CN114478412A - Amine compound, preparation method and application thereof, and antioxidant composition - Google Patents
Amine compound, preparation method and application thereof, and antioxidant composition Download PDFInfo
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- CN114478412A CN114478412A CN202111206736.0A CN202111206736A CN114478412A CN 114478412 A CN114478412 A CN 114478412A CN 202111206736 A CN202111206736 A CN 202111206736A CN 114478412 A CN114478412 A CN 114478412A
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- -1 Amine compound Chemical class 0.000 title claims abstract description 119
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 45
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims description 46
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 230000007797 corrosion Effects 0.000 claims abstract description 34
- 238000005260 corrosion Methods 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims description 218
- 125000000217 alkyl group Chemical group 0.000 claims description 111
- 238000006243 chemical reaction Methods 0.000 claims description 59
- 229920000642 polymer Polymers 0.000 claims description 52
- 239000010687 lubricating oil Substances 0.000 claims description 51
- 125000002947 alkylene group Chemical group 0.000 claims description 38
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 27
- 239000002199 base oil Substances 0.000 claims description 19
- 150000002978 peroxides Chemical class 0.000 claims description 16
- 239000012964 benzotriazole Substances 0.000 claims description 15
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 13
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 230000001050 lubricating effect Effects 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 150000003254 radicals Chemical class 0.000 claims description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- WJUMWVJBOZKPPU-UHFFFAOYSA-N 2,3-bis(6-methylheptyl)-N-phenylaniline Chemical compound C(CCCCC(C)C)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCC(C)C WJUMWVJBOZKPPU-UHFFFAOYSA-N 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 5
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 4
- SVMHJGGEHKZZCC-UHFFFAOYSA-N C(C)(C)(C)C=1C(=C(C=CC1)NC1=CC=CC=C1)C(C)(C)C Chemical compound C(C)(C)(C)C=1C(=C(C=CC1)NC1=CC=CC=C1)C(C)(C)C SVMHJGGEHKZZCC-UHFFFAOYSA-N 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 239000005643 Pelargonic acid Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 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
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 235000003441 saturated fatty acids Nutrition 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 42
- 238000007254 oxidation reaction Methods 0.000 abstract description 42
- 239000007795 chemical reaction product Substances 0.000 description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 26
- 150000002148 esters Chemical class 0.000 description 26
- 239000003921 oil Substances 0.000 description 17
- 235000019198 oils Nutrition 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- 229960000583 acetic acid Drugs 0.000 description 12
- 238000004821 distillation Methods 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 239000012362 glacial acetic acid Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000010705 motor oil Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000004185 ester group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- FMNZBNCPTJEVDS-KVVVOXFISA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;(z)-octadec-9-enoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O FMNZBNCPTJEVDS-KVVVOXFISA-N 0.000 description 5
- JLXMTWOURSPZDJ-UHFFFAOYSA-N 4-(6-methylheptyl)-n-[4-(6-methylheptyl)phenyl]aniline Chemical compound C1=CC(CCCCCC(C)C)=CC=C1NC1=CC=C(CCCCCC(C)C)C=C1 JLXMTWOURSPZDJ-UHFFFAOYSA-N 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000010696 ester oil Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 4
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- 239000010689 synthetic lubricating oil Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012208 gear oil Substances 0.000 description 2
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- 239000006078 metal deactivator Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004237 preparative chromatography Methods 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
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- 150000003335 secondary amines Chemical group 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
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- 238000013112 stability test Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- ZHKBLALOBMBJLL-UHFFFAOYSA-N 1-hexylperoxyhexane Chemical compound CCCCCCOOCCCCCC ZHKBLALOBMBJLL-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- NTZSDOWDFMPAKW-UHFFFAOYSA-N C=C(C=C1N=NN=C11)C(NC2=CC=CC=C2)=C1NC1=CC=CC=C1 Chemical class C=C(C=C1N=NN=C11)C(NC2=CC=CC=C2)=C1NC1=CC=CC=C1 NTZSDOWDFMPAKW-UHFFFAOYSA-N 0.000 description 1
- UNHDTFMBWASCAI-UHFFFAOYSA-N CC(C)(C)N(C(C)(C)C)C(SCSC(N(C(C)(C)C)C(C)(C)C)=S)=S Chemical compound CC(C)(C)N(C(C)(C)C)C(SCSC(N(C(C)(C)C)C(C)(C)C)=S)=S UNHDTFMBWASCAI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BBJBSNVOAFKJLG-UHFFFAOYSA-N N-(6-methylheptyl)-N-phenylnaphthalen-1-amine Chemical compound C(CCCCC(C)C)N(C1=CC=CC2=CC=CC=C12)C1=CC=CC=C1 BBJBSNVOAFKJLG-UHFFFAOYSA-N 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical compound C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 1
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- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical compound C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
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- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003513 tertiary aromatic amines Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
The invention provides an amine compound and a preparation method and application thereof. The structure of the amine compound is shown as the formula (I):
in the formula (I) at least one L is presentI、LIIOr LIIIIs a group represented by formula (III);
Description
Technical Field
The invention relates to an amine compound, in particular to an amine compound which can be used in aviation synthetic ester lubricating oil and has high-temperature oxidation and corrosion resistance.
Background
The high-temperature corrosion and oxidation stability of the aircraft engine lubricating oil are important manifestations of the high-temperature oxidation resistance of the aircraft engine oil. Lubricating oil is subjected to a series of chemical changes under the induction of high-temperature oxygen and the catalytic action of metals, so that a large amount of sediments such as oil sludge and the like are generated in engine oil, and the normal working operation of an aeroengine is seriously influenced. The improvement of the high-temperature corrosion and oxidation stability of the aircraft engine oil has important significance for improving the working efficiency and the service life of lubricating system equipment.
The high-temperature corrosion and oxidation stability of the aircraft engine oil are closely related to the structures and high-temperature properties of the base oil and the antioxidant. Therefore, the high-temperature corrosion and oxidation stability of the aircraft engine oil is effectively improved, and a high-temperature oxidation and corrosion inhibitor with excellent chemical structure and high-temperature oxidation resistance needs to be synthesized, so that the base oil is effectively protected, the generation of oxidation products is reduced, the oil solubility of the oxidation products is improved, the sediment is reduced, and the problems of oil quality deterioration and sediment of the aircraft engine lubricating oil under the high-temperature condition are effectively solved.
Four centistokes (4 mm) with a kinematic viscosity rating of four centistokes at 100 ℃ in the international famous aviation lubricant specification MIL-PRF-7808L specification2/s) the aircraft engine lubricating oil simultaneously requires good high-temperature oxidation resistance and low-temperature fluidity, thereby ensuring the rapid flight of the aircraft under high temperature, high rotating speed and high load and ensuring the rapid take-off and maneuverability of the aircraft in alpine regionsLive cruising at high speed and safe landing. The high-temperature antioxidant with excellent chemical structure and high-temperature antioxidant performance needs to be synthesized, so that the base oil can be effectively protected, the generation of oxidation products is reduced, the sediment is reduced, the deterioration and the sediment problems of the high-temperature oil of the aircraft engine oil are effectively relieved, and the high-temperature safe and stable operation of the aircraft engine is ensured. Meanwhile, the lubricating oil composition has lower kinematic viscosity and better low-temperature fluidity at low temperature, and the kinematic viscosity is less than or equal to 20000 (mm) at the temperature of-51 ℃ in accordance with the MIL-PRF-7808L specification2The index requirement of/s) is more favorable for the low-temperature lubrication service of lubricating oil and the safe and quick start and flight of the aviation aircraft in a low-temperature environment.
The oiliness agent is used for reducing friction, and is dissolved in lubricating oil to form a firm directional adsorption film on a friction surface, reduce friction and abrasion between moving parts and improve the friction performance of the lubricating oil. The oiliness agent has many kinds, and mainly comprises animal and vegetable oil, higher fatty acid, higher fatty alcohol, amine, amide, ester, sulfurized grease and the like. At present, the common oiliness agents in China comprise sulfurized cottonseed oil, fatty acid ester, benzotriazole fatty acid amine salt and the like. The benzotriazole fatty acid amine salt has the performances of oil solubility, wear resistance, oxidation resistance, corrosion resistance, rust resistance and the like, is added into natural mineral oil and lubricating oil to be used as a rust inhibitor, an antioxidant, a metal passivator, an antiwear agent, a preservative and the like, achieves good effects, can be used in gear oil, hyperbolic gear oil, wear-resistant hydraulic oil, oil film bearing oil and lubricating grease, and can also be used as a rust inhibitor and a gas phase corrosion inhibitor to be used in antirust grease.
There are patents and literatures describing a process for producing a benzotriazole derivative, which is strictly controlled in reaction conditions or difficult in separation and purification and has a low product yield.
