US2656316A - Lubricating oils containing metal salts of a condensation product of a substituted phenol and a vinyl compound - Google Patents
Lubricating oils containing metal salts of a condensation product of a substituted phenol and a vinyl compound Download PDFInfo
- Publication number
- US2656316A US2656316A US174367A US17436750A US2656316A US 2656316 A US2656316 A US 2656316A US 174367 A US174367 A US 174367A US 17436750 A US17436750 A US 17436750A US 2656316 A US2656316 A US 2656316A
- Authority
- US
- United States
- Prior art keywords
- oil
- vinyl
- product
- condensation product
- condensation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 45
- 239000002184 metal Substances 0.000 title claims description 45
- 150000003839 salts Chemical class 0.000 title claims description 39
- 239000007859 condensation product Substances 0.000 title claims description 37
- -1 vinyl compound Chemical class 0.000 title claims description 33
- 229920002554 vinyl polymer Polymers 0.000 title claims description 18
- 239000010687 lubricating oil Substances 0.000 title description 23
- 150000002989 phenols Chemical class 0.000 title description 16
- 239000010688 mineral lubricating oil Substances 0.000 claims description 23
- 150000002430 hydrocarbons Chemical group 0.000 claims description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical class CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000002378 acidificating effect Effects 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
- 150000007513 acids Chemical class 0.000 claims description 7
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical class CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229960000834 vinyl ether Drugs 0.000 claims description 4
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 claims 2
- 239000003921 oil Substances 0.000 description 54
- 239000000047 product Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 29
- 238000012360 testing method Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000012141 concentrate Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 238000009833 condensation Methods 0.000 description 15
- 230000005494 condensation Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 159000000009 barium salts Chemical class 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000002199 base oil Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 229910015900 BF3 Inorganic materials 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- 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 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N 3-Pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000158728 Meliaceae Species 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
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- 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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
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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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
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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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/16—Groups 8, 9, or 10
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- oils which: may be used in.
- thei'nvention residesuinclubricating zoils' contain-ing 'b'etween about; 0.05 :and :aloouttlO %1 or as *high as-about- 20% by:weight.ofi'annihsoluble meta-1 salt: of t'he1 condensation product robtained by condensing a hydrocarbon substituted phenol wherein the hydrocarbon substituentbr substituents contain. between about? 4 and: about 30 carbon: atoms with 'awinylicompoundi of. they class consisting .of. vinyl ethers: .andsvinyl J esters: These condensationzproducts are-acidic andrcapable of. reacting with metal'r basesrasiorexample.
- Atypical. oilesolublemetal salt is produced by reacting approximately .one molecular proportion.
- completion-of the 31630131011 can. be determined. by
- the resin maybe convertedsinto its.;metaltsalt,i.as,for:-ex v ample the barium salt, by treatment of a solvent solution, as for example a naphtha, or a hydrocarbon lubricating oil solution of the resin with barium hydroxide octahydrate or with anhydrous barium hydroxide, in which latter case it is necessary to add small amounts of water during the neutralization.
- a solvent solution as for example a naphtha, or a hydrocarbon lubricating oil solution of the resin with barium hydroxide octahydrate or with anhydrous barium hydroxide, in which latter case it is necessary to add small amounts of water during the neutralization.
- the solvent solution of the condensation product is mixed with the desired metal base and, after neutralization and elimination of water, the solvent is evaporated leaving the metal salt of the condensation product.
- the barium salt of the above condensation product is a semi-solid to solid resin of brownish color.
- the neutralization is preferably effected in mineral oil solution.
- the condensation product or the solvent solution of the condensation product is dissolved in about 1 to about 5 volumes of mineral oil and the desired metal base and water is added.
- the resulting product is agitated and heated sufiiciently to efiect complete neutralization and subsequently filtered to remove solid impurities.
- the resulting product will be referred to as an oil concentrate of an oil-soluble metal salt of the condensation product of a hydrocarbon substituted phenol and a vinyl compound of the class described.
- Hydrocarbon substituted phenols which are useful in the preparation of the oil-soluble metal salts of this invention include the phenols having alkyl, cycloalkyl, aryl, aralkyl and alkaryl substituents.
- the substituents may be in the ortho-, metaor para-positions.
- the compound will have either an orthoand a paraposition free of substituents, or if the para-position is substituted then preferably both ortho positions should be free of substituents.
- Alkyl substituents include the butyl, amyl, iso-amyl, hexyl, heptyl, octyl, lauryl, cetyl and like radicals.
- alkyl substituents include the so-called wax radicals, i. e. radicals derived from parafin wax which may contain as high as or more carbon atoms.
- Wax phenols are well known in the art and may be prepared by reacting phenol with chlorinated parafiin wax in the presence of a Friedel-Crafts catalyst.
- Cycloalkyl substituents include cyclohexyl, methylcyclohexyl, cyclopentyl, methyl, ethyl and propyl cyclopentyl radicals and the like.
- Aryl radicals include the phenyl radical, as for example phenyl phenol. clude the benzyl radical and thus benzyl phenol.
- Alkaryl radicals include the radicals such as methylphenyl, ethylphenyl and the like.
- Vinyl compounds which are useful in preparing the condensation products are the lower Aralkyl radicals inmolecular weight vinyl ethers, as for example The molar ratio of hydrocarbon substituted phenol to vinyl compound to be used in preparing desirable condensation productswillbe.
- Catalysts or condensation agents which may be employed and which serve to effect the desired condensation reaction include the acid catalysts, as for example sulfuric acid and phosphoric acid, as well as the Friedel-Crafts type catalysts including aluminum chloride, boron tri fluoride, zinc chloride and the like.
- the acid catalysts as for example sulfuric acid and phosphoric acid
- the Friedel-Crafts type catalysts including aluminum chloride, boron tri fluoride, zinc chloride and the like.
- boron trifluoride this compound is generally employed in the form of its complex with diethyl ether.
- the complex is known as boron trifiuoride etherate and has a boiling point of about C.
- the amount of catalyst to be employed will generally be between about 0.5% and 10% by weight of the total reactants. However, as much as 20% may be employed if desired, with satisfactory results.
- Solvents which may be employed include those which do not react with phenols or with the vinyl compounds under the conditions of condensation. Such solvents include the hydrocarbon naphthas or thinners, aromatic solvents, as for example benzene, toluene, and xylene, and the like as well as chlorinated solvents such as chloroform, carbon tetrachloride and the like. Also, the condensation is satisfactorily effected using mineral oil as the solvent or diluent. Thus, the solvent can be the oil to be used in the preparation of the final lubricating oil composition. The amount of sol vent or diluent to be employed may be widely varied, although generally between 0.5 and 5 volumes of solvent per volume of reactants is found to give satisfactory results.
- the temperature of reaction will depend upon the reactants involved but will generally be between about 20 C. and about C. and preferably between about 0 C. and about 100 C.
- the temperature employed will depend to some extent upon the volatility of the vinyl compound employed. With the more volatile compounds, as for example vinyl chloride, lower temperatures are generally preferred and in this case particularly pressures of 1 to 3 or 4 atmospheres may be employed in order to maintain the reactants in solution or in liquid condition.
- the time of reaction is dependent upon the particular reactants and upon the temperature and catalyst employed, although generally it is found that between about 1 hour and 4 or 5 hours sufiice to effect the desired extent of condensation.
