 | 30.0 | 1.0 | 0.50 | 1.0 | 5.0 | 0.7 | 24.8 | 71.7 | 2.8 |
3 | 0 | 4 | 210 | 158 | 3.9 | 5.0 | 6.0 | 7.00 | 8.5 | 0.0 | 2.0 | 39.0 | 57.7 | 1.3 |
4 | 30 | 4 | 220 | 170 | 3.8 | 0.0 | 0.0 | 0.50 | 1.0 | 8.5 | 0.8 | 25.2 | 71.3 | 2.7 |
5 | 9 | 4 | 220 | 170 | 3.8 | 10.5 | 2.0 | 0.50 | 1.0 | 4.0 | 0.5 | 26.1 | 70.8 | 2.6 |
6 | 0 | 4 | 220 | 160 | 1.5 | 15.0 | 2.0 | 0.25 | 2.0 | 4.0 | 0.3 | 24.1 | 72.8 | 2.8 |
7 | 0 | 2* | 220 | 160 | 1.5 | 7.5 | 4.0 | 0.25 | 2.0 | 4.0 | 0.3 | 24.4 | 72.5 | 2.8 |
8 | 0 | 2* | 220 | 160 | 1.5 | 7.5 | 4.0 | 0.25 | 2.0 | 6.0 | 0.7 | 26.0 | 70.7 | 2.6 |
9 | 0 | 2* | 220 | 160 | 1.5 | 7.5 | 4.0 | 0.25 | 2.0 | 6.0 | 0.8 | 26.5 | 70.2 | 2.5 |
10 | 0 | 2* | 220 | 160 | 1.5 | 7.5 | 4.0 | 0.25 | 2.0 | 6.0 | 0.9 | 27.0 | 69.8 | 2.3 |
实验装置,后处理和分析与实施例2类似,但每一个实验的进行均使用不同的反应步骤。对于每一实验,在玻璃反应器中加入150克二苯胺。随后加入重量为m1的三聚丙烯和重量为m2的催化剂FULCAT 22B(Laporte),并在常压下将反应混合物加热至回流温度,以从催化剂中除去水。然后,在t2的时间内将反应混合物保持回流。然后开始在t1的时间内,每小时计量加入d1克三聚丙烯,结果反应混合物的温度降至T1,这是因为沸腾温度较低。搅拌下,将反应混合物最终保持回流t3小时,结果达到最终温度T2。反应结束后,以如实施例1所述的气相色谱法对反应混合物进行分析。不含三聚丙烯的产物组成可参见表2。表中缩写的含义为:DPA=二苯胺,Mono=单壬基二苯胺,Di=二壬基二苯胺,Tri=三壬基二苯胺。百分数表示的是由实施例1所述的气相色谱法测定的面积百分数。表2
*在实验9-11中,前面实验的催化剂留在反应器中,并且在每一情形下仅加入实验7催化剂量的一半。**在实验6中,所用的是由实验4再生的三聚丙烯,并补充了新鲜的三聚丙烯。在实验8中,所使用的仅是由实验6和7再生的三聚丙烯。
No. | m1 | m2 | T1 | T2 | T3 | d1 | t1 | t2 | t3 | DPA | Mono | Di | Tri |
[g] | [g] | [℃] | [℃] | [℃] | [g/h] | [h] | [h] | [h] | [%] | [%] | [%] | [%] | |
1 | 224 | 15.0 | 164 | 147 | 156 | 56 | 4.0 | 2.0 | 9.0 | 1.5 | 36.0 | 61.1 | 1.4 |
2 | 224 | 15.0 | 165 | 148 | 155 | 56 | 4.0 | 2.0 | 17.0 | 0.7 | 25.2 | 71.8 | 2.3 |
3 | 224 | 15.0 | 164 | 145 | 157 | 84 | 4.0 | 2.0 | 9.0 | 0.4 | 21.1 | 75.3 | 3.2 |
4 | 112 | 15.0 | 175 | 148 | 156 | 33.6 | 10.0 | 2.0 | 5.0 | 0.4 | 23.1 | 73.7 | 2.8 |
5 | 112 | 15.0 | 174 | 147 | 155 | 43** | 9.0 | 2.0 | 5.0 | 0.7 | 24.5 | 72.3 | 2.5 |
6 | 112 | 15.0 | 173 | 146 | 156 | 37 | 9.0 | 2.0 | 5.0 | 0.5 | 22.0 | 74.2 | 3.3 |
7 | 112 | 22.5 | 174 | 147 | 155 | 37** | 9.0 | 2.0 | 5.0 | 0.9 | 23.9 | 72.2 | 3.0 |
8 | 0 | 15.0 | 220 | 148 | 156 | 112 | 4.0 | 0.0 | 6.0 | 0.6 | 27.6 | 69.5 | 2.3 |
9 | 0 | 7.5* | 220 | 147 | 156 | 112 | 4.0 | 0.0 | 6.0 | 0.5 | 28.6 | 68.8 | 2.1 |
10 | 0 | 7.5* | 220 | 148 | 156 | 112 | 4.0 | 0.0 | 6.0 | 0.5 | 27.2 | 70.0 | 2.3 |
11 | 0 | 7.5* | 220 | 147 | 155 | 112 | 4.0 | 0.0 | 11.0 | 0.5 | 23.3 | 73.3 | 2.9 |
Claims (12)
1.一种二苯胺的混合物,该混合物在气相色谱图中各组份的含量为:a)面积为68.0-78.0%的二壬基二苯胺;b)面积为20.0-30.0%的壬基二苯胺;c)面积为1.0-3.5%的三壬基二苯胺;和d)面积为0.1-1.0%的二苯胺。
2.权利要求1的混合物,各组份含量为:a)面积为70.0-75.0%的二壬基二苯胺;b)面积为25.0-30.0%的壬基二苯胺;c)面积为1.0-3.5%的三壬基二苯胺;和d)面积为0.1-1.0%的二苯胺。
3.权利要求1的混合物,各组份含量为:a)面积为70.0-75.0%的二壬基二苯胺;b)面积为25.0-28.0%的壬基二苯胺;c)面积为1.0-3.5%的三壬基二苯胺;和d)面积为0.1-1.0%的二苯胺。
4.权利要求1的混合物,其中在二壬基二苯胺和壬基二苯胺中壬基分别位于二苯胺的4,4’-和4-位上。
5.权利要求1的混合物,40℃下其运动粘度为小于500mm2/sec。
6.一种二苯胺混合物的制备方法,在气相色谱图中该混合物各组份的含量为:a)面积为68.0-78.0%的二壬基二苯胺;b)面积为20.0-30.0%的壬基二苯胺;c)面积为1.0-3.5%的三壬基二苯胺;和d)面积为0.1-1.0%的二苯胺,