The product produced by the prior process is a light yellow flocculent solid, has certain oil solubility, wear resistance, oxidation resistance, corrosion resistance, rust resistance and other properties, and has the defects of poor oil solubility under the low temperature condition, easy precipitation, turbid lubricating oil product, long-term standing precipitation and unfavorable oil product use performance under the low temperature condition. In addition, the flocculent solid benzotriazole fatty ammonium salt is inconvenient for blending oil products in the actual production process of the lubricating oil, and the liquid benzotriazole fatty ammonium salt has obvious advantages in this respect.
US 3,697,427 discloses the use of benzotriazole or certain alkylphenotriazoles as metal deactivators in synthetic lubricating oil compositions. US 3,790,481 discloses the use of methyl bis-benzotriazole, alkylbenzotriazole, naphthoxazole as copper passivators in polyol ester lubricating oil compositions.
US 5,076,946 discloses the use of a dimer derivative of methyl bis-alkyl benzotriazole as a metal deactivator in lubricating oils to improve the oxidation stability of the lubricating oils. US 6,743,759B2 discloses a lubricating oil antioxidant extreme pressure antiwear agent with good performance formed by compounding methylene bis-di-tert-butyl-dithiocarbamate with derivatives of alkylbenzene triazole and diphenylamine according to a certain proportion.
US 6,184,262B1 discloses that alkyl substituted methylene-dianilino-benzotriazole or alkyl benzotriazole and arylamine antioxidant complexing agent is used as a stabilizer in polyether, polyester and polyurethane foam, and has good effects of reducing stain and inhibiting coking, curing and foaming of polyol.
Disclosure of Invention
The invention provides an amine compound, a preparation method and application thereof, which comprise the following contents.
In a first aspect, the present invention provides an amine compound.
The structure of the amine compound is shown as the formula (I):
the formula (I) is an amine compound formed by bonding m structural units shown as the formula (II),
in the formula (I), m is an integer of 1 to 10, preferably 1 to 5More preferably an integer of 1 to 3; each R isIEach independently selected from H, C1～20Straight or branched chain alkyl, preferably selected from H, C1～12Straight or branched chain alkyl, more preferably selected from H, C4～12A linear or branched alkyl group; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1;
each L in the formula (I)I、LII、LIIIEach independently is H, C1～4Alkyl, and L in different structural unitsI、LII、LIIIA bonded binding end, a group represented by formula (III);
in the formula (I) at least one L is presentI、LIIOr LIIIIs a group of formula (III);
in the formula (III), R0' group is selected from C1～6Straight-chain or branched alkylene, preferably selected from C1～4Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group, more preferably located beta to the amine group; the G group is selected from H, C1～20A linear or branched alkyl group, a group of formula (IV);
in the formula (IV), each R0Each "group is independently selected from H, C1～24Straight or branched alkyl, RLThe radicals being selected from single bonds, C1～24Straight or branched chain alkylene.
According to the invention, preferably, in formula (I), L in the same structural unitI、LII、LIIIAre not bonded with each other.
According to the invention, in formula (I), when m is 1, LI、LII、LIIIOne of them is a group of formula (III) and the other two are each independently H, C1～4An alkyl group.
According to the invention, in formula (I), when m is 2, there are 2 structural units as shown in formula (II), L of the 2 structural unitsI、LII、LIII(when they are all bonded binding ends) can be bonded to one another, optionally with only one L each between 2 building blocksI、LIIOr LIIIInter-bonding, i.e. only one covalent bond is formed between 2 different building blocks.
According to the invention, in formula (I), when m is greater than 2, there are m structural units represented by formula (II), L of the m structural unitsI、LII、LIII(when they are bonded ends) and further optionally, m structural units are 1 end structural unit, (m-2) middle structural unit and 1 other end structural unit which are bonded in sequence, and only one L in each end structural unit existsI、LIIOr LIIIAnd L in the intermediate structural unit adjacent theretoI、LIIOr LIIIBonding, there being 2L in each structural unit in the middleI、LIIOr LIIIL in each of the structural units adjacent theretoI、LIIOr LIIIBonding, i.e. the formation of only one covalent bond between each two connected different building blocks.
According to the present invention, examples of the amine compound include:
the amine compound has excellent oxidation and corrosion resistance, can be used as a high-temperature antioxidant of ester-based lubricating oil, and can remarkably improve the high-temperature corrosion and oxidation resistance and stability of the ester-based lubricating oil.
In a second aspect, the present invention provides an ester compound.
The structure of the ester compound is shown as the formula (I'):
in the formula (I'), n is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R' group is independently selected from C1～10Straight-chain or branched alkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each A group is selected from the group consisting of a 1-valent group represented by the formula (II'), H, C1～20A linear or branched alkyl group, preferably selected from the group consisting of the 1-valent group represented by the formula (II'), H, C1～10A linear or branched alkyl group, more preferably selected from the group consisting of the 1-valent group represented by the formula (II'), H, C1～5A linear or branched alkyl group, and at least one A group present in formula (I ') is selected from the group consisting of 1-valent groups represented by formula (II');
the formula (II ') is a 1-valent group formed by bonding m structural units shown as the formula (III'),
in formula (II'), m is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; each R isIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3A linear or branched alkyl group; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1;
each L in the formula (II')I’、LII’、LIII' independently of each other is H, C1～4Alkyl, and L in different structural unitsI’、LII’、LIII'a bonding end bonded to the formula (I'), a 1-valent group represented by the formula (IV '), or a 1-valent group represented by the formula (V'); in the formula (II') only one L is presentI’、LII' or LIII'is a binding moiety bonded to formula (I'); in the formula (II') at least one L is presentI’、LII' or LIII'is a group represented by the formula (V');
delta in the 1-valent group represented by the formula (IV ') represents a group represented by the formula (IV') with LI’、LII' or LIII' a bonded attachment end;
in formula (IV'), n is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R' group is independently selected from C1～10Straight-chain or branched alkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group;
in the formula (V'), R0' group is selected from C1～6Straight or branched alkylene, preferably selected from C1～4Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; the G group is selected from H, C1～20A linear or branched alkyl group, a group of formula (VI');
in the formula (VI'), each R0Each "group is independently selected from H, C1～20Straight or branched alkyl, RLThe radicals being selected from single bonds, C1～24Straight or branched chain alkylene.
According to the invention, preferably, in formula (II'), L in said same structural unitI’、LII’、LIII' are not bonded to each other.
According to the invention, in formula (II'), when m ═ 1, LI’、LII’、LIIIOne of the 'is a binding end bonded to formula (I'), whichTwo of which are each independently H, C1～4Alkyl or a 1-valent group represented by the formula (V').
According to the present invention, in formula (II '), when m ═ 2, there are 2 structural units represented by formula (III'), L of the 2 structural unitsI’、LII’、LIII' (when they are both bonded binding ends) can be bonded to each other, optionally with only one L each between 2 building blocksI’、LII’、LIII' bonding to each other, i.e.only one covalent bond is formed between 2 different building blocks.
According to the invention, in formula (II '), when m is greater than 2, there are m structural units represented by formula (III'), L among the m structural unitsI’、LII’、LIII' (when they are both bonded ends) can be bonded to each other, and further optionally, the m structural units are 1 end structural unit, (m-2) middle structural unit and the other 1 end structural unit which are bonded in sequence, and only one L exists in each end structural unitI’、LII’、LIII' and L in the intermediate structural unit adjacent theretoI’、LII’、LIII' bonding, there being 2L in each structural unit in the middleI’、LII’、LIII' L in the respective structural units adjacent theretoI’、LII’、LIII' bonding, i.e.the formation of only one covalent bond between each two different building blocks connected.
According to the invention, examples which may be mentioned of the radicals of the formula (II') include:
wherein x represents the binding end bonded to formula (I').
According to the present invention, examples of the ester compound include:
in the molecular structural formulas of the ester compounds P-1, P-2 and P-3, the group DPA represents a (II ') group, and comprises a (II' -1) group, a (II '-2) group, a (II' -3) group, a (II '-4) group and a (II' -5) group, and the specific molecular structures of the groups are shown above. Taking (II' -1) as an example, the molecular structural formula of the formed ester compound is shown as follows:
the ester compound can be used as an important component of a high-temperature antioxidant of ester-based lubricating oil, can obviously improve the high-temperature corrosion-resistant antioxidant stability of the ester-based lubricating oil, can obviously improve the solubility and stability of an additive in ester base oil, obviously improves the solubility and dispersibility of consumed additive residues in the base oil, obviously reduces the generation of sediments of the ester oil in a high-temperature environment, and enables the ester lubricating oil to keep better low-temperature fluidity and low-temperature viscosity.
In a third aspect, the present invention provides an antioxidant composition.
The antioxidant composition comprises the amine compound of the first aspect and the ester compound of the second aspect.