- entirely satisfactory condensation products have been prepared when the reaction conditions were maintained for as long as 24 hours. Products so obtained are found to be oil-soluble and metal salts derived from the condensation products are also oil-soluble.
- the metals to be employed in preparing metal salts are preferably the polyvalent metals, although the monovalent alkali metals are satisfactory in some instances.
- the sodium, potassium and lithium salts are found to be oilsoluble and have the desired characteristics when added to mineral lubricating oils.
- the polyvalent metals the alkaline earth metals calcium, magnesium, barium and strontium are particularly effective.
- the zinc, lead and emanate al uminum salts are suitable and insome cases chromium, iron, nickel; cobalt, mercury, tin and other polyvalent metalsalts have utility and areto be consideredpart of this invention, although this latter group of polyvalent metal salts are notto .be considered equivalent to the alkaline earth-metalsandzinc, lead and aluminum salts.
- the mixture is preferably madeby-a method: involving first preparing the alkali metal salt, as for-exampl e the sodium salt, and subsequently metathesizing the alkali metal salt an organic salt of the desired metal.
- the solutions are generally prepared by heating the oil: containing the metal salt to'a temperature of 100 C. to 150 C. and agitatingthe solution to effect rapidandcomplete solution: and/or dispersion.
- Lubricating oils which may be-employed includesubstantially all types of mineral lubricating-oils.
- the oil may be one having a viscosity index of 0 or even loweror-it maybe aparafllnic type oil having a-viscosi-ty index the neighborhood of 100. Particularly satisfactory results have been obtained using a solvent treatedWestern paraffino mineral lubricating" oil having a vis cosity 1 index of between about 85-and 95.
- invention iszwmodifiedz sulfonate prepared .by heating an mllesoluble:7
- merical detergency rating is assigned. The method of rating is similar to that employed in the Lauson engine test and 100% indicates a completely clean engine. Also the volume of carbon present in the top ring groove behind the ring is determined and this result is expressed at per cent by volume of the space behind the top ring at the start of the test.
- Example I A 438 g. (2.12 mols) portion of octylphenol is dissolved in 710 ml. of a light paraflinc naphtha and to this solution is added 182 g. (2.11 mols) of vinyl acetate. This mixture is placed in a flask equipped with a stirrer, thermometer and reflux condenser.
- the product is washed with Water until free of acid and then dissolved in 2500 g. of an SAE 30 solvent extracted Western mineral lubricating oil and the mixture heated to 140 C. to vaporize the paraiiinic naphtha used as solvent in the initial reaction.
- the product is converted into its barium salt by adding 187 g. of anhydrous barium hydroxide and 350 ml. of water. The water is added dropwise at 140 C. The resulting mixture is heated to 175 C., diluted with an additional 1000 g. of the same lubricating oil and filtered while hot using a filter aid.
- This product is an oil concentrate containing approximately 15.4% by weight of the barium salt of the condensation product of octylphenol with vinyl acetate. This product without further dilution operates satisfactorily in a Lauson engine, giving a high detergency and very low bearing weight losses.
- a lubricating oil is prepared by dissolving 21.8 parts by weight of the above oil concentrate and about 3.7 parts by weight of an oil concentrate of calcium petroleum sulfonate in 74.5 parts by weight of the same SAE? 30 mineral lubricating oil described above.
- the resulting oil containing approximately 3.4% by weight of the barium salt and having a calcium sulfate ash due to calcium sulionate of approximately 0.24% is tested in a Caterpillar engine as described above, using a fuel containing 1% of sulfur.
- This oil has a detergency rating at 120 hours of 96% and at 240 hours of 96%.
- the percent of carbon in the top ring groove is 13 at 120 hours and 11 at 240 hours.
- the base oil without additives cannot be tested in this engine using a 1% sulfur fuel for the reason that the deposits are so great as to cause piston and ring sticking at far less than 120 hours to such an extent that it is impossible to complete the test.
- the base oil, 1. e. the oil without additives, run in the same engine using a low sulfur fuel has a detergency rating of approximately 55% at 120 hours.
- Tests on the base oil, on the oil concentrate as produced above, and on the oil prepared for testing in the Caterpillar test engine are as follows:
- Example II To 138 g. (0.67 mol) of octylphenol is added 57.6 g. (0.67 mol) of vinyl acetate. The mixture is stirred and cooled to 10 C. and concentrated sulfuric acid is added drop-wise to the mixture. A total of 7.3 ml. (0.13 mol) of the acid is employed. The temperature of the reaction mixture rises rapidly to 50 C. where violent boiling occurs. The sulfuric acid is added over a period of approximately 20 minutes and the reaction continued for approximately 3 hours, at which time the product is taken up in 500 ml. of benzene and Washed free of acid with water.
- the water-washed benzene solution is evaporated on a steam bath to remove the benzene and the product dissolved in 823 g. of the mineral lubricating oil described in Example I by heating the mixture with stirrin to 140 C.
- To the heated oil solution is added 100 g. of anhydrous barium hydroxide and ml. of water, the latter being added drop-wise, maintaining a temperature of about 140 C.
- the neutralization is complete the product is heated to C. and filtered hot using a filter aid.
- the product has a sulfate ash of 8.4% and a soap number of 36.7 mg. KOH/g.
- a lubricating oil is produced by dissolving a portion of the above product in mineral lubricating oil of the type described in Example I.
- the resulting oil contains 8.54% by weight of the product and has a sulfate ash of 0.72%.
- This oil tested in the Lauson engine has a detergency of 80% and bearing weight losses of 2, 12 and 64 mg. at 20, 40 and 60 hours, respectively.
- a second lubricating oil is prepared which contains 4.27% by weight of the product of this example and approximately 3.2% of calcium mahogany sulfonate oil concentrate.
- This oil has a sulfate ash of 0.36% due to the octylphenol vinyl acetate condensation product salt and 0.21% due to calcium sulfonate.
- the oil employed is the same as that used above. Tests on this product in the Lauson engine show the oil to have a detergency of 79% and bearing weight losses of 90, 265 and 408 mg. at 20, 40 and 60 hours, respectively.
- a Lauson engine test on the base oil without additives shows a detergency of 58% and bearing weight losses of 175 mg. and 500 mg. at 20 and 40 hours, respectively. Because of severe corrosion, in order to continue the engine operation for the required 60 hours the copper-lead bearings must be removed at 40 hours and replaced with Babbitt bearings.
- Example III To 440 g. (2 mols) of nonylphenol dissolved in one liter of naphtha is added 40 ml. (46 g.) of boron trifluoride etherate. The resultin solution is heated to 30 C. and gaseous vinyl chloride is bubbled into the reactionmixture for ithe nonylphenol-vinyl chloride product.
- cium hydroxide using 27g. of calcium hydroxide and approximatelyfifl m1. of water.
- the product is'heated; to 175C. andyfiltered. This prodnot is an oil concentrate, of the. calcium salt of condensation Approximately two-thirds of the condensation product in oil solution is neutralized. by treatment with '59.. gof sodium hydroxide and. 100 The product is heated to 200 C.
- sodium salt as described in the preceding .paragraph is;diluted with .500 mLof. a lightpetroleum naphtha and to this solutionis added 100 g. of 'zinc chloride in 250 ml. of isopropanol. product is heated to evaporate the naphtha and The alcohol and. then filtered. This product. is. an
- Lubricating oils are preparedjby dissolving byweight 01 each of'the above .metal salt concentrates'in additional quantities of the mineral lubricating. oil described in Example '1. Enginetests on “these oils show that the condensation product salts impart both detergency and anticorrosion characteristics to the base oil.
