US3232883A - Basic mixtures of metal salts and lubricants containing them - Google Patents
Basic mixtures of metal salts and lubricants containing them Download PDFInfo
- Publication number
- US3232883A US3232883A US162956A US16295661A US3232883A US 3232883 A US3232883 A US 3232883A US 162956 A US162956 A US 162956A US 16295661 A US16295661 A US 16295661A US 3232883 A US3232883 A US 3232883A
- Authority
- US
- United States
- Prior art keywords
- parts
- phosphorus
- mixture
- metal
- basic
- 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
- 239000000203 mixture Substances 0.000 title claims description 102
- 229910052751 metal Inorganic materials 0.000 title claims description 88
- 239000002184 metal Substances 0.000 title claims description 88
- 150000003839 salts Chemical class 0.000 title claims description 48
- 239000000314 lubricant Substances 0.000 title description 14
- -1 PHOSPHORUS SULFIDES Chemical class 0.000 claims description 31
- 239000011574 phosphorus Substances 0.000 claims description 30
- 229910052698 phosphorus Inorganic materials 0.000 claims description 30
- 229920000098 polyolefin Polymers 0.000 claims description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims description 7
- 230000001050 lubricating effect Effects 0.000 claims description 5
- 239000010688 mineral lubricating oil Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 description 39
- 235000019198 oils Nutrition 0.000 description 39
- 239000002480 mineral oil Substances 0.000 description 23
- 229940042472 mineral oil Drugs 0.000 description 23
- 235000010446 mineral oil Nutrition 0.000 description 23
- 239000000654 additive Substances 0.000 description 22
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 21
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 20
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 20
- 230000007935 neutral effect Effects 0.000 description 19
- 159000000009 barium salts Chemical class 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 229920002367 Polyisobutene Polymers 0.000 description 11
- 150000001447 alkali salts Chemical class 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 229910052728 basic metal Inorganic materials 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- FIWYWGLEPWBBQU-UHFFFAOYSA-N 2-heptylphenol Chemical compound CCCCCCCC1=CC=CC=C1O FIWYWGLEPWBBQU-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000007664 blowing Methods 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000007857 degradation product Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- 150000003017 phosphorus Chemical class 0.000 description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 2
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229940063557 methacrylate Drugs 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000004986 phenylenediamines Chemical class 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-HYXAFXHYSA-N (Z)-2-octene Chemical compound CCCCC\C=C/C ILPBINAXDRFYPL-HYXAFXHYSA-N 0.000 description 1
- ATIMVMORQPKRPC-UHFFFAOYSA-N 1,2,3-trichloro-4-(2,3,4-trichlorophenoxy)benzene Chemical compound ClC1=C(Cl)C(Cl)=CC=C1OC1=CC=C(Cl)C(Cl)=C1Cl ATIMVMORQPKRPC-UHFFFAOYSA-N 0.000 description 1
- WJECKFZULSWXPN-UHFFFAOYSA-N 1,2-didodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCCCCCCCCCCC WJECKFZULSWXPN-UHFFFAOYSA-N 0.000 description 1
- PTYXPKUPXPWHSH-UHFFFAOYSA-N 1-(butyltetrasulfanyl)butane Chemical compound CCCCSSSSCCCC PTYXPKUPXPWHSH-UHFFFAOYSA-N 0.000 description 1
- HDZNCKLMVPZWDN-UHFFFAOYSA-N 1-benzyl-n-[(2-fluorophenyl)methyl]-3,5-dimethylpyrazole-4-carboxamide Chemical group CC1=C(C(=O)NCC=2C(=CC=CC=2)F)C(C)=NN1CC1=CC=CC=C1 HDZNCKLMVPZWDN-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- ILJOIOLSOMYKNF-UHFFFAOYSA-N 2,3-didodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCCCCC ILJOIOLSOMYKNF-UHFFFAOYSA-N 0.000 description 1
- QZLAEIZEPJAELS-UHFFFAOYSA-N 2,4,4-trimethylpentane-2-thiol Chemical compound CC(C)(C)CC(C)(C)S QZLAEIZEPJAELS-UHFFFAOYSA-N 0.000 description 1