According to the present invention, preferably, the mass ratio between the amine compound of the first aspect and the ester compound of the second aspect is 1: 1-10, more preferably 1: 3 to 8.
The antioxidant composition can obviously improve the oxidation stability, high-temperature corrosion resistance, low-temperature viscosity and low-temperature fluidity of lubricating oil (especially synthetic lubricating oil), is especially suitable for aviation synthetic lubricating oil (especially for four centistokes aviation lubricating oil), can effectively protect base oil, reduce the generation of oxidation products, reduce sediments and effectively relieve the problems of high-temperature oil deterioration and sedimentation of aviation engine oil.
In a fourth aspect, the present invention provides the use of the amine compound, the ester compound and the antioxidant composition.
The amine compound can be used as an oxidation and corrosion inhibitor and an efficient synergistic adjuvant, and can improve the high-temperature corrosion and oxidation stability of the antioxidant and the high-temperature oxidation resistance of the whole oil product.
The ester compound in the second aspect can be used as a high-temperature antioxidant for ester-based lubricating oil, can remarkably improve the high-temperature corrosion-resistant antioxidant stability of the ester-based lubricating oil, improve the solubility and stability of an additive in ester base oil, improve the solubility and dispersibility of consumed additive residues in the base oil, reduce the generation of deposits of the ester oil in a high-temperature environment, and keep better low-temperature fluidity and low-temperature viscosity of the ester lubricating oil.
The antioxidant composition of the third aspect can be used as a (ester-based lubricating oil) multi-functional high-temperature antioxidant corrosion inhibitor, can remarkably improve the high-temperature corrosion resistance and oxidation resistance stability of the ester-based lubricating oil, can remarkably improve the solubility and stability of an additive in ester base oil, remarkably improves the solubility and dispersibility of consumed additive residues in the base oil, remarkably reduces the generation of deposits of the ester oil in a high-temperature environment, and can simultaneously keep better low-temperature fluidity and low-temperature viscosity of the ester lubricating oil.
In a fourth aspect, the present invention provides a lubricating oil composition.
The lubricating oil composition comprises lubricating base oil, the amine compound, the ester compound or the antioxidant composition. The amine compound, the ester compound or the antioxidant composition in any one of the aspects accounts for 0.75-10% of the total mass of the lubricating oil composition, and preferably accounts for 1.5-7% of the total mass of the lubricating oil composition. The lubricating base oil is preferably a synthetic hydrocarbon and/or a synthetic ester. Other types of additives may also be added to the lubricating oil compositions of the present invention, such as viscosity index improvers, anti-wear agents, pour point depressants, rust inhibitors, and the like.
The lubricating oil composition is a multi-functional high-temperature antioxidant and corrosion-resistant additive with multiple effects, can obviously improve the high-temperature corrosion-resistant and oxidation-resistant stability of ester-based lubricating oil, can obviously improve the solubility and stability of the additive in ester base oil, obviously improves the solubility and dispersibility of consumed additive residues in the base oil, obviously reduces the generation of deposits of the ester oil in a high-temperature environment, and can simultaneously keep better low-temperature fluidity and low-temperature viscosity of the ester lubricating oil.
The lubricating oil composition disclosed by the invention keeps excellent low-temperature viscosity and low-temperature fluidity at-51 ℃, and can ensure that an aero-engine can safely and stably work at high temperature and can be safely and quickly started at low temperature.
In a fifth aspect, the invention provides a preparation method of an amine compound or an ester compound.
The method for producing an amine compound of the present invention comprises a step of reacting a compound represented by the formula (α), a compound represented by the formula (β), a compound represented by the formula (γ), and/or a polymer thereof;
in the formula (. alpha.), each RIEach independently selected from H, C1～20Straight or branched chain alkyl, preferably selected from H, C1～12Straight or branched chain alkyl, more preferably selected from H, C4～12A linear or branched alkyl group; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1;
in formula (. beta.), the G group is selected from H, C1～20A linear or branched alkyl group, a group represented by the formula (δ);
in the formula (. delta.), each R0Each "group is independently selected from H, C1～20Straight or branched alkyl, RLThe radicals being selected from single bonds, C1～24A linear or branched alkylene group;
in the formula (. gamma.), R0The "` group is selected from H, C1～20Straight or branched alkyl, C6～20And (4) an aryl group.
According to the preparation method of the invention, the molar ratio of the compound represented by the formula (alpha), the compound represented by the formula (beta), the compound represented by the formula (gamma) and/or the polymer thereof is preferably 1: 0.1-1.2, more preferably 1: 0.3-1; the temperature for the reaction of the compound represented by the formula (alpha), the compound represented by the formula (beta), the compound represented by the formula (gamma) and/or the polymer thereof is preferably 60-150 ℃, and more preferably 75-135 ℃; the absolute pressure at which the compound represented by the formula (. alpha.), the compound represented by the formula (. beta.), the compound represented by the formula (. gamma.) and/or the polymer thereof are reacted is not particularly limited, but is preferably 0.01 to 0.15MPa, more preferably 0.01 to 0.12 MPa.
According to the production method of the present invention, the time for the reaction of the compound represented by the formula (α), the compound represented by the formula (β), the compound represented by the formula (γ) and/or the polymer thereof is preferably as long as the reaction proceeds smoothly, and is usually preferably 3 to 12 hours, more preferably 3 to 8 hours.
According to the production method of the present invention, preferably, in the compound represented by the formula (α), one tertiary hydrogen atom is bonded to a carbon atom at the ortho position of each benzene ring to which the amine group is bonded.
According to the preparation method of the present invention, preferably, the compound represented by formula (α) may be selected from one or more of the following compounds: diphenylamine, diisooctyldiphenylamine, di-tert-butyldiphenylamine, p-isooctyldiphenylamine, p-tert-butyldiphenylamine, including but not limited to these alkyldiphenylamines.
According to the preparation method of the present invention, preferably, the compound represented by the formula (β) may be selected from one or more of the following compounds: 1,2, 3-triazole, benzotriazole, methyl benzotriazole, including but not limited to these alkyl benzotriazole, alkyl-triazole.
According to the preparation method of the present invention, preferably, the compound represented by the formula (γ) and/or the polymer thereof may be selected from one or more of the following compounds: formaldehyde, benzaldehyde, paraformaldehyde and paraformaldehyde.
According to the production method of the present invention, preferably, the compound represented by the formula (α), the compound represented by the formula (β), the compound represented by the formula (γ), and/or a polymer thereof is reacted in the presence of a peroxide. The peroxide is preferably an organic peroxide. The organic peroxide may be one or more of an alkyl peroxide, an acyl peroxide, a peroxyketal, and a peroxyorganic ester.
The alkyl peroxide has the structure: r1-O-O-R2
The structure of acyl peroxides is: (R)1)2-C-(O-O-R2)2
The structure of the peroxyketal is:
the peroxide organic ester has the structure:
wherein each R1、R2Each group is independently one or more of alkyl, aryl, alkyl substituted aryl or aryl substituted alkyl with the total number of carbon atoms between 2 and 10, preferably alkyl and/or phenyl with the total number of carbon atoms between 4 and 6, most preferably tert-butyl and/or phenyl.
According to the preparation method of the present invention, the organic peroxide is preferably one or more of tert-butyl-2-ethylperoxyhexanoate, peroxy ketal 2, 2-bis (tert-butylperoxy) butane, di-tert-butyl peroxide, dihexyl peroxide and diphenyl peroxide, and most preferably di-tert-butyl peroxide.
According to the production method of the present invention, the amount of the peroxide is preferably 0.8 to 1.5 times the amount of the compound substance represented by (α). The peroxide can be removed by thermal decomposition and distillation under reduced pressure.
According to the production method of the present invention, the reaction of the compound represented by the formula (α), the compound represented by the formula (β), the compound represented by the formula (γ) and/or the polymer thereof is preferably carried out under protection of an inert gas, preferably nitrogen.
According to the production method of the present invention, a solvent may or may not be added to the reaction of the compound represented by the formula (. alpha.), the compound represented by the formula (. beta.), the compound represented by the formula (. gamma.) and/or the polymer thereof. The solvent is preferably C6～C20Alkanes, most preferably C6～C10Alkanes, such as n-decane, n-heptane, cyclohexane.
According to the preparation method of the invention, the reaction product of the compound represented by the formula (alpha), the compound represented by the formula (beta), the compound represented by the formula (gamma) and/or the polymer thereof can be a single amine compound or a mixture of a plurality of amine compounds. These reaction products are all intended for the present invention, and the difference in the form of their existence does not affect the achievement of the effects of the present invention. Therefore, the reaction products are referred to collectively as the amine compounds without distinction in the context of the present specification. In view of this, according to the present invention, there is no absolute necessity to further purify the reaction product or to further separate the amine compound of a specific structure from the reaction product. Of course, such purification or isolation is preferable for further improvement of the intended effect of the present invention, but is not essential to the present invention. As the purification or separation method, for example, the reaction product may be purified or separated by a column chromatography method, a preparative chromatography method or the like.