- EmampZe'IV "To 529. g. .(3. mols) of oecyclohex-ylphenol is I added 2 liters of alight petroleum thinner con- 'sisting primarily of-hexanes-and heptanes-and 180 g. (2.5mols) of. vinyl ethyl ether.
- the product is anoil concentrate of the lead salt .of
- ApproXimateIyone-third of the oil solution of the condensation product produced as above. is neutralized by treatment with freshly precipitate.d':magnesium hydroxide (32 g) as'a slurry in water. The mixture is heated with stirring to 1175.9 .67; andfilteredto yieldaan oilccncentrate of the: magnesium saltof .o eyclohex-ylphen'olevinyl hyl; ether condensation. product.
- Thezremainins oneethirdincrtionior the-:oilzsolutionofathe. condensation; ypreductaproducedas above is neutralized withjlithium.hydroxideiusin approximately 14.6 g. of the. lithium hydroxide .monohydrate in 250 m1. of water. is. heated with stirring to. 100 C. and filtered move solids.
- each .oi theabove metal salt concentrates, dissolved in mineralljlubricating, oil to give products containing approximately- 2% by weight of the metal. salt,flhave detergency and anti-corrosion characteristics similar to those of the oil prepared as described. in Example I.
- Example- V A paraffin 'wax having .anqaverage molecular weightpf about 350 *istreated; with. gaseous chlorine to, obtain a chlorinated paraffin wax containing-approximately'one; atom of'c'hlorine per molecule ofthewax; This productzis condensediwith phenol in the presence of anhydrous aluminum chloride to obtain awax substituted phenol having a molecular weight of approximately 450.
- Example VI To. 170. g. of p-phenylphenol' in. solution in one. liter :of naphthaisadded 34 g. of boron-trifluoride .etherate. To thismixture is. added 86 g. of vinyl. isopropyl ether. The ether. is added slowly while maintaining. a temperature between 20f C. and 30 C.:and:whenxtheadditionuiscompletethemixtureis maintained at room. temperature .for. approximately three hours and then water washed to-remove condensation agent.
- a lubricatinggoil containing approximately 10 by'weight: of. the above. oiliconcentrate operates satisfactorily in heavy duty-dieselrengine service.
- solvent refined lubricating oil having a viscosity index of approximately 85 and to this solution is added 86 g. of vinyl acetate.
- the mixture is maintained at 75 C. and g. of concentrated sulfuric acid is slowly added. Heating and stirring is continued for approximately 10 hours, at which time the solution is water washed to remove acid.
- the product is neutralized by treatment with 174 g. of barium hydroxide octahydrate and gradually heated to 175 C., at which temperature it is filtered.
- the filtrate is an oil concentrate of the barium salt of an octylphenol-vinyl acetate condensation product.
- This product when dissolved in mineral lubricating oil to give an oil containing approximately 3% by weight of the barium salt, imparts detergency and anti-corrosion characteristics to the oil.
- Example VIII To 305 g. of m-pentadecylphenol and 57 g. of vinyl acetate in solution in 1500 ml. of a light petroleum naphtha is added g. of concentrated sulfuric acid. The temperature of the reaction mixture rises rapidly to about 80 C. where refluxing occurs. This temperature is maintained for approximately 3 hours and the product then water washed.
- the above condensation product is dissolved in 2500 g. of mineral lubricating oil as described in Example I and neutralized with 46 g. of lithium hydroxide monohydrate and 100 ml. of water.
- the product is heated to 175 C. to remove naphtha and water and filtered while hot.
- the resulting product is an oil concentrate of the lithium salt of a m-pentadecylphenol-vinyl acetate condensation product.
- This product when dissolved in additional quantities of lubricating oil, imparts detergency and anti-corrosion characteristics to the oil.
- Example IX Example VIII repeated using carbon tetrachloride in place of light petroleum thinner as the solvent results in a product substantially identical to that obtained with the thinner.
- metals described as being useful for the preparation of metal salts of the condensation products are also useful in preparing metal sulfonates and metal sulfonate complexes which cooperate with the additives of this invention to produce noncorrosive lubricating oils of exceptionally high detergency.
- Such metal sulfonates or metal sulfonate complexes when used in conjunction with the additives of this invention, are used in amounts between about 0.5% and about 10% based on the finished oil.
- uct of a hydrocarbon substituted phenol in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms, and a vinyl compound selected from the class consisting of divinyl ether, Vinyl ethyl ether, vinyl propyl ether, vinyl esters of hydrohalogen acids and vinyl esters of fatty acids containing between 1 and 6 carbon atoms in the fatty acid radical, said condensation product being obtained by condensing said phenol with said.
- vinyl compound in the molar ratio of between 0.5 and 3 to 1 at temperatures between about 20 C. and about 150 C.
- a mineral lubricating oil containing between about 0.05 and about 20% by weight of an oilsoluble alkaline earth metal salt of the acidic condensation product of a hydrocarbon substituted phenol, in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms, and a vinyl compound selected from the class consisting of divinyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl esters of hydrohalogen acids and vinyl esters of fatty acids containing between 1 and 6 carbon atoms in the fatty acid radical, said condensation product being obtained by condensing saidphenol with said vinyl compound in the molar ratio of between 0.5 and 3 to 1 at temperatures between about 0 C. and about C. v
- a mineral lubricating oil containing between about 0.05 and about 20% by weight of an oilsoluble alkali metal salt of the acidic condensation product of a hydrocarbon substituted phenol in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms and a vinyl compound selected from the class consisting of divinyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl esters of hydrohalogen acids and vinyl esters of fatty acids containing between 1 and 6 carbon atoms in the fatty acid radical, said condensation product being obtained by condensing said phenol with said vinyl compound in the molar ratio of between 0.5 and 3 to 1 at temperatures between about -20 C. and about C.
- a mineral lubricating oil containing between about 0.05% and about 20% by weight of an oilsoluble metal salt of the acidic reaction product obtained by condensing at a temperature between 0 C. and 100 C. a hydrocarbon substituted phenol in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms with vinyl actate using a molar ratio of phenol to vinyl acetate of between 0.8 and 2 to 1.
- a mineral lubricating oil containing between about 0.05% and about 20% by weight of an oil-soluble metal salt of the acidic reaction product obtained by condensing cyclohexyl phenol with vinyl ethyl ether using a molar ratio of phenol to vinyl ethyl ether of between 0.8 and 2 to 1, the condensation being effected at temperatures between 0 C. and 100 C.
- a mineral lubricating oil containing between about 0.05% and about 20% by weight of an oil-soluble metal salt of the acidic reaction product obtained by condensing a hydrocarbon substituted phenol in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms with vinyl chloride, at a temperature between about C. and about 100 0., using a molar ratio of phenol to vinyl chloride between 0.8 and 2 to 1.
- a mineral lubricating oil according to claim 1 containing also between about 0.5% and about 10% by weight of an oil-soluble metal sulfonate.