该方法包括,在基于二苯胺为2.0-25.0重量%的酸性粘土存在下,并且在无游离质子酸存在下,用过量的壬烯或壬烯异构体的混合物对二苯胺进行烷基化。
7.权利要求6的方法,其中使用5.0-10.0重量%的酸性粘土。
8.权利要求6的方法,其中使用酸活化的层状硅酸盐。
9.权利要求6的方法,其中使用三聚丙烯作为壬烯。
10.权利要求9的方法,其中使用过量4-6倍摩尔的壬烯。
11.权利要求6的方法,其中烷基化是在150-220℃下进行的。
12.权利要求1的二苯胺混合物在稳定容易发生氧化、热和/或光诱导的降解的有机材料方面的应用。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH137797 | 1997-06-06 | ||
CH1377/1997 | 1997-06-06 | ||
CH1377/97 | 1997-06-06 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1201781A CN1201781A (zh) | 1998-12-16 |
CN1135221C true CN1135221C (zh) | 2004-01-21 |
Family
ID=4209007
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB981096557A Expired - Fee Related CN1135221C (zh) | 1997-06-06 | 1998-06-05 | 壬基化二苯胺 |
Country Status (19)
Country | Link |
---|---|
US (1) | US6315925B1 (zh) |
JP (3) | JP4833387B2 (zh) |
KR (1) | KR100624206B1 (zh) |
CN (1) | CN1135221C (zh) |
BE (1) | BE1013124A3 (zh) |
BR (1) | BR9802365A (zh) |
CA (1) | CA2240971C (zh) |
CZ (1) | CZ294662B6 (zh) |
DE (1) | DE19824790B4 (zh) |
ES (1) | ES2151819B1 (zh) |
FR (1) | FR2764887B1 (zh) |
GB (1) | GB2325929B (zh) |
IT (1) | ITMI981274A1 (zh) |
NL (1) | NL1009331C2 (zh) |
RU (1) | RU2198870C2 (zh) |
SG (1) | SG65759A1 (zh) |
SK (1) | SK285027B6 (zh) |
TW (1) | TW555733B (zh) |
ZA (1) | ZA984871B (zh) |
Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG65759A1 (en) * | 1997-06-06 | 1999-06-22 | Ciba Sc Holding Ag | Nonylated diphenylamines |
US6684759B1 (en) | 1999-11-19 | 2004-02-03 | Vladimir Gorokhovsky | Temperature regulator for a substrate in vapor deposition processes |
US6871700B2 (en) | 2000-11-17 | 2005-03-29 | G & H Technologies Llc | Thermal flux regulator |
US7189875B2 (en) * | 2003-04-04 | 2007-03-13 | Crompton Corporation | Diphenylamine alkylated with olefin mixtures containing fractions with varying degrees of activity |
US6930183B2 (en) * | 2003-04-17 | 2005-08-16 | Crompton Corporation | Alkylated iminodibenzyls as antioxidants |
SK14562003A3 (sk) * | 2003-11-25 | 2005-06-02 | Duslo,A.S. | Antioxidačné kompozície oktylovaných difenylamínov a spôsob ich výroby |
US8030259B2 (en) * | 2004-04-01 | 2011-10-04 | Ciba Speciality Chemicals Corp. | Alkylated PANA and DPA compositions |
US7816308B2 (en) * | 2004-04-14 | 2010-10-19 | Crompton Corporation | Ketone diarylamine condensates |
US8202829B2 (en) * | 2004-11-04 | 2012-06-19 | Afton Chemical Corporation | Lubricating composition |
WO2006130498A1 (en) * | 2005-06-02 | 2006-12-07 | Albemarle Corporation | Improved process for synthesizing alkylated arylamines |
US7390928B2 (en) | 2005-12-14 | 2008-06-24 | Chemtura Corporation | Alkylation of N′-phenyl-N-alkylphenylenediamines in ionic liquid, N′-phenyl-N-alkyl (alkylphenylene) diamines produced thereby, and lubricant compositions containing same |
US7145038B1 (en) | 2005-12-14 | 2006-12-05 | Chemtura Corporation | Alkylation of a diphenylamine compound in ionic liquid |