According to the preparation method of the present invention, in the reaction of the compound represented by the formula (α), the compound represented by the formula (β), the compound represented by the formula (γ) and/or a polymer thereof, the reaction product may be subjected to a purification operation to increase the purity of the reaction product. Examples of the purification method include washing, recrystallization, and the like, and are not particularly limited.
According to the preparation method of the invention, preferably, a two-step method is adopted:
a first step of reacting a compound shown as a formula (alpha) in the presence of the peroxide (preferably under the protection of inert gas) to obtain an intermediate product;
and a second step of reacting the intermediate product with a compound represented by the formula (. beta.), a compound represented by the formula (. gamma.) and/or a polymer thereof, and collecting the product.
According to the production method of the present invention, in the first reaction step, the amount of the peroxide is preferably 0.8 to 1.5 times the amount of the compound represented by (α). The peroxide can be removed by thermal decomposition and distillation under reduced pressure.
According to the preparation method, the temperature of the first step reaction is preferably 60-150 ℃, and more preferably 75-135 ℃; the absolute pressure of the reaction is preferably 0.01 to 0.15MPa, more preferably 0.01 to 0.12 MPa.
According to the preparation method, in the second step of reaction, the molar ratio of the intermediate product, the compound represented by the formula (beta), the compound represented by the formula (gamma) and/or the polymer thereof is preferably 1: 0.1-1.2, more preferably 1: 0.3-1; the temperature for the intermediate product, the compound shown in the formula (beta), the compound shown in the formula (gamma) and/or the polymer thereof to react is preferably 60-150 ℃, and more preferably 75-135 ℃; the absolute pressure at which the intermediate, the compound represented by the formula (. beta.), the compound represented by the formula (. gamma.) and/or the polymer thereof are reacted is preferably 0.01 to 0.15MPa, more preferably 0.01 to 0.12 MPa.
According to the preparation method of the present invention, in the second step reaction, the time for the intermediate product, the compound represented by the formula (β), the compound represented by the formula (γ), and/or the polymer thereof to react is preferably as long as the reaction proceeds smoothly, and is usually preferably 3 to 12 hours, more preferably 3 to 8 hours as long as the reaction proceeds smoothly.
According to the preparation method of the present invention, in the second-step reaction, a catalyst, preferably an acidic catalyst, may be added. The acidic catalyst can be glacial acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, SO3And P2O5Water of one or more of these substances and mixtures thereofThe solution is preferably sulfuric acid and/or glacial acetic acid or an aqueous solution thereof, and most preferably glacial acetic acid or an acetic acid solution with the mass percent of 60-100%. The catalyst can be removed by vacuum distillation, extraction or alkali washing and water washing.
The method for producing an ester compound of the present invention comprises the step of reacting a compound represented by the formula (. alpha. '), a compound represented by the formula (. beta.'), a compound represented by the formula (. gamma. ') and/or a polymer thereof, and a compound represented by the formula (. epsilon.');
in the formula (. alpha.'), each RIEach independently selected from H, C1～20Straight or branched chain alkyl, preferably selected from H, C1～12Straight or branched chain alkyl, more preferably selected from H, C4～12A linear or branched alkyl group; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1;
in formula (. beta.'), the G group is selected from H, C1～20A linear or branched alkyl group, a group represented by the formula (δ');
in the formula (. delta.'), each R0Each "group is independently selected from H, C1～24Straight or branched alkyl, RLThe radicals being selected from single bonds, C1～24A linear or branched alkylene group;
in the formula (. gamma.'), R0The "` group is selected from H, C1～20Straight or branched alkyl, C6～20An aryl group;
in the formula (ε'), n is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R' group is independently selected from C1～10Straight-chain or branched alkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～4A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10Straight or branched chain alkyl.
According to the preparation process of the present invention, the compound represented by the formula (. epsilon.') is preferably selected from C1～18With C3～20Esterification products of fatty acids, said C1～18The polyhydric alcohol of (A) comprises one or more of trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol, and C3～20The fatty acid of (a) includes one or more of valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, isooctanoic acid, 2-ethylhexanoic acid, pelargonic acid, 3,5, 5-trimethylhexanoic acid, capric acid, lauric acid, palmitic acid, and oleic acid. The compound represented by the formula (ε') is more preferably one or more of trimethylolpropane, pentaerythritol and dipentaerythritol, and C3～20Further preferably an esterification product of a saturated fatty acid having a kinematic viscosity of (3-9) mm at 100 DEG C2One or more of trimethylolpropane ester, pentaerythritol ester and dipentaerythritol ester per second, most preferably with a kinematic viscosity of 3.6-4.3 mm at 100 DEG C2Saturated polyol ester per second.
According to the production method of the present invention, the molar ratio between the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or a polymer thereof, and the compound represented by the formula (. epsilon.') is preferably 1: 0.1-1.2: 0.1-1.2: 0.1 to 1.2, more preferably 1: 0.3-1: 0.3-1: 0.3 to 1; the temperature at which the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or the polymer thereof, and the compound represented by the formula (. epsilon.') are reacted is preferably 50 to 190 ℃, more preferably 60 to 180 ℃; the absolute pressure at which the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or the polymer thereof, and the compound represented by the formula (. epsilon.') are reacted is not particularly limited, but is preferably 0.01 to 0.12MPa, more preferably 0.01 to 0.10 MPa.
According to the production method of the present invention, a catalyst, preferably an acidic catalyst, may be added to the reaction of the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or a polymer thereof, and the compound represented by the formula (. epsilon.'), or the polymer thereof. The acidic catalyst can be glacial acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, SO3And P2O5Preferably sulfuric acid and/or glacial acetic acid or an aqueous solution thereof, most preferably glacial acetic acid or an acetic acid solution with a mass percentage of 60% to 100%. The catalyst can be removed by vacuum distillation, extraction or alkali washing and water washing.
According to the production method of the present invention, the time for the reaction of the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or the polymer thereof, and the compound represented by the formula (. epsilon.') is preferably as long as the reaction proceeds smoothly, and is preferably 3 to 12 hours, more preferably 3 to 9 hours.
According to the production method of the present invention, preferably, in the compound represented by the formula (. alpha.'), at least one carbon atom in the ortho-position of each benzene ring to which the amine group is attached contains a tertiary hydrogen atom.
According to the preparation method of the present invention, preferably, the compound represented by the formula (α') may be selected from one or more of the following compounds: diisooctyldiphenylamine, di-tert-butyldiphenylamine, p-isooctyl, p-tert-butyldiphenylamine, dinonyldiphenylamine and diphenylamine.
According to the preparation method of the present invention, preferably, the compound represented by the formula (β') may be selected from one or more of the following compounds: 1,2, 3-triazole, benzotriazole, methyl benzotriazole, including but not limited to these alkyl benzotriazole, alkyl-triazole.
According to the preparation method of the present invention, preferably, the compound represented by the formula (γ') and/or the polymer thereof may be selected from one or more of the following compounds: formaldehyde, paraformaldehyde, benzaldehyde.
According to the production method of the present invention, examples of the compound represented by the formula (. epsilon.') (wherein each group is as defined in any of the above aspects) include one or more of the following compounds:
according to the production method of the present invention, preferably, the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or a polymer thereof, and the compound represented by the formula (. epsilon.') are reacted in the presence of a peroxide. The peroxide is as described above.
According to the production method of the present invention, the amount of the peroxide is preferably 0.8 to 1.5 times the amount of the compound represented by the formula (. alpha.').
According to the production method of the present invention, the reaction of the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or a polymer thereof, and the compound represented by the formula (. epsilon.') is preferably carried out under an inert gas, preferably nitrogen.
According to the production method of the present invention, a solvent may or may not be added to the reaction of the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or the polymer thereof, and the compound represented by the formula (. epsilon.'). The solvent is preferably C6～C20Alkanes, most preferably C6～C10Alkanes, such as n-decane, n-heptane, cyclohexane.
According to the production method of the present invention, the reaction product of the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or a polymer thereof, and the compound represented by the formula (. epsilon.') may be a single ester compound or a mixture of a plurality of ester compounds, which are all contemplated by the present invention, and the presence thereof in different forms does not impair the achievement of the effect of the present invention. Therefore, the reaction products are referred to collectively as the ester compounds without distinction in the context of the present specification. In view of this, according to the present invention, there is no absolute necessity to further purify the reaction product or to further separate an ester compound of a specific structure from the reaction product. Of course, such purification or isolation is preferable for further improvement of the intended effect of the present invention, but is not essential to the present invention. As the purification or separation method, for example, the reaction product may be purified or separated by a column chromatography method, a preparative chromatography method or the like.
