CN115992026A - Industrial gear oil composition and preparation method thereof - Google Patents
Industrial gear oil composition and preparation method thereof Download PDFInfo
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- CN115992026A CN115992026A CN202111209884.8A CN202111209884A CN115992026A CN 115992026 A CN115992026 A CN 115992026A CN 202111209884 A CN202111209884 A CN 202111209884A CN 115992026 A CN115992026 A CN 115992026A
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- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 239000010722 industrial gear oil Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 150000002611 lead compounds Chemical class 0.000 claims abstract description 29
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 239000002199 base oil Substances 0.000 claims abstract description 24
- 230000001050 lubricating effect Effects 0.000 claims abstract description 20
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 48
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 34
- 229910000464 lead oxide Inorganic materials 0.000 claims description 32
- -1 phenolic ester Chemical class 0.000 claims description 22
- 239000000654 additive Substances 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 13
- 238000007127 saponification reaction Methods 0.000 claims description 13
- 235000010233 benzoic acid Nutrition 0.000 claims description 11
- 229960004365 benzoic acid Drugs 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 238000005649 metathesis reaction Methods 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- 229940046892 lead acetate Drugs 0.000 claims description 5
- 239000013556 antirust agent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 4
- 239000011133 lead Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 24
- 150000003254 radicals Chemical class 0.000 description 22
- 239000002904 solvent Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 18
- 239000003921 oil Substances 0.000 description 18
- 230000000996 additive effect Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000010687 lubricating oil Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- CWAYWNAJAOJVPR-UHFFFAOYSA-N 2-tetradecylbenzoic acid Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1C(O)=O CWAYWNAJAOJVPR-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000012208 gear oil Substances 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- IIOLAWJMOGLOIB-UHFFFAOYSA-N 1-phenylhexadecan-1-one Chemical compound CCCCCCCCCCCCCCCC(=O)C1=CC=CC=C1 IIOLAWJMOGLOIB-UHFFFAOYSA-N 0.000 description 3
- DBLXXVQTWJFJFI-UHFFFAOYSA-N 1-phenyloctadecan-1-one Chemical compound CCCCCCCCCCCCCCCCCC(=O)C1=CC=CC=C1 DBLXXVQTWJFJFI-UHFFFAOYSA-N 0.000 description 3
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- RAMRROOXFMYSNA-UHFFFAOYSA-N hexadecyl benzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1 RAMRROOXFMYSNA-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- 229910019093 NaOCl Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 101100407037 Oryza sativa subsp. japonica PAO6 gene Proteins 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- XCPFSALHURPPJE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XCPFSALHURPPJE-UHFFFAOYSA-N 0.000 description 1
- XOGODJOZAUTXDH-UHFFFAOYSA-M (N-methylanilino)methanesulfonate Chemical compound CN(CS([O-])(=O)=O)c1ccccc1 XOGODJOZAUTXDH-UHFFFAOYSA-M 0.000 description 1
- LFZHZESLICTXPD-UHFFFAOYSA-N 1-(4-tetradecylphenyl)ethanone Chemical compound CCCCCCCCCCCCCCC1=CC=C(C(C)=O)C=C1 LFZHZESLICTXPD-UHFFFAOYSA-N 0.000 description 1
- CJAYHOLRQJHSIP-NXVVXOECSA-N 2-[(z)-heptadec-2-enyl]-4,5-dihydro-1h-imidazole Chemical compound CCCCCCCCCCCCCC\C=C/CC1=NCCN1 CJAYHOLRQJHSIP-NXVVXOECSA-N 0.000 description 1
- 101100407030 Arabidopsis thaliana PAO2 gene Proteins 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- RSGYWRIKINRJBA-UHFFFAOYSA-N CC(=O)C1=CC=C(C=C1)CCCCCCCCCCCCCCCC Chemical compound CC(=O)C1=CC=C(C=C1)CCCCCCCCCCCCCCCC RSGYWRIKINRJBA-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101150092791 PAO4 gene Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- JDNXJDVNUNHQHX-UHFFFAOYSA-N azane;trihydroxy(sulfanylidene)-$l^{5}-phosphane Chemical compound N.OP(O)(O)=S JDNXJDVNUNHQHX-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010725 compressor oil Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- DEQLTFPCJRGSHW-UHFFFAOYSA-N hexadecylbenzene Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1 DEQLTFPCJRGSHW-UHFFFAOYSA-N 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 150000003012 phosphoric acid amides Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
Landscapes
- Lubricants (AREA)
Abstract
The invention provides industrial gear oilA composition comprising a lead compound, an extreme pressure antiwear agent, an antioxidant, a rust inhibitor, and a major amount of a lubricating base oil, wherein the lead compound has a structure according to formula (I):
the A group in the formula (I) is selected from a group shown in the formula (II) and/or a group shown in the formula (III);
Description
Technical Field
The invention relates to the field of lubricating oil, in particular to an industrial gear oil composition and a preparation method thereof.
Background
With the rapid development of the economy in China, the number of transmission machines in the industries of steelmaking, transportation, spinning and construction is continuously increased, and the use amount of medium and heavy load industrial gear oil is increasingly large. Meanwhile, the gear transmission parts in the equipment are also developed towards the directions of small volume, light weight, high speed, heavy load and high power, and the requirements on gear oil are higher and higher, and besides better extreme pressure wear resistance and longer service life, the gear oil is also required to have better thermal oxidation stability, rust resistance, emulsification resistance, foaming resistance, low dosage and better environmental protection.
The main components of the industrial gear oil are base oil and additives, wherein the base oil mainly provides an oil film with certain viscosity required by a friction pair for lubrication between gears, the additives mainly provide an antiwear film on the contact surface of the friction pair, and active elements such as sulfur, phosphorus, nitrogen, lead and the like in the additives play a key role in the formation of an extreme pressure film. Currently, medium and heavy duty industrial gear oil is a main variety of industrial gear oil, and the performance requirement is higher than that of open gear oil. The base oil in the gear oil mainly comprises mineral oil, polyether and poly alpha-olefin synthetic oil, the additive comprises sulfur-containing and phosphorus-containing extreme pressure antiwear agent as main agent, and other additives such as oiliness agent, antirust agent, antioxidant, anti-foaming agent, etc. Therefore, to improve the performance of the existing industrial gear oil, a lot of related patents have been reported at present mainly starting from the screening of various antiwear additives.