US8003583B2 (en) * | 2005-12-21 | 2011-08-23 | Chevron Oronite Company Llc | Benzo[b]perhydroheterocyclic arylamines and lubricating oil compositions |
US7285518B2 (en) * | 2005-12-21 | 2007-10-23 | Chevron Oronite Company Llc | Dibenzo[b]perhydroheterocyclic amines and lubricating oil compositions |
US7501386B2 (en) * | 2005-12-21 | 2009-03-10 | Chevron Oronite Company, Llc | Synergistic lubricating oil composition containing a mixture of a benzo[b]perhydroheterocyclic arylamine and a diarylamine |
US8828916B2 (en) * | 2006-12-28 | 2014-09-09 | Chevron Oronite Company Llc | Method to prepare nonylated diphenylamine using recycle sequential temperatures |
CA2690200C (en) | 2007-06-08 | 2014-09-30 | Infineum International Limited | Additives and lubricating oil compositions containing same |
US7683017B2 (en) * | 2007-06-20 | 2010-03-23 | Chevron Oronite Company Llc | Synergistic lubricating oil composition containing a mixture of a nitro-substituted diarylamine and a diarylamine |
US8110532B2 (en) * | 2008-11-24 | 2012-02-07 | Chemtura Corporation | Antioxidant compositions |
RU2476587C2 (ru) * | 2010-11-12 | 2013-02-27 | Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации | Смазочная композиция высокотемпературного масла для теплонапряженных газотурбинных двигателей сверхзвуковой авиации |
CN102659606B (zh) * | 2012-05-07 | 2014-04-09 | 常州大学 | 一种色泽稳定的烷基化二苯胺抗氧剂的制备方法 |
US9617201B2 (en) | 2013-10-14 | 2017-04-11 | Chemtura Corporation | Fixed bed process for clay catalyzed alkylation of aromatic amines |
GB2523756B (en) | 2014-03-03 | 2017-01-11 | Addivant Switzerland Gmbh | Antioxidant compositions |
US9890346B2 (en) | 2014-07-21 | 2018-02-13 | Lanxess Solutions Us Inc. | Selective alkylation method for producing p, p′-di-alkylated diphenylamine antioxidants |
US9744531B2 (en) | 2015-03-03 | 2017-08-29 | Lanxess Solutions Us Inc. | Regeneration of clay catalysts for alkylation of aromatic rings |
WO2017011159A1 (en) | 2015-07-15 | 2017-01-19 | Chemtura Corporation | Diaryl amine antioxidants prepared from branched olefins |
CA3047284C (en) | 2016-12-27 | 2024-05-14 | The Lubrizol Corporation | Lubricating composition with alkylated naphthylamine |
EP3562921B1 (en) | 2016-12-27 | 2022-04-27 | The Lubrizol Corporation | Lubricating composition including n-alkylated dianiline |
CN106699677B (zh) * | 2016-12-28 | 2019-07-09 | 利安隆(中卫)新材料有限公司 | 紫外线吸收剂uv-571的制备方法 |
MX2023005680A (es) * | 2020-11-17 | 2023-06-29 | Songwon Ind Co Ltd | Composiciones que comprenden difenilaminas alquiladas con propiedades mejoradas. |
CN115254088B (zh) * | 2022-08-30 | 2023-11-21 | 华东理工大学 | 一种生产烷基二苯胺的催化剂及其制备方法和应用 |
WO2024158648A1 (en) | 2023-01-24 | 2024-08-02 | The Lubrizol Corporation | Lubricating composition with phenolic antioxidant and low active sulfur |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2776994A (en) | 1954-03-03 | 1957-01-08 | Goodrich Co B F | Preparation of a solid diphenylamine antioxidant |