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- VXZBYIWNGKSFOJ-UHFFFAOYSA-N 2-[4-[5-(2,3-dihydro-1H-inden-2-ylamino)pyrazin-2-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC=1N=CC(=NC=1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 VXZBYIWNGKSFOJ-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- BBCLXYJRPRRZQW-UHFFFAOYSA-N 2-phenylnaphthalen-1-amine Chemical compound C1=CC2=CC=CC=C2C(N)=C1C1=CC=CC=C1 BBCLXYJRPRRZQW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenylpropanol Natural products OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- MGGVALXERJRIRO-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-2-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-1H-pyrazol-5-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)O MGGVALXERJRIRO-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- CETAGCPEESRQJY-UHFFFAOYSA-M [Zn+].CCCCCCCCOP([S-])(=S)OCCCCCCCC Chemical compound [Zn+].CCCCCCCCOP([S-])(=S)OCCCCCCCC CETAGCPEESRQJY-UHFFFAOYSA-M 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- VAGZAKMKSMNQJC-UHFFFAOYSA-L barium(2+);di(nonoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Ba+2].CCCCCCCCCOP([S-])(=S)OCCCCCCCCC.CCCCCCCCCOP([S-])(=S)OCCCCCCCCC VAGZAKMKSMNQJC-UHFFFAOYSA-L 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VNBGVYNPGOMPHX-UHFFFAOYSA-N but-3-en-2-ylcyclohexane Chemical compound C=CC(C)C1CCCCC1 VNBGVYNPGOMPHX-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229940054025 carbamate anxiolytics Drugs 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- GHKVUVOPHDYRJC-UHFFFAOYSA-N didodecyl hexanedioate Chemical compound CCCCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCCCC GHKVUVOPHDYRJC-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical class CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- LZXXNPOYQCLXRS-UHFFFAOYSA-N methyl 4-aminobenzoate Chemical compound COC(=O)C1=CC=C(N)C=C1 LZXXNPOYQCLXRS-UHFFFAOYSA-N 0.000 description 1
- QXOUFQKDZIMOMU-UHFFFAOYSA-N methyl n-octylcarbamate Chemical compound CCCCCCCCNC(=O)OC QXOUFQKDZIMOMU-UHFFFAOYSA-N 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- SOOARYARZPXNAL-UHFFFAOYSA-N methyl-thiophenol Natural products CSC1=CC=CC=C1O SOOARYARZPXNAL-UHFFFAOYSA-N 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- SUSXWKRWORPGPG-UHFFFAOYSA-M n-phenylcarbamodithioate Chemical compound [S-]C(=S)NC1=CC=CC=C1 SUSXWKRWORPGPG-UHFFFAOYSA-M 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- RWQFRHVDPXXRQN-UHFFFAOYSA-N phosphorus sesquisulfide Chemical compound P12SP3SP1P2S3 RWQFRHVDPXXRQN-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- OWNZHTHZRZVKSQ-UHFFFAOYSA-N tribromo(sulfanylidene)-$l^{5}-phosphane Chemical compound BrP(Br)(Br)=S OWNZHTHZRZVKSQ-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/04—Reaction products of phosphorus sulfur compounds with hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
Definitions
- EXAMPLE 4 A polyisobutene having a molecular weight of 48,000 is phosphosulfurized by mixing 123 parts (by Weight) of a 38% mineral oil solution of the polymer with 2.8 parts of phosphorus pentasulfide at 94 C. and heating the mixture to 260 C..in 6 hours and then at 260 C. for 2 additional hours. The product is hydrolyzed with steam at 150 C. to give an acid having a phosphorus content of 0.64% and a sulfur content of 0.48%. A basic barium salt of the acid is prepared by carbonating at 150 C.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Lubricants (AREA)
Description
United States Patent 3,232,883 BASIC MIXTURES 0F METAL SALTS ANZ) LUBRICANTS CONTAINING THEM William M. Le Suer, Cleveland, ()hio, assignor to The Lubrizol Corporation, Wickliffe, Ohio, a corporation of Ohio N0 Drawing. Filed Dec. 28, 1961, Ser. No. 162,956 11 Claims. (Cl. 252-325) This invention relates to metal salts of organic phosphorus acids and in a more particular sense to mixtures of at least two alkaline earth metal salts of oil-soluble phosphorus acids. Such mixtures are suitable for use as additives in hydrocarbon oil compositions such as fuel oils, gasolines, greases, and fluid lubricants.