CN 1057477a describes a medium-load industrial gear oil composition, which consists of a thiophosphine-nitrogen extreme pressure antiwear agent, a sulfurized hydrocarbon extreme pressure antiwear agent, a benzotriazole amine salt multi-effect additive, an antioxidant and a composite anti-emulsifying agent, wherein the thiophosphine-nitrogen extreme pressure antiwear agent is formed by condensing dialkyl dithiophosphonic acid-formaldehyde-fatty amine.
CN 1403549a describes an industrial gear oil additive composition comprising at least one sulfur-containing extreme pressure antiwear agent, at least one antioxidant corrosion inhibitor, at least one phosphorus-containing antiwear agent, at least one metal deactivator, at least one metal detergent, at least one rust inhibitor.
CN 101298574a provides a general industrial gear lubricating oil additive composition comprising at least one sulfur-containing extreme pressure antiwear agent, at least one phosphorus-containing multifunctional antiwear agent, at least one rust inhibitor. The additive composition is added into base oil with medium viscosity index or high viscosity index according to the dosage of 1.0-1.4%, and heavy-load industrial gear oil with the brands of 100, 220, 320, 460, 680, 1000 and the like reaching the specification index of GB5903-95 can be prepared.
CN 102417846B provides an industrial lubricating oil additive composition comprising at least one antioxidant antiwear multifunctional additive, at least one high temperature antioxidant, at least one phosphorus-containing antiwear agent, at least one high temperature detergent, at least one rust inhibitor, at least one friction modifier, at least one metal deactivator. The additive composition is added into the total synthetic base oil according to the dosage of 0.5-3.0%, and can be used for preparing industrial lubricating oil such as compressor oil, hydraulic oil, bearing oil, worm gear scroll bar oil, industrial gear oil and the like.
The industrial gear oil compositions of the above patents have either high additive amounts or poor antiwear and antifriction properties, and in addition, have the problem that some of the additives in the formulations are poor in oil solubility, and therefore, the existing industrial gear oil formulations need further improvement.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides an industrial gear oil composition and a preparation method thereof.
The industrial gear oil composition comprises a lead compound, an extreme pressure antiwear agent, an antioxidant, an antirust agent and a main amount of lubricating base oil, wherein the lead compound has a structure shown in a formula (I):
the A group in the formula (I) is selected from a group shown in the formula (II) and/or a group shown in the formula (III);
in formula (II), R 0 The radical being C 1～6 Straight or branched alkylene of (a); x is an integer of 0 to 4, x R 1 The radicals are each independently selected from C 2～40 Straight or branched alkyl of (a);
the ring radical being C having a valence of (x+1) 3～20 Is selected from the group consisting of a cycloalkyl group,
the ring group is a cycloalkyl group with 1-5 rings;
in formula (III), R 2 The radical being C 2～30 Straight or branched alkyl of (a).
According to the present invention, preferably,
the ring radical being C having a valence of (x+1) 3～10 Cycloalkyl group of->
The ring radical being a cycloalkyl radical having 1 to 3 rings, R 0 The radical being C 1～5 Straight or branched alkylene of (a); x is an integer of 1 to 3, x R 1 The radicals are each independently selected from C 2～30 Straight or branched alkyl of (a); r is R 2 The radical being C 8～24 Straight or branched alkyl of (a).
According to the present invention, the lead compound may be selected from one or more of the following lead compounds:
(1) The structure of the lead alkyl benzene carboxylic acid cyclopentane acid is as follows:
wherein R is a0 Is C 8 ～C 24 Alkyl, R a1 Is C 1 ～C 3 Alkylene group, R a2 Is C 8 ～C 24 An alkyl group;
(2) The structure of the lead alkyl benzene carboxylic acid cyclohexane acid is as follows:
wherein R is b0 Is C 8 ～C 24 Alkyl, R b1 Is C 1 ～C 3 Alkylene group, R b2 Is C 8 ～C 24 An alkyl group;
(3) The structure of the alkyl benzene carboxylic acid dicyclopentanoic acid lead is as follows:
wherein R is c0 Is C 8 ～C 24 Alkyl, R c1 Is C 1 ～C 3 Alkylene group, R c2 Is C 8 ～C 24 An alkyl group;
(4) The structure of the alkyl benzene carboxylic acid dicyclohexyl acid is as follows:
wherein R is d0 Is C 8 ～C 24 Alkyl, R d1 Is C 1 ～C 3 Alkylene group, R d2 Is C 8 ～C 24 An alkyl group;
(5) The structure of the lead alkyl benzene carboxylic acid dicyclo-alkanoic acid is as follows:
wherein R is e0 Is C 8 ～C 24 Alkyl, R e1 Is C 1 ～C 3 Alkylene group, R e2 Is C 8 ～C 24 An alkyl group;
(6) Lead alkyl benzene carboxylate tricycloalkylate with the structure as follows:
wherein R is f0 Is C 8 ～C 24 Alkyl, R f1 Is C 1 ～C 3 Alkylene group, R f2 Is C 8 ～C 24 An alkyl group;
(7) Lead alkyl benzene carboxylate tricycloalkylate with the structure as follows:
wherein R is g0 Is C 8 ～C 24 Alkyl, R g1 Is C 1 ～C 3 Alkylene group, R g2 Is C 8 ～C 24 An alkyl group.
The lead compound has excellent oil solubility, abrasion resistance and antifriction property, is an antiwear agent with excellent performance, and can be used for lubrication of vehicle gears and industrial gears and lubrication of transmission of other mechanical parts.