According to the preparation method of the present invention, the reaction product of the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or the polymer thereof, and the compound represented by the formula (. epsilon.') may be a mixture of one or more ester compounds and the amine compound as described in the first aspect, which is the antioxidant composition as described in the third aspect of the present invention.
According to the production method of the present invention, when the reaction product of the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or a polymer thereof, the compound represented by the formula (. epsilon.') is a mixture of one or more ester compounds and the amine compound described in the first aspect, the amine compound can be separated therefrom; the amine compound may be used as it is as the antioxidant composition of the present invention without separating it out.
According to the production method of the present invention, the reaction product of the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or a polymer thereof,. epsilon.') and the compound represented by the formula (. epsilon. '), may be a mixture of one or more ester compounds with the amine compound described in the first aspect and the compound represented by the formula (. epsilon.'). The reaction product may contain a compound represented by the formula (. epsilon. '), i.e., an unreacted compound represented by the formula (. epsilon.').
According to the production method of the present invention, when the reaction product of the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or a polymer thereof, the compound represented by the formula (. epsilon.'), and the compound represented by the formula (. epsilon. ') is a mixture of one or more ester compounds with the amine compound described in the first aspect and the compound represented by the formula (. epsilon.'); it is also possible to use the compound of the formula (. epsilon. ') as an additional component without isolating the compound of the formula (. epsilon.'). Since the compound represented by the formula (. epsilon.') can be used as a lubricating base oil or an antiwear agent, a friction modifier, by itself, it can be used as an additional component.
According to the production method of the present invention, in the reaction of the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or a polymer thereof, and the compound represented by the formula (. epsilon.'), the reaction product may be subjected to a purification operation to increase the purity of the reaction product. Examples of the purification method include washing, recrystallization, and the like, and are not particularly limited.
According to the preparation method of the invention, preferably, a two-step method is adopted:
a first step of reacting a compound represented by the formula (. alpha. ') with a compound represented by the formula (. epsilon.') in the presence of a peroxide (preferably in the presence of an inert gas) to obtain an intermediate;
in the second step, the intermediate product is reacted with the compound represented by the formula (. beta. '), the compound represented by the formula (. gamma.'), and/or a polymer thereof, and the product is collected.
According to the production method of the present invention, in the first-step reaction, the molar ratio between the compound represented by the formula (. alpha. ') and the compound represented by the formula (. epsilon.') is preferably 1:0.1 to 1.2, more preferably 1:0.3 to 1; the amount of the peroxide is preferably 0.8 to 1.5 times the amount of the compound represented by the formula (. alpha.').
According to the preparation method, the temperature of the first step reaction is preferably 50-190 ℃, and more preferably 60-180 ℃; the absolute pressure of the reaction is preferably 0.01 to 0.12MPa, more preferably 0.01 to 0.10 MPa; the reaction time is preferably such that the chemical reaction proceeds smoothly, and usually the reaction time is preferably 2 to 8 hours, more preferably 3 to 6 hours.
According to the production method of the present invention, in the second-step reaction, the molar ratio between the intermediate product, the compound represented by the formula (β '), the compound represented by the formula (γ'), and/or the polymer thereof is preferably 1: 0.1-1.2: 0.1 to 1.2, more preferably 1: 0.3-1: 0.3 to 1; the temperature for the reaction of the intermediate product, the compound represented by the formula (beta '), the compound represented by the formula (gamma'), and/or the polymer thereof is preferably 50 to 190 ℃, and more preferably 60 to 180 ℃; the absolute pressure at which the intermediate, the compound represented by the formula (. beta. '), the compound represented by the formula (. gamma.'), and/or the polymer thereof are reacted is preferably 0.01 to 0.12MPa, more preferably 0.01 to 0.10 MPa; the reaction time of the intermediate product, the compound represented by the formula (β '), the compound represented by the formula (γ'), and/or the polymer thereof is preferably as long as the reaction proceeds smoothly, and is usually preferably 3 to 12 hours, more preferably 3 to 9 hours.
In a seventh aspect, the present invention also provides a method for improving oxidation and corrosion resistance of a lubricating oil composition, which comprises adding the amine compound, the ester compound or the antioxidant composition of any one of the preceding aspects to a lubricating base oil.
Drawings
FIG. 1 is a superimposed IR spectrum of the multifunctional agent B1 and the reaction product A1, wherein the upper spectrum is the IR spectrum of the multifunctional agent B1 and the lower spectrum is the IR spectrum of the reaction product A1.
Detailed Description
In the context of the present specification, the expression "number + valence + group" or the like refers to a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring, a combination thereof, or the like) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure. For example, "3-valent straight or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight or branched alkane (i.e., the base chain to which the straight or branched alkyl corresponds), and "2-valent straight or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom).
The percentages and ratios mentioned below are percentages by mass or ratios by mass unless otherwise stated.
The raw materials used were as follows:
antirust agent 5-methyl benzotriazole, Shanghai chemical plant, chemical purity
Antioxidant T534, antioxidant alkyldiphenylamine, Kyopu, institute of petrochemical technology
Antioxidant T501, 2, 6-di-tert-butyl-4-methylphenol, Liyunnangning chemical Co., Ltd
Antioxidant T558, dinonyldiphenylamine, Liaoning Tianhe Fine chemical Co., Ltd
Antioxidant T531, N-phenyl-1-naphthylamine, Tianjin City Maofeng chemical Co., Ltd
VANLUBEV81, 4, 4' -diisooctyl diphenylamine, Van der Bill Ltd
Saturated fatty acid ester of trimethylolpropane in a viscosity of 3.8mm at 100 deg.C2(s), Shaandong Rijie chemical Co., Ltd.,>98％
pentaerythritol ester, Zhejiang Quzhou chemical Co., Ltd., kinematic viscosity at 100 ℃ of 5.02mm2/s，>98％
Heptalis dipentaerythritol ester, shariki chemical limited of Shandong, kinematic viscosity at 100 ═ 7mm2/s，>98％
Trimethylolpropane oleate, Shanto Ruijie chemical Co., Ltd., kinematic viscosity at 100 ℃ of 8.5mm2/s，>97％
Penricus trimethylolpropane ester, Chongqing Brand of China petrochemical great wall lubricating oil, great wall 5101 high temperature synthetic lubricating oil with kinematic viscosity of 5.05mm at 100 ℃2/s，>98％
Di-tert-butyl peroxide, Jiangsu Qiangsheng functional Chemicals GmbH, chemically pure.
Paraformaldehyde, Zhenjiang Lizhong comprehensive chemical industry Co., Ltd., the mass percentage is 98%.
Example 1
78g of 4, 4' -diisooctyl-diphenylamine are added to 78g of trimethylolpropane saturated fatty acid ester, the kinematic viscosity at 100 ℃ being 3.8mm2Heating, stirring and dissolving the mixed system in a nitrogen environment, maintaining the mixed system at 145 ℃, and adding 56g of initiator di-tert-butyl peroxide into the reaction system; carrying out reaction at 145 ℃ for 4h, and carrying out reduced pressure distillation on the mixed reaction system at 160 ℃ and under the vacuum degree of less than 500Pa for 180mins to obtain 152g of a reaction product A1;
adding 26g of reaction raw material 5-methylbenzotriazole into 152g of reaction product A1, heating and dissolving to form a mixed solution, adding 9g of paraformaldehyde condensing agent into the mixed solution, adding 16g of glacial acetic acid into a reaction system at the temperature of 100 ℃, reacting for 6 hours, and carrying out full reduced pressure distillation on the mixed reaction system at the temperature of 110 ℃ and the vacuum degree of less than 500Pa for 120mins to obtain 206g of transparent bright orange liquid reaction product B1; the reaction product B1 mainly contains the compounds of the structural formulas P-1, P-2 and P-3, and also contains a small amount of the compounds of the structural formulas (P-MBZT-1, P-MBZT-2 and P-MBZT-3) and a small amount of trimethylolpropane saturated fatty acid ester in the example.
The reaction product A1 and the multifunctional agent B1 are respectively subjected to infrared analysis and characterization, and superposed spectrograms of the reaction product A1 and the multifunctional agent B1 are shown in figure 1, wherein the upper spectrogram is an infrared spectrogram of the multifunctional agent B1, and the lower spectrogram is an infrared spectrogram of the reaction product A1.