Hydrocarbon oils are prone to degradation in service. A substantial portion of the degradation products consists of acidic substances which are corrosive to metals and tend to form sludge-like and varnish-like deposits. To inhibit such degradation and to minimize the harmful effects of the degradation products, it is a common practice to incorporate into the hydrocarbon oil one or more chemical additives. Metal salts of oil-soluble organic acids, e.g., phosphorus acids, are useful as such additives. The basic metal salts, i.e., those in which the metal is present in a stoichiometrically greater amount than the organic acid radical, are especially efiective because of their ability to neutralize the acidic degradation products. In general, it is recognized also that the higher the basicity of the metal salt, the greater its capacity to counteract the undesirable acidic products, and the greater its effectiveness as an oil additive.
Accordingly it is a principal object of this invention to provide additives for use in hydrocarbon oils.
It is also an object of this invention to provide hydrocarbon oil concentrates of such additives.
It is also an object of this invention to provide hydrocarbon oil compositions.
It is further an object of this invention to provide lubricating compositions.
These and other objects are attained in accordance with this invention by providing a basic mixture of alkaline earth metal salts of acidic phosphorized substantially aliphatic hydrocarbons, said mixture being characterized by a metal ratio greater than about 2.5 and comprising (A) from 40 parts to 95 parts by weight of a said metal salt having a metal ratio greater than 4 and (B) from parts to 60 parts by weight of a said metal salt having a metal ratio less than 2.
The metal ratio of a metal salt designates the ratio of the total chemical equivalents of the metal to the chemical equivalents of the metal which is in the form of the normal salt (i.e., the neutral salt) of the organic acid. To illustrate, a metal salt containing 5 equivalents of the metal per equivalent of the organic acid radical has a metal ratio of 5, and a neutral metal salt has a metal ratio of 1.0. It will be noted that the metal ratio of a mixture of two or more metal salts is the average value based upon the metal ratios and the relative proportions of the individual component metal salts in the mixture.
A principal significance of the above basic mixture of this invention is its unusual effectiveness as an oil additive to inhibit degradation of hydrocarbon oils and to combat the harmful effects of the oil degradation products. This effectiveness is associated with several critical aspects of this invention, namely, that the mixture contain at least one relatively highly basic metal salt characterized by a metal ratio greater than 4 and at least one neutral metal salt or a relatively less basic metal salt characterized by a metal ratio of less than 2, that the reltive proportions of these two types of metal salts be within the above stated range, and that the mixture itself be char- 3,232,383 Patented Feb. 1, 1966 acterized by a metal ratio of at least about 2.5, preferably from about 3 to about 7.
The relatively highly basic metal salt of the mixture preferably has a metal ratio greater than about 5 or 6 and may have a metal ratio of about 10 or higher. The relatively less basic metal salt of the mixture may have a metal ratio of about 1, 1.5, or up to about 2.
As indicated previously, the metal salts are derived from acidic phosphorized substantially aliphatic hydrocarbons. Such hydrocarbons include, for example, the white oils and other liquid petroleum oils having at least about twelve carbon atoms and include also synthetic hydrocarbons such as are obtained by the reduction of fatty oils.
A convenient source of the substantially aliphatic hydrocarbons are the olefin polymers having molecular Weights of at least about 150 and up to about 48,000 preferably from about 500 to about 5000. The polymers include the homopolymers and the interpolymers of monoolefins having from two to twelve carbon atoms, e.g., ethylene, propene, l-butene, isobutene, l-hexene, l-octene, Z-methyl-l-heptene, 3-cyclohexyl-l-butene, l-decane, 2- methyl-S-propyl-l-hexene, etc.