According to the present invention, the method for producing a lead compound includes a saponification reaction or a metathesis reaction;
the saponification reaction is a step of reacting a compound represented by the formula (α) and/or a compound represented by the formula (β) with lead oxide;
in formula (. Alpha.), R 0 The radical being C 1～6 Straight or branched alkylene of (a); x is between 0 and 4Integer, x R 1 The radicals are each independently selected from C 2～40 Straight or branched alkyl of (a);
the ring radical being C having a valence of (x+1) 3～20 Cycloalkyl group of->
The ring group is a cycloalkyl group with 1-5 rings; in formula (. Beta.), R 2 The radical being C 2～30 Straight or branched alkyl of (a);
the metathesis reaction is a step of reacting a compound represented by the formula (α ') and/or a compound represented by the formula (β') with a lead salt;
in formula (. Alpha.'), R 0 The radical being C 1～6 Straight or branched alkylene of (a); x is an integer of 0 to 4, x R 1 The radicals are each independently selected from C 2～40 Straight or branched alkyl of (a);
the ring radical being C having a valence of (x+1) 3～20 Is selected from the group consisting of a cycloalkyl group,
the ring group is a cycloalkyl group with 1-5 rings; in formula (. Beta.'), R is 2 The radical being C 2～30 Straight or branched alkyl of (a); m in the formula (. Alpha. ') and the formula (. Beta.') is each independently Na or K.
According to the method for producing a lead compound of the present invention, preferably,
the ring radical being C having a valence of (x+1) 3～10 Cycloalkyl group of->
The ring radical being a cycloalkyl radical having 1 to 3 rings, R 0 The radical being C 1～5 Straight or branched alkylene of (a); x is an integer of 1 to 3, x R 1 The radicals are each independently selected from C 2～30 Straight or branched alkyl of (a); r is R 2 The radical being C 8～24 Straight or branched alkyl of (a); m is Na.
According to the preparation method of the lead compound, the lead oxide can be litharge and/or yellow lead, and preferably yellow lead is selected. The litharge is a red tetragonal crystal, and the yellow lead is a yellow orthorhombic crystal.
According to the preparation method of the lead compound, the lead salt can be one or more of lead nitrate, lead chloride and lead acetate, and preferably lead acetate is selected.
According to the method for producing a lead compound of the present invention, in the saponification reaction, the molar ratio of the compound represented by the formula (α) and/or the compound represented by the formula (β) to lead oxide is 0.6 to 1.6:0.3 to 0.8, preferably 0.8 to 1.4:0.4 to 0.7, most preferably 0.9 to 1.1:0.45 to 0.55, preferably, the molar ratio between the compound represented by the formula (α) and the compound represented by the formula (β) is 0.5 to 6:1, preferably 0.8 to 3:1, most preferably 1.5 to 2.5:1. in the reaction of the compound represented by the formula (α) and/or the compound represented by the formula (β) with lead oxide, the compound represented by the formula (α) and/or the compound represented by the formula (β) and lead oxide may be added in one or more portions, for example, 1 to 5 times, preferably 1 to 3 times, and most preferably 2 to 3 times.
According to the method for producing a lead compound of the present invention, in the saponification reaction, an accelerator may be added to the reaction of the compound represented by the formula (α) and/or the compound represented by the formula (β) with lead oxide. The promoter may be one or more of a low molecular alcohol, an acid and water, preferably a low molecular alcohol and/or an acid, most preferably a low molecular alcohol. The low molecular alcohol is C 1～5 Alcohols, preferably C 1～3 Alcohols, most preferably C 2～3 An alcohol. The accelerator is preferably added in an amount of 0.01 to 1%, more preferably 0.05 to 0.8% of the total mass of the compound represented by the formula (α) and/or the compound represented by the formula (β) and lead oxide.
According to the method for producing a lead compound of the present invention, in the saponification reaction, the temperature at which the compound represented by the formula (α) and/or the compound represented by the formula (β) is reacted with lead oxide may be 40 to 300 ℃, preferably 60 to 200 ℃, most preferably 100 to 150 ℃, and the reaction time may be 2 to 10 hours, preferably 3to 8 hours, most preferably 4 to 6 hours.
According to the method for producing a lead compound of the present invention, the saponification reaction may be carried out by a filtration operation after the completion of the reaction of the compound represented by the formula (α) and/or the compound represented by the formula (β) with lead oxide to remove unreacted lead oxide, and a solvent may or may not be added before the filtration operation, and preferably a solvent is added. The solvent is preferably a hydrocarbon solvent, and may be, for example, one or more of solvent gasoline, n-octane, and xylene.
According to the method for producing a lead compound of the present invention, in the metathesis reaction, the molar ratio of the compound represented by the formula (α ') and/or the compound represented by the formula (β') to the lead salt is 0.6 to 1.6:0.3 to 0.8, preferably 0.8 to 1.4:0.4 to 0.7, most preferably 0.9 to 1.1:0.45 to 0.55, preferably, the molar ratio between the compound represented by the formula (α ') and the compound represented by the formula (β') is 0.5 to 6:1, preferably 0.8 to 3:1, most preferably 1.5 to 2.5:1. in the reaction of the compound represented by the formula (α ') and/or the compound represented by the formula (β') with the lead salt, the compound represented by the formula (α ') and/or the compound represented by the formula (β') and the lead salt may be added in one or more portions, for example, 1 to 5 times, preferably 1 to 3 times, and most preferably 2 to 3 times.
According to the method for producing a lead compound of the present invention, in the metathesis reaction, the temperature at which the compound represented by the formula (α ') and/or the compound represented by the formula (β') is reacted with a lead salt may be 40 to 300 ℃, preferably 60 to 200 ℃, most preferably 100 to 150 ℃, and the reaction time may be 2 to 10 hours, preferably 3to 8 hours, most preferably 4 to 6 hours.