In the spectrum of the reaction product A1, 1606cm in it-1(1616±8)、1511cm-1(1510±8)、1467cm-1Is nu on benzene ringC＝CCharacteristic absorption peak of (8), 3036.3cm-1Is nu on benzene ring＝C-HCharacteristic absorption peaks, and the existence of benzene rings in the generated product can be judged according to the characteristic absorption peaks; 731.63cm-1Is a typical characteristic absorption peak of out-of-plane deformation vibration of C-H on an aromatic ring when the benzene ring is substituted at the ortho position; 1159.92cm-1(1225～1175)、1104.92cm-1(1125～1090)、1019.00cm-1(1070～1000) Absorption peak beta is the characteristic absorption peak beta of the typical asymmetric trisubstituted out-of-plane deformation vibration on a benzene ringC＝C-H；826cm-1(860～800,2H)、871.29cm-1(860 to 900,1H) is benzene ring asymmetric trisubstituted gammaC＝CHCharacteristic absorption peak of (a);
in an infrared spectrogram of the reaction product B1, no strong absorption peak bands appear at 3450-3430 and 3406-3300, and no aromatic secondary amine N-H bond exists in the product compound, which indicates that the product compound does not contain diisooctyl diphenylamine molecules; it also shows that the condensation reaction of the secondary amine group on the alkyl diphenylamine oligomer molecule and the secondary amine group on the benzotriazole molecule occurs through the formaldehyde molecule. At 2855-2200 cm-1Very broad v with (weak) no N-H bondsN-HA telescopic vibration absorption peak band; the product compound does not contain 5-methylbenzotriazole molecules; 1365cm-1、1322.9cm-1The tertiary aromatic amine C-N is in the range of 1360-1310 cm-1Emerging vC-NStretching the shock absorption peak. 1250.4cm-1、1236.1cm-1、1192.08cm-1Is alkyl C-N (1250-1180) cm-1The stretching vibration absorption peak of (2). Furthermore, at 1105cm-1No strong stretching vibration absorption peak appears at the position, which shows that the product compound has no ether compound paraformaldehyde, and can show that all three reaction raw materials of diisooctyl diphenylamine, 5-methylbenzotriazole and paraformaldehyde participate in polycondensation reaction to generate the target product of the invention.
Example 2
155g of raw material 4, 4' -diisooctyl-diphenylamine is added to 150g of 5.02mm kinematic viscosity at 100 DEG C2In the mixed polyol saturated acid ester of/s (wherein the mass ratio of the trimethylolpropane ester to the dipentaerythritol ester is 3:1), heating, stirring and dissolving a mixed system in a nitrogen environment, maintaining the mixed system at 140 ℃, and adding 44g of a reaction initiator, namely di-tert-butyl peroxide into the reaction system; carrying out reaction at 140 ℃ for 3h, and carrying out full reduced pressure distillation on the mixed reaction system at 160 ℃ and under the vacuum degree of less than 500Pa for 180mins to obtain 310g of a reaction product A2;
adding 50g of reaction raw material 5-methylbenzotriazole into 310g of reaction product A2, heating and dissolving to form a mixed solution, adding 9g of paraformaldehyde condensing agent into the mixed solution, adding 16g of glacial acetic acid into a reaction system at the temperature of 100 ℃, reacting for 6 hours, and carrying out full reduced pressure distillation on the mixed reaction system at the temperature of 110 ℃ and the vacuum degree of less than 500Pa for 120mins to obtain 350g of transparent bright orange liquid reaction product B2; the reaction product B2 mainly contains compounds with similar structures to those of the structural formula P-1, the structural formula P-2 and the structural formula P-3 (except that the ester group is the ester group of the mixed polyol saturated fatty acid ester used in the embodiment), and also contains a small amount of the compounds of the structural formula (P-MBZT-1), the structural formula (P-MBZT-2) and the structural formula (P-MBZT-3), and a small amount of the mixed polyol saturated acid ester in the embodiment.
Example 3
80g of raw material 4, 4' -diisooctyl-diphenylamine is added into 80g of mixture with the kinematic viscosity of 7.5mm at 100 DEG C2In dipentaerythritol ester/s, heating, stirring and dissolving a mixed system in a nitrogen environment, maintaining the mixed system at 140 ℃, and adding 80g of a reaction initiator di-tert-butyl peroxide into the reaction system; carrying out reaction at 140 ℃ for 3h, and carrying out full reduced pressure distillation on the mixed reaction system at 160 ℃ and under the vacuum degree of less than 500Pa for 180mins to obtain 156g of a reaction product A3;
adding 85g of reaction raw material 5-methylbenzotriazole into 156g of reaction product A3, heating and dissolving to form a mixed solution, adding 9g of paraformaldehyde condensing agent into the mixed solution, adding 32g of glacial acetic acid into a reaction system at the temperature of 100 ℃, reacting for 6 hours, and carrying out full reduced pressure distillation on the mixed reaction system at the temperature of 110 ℃ and the vacuum degree of less than 500Pa for 120mins to obtain 26g of transparent bright orange liquid reaction product B3; the reaction product B3 mainly contained compounds having a structure similar to that of the structural formula P-1, P-2 or P-3 (except that the ester group was the ester group of dipentaerythritol ester used in this example), and also contained smaller amounts of the compounds of the structural formula (P-MBZT-1), the structural formula (P-MBZT-2) or the structural formula (P-MBZT-3), and a smaller amount of dipentaerythritol ester in this example.
Example 4
100g of raw material 4, 4' -diisooctyl-diphenylamine is added into 100g of raw material with the kinematic viscosity of 8.5mm at 100 DEG C2Heating, stirring and dissolving a mixed system in trimethylolpropane oleate in a nitrogen environment, maintaining the mixed system at 140 ℃, and adding 70g of a reaction initiator, namely di-tert-butyl peroxide into the reaction system; carrying out reaction at 140 ℃ for 4h, carrying out reduced pressure distillation on the mixed reaction system at 160 ℃ and under the vacuum degree of less than 500Pa for 60mins, and continuously carrying out full reduced pressure distillation at 180 ℃ or less and under the vacuum degree of less than 500Pa for 30 mins-180 mins to obtain 188g of a reaction product A4;
adding 120g of reaction raw material 5-methylbenzotriazole into 156g of reaction product A4, heating and dissolving to form a mixed solution, adding 15g of paraformaldehyde condensing agent into the mixed solution, adding 45g of glacial acetic acid into a reaction system at the temperature of 100 ℃, reacting for 6 hours, and carrying out full reduced pressure distillation on the mixed reaction system at the temperature of 110 ℃ and the vacuum degree of less than 500Pa for 120mins to obtain 326g of transparent bright orange liquid reaction product B4; reaction product B4 contained a compound having a structure similar to that of structural formula P-1, structural formula P-2, structural formula P-3 (except that the ester group was the ester group of trimethylolpropane oleate used in this example), as well as compounds of structural formula (P-MBZT-1), structural formula (P-MBZT-2), structural formula (P-MBZT-3), and a small amount of trimethylolpropane oleate in this example.
Comparative antioxidant
Commonly used antioxidants, namely diisooctyl diphenylamine (V81), N-isooctylphenyl-1-naphthylamine (L06), N-phenyl-1-naphthylamine and diphenylamine, are compounded with methylbenzotriazole respectively to form a binary compound which is used as a contrast antioxidant.
Evaluation of high temperature Corrosion resistance and Oxidation stability
The reaction product of the present invention or the comparative antioxidant and tricresyl phosphate (TCP) were added to the lubricating base oil of the tetra centis polyol saturated ester, respectively, and heated and stirred to prepare examples 5 to 8 and comparative examples 1 to 4 of the lubricating oil composition, in which the mass percentage of tricresyl phosphate was 1%, and the formulation ratios thereof are shown in table 1.
TABLE 1 lubricating oil compositions examples 5-8 and comparative examples 1-4
The kinematic viscosity at-51 ℃ of all four centistokes lubricating oil compositions corresponding to all examples 5-8 and comparative examples 1-4 in table 1 is measured, and high-temperature corrosion and oxidation stability tests are carried out on all four centistokes lubricating oil compositions in table 1 to evaluate the high-temperature oxidation resistance and the high-temperature deposition resistance, the adopted evaluation method is ASTM D4636 corrosion and oxidation stability determination method specified in 4 centistokes aviation lubricating oil high-temperature corrosion and oxidation stability evaluation in MIL-PRF-7808L specification, and the test conditions are as follows: the temperature is 220 ℃, the time is 40h, the air flow is 50mL/min, and the usage amount of the oil sample is 100 mL.
The evaluation indexes of the method are as follows: the change of total acid value (delta TAN/mgKOH. g) before and after oil sample oxidation-1) (ii) a Viscosity change at 40 ℃ (Δ Viscosity%); 100mL test oil sample Deposit formation (Deposit/mg (100mL)-1) (ii) a The mass per unit area of the metal test piece such as copper, steel, silver, aluminum, titanium and the like. The experimental results are illustrated herein in terms of the mass change data of the copper sheet.