US2943112A (en) * | 1957-11-06 | 1960-06-28 | Pennsalt Chemicals Corp | Alkylation of diphenylamine |
US3496230A (en) * | 1966-02-17 | 1970-02-17 | American Cyanamid Co | Process for mixture of mono- and dialkyl-diphenylamines |
CA1083606A (en) * | 1975-04-18 | 1980-08-12 | Vipin M. Kothari | Process of preparing para styrenated diphenylamine. |
JPS58108296A (ja) * | 1981-12-21 | 1983-06-28 | Sumitomo Chem Co Ltd | 燃料油用液状酸化防止剤 |
GB8332797D0 (en) * | 1983-12-08 | 1984-01-18 | Ciba Geigy Ag | Antioxidant production |
JPS60202845A (ja) * | 1984-03-28 | 1985-10-14 | Seikou Kagaku Kk | 白度または透明度の高いp−置換ジフエニルアミン類の製造法 |
US4739121A (en) | 1984-05-24 | 1988-04-19 | The B. F. Goodrich Company | Process for otho- and para-alkylating diphenylamines |
JPS6197378A (ja) * | 1984-10-18 | 1986-05-15 | Toyoda Gosei Co Ltd | エアダクト用シ−ラント |
US4769164A (en) * | 1987-05-22 | 1988-09-06 | The Lubrizol Corporation | Anti-oxidant products |
US4798684A (en) * | 1987-06-09 | 1989-01-17 | The Lubrizol Corporation | Nitrogen containing anti-oxidant compositions |
JP2539677B2 (ja) * | 1989-01-13 | 1996-10-02 | 日本石油株式会社 | 潤滑油組成物 |
JPH0959227A (ja) * | 1995-08-11 | 1997-03-04 | Seiko Kagaku Kk | スチレン化ジフェニルアミンの製造方法 |
US5672752A (en) * | 1995-09-13 | 1997-09-30 | The Bfgoodrich Company | Liquid alkylated diphenylamine antioxidant |
US5750787A (en) * | 1995-09-13 | 1998-05-12 | B. F. Goodrich Company | Liquid alkylated diphenylamine antioxidant |
SG65759A1 (en) * | 1997-06-06 | 1999-06-22 | Ciba Sc Holding Ag | Nonylated diphenylamines |
-
1998
- 1998-05-21 SG SG1998001100A patent/SG65759A1/en unknown
- 1998-06-01 GB GB9811583A patent/GB2325929B/en not_active Expired - Fee Related
- 1998-06-02 RU RU98110273/04A patent/RU2198870C2/ru not_active IP Right Cessation
- 1998-06-03 CZ CZ19981716A patent/CZ294662B6/cs not_active IP Right Cessation
- 1998-06-03 DE DE19824790A patent/DE19824790B4/de not_active Expired - Fee Related
- 1998-06-04 FR FR9806996A patent/FR2764887B1/fr not_active Expired - Fee Related
- 1998-06-04 JP JP17230998A patent/JP4833387B2/ja not_active Expired - Fee Related
- 1998-06-04 ES ES009801159A patent/ES2151819B1/es not_active Expired - Lifetime
- 1998-06-04 CA CA002240971A patent/CA2240971C/en not_active Expired - Fee Related
- 1998-06-04 SK SK743-98A patent/SK285027B6/sk not_active IP Right Cessation
- 1998-06-04 TW TW087108805A patent/TW555733B/zh not_active IP Right Cessation
- 1998-06-05 IT IT98MI001274A patent/ITMI981274A1/it unknown
- 1998-06-05 NL NL1009331A patent/NL1009331C2/nl not_active IP Right Cessation
- 1998-06-05 KR KR1019980020780A patent/KR100624206B1/ko not_active IP Right Cessation
- 1998-06-05 BE BE9800425A patent/BE1013124A3/fr active
- 1998-06-05 BR BR9802365-9A patent/BR9802365A/pt not_active Application Discontinuation