According to the method for producing a lead compound of the present invention, for the metathesis reaction, a filtration operation may be performed after the reaction of the compound represented by the formula (α ') and/or the compound represented by the formula (β') with a lead salt is completed to remove by-products and unreacted reactants, and a solvent may or may not be added before the filtration operation is performed, and preferably a solvent is added. The solvent is preferably a hydrocarbon solvent, and may be, for example, one or more of solvent gasoline, n-octane, and xylene.
According to the invention, the extreme pressure antiwear agent is selected from one or more of a sulfur-containing extreme pressure antiwear agent, a phosphorus-containing extreme pressure antiwear agent and a sulfur-containing phosphorus extreme pressure antiwear agent; the sulfur-containing extreme pressure antiwear agent is preferably selected from one or more of sulfurized isobutylene, sulfurized whale oil, dibenzyl disulfide and alkyl polysulfide, more preferably sulfurized isobutylene; the phosphorus-containing extreme pressure antiwear agent is preferably selected from one or more of phosphate amine salts, phosphoric acid amides, phosphites, acid phosphates, phosphoric acid esters, phosphonic acid esters and hypophosphites, more preferably one or more of phosphites, acid phosphates and phosphoric acid esters; the sulfur-containing, phosphorus-containing, extreme pressure antiwear agent is preferably selected from one or more of a thiophosphonate salt, a thiophosphonate ester and an amine salt of a thiophosphonate ester, more preferably one or more of a thiophosphonate salt, a thiophosphonate ester and an amine salt of a thiophosphonate ester.
According to the invention, the antioxidant is selected from one or more of amine antioxidant, phenolic ester antioxidant, phenolic antioxidant and thiocarbamate antioxidant, for example, dialkyl diphenylamine (T534), N-phenyl-alpha-naphthylamine (T531), 3, 5-di-tert-butyl-4-hydroxy phenyl propionate (T512), 2, 6-di-tert-butyl-p-cresol (T501) and thiocarbamate (T323) can be selected. The antioxidant is preferably a mixture of an amine antioxidant and a phenolic ester antioxidant, and the ratio of the amine antioxidant to the phenolic ester antioxidant is 1:1 to 5, preferably 1: 1-3, for example, the antioxidant may preferably be a mixture of alkylated diphenylamine and 3, 5-di-tert-butyl-4-hydroxyphenyl propionate in a ratio of 1:1 to 5, preferably 1:1 to 3.
According to the invention, the rust inhibitor is selected from one or more of sulfonate, imidazoles, imidazoline alkenyl succinate, alkenyl succinic acid and alkenyl succinate, for example, sodium petroleum sulfonate, calcium petroleum sulfonate, barium petroleum sulfonate, synthetic calcium sulfonate, barium dinonyl sulfonate, 4, 5-dihydroimidazole, heptadecenyl imidazoline alkenyl succinate, dodecenyl succinic acid and dodecenyl succinate, and common commercial grades include T701, T702, T703, T746 and T747 manufactured by Konta lubricating oil additive Co. The rust inhibitor is preferably a sulfonate and/or alkenyl succinic acid, more preferably dodecenyl succinic acid.
According to the invention, the lubricating base oil is selected from one or more of API I, II, III, IV and V lubricating base oils, for example, 100SN, 150SN, 200SN, 500SN, 650SN, 150BS lubricating oil, three sets of process treatment oil, 100N, 150N, 200N, 500N, 600N hydrofined oil, lubricating base oil prepared by a high-pressure hydrocracking process and one or more of PAO2, PAO4, PAO6, PAO8, PAO10 and PAO40 synthetic oil can be selected. The lubricating base oil is preferably API IV lubricating base oil, more preferably has an kinematic viscosity of 2-50 mm at 100 DEG C 2 Poly alpha-olefin synthetic oil per s.
According to the present invention, preferably, the lead compound accounts for 0.1 to 2.0% of the total mass of the composition; the extreme pressure antiwear agent accounts for 0.1-3.0% of the total mass of the composition; the antioxidant accounts for 0.1-2% of the total mass of the composition; the rust inhibitor accounts for 0.01 to 0.5 percent of the total mass of the composition; the lubricating base oil comprises the major component of the composition.
The method for preparing the industrial gear oil composition comprises the step of mixing various additives in the industrial gear oil composition and lubricating base oil. The temperature of the mixing is preferably 40-90 ℃, and the mixing time is preferably 1-6 hours.
The industrial gear oil composition has excellent oxidation stability, wear resistance, antifriction performance, storage stability and lower corrosiveness.
The industrial gear oil composition overcomes the defects of poor stability and poor solubility of the lead-containing lubricating oil composition. Compared with the traditional industrial gear oil, the industrial gear oil composition provided by the invention has better antiwear and antifriction effects and lower corrosiveness at a lower dosage, which is related to the improvement of the stability of lead compounds in friction pairs and the reduction of the rate of lead soap decomposition to form inorganic lead salts after alkyl phenyl carboxylic acid groups and naphthenic acid groups are introduced, so that the lead compounds provided by the invention can play the antiwear and antifriction roles for a longer time, thereby reducing the addition amount of the lead compounds in a formula, and meanwhile, the unexpected discovery is that the lead compounds provided by the invention have improved oxidation resistance after the alkyl phenyl carboxylic acid groups are introduced, thus reducing the oxidation of oil products, and further reducing the corrosiveness of acidic substances generated by the oxidation of the oil products on metals. Therefore, the industrial gear oil composition of the present invention is an industrial gear oil composition excellent in performance.
Detailed Description
The invention will be further illustrated by the following examples, but the invention is not limited thereby.
The percentages mentioned below are percentages by mass unless otherwise indicated.