- a mineral lubricating oil according to claim 1 containing also between 0.5% and 10% of a modified sulfonate prepared by heating an oilsoluble metal sulfonate with an inorganic base selected from the class consisting of metal oxides, hydroxides, carbonates and bicarbonates to solubilize said base, said modified sulfonate having a ratio of equivalents of metal to equivalents of sulfonic acids between 1.1 and 3 to 1.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
Patented Oct. 20, 1953 UNITED STATE S P UF F'I CE LUBBICATING OILS CONTAINING:
' y SALTS 0F A.CONDENSATIONBPRODUUE.QF i SUBSTITUTED PHENOLHANDWAYVINYL "COMPOUND Loren. L.. Nefi, .Long vBeach, Galif;,iassi'gnor to .Unionfiil'company of Caliionnia LoszAngeles', Calif .21.. corporation-of California.
' N'o Drawing. Application 11113:. 1'7, 1950,v Serial-No. 174:3.67
vinylzcompoundsiandrtolubrieatinggoils containing suchimetal salts.
Thepresent trcnd internal combustion .611.- gin'es, .particularlyof :theydiesel engine :type, isin the direction ..ofihigher. compressioniratios', higher operating ltemperaturesiand thus. higherhorsa power output. "per, unit weight :of :the engine. Moreover, it is the i160 operate engines of. this type for;longerperiods;withouttoihchangeso that oils which'are satisfactory for'zuse in the present-day high output..diesel..engines,..ior .ex
ample, must have: not; only an initially high detergency and initially high anti=corrosion characteristics. bpt thesehproperti'es must .:.be";retained undersever conditionsrofuse .for'relativelyxlong,
periodsof use in anengine. To furthercomplb cate thepreparation oi'ra satisfactory oil for the;
lubrication of such; engines. the. fuels-available often contain higher proportions :of. :sulfurathan those: [which-have .been: used in the past and itis.
well. recognized: that high. sulfur. .fuels" tend to produce: corrosive.- conditions: in an engine which must be overcome by thexlubricatingt'oil employed, otherwise notonly does corrosion take place in the enginebutwearratesraresufliciently' high that frequent overhaul and replacement of parts becomes necessary, therebyunduly increasing: engine operation; cost.
In order to prepare oils. which: may be used in.
engines, of the character described it has been the practice to merely increase-thepercentage of.
additive. materials which have been. used, inxthe past in ordinarydiesel engines,;automotive *enginesand the like;, hoping toagainthe GXEIELQPID-L tectionnecessary byzthe. useof these larger proportions. i
It is an object of. this invention:to prepare' a lubricating oil which. will operatesatisfactorily in internal combustion engines and particularlyin the high output :diesel engines over relatively long-periods of service. It is another objectto prepare such lubricating oils which will protect engines of: this type:operatingundersevere conditions even while using aqfuel'containi'ngaas high as 1% or moreof sulfur;
It is round-that these and other objects can 3 of hydrohalogen. acidsxand. fatty. .acids.
be 'obtained by adding Ito :mineral lubricatingml.
relatively small amounts iof :an oil-soluble metal. salt i of the :condensation product. oifa .hydrocar bon substituted phenol-and vinyh compound .of .the' type described hereinb'elo w.
Thus thei'nvention residesuinclubricating zoils' contain-ing 'b'etween about; 0.05 :and :aloouttlO %1 or as *high as-about- 20% by:weight.ofi'annihsoluble meta-1 salt: of t'he1 condensation product robtained by condensing a hydrocarbon substituted phenol wherein the hydrocarbon substituentbr substituents contain. between about? 4 and: about 30 carbon: atoms with 'awinylicompoundi of. they class consisting .of. vinyl ethers: .andsvinyl J esters: These condensationzproducts are-acidic andrcapable of. reacting with metal'r basesrasiorexample. metal; oxides, hydroxides and: carbonates, undenappropriate conditions. to .form. .the. corresponding metalsalts. hydrohalogen. acids used'herein ini itszusual sense andincludes. hydrogen chloride, hydrogen brmnide hydrogen Jfluoride andhydrogeniodidei. Theseacidszmay also be termed hydrogen ::halides..
Atypical. oilesolublemetal salt. is produced by reacting approximately .one molecular proportion.
of:octy1 .phenoli with. one .=molecular proportion of vinyl acetate. The tphenoliandacetate are dissolved inzabout52i parts; Icy-volume of a petroleum naphtha. and 'tO".t'hBi. S01utiOIL is-added. about 2. parts by rvolume .ofa condensation catalyst, e. g.;. sulfuric acid; IIhecatalystis; added slowly -.andthe 'temperature. of the reaction. mixture isinaintainedzat aepoint suchgthatthe vinyl acetate is not vaporized: excessively. Preferably, because of .thedowjsboilinspomt ofuvinyl acetate, the .re-
action-is conducted under a. reflux condenser. Under any circumstance, by maintaining; a. temperature in. this instance-between about 30 'C. and. about 0 .C.. .the reaction proceeds rapidly andasmoothly and is:.comp1ete in approximately. 1.5,:t0p2 hours; SiIlGQat-he reactionaisi-exothermic,
completion-of the 31630131011: can. be determined. by
following the temperature of the reaction. mixture. Thus,.whereasduringtheearly part-of the reaction; cooling; is necessary order. to maintain the temperature within the-rrange .of. 30-
C. to 40"C.,.t0wardIthe:end of the reaction-heat.
maybe necessary in ordertoimaintain this-temp .peraturer Fo'llowingzthe completion:- ofuthe zreac tion the product is:ooo1ed=and wateriwashed' til free of mineral acidz. Uponevap'orationaof the solvent. naphtha employed: there remains: a; semisolid resin havingia brownishcolor- .The resin maybe convertedsinto its.;metaltsalt,i.as,for:-ex v ample the barium salt, by treatment of a solvent solution, as for example a naphtha, or a hydrocarbon lubricating oil solution of the resin with barium hydroxide octahydrate or with anhydrous barium hydroxide, in which latter case it is necessary to add small amounts of water during the neutralization. Where the metal salt is the desired product, the solvent solution of the condensation product is mixed with the desired metal base and, after neutralization and elimination of water, the solvent is evaporated leaving the metal salt of the condensation product. The barium salt of the above condensation product is a semi-solid to solid resin of brownish color. Where it is desirable to prepare a lubricating oil concentrate of the metal salt of the condensation product the neutralization is preferably effected in mineral oil solution. In this case the condensation product or the solvent solution of the condensation product is dissolved in about 1 to about 5 volumes of mineral oil and the desired metal base and water is added. The resulting product is agitated and heated sufiiciently to efiect complete neutralization and subsequently filtered to remove solid impurities. The resulting product will be referred to as an oil concentrate of an oil-soluble metal salt of the condensation product of a hydrocarbon substituted phenol and a vinyl compound of the class described.
Hydrocarbon substituted phenols which are useful in the preparation of the oil-soluble metal salts of this invention include the phenols having alkyl, cycloalkyl, aryl, aralkyl and alkaryl substituents. The substituents may be in the ortho-, metaor para-positions. Preferably the compound will have either an orthoand a paraposition free of substituents, or if the para-position is substituted then preferably both ortho positions should be free of substituents. Alkyl substituents include the butyl, amyl, iso-amyl, hexyl, heptyl, octyl, lauryl, cetyl and like radicals. These radicals may be normal or branched chain groups and the phenol may contain one or more of these substituents. Moreover, the alkyl substituents include the so-called wax radicals, i. e. radicals derived from parafin wax which may contain as high as or more carbon atoms. Wax phenols are well known in the art and may be prepared by reacting phenol with chlorinated parafiin wax in the presence of a Friedel-Crafts catalyst. Cycloalkyl substituents include cyclohexyl, methylcyclohexyl, cyclopentyl, methyl, ethyl and propyl cyclopentyl radicals and the like. Aryl radicals include the phenyl radical, as for example phenyl phenol. clude the benzyl radical and thus benzyl phenol. Alkaryl radicals include the radicals such as methylphenyl, ethylphenyl and the like.