Also useful are the interpolymers of such mono-olefins with other interpolymerizable olefinic substances such as aromatic olefins, cycloaliphatic olefins, and polyolefins. The interpolymers, include, for example, those prepared by polymerizing isobutene with styrene; isobutene with butadiene; propene with isoprene; ethylene with piperylene; isobutene with chloroprene; isobutene with p-methyl styrene; l-hexene with 1,3-hexadiene; isobutene with styrene and piperylene; etc.
The relative proportions of the mono-olefins to the other olefinic monomers in the interpolymers may vary within wide ranges provided that the polyolefin, if used, is not present in sufficiently high proportions as to cause substantial cross-linking and insolubility. Specific examples of the useful interpolymers include the copolymer of 95 (by weight) of isobuene with 5% of styrene; the terpolymer of 98% of isobutene with 1% of piperylene and 1% of chloroprene; the terpolymer of 95% of isobutene with 2% of l-butene and 3% of l-hexene; the terpolymer of 60% of isobutene with 20% of l-pentene and 20% of l-octene; the copolymer of of l-hexene and 20% of l-heptene; the terpolymer of ofisobutene with 2% of cyclohexene and 8% of propene; and the copolymer of 80% of ethylene and 20% of propene.
Methods of preparing the polymers and the interpolymers illustrated above are known. A particularly useful method comprises the treatment of an olefin (e.g., isobutene) at a temperature from about -60 C. to about 20 C. with a Friedel-Crafts catalyst, e.g., boron trifluoride. The use of a solvent to facilitate mixing and transfer of the heat of reaction is advantageous. Such solvents include n-butane, isobutane, n-hexane, naphtha, carbon tetrachloride, and ethane.
The olefin polymers may be phosphorized by treatment with a phosphorus sulfide such as phosphorus pentasulfide, phosphorus sesquisulfide, phosphorus heptasulfide, or phosphorus thiochloride. Other useful phosphorizing agents are exemplified by phosphorus thiobromide, chlorine and phosphorus trichloride, phosphorus trichloride and sulfur, yellow phosphorus and sulfur monochloride, yellow phosphorus and sulfur, phosphorus oxychloride, phosphorus trichloride, phosphorus tribromide, and yellow phosphorus and sulfur dichloride.
Various techniques to effect the phosphorization are known. A very commonly used method involves simply mixing the olefin polymer with the phosphorizing agent at the desired temperature, usually above 80 C. and preferably between C. and 300 C. Another method consists of chlorinating the olefin polymer and reactphenol, amine, or thiol.
1 ing the chlorinated polymer with a phosphorizing agent.
The amount of the phosphorizing agent to be used in the treatment of an olefin polymer depends upon the na ture of the product desired. For most applications, products having aphosphorus content from 0.05% to 10%,
more often from 0.1% to 5%, are desirable. Thus, the relative proportion of the phosphorizing agent to be used is such as to provide from about 0.05 to parts (by weight), more often from 0.1 to 5 parts, of phosphorus per 100 parts of the olefin polymer in the reaction mixture. In most instances, from 0.1 part to 50 parts of a phosphorizing agent is used per 100 parts of the olefin polymer.
The phosphorized olefin polymers are acidic composil tions, susceptible to neutralization with a basic metal reagent to form a metal salt.
A preferred method for preparing the metal salt, however, involves first hydrolyzing the phosphorized olefin polymer by treatment with water or steam and then neutralizing the hydrolyzed intermediate with the basic metal reagent. The hydrolysis removes from the phosphorized olefin polymer that portion of the A phosphorus which is loosely held and results in a product of light color and high stability. The temperature at ;which the hydrolysis is carried out is preferably between 100 C. and 200 0., although it can be 80 C., or even compounds are preferred.
A convenient method for preparing the basic salts involves mixing the phosphorized olefin polymer with an excess (e.g., two to three times the stoichiornetric amount) of an alkaline earth metal base or preparing such a mixture and subsequently treating the mixture with carbon dioxide. The incorporation of a still larger excess of a metal base is usually facilitated by the use in the neutralization mixture of a promoting agent which in most instances is an active hydrogen compound, i.e., an alcohol,
Specific examples of such promoting agents are methanol, propanol, cyclohexanol, octanol, dodecanol, behenyl alcohol, benzyl alcohol, phenol, naphthol, didodecylphenol, condensation product of octylphenol and formaldehyde, aniline, toluidine, phenothiazine, phenylene diamine, cyclohexylamine, octylamine, dimethylamine, methyl mercaptan, thiophenol, and tert-octyl mercaptan. The neutralization and the carbonation steps are carried out at temperatures between room temperature and 300 C.