The main raw material sources are as follows:
naphthenic acid A
Crude acid number: 88mgKOH/g, pure acid number: 120mgKOH/g, average relative molecular mass: 467, purity: 73.33%, density: 0.9710g/cm 3 Kinematic viscosity at 100 ℃): 94.6mm 2 Industrial product
Naphthenic acid B
Crude acid number: 257.3mgKOH/g, pure acid number: 292.42mgKOH/g, average relative molecular mass: 192, purity: 88%, density: 0.950g/cm 3 Industrial product
Naphthenic acid C
Crude acid number: 220.8mgKOH/g, pure acid number: 253.8mgKOH/g, average relative molecular mass: 221, purity: 87%, density: 0.949g/cm 3 Industrial product
Tetradecylbenzoic acid, the preparation method thereof is as follows:
1) Preparation of tetradecylacetophenone
Into a 1000ml three-necked flask with temperature-controlled stirring, 350ml of CCl was added 4 50g of anhydrous AlCl 3 And 50g of acetyl chloride (0.637 mol), tetradecylbenzene 1 was added dropwise74g (0.634 mol), controlling the dropping speed to enable the temperature of the material to be between 0 and 5 ℃, reacting for lh at 20 to 25 ℃ after the dropping is finished, separating an organic layer from the reaction mixture, washing with acid, washing with water until the organic layer is neutral, drying with anhydrous sodium sulfate, filtering, and evaporating the solvent to obtain the tetradecylacetophenone.
2) Oxidation of tetradecylacetophenone to alkylbenzoic acid
200ml of chloroform, 120ml of NaOCl and 20g of NaOH mixed solution were placed in a 1000ml three-necked flask at room temperature. 31.65g (0.1 mol) of p-tetradecylacetophenone is added dropwise, and after the addition, the temperature is raised and the reflux is carried out, and the temperature is kept for 1.5h. The solvent was distilled off under reduced pressure, washed with water and filtered to give 32.5g of tetradecylbenzoic acid, an acid value of 167.04mgKOH/g and a purity of 95%.
Hexadecylbenzoic acid
1) Preparation of hexadecylacetophenone
Into a 1000ml three-necked flask with temperature-controlled stirring, 350ml of CCl was added 4 50g of anhydrous AlCl 3 And 50g of acetyl chloride (0.637 mol), 191.8g of hexadecyl benzene (0.634 mol) is added dropwise, the dropping speed is controlled to ensure that the temperature of the material is between 0 and 5 ℃, after the dripping is finished, the material is reacted for lh at 20 to 25 ℃, then the reaction mixture is separated from an organic layer, and the organic layer is washed by acid and water until the organic layer is neutral, dried by anhydrous sodium sulfate, filtered and distilled to remove the solvent, thus obtaining the hexadecyl acetophenone.
2) Oxidation of hexadecyl acetophenone to para-alkyl benzoic acid
200ml of chloroform, 120ml of NaOCl and 20g of NaOH mixed solution were placed in a 1000ml three-necked flask at room temperature. 34g (0.1 mol) of p-hexadecylacetophenone is added dropwise, and after the addition is finished, the temperature is raised for reflux, and the temperature is kept for 1.5h. The solvent was distilled off under reduced pressure, washed with water and filtered to give 35.5g of hexadecylbenzoic acid, an acid value of 151.9mgKOH/g and a purity of 94%.
Lead oxide, propanol, ethylene glycol were all purchased from Beijing chemical reagent company, analytical grade
Solvent gasoline No. 120:
the distillation range is 80-120 ℃ and the industrial product
150SN lubricating base oil:
kinematic viscosity at 40 ℃ of 30.21mm 2 S,100 ℃ is the kinematic viscosity of 5.62mm 2 S, pour point, -12 ℃, china petroleum major company
Hydrogenated oil No. 6:
kinematic viscosity at 40 ℃ of 31.85mm 2 S, kinematic viscosity at 100℃of 6.23mm 2 S, china Shanghai high bridge petrochemical division
PAO6 with kinematic viscosity of 29mm at 40 DEG C 2 S, kinematic viscosity at 100℃of 5.7mm 2 Industrial product
Vulcanized isobutene T321 with a sulfur content of 46% and a Bobo Hui Hua additive Co.Ltd
Dialkyl dithiocarbamate T323, nitrogen content of 6.7% and sulfur content of 30.5%, produced by Henan New Country Ruifeng New Material Co., ltd
Tricresyl phosphate T306, phosphorus content of 8.4%, acid value less than or equal to 0.1mgKOH/g, zibo Hui Hua additive Co., ltd
Tri-n-butyl phosphite T304, phosphorus content of 15.0%, acid value of less than or equal to 15mgKOH/g, zibo Hui Hua additive Co., ltd
Butyl isooctyl dodecylamine phosphate T308B, nitrogen content 3.5%, phosphorus content 5.6%, zibo Hui Hua additive Co., ltd
The phosphorothioate nitrogen-containing derivative T305 has a sulfur content of 10.6%, a phosphorus content of 6.0% and a nitrogen content of 1.2%, and is prepared from Tianyu petroleum additive plant in Danyang city
Phosphorothioate complex amine salt T307, sulfur content of 10.8%, phosphorus content of 8.6%, nitrogen content of 1.4%, zibo Hui Hua additive Co., ltd
Amine antioxidant T534 with nitrogen content greater than 3.0%, produced by Henan Xinxiang Ruifeng New Material Co., ltd
Phenolic antioxidant T512, flash point 180 deg.c and density 950-1000 kg/m 3 Production of Henan New Country Ruifeng New Material Co., ltd
Dodecenyl succinic acid T746 with an acid value of 252mgKOH/g, manufactured by Lanzhou Roxbu additive Co
Barium dinonyl naphthalene disulfonate T705, total base number 45mgKOH/g, flash point 165 ℃, donggong petrochemical Co., ltd
Benzotriazole derivative T551 with viscosity of 12.5mm at 100deg.C 2 S, zibo-chemical additives Co., ltd
Example 1
127.5g (0.27 mol) of naphthenic acid A, 63.6g (0.2 mol) of tetradecylbenzoic acid (total acid value: 167mgKOH/g, mass fraction: 95%, average relative molecular weight: 318) and 35.7g (0.16 mol) of lead oxide and 1.7g of propanol are added into a 1000ml three-necked flask with temperature control, water cooling and stirring, and the materials are stirred, and when the temperature of the materials is raised to 115 ℃, 35.7g (0.16 mol) of lead oxide and 1.7g of propanol are slowly added within 30 min. After reacting for 2h at constant temperature, then adding 100g (0.21 mol) of naphthenic acid A, slowly adding 35.7g (0.16 mol) of lead oxide within 30min, then reacting for 4h, cooling when the materials are transparent, adding 200g of No. 120 solvent gasoline at 60 ℃, diluting and filtering, and distilling the filtrate to obtain 348g (357 g of theoretical product quantity) of viscous dark brown extreme pressure antiwear agent A, wherein the yield is 97.5%. The mass fraction of Pb in the product is 18.5%.