Vinyl compounds which are useful in preparing the condensation products are the lower Aralkyl radicals inmolecular weight vinyl ethers, as for example The molar ratio of hydrocarbon substituted phenol to vinyl compound to be used in preparing desirable condensation productswillbe. be-
4 tween about 0.5 and about 3 to 1. Preferably this molar ratio will fall between about 0.8 and about 2 to 1. Particularly satisfactory results have been obtained using approximately equal molecular proportions of hydroxy compound and vinyl compound.
Catalysts or condensation agents which may be employed and which serve to effect the desired condensation reaction include the acid catalysts, as for example sulfuric acid and phosphoric acid, as well as the Friedel-Crafts type catalysts including aluminum chloride, boron tri fluoride, zinc chloride and the like. In the case of boron trifluoride, this compound is generally employed in the form of its complex with diethyl ether. The complex is known as boron trifiuoride etherate and has a boiling point of about C. The amount of catalyst to be employed will generally be between about 0.5% and 10% by weight of the total reactants. However, as much as 20% may be employed if desired, with satisfactory results.
Although the condensation reaction will take place in the absence of solventor diluent, it is generally desirable to employ a solvent during the condensation reaction. Solvents which may be employed include those which do not react with phenols or with the vinyl compounds under the conditions of condensation. Such solvents include the hydrocarbon naphthas or thinners, aromatic solvents, as for example benzene, toluene, and xylene, and the like as well as chlorinated solvents such as chloroform, carbon tetrachloride and the like. Also, the condensation is satisfactorily effected using mineral oil as the solvent or diluent. Thus, the solvent can be the oil to be used in the preparation of the final lubricating oil composition. The amount of sol vent or diluent to be employed may be widely varied, although generally between 0.5 and 5 volumes of solvent per volume of reactants is found to give satisfactory results.
The temperature of reaction will depend upon the reactants involved but will generally be between about 20 C. and about C. and preferably between about 0 C. and about 100 C. The temperature employed will depend to some extent upon the volatility of the vinyl compound employed. With the more volatile compounds, as for example vinyl chloride, lower temperatures are generally preferred and in this case particularly pressures of 1 to 3 or 4 atmospheres may be employed in order to maintain the reactants in solution or in liquid condition.
The time of reaction is dependent upon the particular reactants and upon the temperature and catalyst employed, although generally it is found that between about 1 hour and 4 or 5 hours sufiice to effect the desired extent of condensation. However, entirely satisfactory condensation products have been prepared when the reaction conditions were maintained for as long as 24 hours. Products so obtained are found to be oil-soluble and metal salts derived from the condensation products are also oil-soluble.
The metals to be employed in preparing metal salts are preferably the polyvalent metals, although the monovalent alkali metals are satisfactory in some instances. Thus the sodium, potassium and lithium salts are found to be oilsoluble and have the desired characteristics when added to mineral lubricating oils. Of the polyvalent metals, the alkaline earth metals calcium, magnesium, barium and strontium are particularly effective. However, the zinc, lead and emanate al uminum salts are suitable and insome cases chromium, iron, nickel; cobalt, mercury, tin and other polyvalent metalsalts have utility and areto be consideredpart of this invention, although this latter group of polyvalent metal salts are notto .be considered equivalent to the alkaline earth-metalsandzinc, lead and aluminum salts.
In preparing metal salts of'the condensation products asolvent solution or a lubricating oil solution of the condensation.produutisheated with the desired metal base, i; e. oxide, hydroxide or carbonate, in the presence of a small amount of water or in the presence of a small amount of alcohol. The mixture ;,isagitated and heated to eliminate water and efiect neutralization. In the-case of the more weakly basic metals the metal salt is preferably madeby-a method: involving first preparing the alkali metal salt, as for-exampl e the sodium salt, and subsequently metathesizing the alkali metal salt an organic salt of the desired metal. This metathesis is carried out in alcoholic solution=in or- 'der'='to prevent "hydrolysis whichwould- -occur aqueous solution. Methodsofmetathesizingayeah aci'ol salts are Well known-in theart and there- 1 foreneecl no=further descriptionhere; This-same method of preparation may -be--employed in "producing any of the*p'olyvalent metal salts-if so desired.
"In preparing finished lubricating oils the'oilsoluble-metal salts or theoil concentrates'thereof, produced as indicated-above, are added-to mineral lubricating oil in proportions such that the final oil will contain *between about 0.05%
and a-bout 20% and preferably between about 0.5 and %byweight ofthe salt. Although'no diflieulty is encountered in preparing oil-solutions becauseof the readyoil-solubilityor oildispersibility of these com-pounds, the solutions are generally prepared by heating the oil: containing the metal salt to'a temperature of 100 C. to 150 C. and agitatingthe solution to effect rapidandcomplete solution: and/or dispersion.
Lubricating oils which may be-employed includesubstantially all types of mineral lubricating-oils.
Thus 'the oilmay be one having a viscosity index of 0 or even loweror-it maybe aparafllnic type oil having a-viscosi-ty index the neighborhood of 100. Particularly satisfactory results have been obtained using a solvent treatedWestern paraffino mineral lubricating" oil having a vis cosity 1 index of between about 85-and 95.
Although lubricating oils containing the addi-- knownin the art, appear to. cooperate with the additivesyof this inventionto produce outstanding lubricating oils. Thus by .addingbetyeeen,..abo.ut
0.5 and 5% by weight-of a metalgpetroleumsule fonate it is found that the detergency of the oil is improved withoutadverselyafiecting the anticorrosion or anti-oxidation characteristics of .the oiL.
..Another detergent which. appears to :cooperate.
with-theadditivesof this. invention iszwmodifiedz sulfonate prepared .by heating an mllesoluble:7
metal petrcleumssulfonateiwithraniinorganica'baseJ Thus; 1
to solubiliZe the base the :sulf'onate. mahogan-y sulronic.acids:may:be:reacted withim organic -bases as, Lfor==examp1e, withimetal oxides;
5 hydroxides, carbonates:andibicarbonates,.torpro Such-:oil-soldble complexes of sulionic acidsand" metallhydroxides oxides, carbonates andrlthealike.
which may be employed together with=the=addi- 15; itive of this invention; are .those described by Mertes in U. S. Patents Nos. 2,501,731 and 137 1 Three different engine tests have been em ployed in'- the evaluation of lubricatingoils contaming-theoil soluble'metaisalts-ofthis -inventi'on; Thesetestshavebeen carried out in lnauson single cylinder engines, standard G cylinderChevrol'et engines and a single cylinder Caterpillar dieselstandard test engine. The tests are re-- :ferredto as the Lauson engine test, the Chevrolet'enginetest and the Caterpillar test, respectively.