The evaluation data of the high temperature corrosion and oxidation stability tests of all the above-mentioned lubricating oil compositions in terms of viscosity at-51 ℃ and kinematic viscosity at low temperature are shown in tables 2 and 3.
TABLE 2 evaluation test results of high temperature corrosion and oxidation stability
Comparing the MIL-PRF-7808L specification index requirements with the results of the corrosion and oxidation stability evaluation data in tables 2 and 3, it can be seen that the lubricating oil compositions of examples 5-8, to which the ester compounds of the present invention are added, of 4 centistokes grade have significant advantages over the lubricating oil compositions of comparative examples in terms of the change in sheet metal mass, the change in total acid value, the change in viscosity, and the amount of deposit formation before and after oxidation, and the high temperature oxidation resistance of examples 5-7 is significantly superior to that of comparative examples 1-4. The ester compound can better control the change of the total acid value of the oil product, the change rate of viscosity and the sedimentation before and after the oxidation of the lubricating oilThe product formation amount well meets the requirements of MIL-PRF-7808L index corrosion and oxidation stability index. The data of example 7 show that the antioxidant synthesized from the base oil of saturated acid ester of heptacentistokes dipentaerythritol also has good high-temperature oxidation resistance and deposit formation resistance, but the kinematic viscosity of the 4 centistokes lubricating oil composition prepared from the antioxidant at-51 ℃ is more than or equal to 25000 (mm)2S) not conforming to MIL-PRF-7808L, and has a kinematic viscosity of 20000 (mm) or less at-51 deg.C2Pers), example 8 adopts trimethylolpropane oleate during synthesis, and the corrosion and oxidation stability of the product still meets the requirements of MIL-PRF-7808L, but the kinematic viscosity at-51 ℃ is more than or equal to 25000 (mm)2S) does not conform to MIL-PRF-7808L, and the kinematic viscosity at-51 ℃ is less than or equal to 20000 (mm)2S) requirements.
TABLE 3 evaluation test results of high temperature corrosion and oxidation stability
The 4 centistokes lubricating oil composition prepared by blending the ester compound of the invention has better high-temperature oxidation resistance and sediment formation resistance, and is obviously superior to the monomer arylamine antioxidant. Meanwhile, the low-temperature-resistant high-temperature-resistant rubber has smaller kinematic viscosity at low temperature and better low-temperature fluidity, and the kinematic viscosity is less than or equal to 20000 (mm) at the temperature of-51 ℃ in accordance with the specification of MIL-PRF-7808L2The index requirement of/s) is more favorable for the low-temperature lubricating property of the lubricating oil and the low-temperature quick start of the engine.
Claims (28)
1. The structure of the amine compound is shown as the formula (I):
the formula (I) is an amine compound formed by bonding m structural units shown as the formula (II),
in the formula (I), m is an integer between 1 and 10, preferably an integer between 1 and 5, and more preferably an integer between 1 and 3; each R isIEach independently selected from H, C1～20Straight or branched chain alkyl, preferably selected from H, C1～12Straight or branched chain alkyl, more preferably selected from H, C4～12A linear or branched alkyl group; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1;
each L in the formula (I)I、LII、LIIIEach independently is H, C1～4Alkyl, and L in different structural unitsI、LII、LIIIA bonded binding end, a group represented by formula (III);
in the formula (I) at least one L is presentI、LIIOr LIIIIs a group represented by formula (III);
in the formula (III), R0' group is selected from C1～6Straight-chain or branched alkylene, preferably selected from C1～4Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group, more preferably located beta to the amine group; the G group is selected from H, C1～20A linear or branched alkyl group, a group of formula (IV);
in the formula (IV), each R0Each "group is independently selected from H, C1～24Straight or branched alkyl, RLThe radicals being selected from single bonds, C1～24Straight or branched chain alkylene.
2. The amine compound according to claim 1,
in formula (I), when m is 1, LI、LII、LIIIOne of them is a group of formula (III) and the other two are each independently H, C1～4An alkyl group;
in formula (I), when m is 2, there are 2 structural units represented by formula (II), and only one L exists between each of the 2 structural unitsI、LIIOr LIIIBonding with each other;
in formula (I), when m is greater than 2, m structural units shown in formula (II) exist, m structural units are 1 end structural unit, (m-2) middle structural unit and the other 1 end structural unit which are sequentially bonded, and only one L exists in each end structural unitI、LIIOr LIIIAnd L in the intermediate structural unit adjacent theretoI、LIIOr LIIIBonding, there being 2L in each structural unit in the middleI、LIIOr LIIIL in the structural units adjacent to each otherI、LIIOr LIIIAnd (4) bonding.
3. The amine compound of claim 1, wherein the amine compound comprises:
4. the structure of the ester compound is shown as the formula (I'):
in the formula (I'), n is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight or branched chainHeteroalkyl, preferably selected from n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R' group is independently selected from C1～10Straight-chain or branched alkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each A group is selected from the group consisting of a 1-valent group represented by the formula (II'), H, C1～20A linear or branched alkyl group, preferably selected from the group consisting of the 1-valent group represented by the formula (II'), H, C1～10A linear or branched alkyl group, more preferably selected from the group consisting of the 1-valent group represented by the formula (II'), H, C1～5A linear or branched alkyl group, and at least one A group present in formula (I ') is selected from the group consisting of 1-valent groups represented by formula (II');
the formula (II ') is a 1-valent group formed by bonding m structural units shown as the formula (III'),
in formula (II'), m is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; each R isIEach independently selected from H, C1～10Straight or branched chain alkyl, preferably selected from H, C1～5Straight or branched chain alkyl, more preferably selected from H, C1～3Straight or branched chain alkanesA group; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1;
each L in the formula (II')I’、LII’、LIII' independently of each other is H, C1～4Alkyl, and L in different structural unitsI’、LII’、LIII'a bonding end bonded to the formula (I'), a 1-valent group represented by the formula (IV '), or a 1-valent group represented by the formula (V'); in the formula (II') only one L is presentI’、LII' or LIII'is a binding moiety bonded to formula (I'); in the formula (II') at least one L is presentI’、LII' or LIII'is a group represented by the formula (V');
delta in the 1-valent group represented by the formula (IV ') represents a group represented by the formula (IV') with LI’、LII' or LIII' a bonded attachment end;
in formula (IV'), n is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight or branched heteroalkyl, preferably selected from the group consisting of n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R' group is independently selected from C1～10Straight-chain or branched alkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight chain orBranched alkyl, more preferably selected from C1～10A linear or branched alkyl group;
in the formula (V'), R0' group is selected from C1～6Straight-chain or branched alkylene, preferably selected from C1～4Straight or branched alkylene, more preferably selected from C1～3A linear or branched alkylene group; the G group is selected from H, C1～20A linear or branched alkyl group, a group of formula (VI');
in the formula (VI'), each R0Each "group is independently selected from H, C1～20Straight or branched alkyl, RLThe radicals being selected from single bonds, C1～24Straight or branched chain alkylene.
5. An ester compound according to claim 4,
in formula (II'), when m is 1, LI’、LII’、LIIIOne of which is a binding end bonded to formula (I'), and the other two are each independently H, C1～4Alkyl or a 1-valent group represented by the formula (V');
in formula (II '), when m is 2, there are 2 structural units represented by formula (III'), and only one L exists between each of the 2 structural unitsI’、LII’、LIII' mutual bonding, i.e. the formation of only one covalent bond between 2 different building blocks;
in the formula (II '), when m is greater than 2, m structural units represented by the formula (III') exist, the m structural units are 1 end structural unit, (m-2) middle structural unit and the other 1 end structural unit which are bonded in sequence, and only one L exists in each end structural unitI’、LII’、LIII' and L in the intermediate structural unit adjacent theretoI’、LII’、LIII' bonding, there being 2L in each structural unit in the middleI’、LII’、LIII' L in the respective structural units adjacent theretoI’、LII’、LIII' bonding.
6. An ester compound according to claim 4, wherein the group represented by the formula (II') comprises:
wherein x represents the binding end bonded to formula (I').
7. An ester compound according to claim 4, wherein the ester compound comprises:
wherein the group DPA represents a group of formula (II').
8. An antioxidant composition comprising the amine compound according to any one of claims 1 to 3 and the ester compound according to any one of claims 4 to 7.
9. The antioxidant composition as claimed in claim 8, wherein the mass ratio between said amine compound and said ester compound is 1: 1 to 10.
10. Use of the amine compound according to any one of claims 1 to 3 as an antioxidant and corrosion inhibitor or a highly effective synergistic adjuvant.
11. Use of the ester compound according to any one of claims 4 to 7 as a high temperature antioxidant.
12. Use of the antioxidant composition of claim 8 or 9 as a multi-functional, high temperature, antioxidant, corrosion inhibitor.