Example 2
In a 1000ml three-necked flask with temperature control, water cooling and stirring, 76.8g (0.4 mol) of naphthenic acid B, 95.4g (0.3 mol) of tetradecylbenzoic acid (total acid value: 167mgKOH/g, mass fraction: 95%, average relative molecular weight: 318) and stirring the materials were added, and when the temperature of the materials was raised to 120 ℃, 61.4g (0.275 mol) of lead oxide and 1.8g of ethylene glycol were slowly added within 40 minutes. After 3h of constant temperature reaction, 76.8g (0.4 mol) of naphthenic acid B is added, 62.5g (0.28 mol) of lead oxide is slowly added within 30min, then the reaction is carried out for 3h, when no lead oxide solid particles exist in the materials, the temperature is reduced when the materials are transparent, 300g of No. 120 solvent gasoline is added at 60 ℃, after dilution and filtration are carried out, and the filtrate is distilled to obtain 353g (theoretical product quantity is 363 g) of viscous dark brown extreme pressure antiwear agent B, and the yield is 97.2%. The mass fraction of Pb in the product is 29.3%.
Example 3
In a 1000ml three-necked flask with temperature control, water cooling and stirring, 88g (0.4 mol) of naphthenic acid, 127.2g (0.4 mol) of tetradecylbenzoic acid (total acid value: 167mgKOH/g, mass fraction: 95%, average relative molecular weight: 318) and stirring the materials were added, and when the temperature of the materials was raised to 120 ℃, 93.66g (0.42 mol) of lead oxide and 3.4g of propanol were slowly added within 30 minutes. After reacting for 4 hours at constant temperature, then adding 44g (0.2 mol) of naphthenic acid C, slowly adding 23.4g (0.1 mol) of lead oxide within 30min, then reacting for 2 hours, cooling when the materials are transparent, adding 200g120 # solvent gasoline at 60 ℃, diluting and filtering, and distilling the filtrate to obtain 350.2g (the theoretical product amount is 366.9 g) of viscous dark brown extreme pressure antiwear agent C, wherein the yield is 95.5%. The mass fraction of Pb in the product is 29.8%.
Example 4
127.5g (0.27 mol) of naphthenic acid A, 69.2g (0.2 mol) of hexadecylbenzoic acid (total acid value of 151.9mgKOH/g, mass fraction of 94%, average relative molecular weight of 346) and 35.7g (0.160 mol) of lead oxide and 1.7g of propanol are firstly added into a 1000ml three-neck flask with temperature control, water cooling and stirring, the materials are stirred, and when the temperature of the materials is raised to 121 ℃, 35.7g (0.160 mol) of lead oxide and 1.7g of propanol are slowly added within 35 min. After 3h of constant temperature reaction, 100g (0.21 mol) of naphthenic acid A is then added, 35.7g (0.160 mol) of lead oxide is slowly added within 30min, then the reaction is carried out for 3h, when no lead oxide solid particles exist in the materials, the temperature is reduced when the materials are transparent, 180g of No. 120 solvent gasoline is added at 60 ℃, after dilution and filtration are carried out, and the filtrate is distilled to obtain 351g of viscous dark brown extreme pressure antiwear agent D (the theoretical product amount is 362.3 g), and the yield is 96.9%. The mass fraction of Pb in the product is 17.9%.
Comparative example 1
219.5g (0.47 mol) of naphthenic acid A is firstly added into a 1000ml three-neck flask with temperature control, water cooling and stirring, the materials are stirred, and 35.7g (0.16 mol) of lead oxide and 1.7g of propanol are slowly added within 30min when the temperature of the materials is raised to 115 ℃. After reacting for 2h at constant temperature, then adding 100g (0.21 mol) of naphthenic acid A, slowly adding 35.7g (0.16 mol) of lead oxide within 30min, then reacting for 4h, cooling when the materials are transparent, adding 200g of No. 120 solvent gasoline at 60 ℃, diluting and filtering, and distilling the filtrate to obtain viscous dark brown extreme pressure antiwear agent A-1.9 g (the theoretical product amount is 385.1 g), wherein the yield is 95%. The mass fraction of Pb in the product is 17.3%.
Comparative example 2
134.4g (0.7 mol) of naphthenic acid B is firstly added into a 1000ml three-neck flask with temperature control, water cooling and stirring, the materials are stirred, 61.4g (0.275 mol) of lead oxide and 1.8g of ethylene glycol are slowly added within 40min when the temperature of the materials is raised to 120 ℃. After 3h of constant temperature reaction, 76.8g (0.4 mol) of naphthenic acid B is added, 62.5g (0.28 mol) of lead oxide is slowly added within 30min, then the reaction is carried out for 3h, when no lead oxide solid particles exist in the materials, the temperature is reduced when the materials are transparent, 300g of No. 120 solvent gasoline is added at 60 ℃, after dilution and filtration are carried out, the filtrate is distilled to obtain thick dark brown extreme pressure antiwear agent B-1.6 g (325.1 g of theoretical product quantity), and the yield is 97.3%. The mass fraction of Pb in the product is 34.8%.