'Tests in'the Liausonsingle cylinder test engines are-carried out such amanner that the oil is .-:subjected to severe service conditions. "Ihis test is employed to determine the-corrosiontendencies of the oil and to determine the tGHdGHGY-TOIWIIQ oil to deposit resinous and lacquer-like materials in theengine. in carrying out the Lauson 1 engine itest the engine is operated for a total of 60 hours undera load of about 3.5 horsepowenwith acoolant temperature of about 295 F. and an oiltemperature of about 280 F. At the endof -the test the cleanliness of-the engine is observed andthe 011' isgi-ven anumericaldetergencyrating between 0 and.- 100 where 100 indicates a perfectly I clean-engine.- Thuaadetergency rating of 100%- would indicate-thatduring the test witha given oilthereweresubstantially-no. lacquer or varnishlikedeposits withinthe engine. The -eorrosivity of the oil is measured by -determining the-loss :inweight of corrosion-sensitive copper-lead bearings duringtheperiod of test.
In those casesin whieh corrosion is extremely severeiandthereappearsto be danger of :engine failure due toexcessive corrosiono-r thebearings as indicated-by an examination made-at the 40- =hour period, the copper-lead bearings are are placedwithBabbitt bearings-in order to complete thefSO-hourtest. The results of such enginetests are shownin connection-with some of the examplespresented hereinbelow.
In the Chevroletengine'test the engine is op erated under a loadof about horsepower with a coolant temperature of aboutZQO -F. and an oi1 temperatureof about 280" F. This test -is-.used to evaluate corrosivity of A the lubricant. The loss diesel fuel. containing: 12%. by Wei h 1 f .fiulfl r- Generally, the bearingsare removedandweighed after 20-, and hours of operation.
.in weight of copper-lead bearings is determined "After 120..hours.and atithezendv ofthe test.a.nu;-
merical detergency rating" is assigned. The method of rating is similar to that employed in the Lauson engine test and 100% indicates a completely clean engine. Also the volume of carbon present in the top ring groove behind the ring is determined and this result is expressed at per cent by volume of the space behind the top ring at the start of the test.
The following examples illustrate some modifications of the invention, however it is to be realized that various modifications of the described methods of preparation and the described condensation product salts come within the scope of the invention.
Example I A 438 g. (2.12 mols) portion of octylphenol is dissolved in 710 ml. of a light paraflinc naphtha and to this solution is added 182 g. (2.11 mols) of vinyl acetate. This mixture is placed in a flask equipped with a stirrer, thermometer and reflux condenser.
Sulfuric acid (98% concentration) is added drop-wise through the reflux condenser until a total of 23.3 ml. (approximately 0.42 mols) has been added. During the initial addition the temperature rises to a point of rapid reflux (about 60 (3.), and the addition is continued at a rate such that refluxing continues. Following the addition of the sulfuric acid the mixture is heated at its reflux temperature for 2.5-3 hours and then cooled.
The product is washed with Water until free of acid and then dissolved in 2500 g. of an SAE 30 solvent extracted Western mineral lubricating oil and the mixture heated to 140 C. to vaporize the paraiiinic naphtha used as solvent in the initial reaction.
The product is converted into its barium salt by adding 187 g. of anhydrous barium hydroxide and 350 ml. of water. The water is added dropwise at 140 C. The resulting mixture is heated to 175 C., diluted with an additional 1000 g. of the same lubricating oil and filtered while hot using a filter aid. This product is an oil concentrate containing approximately 15.4% by weight of the barium salt of the condensation product of octylphenol with vinyl acetate. This product without further dilution operates satisfactorily in a Lauson engine, giving a high detergency and very low bearing weight losses.
A lubricating oil is prepared by dissolving 21.8 parts by weight of the above oil concentrate and about 3.7 parts by weight of an oil concentrate of calcium petroleum sulfonate in 74.5 parts by weight of the same SAE? 30 mineral lubricating oil described above. The resulting oil containing approximately 3.4% by weight of the barium salt and having a calcium sulfate ash due to calcium sulionate of approximately 0.24% is tested in a Caterpillar engine as described above, using a fuel containing 1% of sulfur. This oil has a detergency rating at 120 hours of 96% and at 240 hours of 96%. The percent of carbon in the top ring groove is 13 at 120 hours and 11 at 240 hours.
In comparison, the base oil without additives cannot be tested in this engine using a 1% sulfur fuel for the reason that the deposits are so great as to cause piston and ring sticking at far less than 120 hours to such an extent that it is impossible to complete the test. The base oil, 1. e. the oil without additives, run in the same engine using a low sulfur fuel has a detergency rating of approximately 55% at 120 hours.
Tests on the base oil, on the oil concentrate as produced above, and on the oil prepared for testing in the Caterpillar test engine are as follows:
Base Concentrate Oil T sted on (15.4% of in Cater- Barium Salt) pillar Engine Viscosity, SSU at:
Example II To 138 g. (0.67 mol) of octylphenol is added 57.6 g. (0.67 mol) of vinyl acetate. The mixture is stirred and cooled to 10 C. and concentrated sulfuric acid is added drop-wise to the mixture. A total of 7.3 ml. (0.13 mol) of the acid is employed. The temperature of the reaction mixture rises rapidly to 50 C. where violent boiling occurs. The sulfuric acid is added over a period of approximately 20 minutes and the reaction continued for approximately 3 hours, at which time the product is taken up in 500 ml. of benzene and Washed free of acid with water. The water-washed benzene solution is evaporated on a steam bath to remove the benzene and the product dissolved in 823 g. of the mineral lubricating oil described in Example I by heating the mixture with stirrin to 140 C. To the heated oil solution is added 100 g. of anhydrous barium hydroxide and ml. of water, the latter being added drop-wise, maintaining a temperature of about 140 C. When the neutralization is complete the product is heated to C. and filtered hot using a filter aid. The product has a sulfate ash of 8.4% and a soap number of 36.7 mg. KOH/g.
A lubricating oil is produced by dissolving a portion of the above product in mineral lubricating oil of the type described in Example I. The resulting oil contains 8.54% by weight of the product and has a sulfate ash of 0.72%. This oil tested in the Lauson engine has a detergency of 80% and bearing weight losses of 2, 12 and 64 mg. at 20, 40 and 60 hours, respectively.
A second lubricating oil is prepared which contains 4.27% by weight of the product of this example and approximately 3.2% of calcium mahogany sulfonate oil concentrate. This oil has a sulfate ash of 0.36% due to the octylphenol vinyl acetate condensation product salt and 0.21% due to calcium sulfonate. The oil employed is the same as that used above. Tests on this product in the Lauson engine show the oil to have a detergency of 79% and bearing weight losses of 90, 265 and 408 mg. at 20, 40 and 60 hours, respectively.
A Lauson engine test on the base oil without additives shows a detergency of 58% and bearing weight losses of 175 mg. and 500 mg. at 20 and 40 hours, respectively. Because of severe corrosion, in order to continue the engine operation for the required 60 hours the copper-lead bearings must be removed at 40 hours and replaced with Babbitt bearings.
Example III To 440 g. (2 mols) of nonylphenol dissolved in one liter of naphtha is added 40 ml. (46 g.) of boron trifluoride etherate. The resultin solution is heated to 30 C. and gaseous vinyl chloride is bubbled into the reactionmixture for ithe nonylphenol-vinyl chloride product.
m1; of water. andfiltered. This product is .an oil concentrate .three hours. at which. time ap roximately 12'? g.
naphtha.