To illustrate, the preparation of a highly basic metal salt can be effected by carbonating (preferably at 100- 300 C.) a mixture of a phosphorized olefin polymer, a phenolic compound such as p-octylphenol, and a large excess of a metal base such as barium oxide or barium hydroxide until a substantial portion of the metal base is converted to the carbonate. In the case of an alcohol being present as the promoting agent, the carbonation temperature is within the range from about 25 C. to the boiling point of the alcohol.
The methods for phosphorizing olefin polymers as well as for preparing the metal salts of phosphorized olefin polymers are known in the art, e.g., US. Patents 2,316,- 078, 2,316,079, 2,316,085, 2,616,904, 2,616,905, 2,616; 906, 2,616,911, 2,616,924, 2,616,915, 2,950,378, and 2,938,894; and co-pending applications Ser. No. 809,523, filed April 29, 1959 now abandoned; Ser. No. 838,024, filed September 4, 1959 now US. Patent No. 3,033,890; Ser. No. 30,477, filed May 20, 1960 now US. Patent No. 3,089,867; and Ser. No. 10,104, filed February 23, 1960 now US. Patent No. 3,049,531.
' The following examples illustrate the alkaline earth metal salts of this invention and the methods by which they are prepared. The neutralization number of the metal salts is determined according to ASTM Test procedure D974-487. The reflux base number is a mcasurement of the basicity of the metal salts. It is determined by the following procedure: A sample (l-1.2 grams) of the metal salt is dissolved in 25 cc. of a solvent mixture consisting of benzene and isopropanol in equal Weight proportions and a trace of Water. The solution is mixed with an excess and known quantity of a standardized hydrochloric solution of 0.1N and the mixture refluxed for 30 minutes. The residual acidity of the mixture is then determined by titration with a standardizedpotassium hydroxide solution according to ASTM Test procedure No. D66458. The basicity of the metal salt is indicated by the quantity of the hydrochloric acid consumed in the process.
EXAMPLE 1 To a refluxing (99 C.) mixture of 1000 parts (by weight) of a chlorinated polyisobutene having a molecular weight of 1000 and a chlorine content of 4.3%, and 61 parts of heptylphenol, there is added parts of phosphorus trichloride. The mixture is heated until the reflux temperature reaches 200 C. (in 4 hours). To this mixture there is added 110 parts of phosphorus trichloride and the resulting mixture is heated at 200 C. for 6.5 hours, and then blown with nitrogen at 180 200 C. for 2 hours. The phosphorized polymer thus obtained is hydrolyzed by treatment with steam at 150 160 C. for 3 hours. The hydrolyzed product has a phosphorus content of 2.2% and a chlorine content of 0.3%. A basic barium salt is prepared by carbonating a mixture of 270 parts of a mineral oil, 18 parts of water, 143 parts of the above hydrolyzed acid, 38 parts of heptylphenol, and parts of barium oxide at 130140 C. until the mixture is substantially neutral to phenolphthalein. The mixture is then dried by blowing it with nitrogen at 155 C. and diluted with mineral oil to an oil solution having a barium sulfate ash of 25%. The final solution is found to contain 0.41% of phosphorus, a neutralization number less than 5 (basic), a reflux base number of 107, and a 0 metal ratio of 8.3.