Comparative example 3
120g (acid value 216mgKOH/g, molecular weight 259.7) of refined acid obtained by distilling naphthenic acid C (distilled at 130-145 ℃ C., vacuum degree of 3 torr) is added into a 1000ml three-neck flask with temperature control, water cooling and stirring, 186g of 10% sodium hydroxide solution is added for saponification (molar ratio of naphthenic acid to sodium hydroxide is 1:1), saponification temperature is 85 ℃ C., saponification time is 1h, toluene is added for full dissolution, stirring is carried out, 498g of 15% lead acetate solution (molar ratio of naphthenic acid to lead acetate is 1:0.5) is added under toluene reflux condition, and lead naphthenate is generated after 2h of reaction. After the reaction is finished, discarding the water phase, washing the organic phase with hot water at 80 ℃ for 4 times, dehydrating, and distilling under reduced pressure to obtain the extreme pressure antiwear agent C-1 167g, wherein the mass fraction of Pb in the product is 27.9%.
Examples 5 to 9 and comparative examples 4 to 10, in which the above-synthesized lead-containing antiwear agent and commercially available additives and lubricating base oil were each prepared to industrial gear oil compositions according to the formulation compositions of tables 1 and 2. The lubricating base oil is L-CKD N220 full synthetic industrial gear oil base oil, which is prepared from PAO10 oil and PAO40 oil (the mass ratio of PAO10 to PAO40 is 27:73), wherein the kinematic viscosity of the PAO10 oil at 100 ℃ is 9.8mm 2 The kinematic viscosity at 40 ℃ is 59.8mm 2 And/s, the viscosity index is 149,PAO No. 40 oil with kinematic viscosity of 40.5mm at 100 DEG C 2 S, kinematic viscosity at 40℃of 395mm 2 And/s, the viscosity index is 153. The kinematic viscosity of the L-CKD N220 base oil at 40 ℃ is 223mm 2 And/s, pour point of-40 ℃ and flash point of 252 ℃.
Table 1 example formulation of industrial gear oil composition
Table 2 comparative formulation of industrial gear oil compositions
Copper flake corrosion test, rust inhibitive performance test, extreme pressure lubricating oil oxidation performance test, lubricating fluid extreme pressure performance test (timken method), lubricant bearing capacity test (CL-100 gear method), lubricant anti-emulsification test, lubricant antiwear test, and lubricating friction test were performed on examples and comparative examples of the industrial gear oil composition, respectively.
The test method comprises the following steps:
GB/T5096, copper sheet corrosion measurement method of petroleum products, test conditions are 121 ℃ for 3 hours;
GB/T11143, anti-rust property test method of inhibitor-added mineral oil in the presence of water is carried out in distilled water or synthetic seawater respectively;
SH/T0024, an extreme pressure lubricating oil oxidation performance measuring method, wherein the test condition is 95 ℃ and 312 hours, and the 100 ℃ kinematic viscosity increase rate of the sample before and after the test is used as an index for evaluating the oxidation stability of the sample;
GB/T8022 method for measuring anti-emulsifying property of lubricating oil
GB/T11144, lubricating fluid extreme pressure property determination method (Timken method);
SH/T0306, lubricant carrying capacity assay (CL-100 gear method).
GB/T3142 method for determining the bearing capacity of lubricants
SH/T0189 method for measuring abrasion resistance of lubricating oil (four-ball machine method)
SH/T0847, SRV test method for measuring friction and wear properties of extreme pressure lubricating oil
The appearance 1 test method comprises storing at-15deg.C for 15 days, and observing appearance
Appearance 2 test method is to observe appearance after 30 days of storage at room temperature
In the quality standard GB5903-95 of gear oil composition, the corrosion grade of copper sheets is not more than 1 grade, the liquid phase corrosion test result in distilled water or synthetic seawater is no rust, the kinematic viscosity increase rate of 100 ℃ for representing the oxidation performance is not more than 6, the water in oil is not more than 2% in an anti-emulsion test, the emulsion layer is not more than 1%, the water division amount is not less than 80mL, the passing load of Timken test is not less than 267N, the sintering load of a four-ball machine is not less than 2450N, the abrasive spot diameter is not more than 0.35mm, the passing grade of a CL-100 gear machine is not less than 11 grade, and the appearance is transparent and free of turbidity.
The test results of examples 5 to 9 and comparative examples 4 to 10 of the industrial gear oil compositions are shown in Table 3.
TABLE 3 Industrial Gear oil composition test results
The industrial gear oil composition has good storage stability, low corrosiveness, good oxidation stability and wear resistance, and is an industrial gear oil composition with comprehensive performance.
Claims (12)
1. An industrial gear oil composition comprising a lead compound, an extreme pressure antiwear agent, an antioxidant, an anti-rust agent, and a major amount of a lubricating base oil, wherein the lead compound has a structure as shown in formula (I):
the A group in the formula (I) is selected from a group shown in the formula (II) and/or a group shown in the formula (III);
in formula (II), R 0 The radical being C 1～6 Straight or branched alkylene of (a); x is an integer of 0 to 4, x R 1 The radicals are each independently selected from C 2～40 Straight or branched alkyl of (a);
the ring radical being C having a valence of (x+1) 3～20 Cycloalkyl group of->
The ring group is a cycloalkyl group with 1-5 rings;
in formula (III), R 2 The radical being C 2～30 Straight or branched alkyl of (a).
2. The composition of claim 1, wherein said
The ring radical being C having a valence of (x+1) 3～10 Cycloalkyl group of->
The ring radical being a cycloalkyl radical having 1 to 3 rings, R 0 The radical being C 1～5 Straight or branched alkylene of (a); x is an integer of 1 to 3, x R 1 The radicals are each independently selected from C 2～30 Straight or branched alkyl of (a); r is R 2 The radical being C 8～24 Straight or branched alkyl of (a).