Approximately.one third of the above product .isfheated to 125 and neutralized with. .cal-
cium hydroxide using 27g. of calcium hydroxide and approximatelyfifl m1. of water. The product is'heated; to 175C. andyfiltered. This prodnot is an oil concentrate, of the. calcium salt of condensation Approximately two-thirds of the condensation product in oil solution is neutralized. by treatment with '59.. gof sodium hydroxide and. 100 The product is heated to 200 C.
ofthe sodium, salt of the nonylphenol-vinylichloride condensation product.
Approximately one-half of the oil solution. of
"sodium salt as described in the preceding .paragraph is;diluted with .500 mLof. a lightpetroleum naphtha and to this solutionis added 100 g. of 'zinc chloride in 250 ml. of isopropanol. product is heated to evaporate the naphtha and The alcohol and. then filtered. This product. is. an
oil concentrate of the:zinc, salt of the. nonylphenol-vinyl chloride .condensation product.
Lubricating oils are preparedjby dissolving byweight 01 each of'the above .metal salt concentrates'in additional quantities of the mineral lubricating. oil described in Example '1. Enginetests on "these oils show that the condensation product salts impart both detergency and anticorrosion characteristics to the base oil.
EmampZe'IV "To 529. g. .(3. mols) of oecyclohex-ylphenol is I added 2 liters of alight petroleum thinner con- 'sisting primarily of-hexanes-and heptanes-and 180 g. (2.5mols) of. vinyl ethyl ether.
in Example ,I andthe .oil: solution. heatedto: evaporate hydrocarbon thinner.
Approximately. one-third of the? above oil .so-
lutionofcondensation product is treated with 123g. .olflead oxide and 10.0. ml. of water; The
.mixtureis heated. with stirring to 175 C...and then...filter.ed while hot, using a filter aid. The product is anoil concentrate of the lead salt .of
'o-cyclohexylphenol vinyl ethyl ether condensation'product.
ApproXimateIyone-third of the oil solution of the condensation product produced as above. is neutralized by treatment with freshly precipitate.d':magnesium hydroxide (32 g) as'a slurry in water. The mixture is heated with stirring to 1175.9 .67; andfilteredto yieldaan oilccncentrate of the: magnesium saltof .o eyclohex-ylphen'olevinyl hyl; ether condensation. product.
Thezremainins oneethirdincrtionior the-:oilzsolutionofathe. condensation; ypreductaproducedas above is neutralized withjlithium.hydroxideiusin approximately 14.6 g. of the. lithium hydroxide .monohydrate in 250 m1. of water. is. heated with stirring to. 100 C. and filtered move solids.
The mixture while hotto yield the corresponding lithium salt .in oil solution.
.Each .oi theabove metal salt concentrates, dissolved in mineralljlubricating, oil to give products containing approximately- 2% by weight of the metal. salt,flhave detergency and anti-corrosion characteristics similar to those of the oil prepared as described. in Example I.
Example- V .A paraffin 'wax having .anqaverage molecular weightpf about 350 *istreated; with. gaseous chlorine to, obtain a chlorinated paraffin wax containing-approximately'one; atom of'c'hlorine per molecule ofthewax; This productzis condensediwith phenol in the presence of anhydrous aluminum chloride to obtain awax substituted phenol having a molecular weight of approximately 450.
About 450 g. of the wax substituted phenol prepared as just described is mixed with 86 g; of vinyl acetate and 20 g. of concentrated sulfuric acid isadded to themixture slowly withstirring. The rate of addition is so controlled-that the-temperature of the reaction mixture is maintained between C. and C. After the addition of sulfuric acid is complete the reaction mixture is-maintained at about the same temperature'and stirred for an additional two hours. The product is dissolved in one liter ofpetroleum naphtha and water-washed to remove acid; The water- Washed product is neutralized 'with calcium hydroxide in the presence of a small amount of'water by refluxing thenaphtha solution for three hours. Excess water is removed by continuing the refluxing with a watertrap in the reflux line and the dehydrated solution is filtered to re- After evaporation of the naphtha the product consists of the calcium salt of awax substituted phenol-vinyl acetate condensation product.
.A lubricating oilprepared by'dissolving 6% by weight of the'aboveproduct in ans All 30mineral lubricating oil: having .a viscosity index of about 50 has good detergencyand exceptional anti-corrosioncharacteristics :as indicated by a bearing weight lossof less-than lDOrmg; in the Chevrolet engine test.
Example VI To. 170. g. of p-phenylphenol' in. solution in one. liter :of naphthaisadded 34 g. of boron-trifluoride .etherate. To thismixture is. added 86 g. of vinyl. isopropyl ether. The ether. is added slowly while maintaining. a temperature between 20f C. and 30 C.:and:whenxtheadditionuiscompletethemixtureis maintained at room. temperature .for. approximately three hours and then water washed to-remove condensation agent.
To theabove productisadded 1000 g. :01 mineral lubricating oiland the .oil: solution isneutralized with 94 .g. .of anhydrous barium hydroxide .using ml. of water. The. mixture is. heated slowly to C; toremoveesolvent andwat'er-and then filtered. The filtered product consistsoi an oil concentrate of the bariumsalt of aphenylphenol-vinylisopropyl ether condensation prodnot.
A lubricatinggoil containing approximately 10 by'weight: of. the above. oiliconcentrate operates satisfactorily in heavy duty-dieselrengine service.
Example VII.
A. 200 v.g. portion. of -.octylphenol dissolved in 1000. g.. ofv an SAE 10. solvent refined lubricating oil having a viscosity index of approximately 85 and to this solution is added 86 g. of vinyl acetate. The mixture is maintained at 75 C. and g. of concentrated sulfuric acid is slowly added. Heating and stirring is continued for approximately 10 hours, at which time the solution is water washed to remove acid.
The product is neutralized by treatment with 174 g. of barium hydroxide octahydrate and gradually heated to 175 C., at which temperature it is filtered. The filtrate is an oil concentrate of the barium salt of an octylphenol-vinyl acetate condensation product. This product, when dissolved in mineral lubricating oil to give an oil containing approximately 3% by weight of the barium salt, imparts detergency and anti-corrosion characteristics to the oil.
Example VIII To 305 g. of m-pentadecylphenol and 57 g. of vinyl acetate in solution in 1500 ml. of a light petroleum naphtha is added g. of concentrated sulfuric acid. The temperature of the reaction mixture rises rapidly to about 80 C. where refluxing occurs. This temperature is maintained for approximately 3 hours and the product then water washed.
The above condensation product is dissolved in 2500 g. of mineral lubricating oil as described in Example I and neutralized with 46 g. of lithium hydroxide monohydrate and 100 ml. of water. The product is heated to 175 C. to remove naphtha and water and filtered while hot. The resulting product is an oil concentrate of the lithium salt of a m-pentadecylphenol-vinyl acetate condensation product. This product, when dissolved in additional quantities of lubricating oil, imparts detergency and anti-corrosion characteristics to the oil.
Example IX Example VIII repeated using carbon tetrachloride in place of light petroleum thinner as the solvent results in a product substantially identical to that obtained with the thinner.