13. A lubricating oil composition comprising a lubricating base oil, the amine compound according to any one of claims 1 to 3 or the ester compound according to any one of claims 4 to 7, or the antioxidant composition according to claim 8 or 9.
14. A process for producing an amine compound, which comprises the step of reacting a compound represented by the formula (α), a compound represented by the formula (β), a compound represented by the formula (γ) and/or a polymer thereof;
in the formula (. alpha.), each RIEach independently selected from H, C1～20Straight or branched chain alkyl, preferably selected from H, C1～12Straight or branched chain alkyl, more preferably selected from H, C4～12A linear or branched alkyl group; each x is independently selected from an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1;
in formula (. beta.), the G group is selected from H, C1～20A linear or branched alkyl group, a group represented by the formula (δ);
in the formula (. delta.), each R0Each "group is independently selected from H, C1～20Straight or branched alkyl, RLThe radicals being selected from single bonds, C1～24A linear or branched alkylene group;
in the formula (. gamma.), R0The "` group is selected from H, C1～20Straight or branched alkyl, C6～20And (4) an aryl group.
15. The production method according to claim 14, characterized in that the molar ratio between the compound represented by the formula (α), the compound represented by the formula (β), the compound represented by the formula (γ) and/or a polymer thereof is preferably 1:0.1 to 1.2; the temperature for the reaction of the compound represented by the formula (alpha), the compound represented by the formula (beta), the compound represented by the formula (gamma) and/or the polymer thereof is 60-150 ℃.
16. The production method according to claim 14, characterized in that, in the compound represented by the formula (α), a tertiary hydrogen atom is bonded to a carbon atom at the ortho position of each benzene ring to which the amine group is bonded.
17. The process according to claim 14, wherein the compound represented by the formula (α) is one or more selected from the group consisting of: diphenylamine, diisooctyldiphenylamine, di-tert-butyldiphenylamine, p-isooctyl, p-tert-butyldiphenylamine; the compound represented by the formula (β) is selected from one or more of the following compounds: 1,2, 3-triazole, benzotriazole, methyl benzotriazole; the compound represented by the formula (gamma) and/or the polymer thereof is selected from one or more of the following compounds: formaldehyde, benzaldehyde, paraformaldehyde and paraformaldehyde.
18. The process according to claim 14, wherein the compound of formula (α), the compound of formula (β), the compound of formula (γ) and/or the polymer thereof is reacted in the presence of a peroxide, preferably an organic peroxide.
19. The process according to claim 14, wherein the reaction of the compound of formula (α), the compound of formula (β), the compound of formula (γ) and/or the polymer thereof is preferably carried out under an inert gas atmosphere.
20. The method of claim 14, wherein the method comprises a two-step process:
a first step of reacting a compound shown as a formula (alpha) in the presence of the peroxide (preferably under the protection of inert gas) to obtain an intermediate product;
and a second step of reacting the intermediate product with a compound represented by the formula (. beta.), a compound represented by the formula (. gamma.) and/or a polymer thereof, and collecting the product.
21. A method for producing an ester compound, comprising the step of reacting a compound represented by the formula (. alpha. '), a compound represented by the formula (. beta.'), a compound represented by the formula (. gamma. ') and/or a polymer thereof, and a compound represented by the formula (. epsilon.');
in the formula (. alpha.'), each RIEach independently selected from H, C1～20Straight or branched chain alkyl, preferably selected from H, C1～12Straight or branched chain alkyl, more preferably selected from H, C4～12A linear or branched alkyl group; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1;
in formula (. beta.'), the G group is selected from H, C1～20A linear or branched alkyl group, a group represented by the formula (δ');
in the formula (. delta.'), each R0Each "group is independently selected from H, C1～24Straight or branched alkyl, RLThe radicals being selected from single bonds, C1～24A linear or branched alkylene group;
in the formula (. gamma.'), R0The "` group is selected from H, C1～20Straight chainOr branched alkyl, C6～20An aryl group;
in the formula (ε'), n is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; r0Selected from the group consisting of n-valent C1～30Straight or branched alkyl, C2～30Straight-chain or branched heteroalkyl, preferably selected from the group consisting of n-valent C1～20Straight or branched alkyl, C2～20A linear or branched heteroalkyl radical, more preferably selected from the group consisting of n-valent C1～10Straight or branched alkyl, C2～10A linear or branched heteroalkyl group; each R' group is independently selected from C1～10Straight-chain or branched alkylene, preferably selected from C1～5Straight or branched alkylene, more preferably selected from C1～4A linear or branched alkylene group; each R' group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10A linear or branched alkyl group; each R' "group is independently selected from C1～30Straight or branched alkyl, preferably selected from C1～20Straight or branched alkyl, more preferably selected from C1～10Straight or branched chain alkyl.
22. The process according to claim 21, wherein the compound of formula (ε') is selected from the group consisting of C1～18With C3～20Esterification products of fatty acids, said C1～18The polyhydric alcohol of (A) includes one or more of trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol, and C3～20The fatty acid of (a) includes one or more of valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, isooctanoic acid, 2-ethylhexanoic acid, pelargonic acid, 3,5, 5-trimethylhexanoic acid, capric acid, lauric acid, palmitic acid, and oleic acid.
23. A process according to claim 21, wherein said compound of formula (ε') is one or more compounds selected from the group consisting of trimethylolpropane, pentaerythritol and dipentaerythritol, and C3～20Esterification products of saturated fatty acids (preferably kinematic viscosity at 100 ℃)Degree of (3-9) mm2One or more of trimethylolpropane ester, pentaerythritol ester and dipentaerythritol ester per second, most preferably with a kinematic viscosity of 3.6-4.3 mm at 100 DEG C2Saturated polyol ester/s).
24. The process according to claim 21, wherein the molar ratio of the compound represented by the formula (α '), the compound represented by the formula (β'), the compound represented by the formula (γ '), and/or the polymer thereof, and the compound represented by the formula (ε') is 1: 0.1-1.2: 0.1-1.2: 0.1 to 1.2; the temperature at which the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or the polymer thereof, and the compound represented by the formula (. epsilon.') are reacted is 50 to 190 ℃.
25. The production method according to claim 21, characterized in that, in the compound represented by the formula (α'), at least one carbon atom in the ortho position of each benzene ring to which the amine group is attached contains a tertiary hydrogen atom.
26. The process according to claim 21, wherein the compound represented by the formula (α') is one or more selected from the group consisting of: diisooctyldiphenylamine, di-tert-butyldiphenylamine, p-isooctyl, p-tert-butyldiphenylamine, dinonyldiphenylamine, diphenylamine; the compound represented by the formula (β') is selected from one or more of the following compounds: 1,2, 3-triazole, benzotriazole, methyl benzotriazole; the compound represented by the formula (γ') and/or the polymer thereof is selected from one or more of the following compounds: formaldehyde, paraformaldehyde, benzaldehyde; the compound represented by the formula (epsilon') includes one or more of the following structural compounds:
27. the process according to claim 21, wherein the compound represented by the formula (α '), the compound represented by the formula (β'), the compound represented by the formula (γ ') and/or a polymer thereof, the compound represented by the formula (ε') are reacted in the presence of a peroxide; the reaction of the compound represented by the formula (. alpha. '), the compound represented by the formula (. beta.'), the compound represented by the formula (. gamma. ') and/or a polymer thereof, and the compound represented by the formula (. epsilon.') is carried out under an inert gas atmosphere.
28. The method of claim 21, wherein the method comprises a two-step process:
a first step of reacting a compound represented by the formula (. alpha. ') with a compound represented by the formula (. epsilon.') in the presence of a peroxide (preferably in the presence of an inert gas) to obtain an intermediate;
in the second step, the intermediate product is reacted with the compound represented by the formula (. beta. '), the compound represented by the formula (. gamma.'), and/or a polymer thereof, and the product is collected.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1061904A (en) * | 1963-01-22 | 1967-03-15 | Castrol Ltd | Improvements in or relating to compositions containing metal deactivators |
| US20080132434A1 (en) * | 2006-11-30 | 2008-06-05 | R. T. Vanderbilt Company, Inc. | Vegetable Oil Lubricating Composition |
| CN103917632A (en) * | 2011-11-11 | 2014-07-09 | 范德比尔特化学品有限责任公司 | Lubricant composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1061904A (en) * | 1963-01-22 | 1967-03-15 | Castrol Ltd | Improvements in or relating to compositions containing metal deactivators |
| US20080132434A1 (en) * | 2006-11-30 | 2008-06-05 | R. T. Vanderbilt Company, Inc. | Vegetable Oil Lubricating Composition |
| CN103917632A (en) * | 2011-11-11 | 2014-07-09 | 范德比尔特化学品有限责任公司 | Lubricant composition |
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