3. The composition of claim 1, wherein the lead compound is selected from one or more of the following lead compounds:
(1) The structure of the lead alkyl benzene carboxylic acid cyclopentane acid is as follows:
wherein R is a0 Is C 8 ～C 24 Alkyl, R a1 Is C 1 ～C 3 Alkylene group, R a2 Is C 8 ～C 24 An alkyl group;
(2) The structure of the lead alkyl benzene carboxylic acid cyclohexane acid is as follows:
wherein R is b0 Is C 8 ～C 24 Alkyl, R b1 Is C 1 ～C 3 Alkylene group, R b2 Is C 8 ～C 24 An alkyl group;
(3) The structure of the alkyl benzene carboxylic acid dicyclopentanoic acid lead is as follows:
wherein R is c0 Is C 8 ～C 24 Alkyl, R c1 Is C 1 ～C 3 Alkylene group, R c2 Is C 8 ～C 24 An alkyl group;
(4) The structure of the alkyl benzene carboxylic acid dicyclohexyl acid is as follows:
wherein R is d0 Is C 8 ～C 24 Alkyl, R d1 Is C 1 ～C 3 Alkylene group, R d2 Is C 8 ～C 24 An alkyl group;
(5) The structure of the lead alkyl benzene carboxylic acid dicyclo-alkanoic acid is as follows:
wherein R is e0 Is C 8 ～C 24 Alkyl, R e1 Is C 1 ～C 3 Alkylene group, R e2 Is C 8 ～C 24 An alkyl group;
(6) Lead alkyl benzene carboxylate tricycloalkylate with the structure as follows:
wherein R is f0 Is C 8 ～C 24 Alkyl, R f1 Is C 1 ～C 3 Alkylene group, R f2 Is C 8 ～C 24 An alkyl group;
(7) Lead alkyl benzene carboxylate tricycloalkylate with the structure as follows:
wherein R is g0 Is C 8 ～C 24 Alkyl, R g1 Is C 1 ～C 3 Alkylene group, R g2 Is C 8 ～C 24 An alkyl group.
4. The composition according to claim 1, wherein the lead compound is produced by a process comprising a saponification reaction or a metathesis reaction;
the saponification reaction is a step of reacting a compound represented by the formula (α) and/or a compound represented by the formula (β) with lead oxide;
in formula (. Alpha.), R 0 The radical being C 1～6 Straight or branched alkylene of (a); x is an integer of 0 to 4, x R 1 The radicals are each independently selected from C 2～40 Straight or branched alkyl of (a);
the ring radical being C having a valence of (x+1) 3～20 Cycloalkyl group of->
The ring group is a cycloalkyl group with 1-5 rings; in formula (. Beta.), R 2 The radical being C 2～30 Straight or branched alkyl of (a);
the metathesis reaction is a step of reacting a compound represented by the formula (α ') and/or a compound represented by the formula (β') with a lead salt;
in formula (. Alpha.'), R 0 The radical being C 1～6 Straight or branched alkylene of (a); x is an integer of 0 to 4, x R 1 The radicals are each independently selected from C 2～40 Straight or branched alkyl of (a);
the ring radical being C having a valence of (x+1) 3～20 Cycloalkyl group of->
The ring group is a cycloalkyl group with 1-5 rings; in formula (. Beta.'), R is 2 The radical being C 2～30 Straight or branched alkyl of (a); m in the formula (. Alpha. ') and the formula (. Beta.') is each independently Na or K.
5. A composition according to claim 4, wherein,
the ring radical being C having a valence of (x+1) 3～10 Cycloalkyl group of->
The ring radical being a cycloalkyl radical having 1 to 3 rings, R 0 The radical being C 1～5 Straight or branched alkylene of (a); x is an integer of 1 to 3, x R 1 The radicals are each independently selected from C 2～30 Straight or branched alkyl of (a); r is R 2 The radical being C 8～24 Straight or branched alkyl of (a); m is Na.
6. The composition according to claim 4, wherein the lead oxide is selected from litharge and/or Plumbum Preparatium; the lead salt is selected from one or more of lead nitrate, lead chloride and lead acetate.
7. The composition according to claim 4, wherein in the saponification reaction, the molar ratio of the compound represented by formula (α) and/or the compound represented by formula (β) to lead oxide is 0.6 to 1.6:0.3 to 0.8; in the metathesis reaction, the molar ratio of the compound represented by the formula (α ') and/or the compound represented by the formula (β') to the lead salt is 0.6 to 1.6:0.3 to 0.8.
8. The composition according to claim 7, wherein the molar ratio between the compound represented by formula (α) and the compound represented by formula (β) is 0.5 to 6:1, a step of; the molar ratio between the compound represented by the formula (alpha ') and the compound represented by the formula (beta') is 0.5 to 6:1.
9. the composition according to claim 4, wherein the temperature at which the compound represented by the formula (α) and/or the compound represented by the formula (β) is reacted with lead oxide in the saponification reaction is 40 to 300 ℃; in the metathesis reaction, the compound represented by the formula (α ') and/or the compound represented by the formula (β') is reacted with a lead salt at a temperature of 40 to 300 ℃.
10. The composition according to one of claims 1 to 9, characterized in that the extreme pressure antiwear agent is selected from one or more of a sulfur-containing extreme pressure antiwear agent, a phosphorus-containing extreme pressure antiwear agent and a sulfur-containing phosphorus extreme pressure antiwear agent; the antioxidant is selected from one or more of amine antioxidant, phenolic ester antioxidant, phenolic antioxidant and thiocarbamate antioxidant; the antirust agent is one or more selected from sulfonate, imidazoles, imidazoline alkenyl succinate, alkenyl succinic acid and alkenyl succinate; the lubricating base oil is selected from one or more of API I, II, III, IV and group V lubricating base oils.
11. Composition according to one of claims 1 to 9, characterized in that the lead compound represents 0.1% to 2.0% of the total mass of the composition; the extreme pressure antiwear agent accounts for 0.1-3.0% of the total mass of the composition; the antioxidant accounts for 0.1-2% of the total mass of the composition; the rust inhibitor accounts for 0.01 to 0.5 percent of the total mass of the composition; the lubricating base oil comprises the major component of the composition.
12. A method of preparing an industrial gear oil composition according to any one of claims 1 to 11, comprising the step of mixing various additives in the industrial gear oil composition with a lubricating base oil.
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