It is to be pointed out that the preceding examples are illustrative of the invention and are not to be considered as limiting because the phenols having one or more of the other hydrocarbon substituents described herein and other vinyl compounds described herein are found to condense under similar conditions to form comparable condensation products. Moreover, the other metals described herein as being useful in preparing the metal salts of the condensation products may be substituted for the metals employed in the examples to give salts which are effective as detergents and anti-corrosion agents when added to mineral lubricating oils. Furthermore, it is to be pointed out that an of the metals described as being useful for the preparation of metal salts of the condensation products are also useful in preparing metal sulfonates and metal sulfonate complexes which cooperate with the additives of this invention to produce noncorrosive lubricating oils of exceptionally high detergency. Such metal sulfonates or metal sulfonate complexes, when used in conjunction with the additives of this invention, are used in amounts between about 0.5% and about 10% based on the finished oil.
I claim:
1. A mineral lubricating oil containing between about 0.05 and about 20% by weight of an oilsoluble metal salt of the acidic condensation prod:
uct of a hydrocarbon substituted phenol, in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms, and a vinyl compound selected from the class consisting of divinyl ether, Vinyl ethyl ether, vinyl propyl ether, vinyl esters of hydrohalogen acids and vinyl esters of fatty acids containing between 1 and 6 carbon atoms in the fatty acid radical, said condensation product being obtained by condensing said phenol with said. vinyl compound in the molar ratio of between 0.5 and 3 to 1 at temperatures between about 20 C. and about 150 C.
2. A mineral lubricating oil containing between about 0.05 and about 20% by weight of an oilsoluble alkaline earth metal salt of the acidic condensation product of a hydrocarbon substituted phenol, in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms, and a vinyl compound selected from the class consisting of divinyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl esters of hydrohalogen acids and vinyl esters of fatty acids containing between 1 and 6 carbon atoms in the fatty acid radical, said condensation product being obtained by condensing saidphenol with said vinyl compound in the molar ratio of between 0.5 and 3 to 1 at temperatures between about 0 C. and about C. v
3. A mineral lubricating oil containing between about 0.05 and about 20% by weight of an oilsoluble alkali metal salt of the acidic condensation product of a hydrocarbon substituted phenol in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms and a vinyl compound selected from the class consisting of divinyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl esters of hydrohalogen acids and vinyl esters of fatty acids containing between 1 and 6 carbon atoms in the fatty acid radical, said condensation product being obtained by condensing said phenol with said vinyl compound in the molar ratio of between 0.5 and 3 to 1 at temperatures between about -20 C. and about C.
4. A mineral lubricating oil according to claim 1 in which the molar ratio of phenol to vinyl compound is between 0.8 and 2 to 1.
5. A mineral lubricating oil according to claim 2 in which said alkaline earth metal salt is a barium salt.
6. A mineral lubricating oil according to claim 2 in which said alkaline earth metal salt is a calcium salt.
7. A lubricating oil according to claim 3 in which said alkali metal salt is a lithium salt.
8. A lubricating oil according to claim 3 in which said alkali metal salt is a sodium salt.
9. A mineral lubricating oil containing between about 0.05% and about 20% by weight of an oilsoluble metal salt of the acidic reaction product obtained by condensing at a temperature between 0 C. and 100 C. a hydrocarbon substituted phenol in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms with vinyl actate using a molar ratio of phenol to vinyl acetate of between 0.8 and 2 to 1.
10. A mineral lubricating oil containing between about 0.05% and about 20% by weight of an oil-soluble metal salt of the acidic reaction product obtained by condensing cyclohexyl phenol with vinyl ethyl ether using a molar ratio of phenol to vinyl ethyl ether of between 0.8 and 2 to 1, the condensation being effected at temperatures between 0 C. and 100 C.
11. A mineral lubricating oil containing between about 0.05% and about 20% by weight of an oil-soluble metal salt of the acidic reaction product obtained by condensing a hydrocarbon substituted phenol in which the hydrocarbon substituent contains between about 4 and about 30 carbon atoms with vinyl chloride, at a temperature between about C. and about 100 0., using a molar ratio of phenol to vinyl chloride between 0.8 and 2 to 1.
12. A mineral lubricating oil containing between about 0.5% and about 10% by weight of the tween about 0.5% and about 10% by weight of the barium salt of the acidic condensation product obtained by condensing approximately equal molar proportions of octylphenol and vinyl acetate at temperatures between about 0 C. and about C.
14. A mineral lubricating oil according to claim 1 containing also between about 0.5% and about 10% by weight of an oil-soluble metal sulfonate.
15. A mineral lubricating oil according to claim 1 containing also between 0.5% and 10% of a modified sulfonate prepared by heating an oilsoluble metal sulfonate with an inorganic base selected from the class consisting of metal oxides, hydroxides, carbonates and bicarbonates to solubilize said base, said modified sulfonate having a ratio of equivalents of metal to equivalents of sulfonic acids between 1.1 and 3 to 1.
LOREN L. NEFF.
References Cited in the file of this patent UNITED STATES PATENTS
Claims (1)
1. A MINERAL LUBRICATING OIL CONTAINING BETWEEN ABOUT 0.05 AND ABOUT 20% BY WEIGHT OF AN OILSOLUBLE METAL SALT OF THE ACIDIC CONDENSATION PRODUCT OF A HYDROCARBON SUBSTITUTED PHENOL, IN WHICH THE HYDROCARBON SUBSTITUTED CONTAINS BETWEEN ABOUT 4 AND ABOUT 30 CARBON ATOMS, AND A VINYL COMPOUND SELECTED FORM THE CLASS CONSISTING OF DIVINYL ETHER, VINYL ETHYL ETHER, VINYL PROPYL ETHER, VINYL ESTERS OF HYDROHALOGEN ACIDS AND VINYL ESTERS OF FATTY ACIDS CONTAINING BETWEEN 1 AND 6 CARBON ATOMS IN THE FATTY ACID RADICAL, SAID CONDENSATION PRODUCT BEING OBTAINED BY CONDENSING SAID PHENOL WITH SAID VINYL COMPOUND IN THE MOLAR RATIO OF BETWEEN 0.5 AND 3 TO 1 AT TEMPERATURES BETWEEN ABOUT -20* C. AND ABOUT 150* C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US174367A US2656316A (en) | 1950-07-17 | 1950-07-17 | Lubricating oils containing metal salts of a condensation product of a substituted phenol and a vinyl compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US174367A US2656316A (en) | 1950-07-17 | 1950-07-17 | Lubricating oils containing metal salts of a condensation product of a substituted phenol and a vinyl compound |
Publications (1)
Publication Number | Publication Date |
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US2656316A true US2656316A (en) | 1953-10-20 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US174367A Expired - Lifetime US2656316A (en) | 1950-07-17 | 1950-07-17 | Lubricating oils containing metal salts of a condensation product of a substituted phenol and a vinyl compound |
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US (1) | US2656316A (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2307885A (en) * | 1940-07-16 | 1943-01-12 | Standard Oil Dev Co | Lubricating product |
US2375222A (en) * | 1943-09-15 | 1945-05-08 | Shell Dev | Aviation lubricating oil |
US2422276A (en) * | 1943-09-14 | 1947-06-17 | Standard Oil Dev Co | Compounded lubricating oil |
-
1950
- 1950-07-17 US US174367A patent/US2656316A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2307885A (en) * | 1940-07-16 | 1943-01-12 | Standard Oil Dev Co | Lubricating product |
US2422276A (en) * | 1943-09-14 | 1947-06-17 | Standard Oil Dev Co | Compounded lubricating oil |
US2375222A (en) * | 1943-09-15 | 1945-05-08 | Shell Dev | Aviation lubricating oil |
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