- 1998-06-05 CN CNB981096557A patent/CN1135221C/zh not_active Expired - Fee Related
- 1998-06-05 ZA ZA984871A patent/ZA984871B/xx unknown
-
2000
- 2000-02-14 US US09/503,264 patent/US6315925B1/en not_active Expired - Lifetime
-
2009
- 2009-06-08 JP JP2009137187A patent/JP2009197026A/ja active Pending
-
2012
- 2012-07-27 JP JP2012167148A patent/JP5650692B2/ja not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
NL1009331A1 (nl) | 1998-12-08 |
SG65759A1 (en) | 1999-06-22 |
KR100624206B1 (ko) | 2006-12-05 |
SK285027B6 (sk) | 2006-04-06 |
CZ171698A3 (cs) | 1998-12-16 |
SK74398A3 (en) | 1999-04-13 |
JP5650692B2 (ja) | 2015-01-07 |
FR2764887A1 (fr) | 1998-12-24 |
JP2009197026A (ja) | 2009-09-03 |
BE1013124A3 (fr) | 2001-10-02 |
US6315925B1 (en) | 2001-11-13 |
JPH1112234A (ja) | 1999-01-19 |
ITMI981274A1 (it) | 1999-12-05 |
GB2325929A (en) | 1998-12-09 |
JP4833387B2 (ja) | 2011-12-07 |
GB9811583D0 (en) | 1998-07-29 |
FR2764887B1 (fr) | 2004-04-02 |
DE19824790A1 (de) | 1999-04-15 |
BR9802365A (pt) | 2000-03-28 |
JP2012197462A (ja) | 2012-10-18 |
NL1009331C2 (nl) | 2001-05-08 |
CN1201781A (zh) | 1998-12-16 |
CZ294662B6 (cs) | 2005-02-16 |
DE19824790B4 (de) | 2013-06-20 |
CA2240971C (en) | 2008-02-12 |
ZA984871B (en) | 1998-12-07 |
TW555733B (en) | 2003-10-01 |
ES2151819A1 (es) | 2001-01-01 |
CA2240971A1 (en) | 1998-12-06 |
ES2151819B1 (es) | 2001-08-16 |
RU2198870C2 (ru) | 2003-02-20 |
GB2325929B (en) | 2001-08-29 |
KR19990006677A (ko) | 1999-01-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1135221C (zh) | 壬基化二苯胺 | |
CN1938260B (zh) | 烷基化pana和dpa组合物 | |
CN101528668B (zh) | 大分子胺-酚抗氧化剂组合物、其生产技术和使用 | |
RU2134689C1 (ru) | 3-арилбензофураноны, стабилизированная композиция, способ стабилизации | |
RU2470067C2 (ru) | Жидкие композиции стиролсодержащих фенольных соединений и способы их получения | |
CN101283031A (zh) | 二芳基胺 | |
US7902280B2 (en) | Liquid styrenated phenolic compositions and processes for forming same | |
EP1364955B1 (en) | Phosphorothionates | |
KR100340920B1 (ko) | 알킬화디페닐아민및페노티아진을포함하는반응생성물및이를함유하는조성물 | |
JP4355986B2 (ja) | 液体多機能性添加剤 | |
KR100402709B1 (ko) | (벤조)트리아졸라디칼과의화합물 | |
US3773830A (en) | N-aroyl-n'-(alkylhydroxyphenyl)alkanoylhydrazines | |
RU2369596C2 (ru) | Дифениламин, алкилированный олефиновыми смесями, содержащими фракции с различной степенью активности | |
CN100387579C (zh) | 可接枝的位阻胺光稳定剂 | |
US4456541A (en) | Antioxidant diamine | |
WO2010030421A1 (en) | Anti-oxidants | |
CN100430368C (zh) | 生产烷基化二苯胺的方法 | |
GB2290083A (en) | Alkanolamine esters of acyclic phosphites | |
EP0191983A1 (en) | Dithiodialkanoamidophenol compounds and organic material stabilized therewith | |
MXPA98004486A (es) | Difenilaminas noniladas |
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 | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040121 Termination date: 20170605 |