EXAMPLE 2 A mixture of 1000 parts (by weight) of a polyisobutene having a molecular weight of 1000 and 90 parts of phosphorus pentasulfide is prepared at room temperature, heated to 260 C. in 5 hours, and maintained at this temperature for 5 hours. It is then cooled to 150 C. and hydrolyzed by treatment with steam at this temperature for 5 hours. The hydrolyzed acid has a phosphorus content of 2.4% and a sulfur content of 2.8%. In a separate vessel a mixture of oil and barium hydroxide is prepared by mixing 2200 parts of a mineral oil and 1150 parts of barium oxide at 88 C. and blowing the mixture with steam for 3 hours at 150 C. To this mixture there is added, portionwise, throughout a period of 3 hours, 1060 parts of the above hydrolyzed acid at 145-150 C., and then 360 parts of heptylphenol in 1.5 hours. The resulting mixture is blown with carbon dioxide at a rate of 100 pounds per hour for 3 hours at 157 C. The carbonated product is mixed with 850 parts of a mineralo-il and dried by blowing it with nitrogen and 150 C. The dried product is filtered and the filtrate is diluted with mineral oil to a solution having a barium sulfate ash content of 25%. The final solution is found to have a phosphorus content of 0.38%, a sulfur content of 0.48%, a neutralization number less than 5 (basic), a reflux base number of 109, and a metal ratio of 7.2.
EXAMPLE 3 A hydrolyzed, acidic phosphorized polyisobutene is prepared by the procedure of Example 1 except that the amount of heptylphenol used in the preparation of the phosphorized polymer is 30 parts (by Weight) per 1000 parts of the chlorinated polyisobutene. A basic barium salt is prepared by mixing 240 parts of a mineral oil, 24
parts of water, 168 parts of the hydrolyzed acid, 44 parts of heptylphenol, and 275 parts of barium oxide at 88- 120C., blowing the mixture with steam at 135 C., and carbonating the mixture at 132-140 C. for 21 hours until the mixture is substantially neutral to phenolphthalein. The mixture is then diluted with 83 parts of mineral oil, dried by blowing it with nitrogen at 150 C. for 2 hours and then filtered. The filtrate is diluted further with mineraloil to a solution having a barium sulfate ash -content of 38.5%. The final solution is found to contain 1 also a phosphorus content of 0.4%, a neutralization number less than5 (basic), a reflux base number of 173, and a metal ratio of 12.8. i
EXAMPLE 4 A polyisobutene having a molecular weight of 48,000 is phosphosulfurized by mixing 123 parts (by Weight) of a 38% mineral oil solution of the polymer with 2.8 parts of phosphorus pentasulfide at 94 C. and heating the mixture to 260 C..in 6 hours and then at 260 C. for 2 additional hours. The product is hydrolyzed with steam at 150 C. to give an acid having a phosphorus content of 0.64% and a sulfur content of 0.48%. A basic barium salt of the acid is prepared by carbonating at 150 C. a mixture of 1000 parts of the acid, 79 parts of heptylphenol, parts of water, and 224 parts of barium oxide until the mixture is substantially neutral to phenolphthalein. The carbonating mixture is diluted with 400 parts I of mineral oil, 50 parts of isooctyl alcohol, and 500 parts of benzene, filtered, and the filtrate is heated to 150 C./ 30 mm. to distill off the volatile components. The residue is found to have a barium sulfate ash content of 18.2%, a phosphorus content of 0.14%, a neutralization number of 1.5 (acid), a reflux base number of 76.5, a sulfur content of 0.2%, and a metal ratio of 7.6.
EXAMPLE 5 A barium salt is obtained by mixing 2000 parts (by Weight) of the hydrolyzed acid of Example 1, 500 parts of mineral oil, 100 parts of water, and 163 parts of barium oxide, heating the mixture at 150 C. for 2 hours, and filtering the mixture. The filtrate is found to have a barium sulfate ash content of 10.1%, a phosphorus content of 1.9%, and a metal ratio of 1.04.
EXAMPLE 6 A polyisobutene having a molecular weight of 1000 is phosphosulfurized by heating 100 parts of the polyisobutenewith 9 parts of phosphorus pentasulfide at 260 C. for 5 hours. The phosphosulfurized polymer is hydrolyzed by treatment with steam at 155 C. to produce an acid having a phosphorus content of.2.3%, a sulfur content of 2.7% and an acid number of 48. A slightly basic barium salt of the hydrolyzed acid is prepared by mixing 2330 parts of the acidwith 185 parts of barium oxide and 100 parts of water and 700 parts of mineral oil at 70 C. and heating the mixture at the reflux temperature for 1 hour and then drying the mixture at 150 C. for 2 hours. The mixture is then filtered and the filtrate has a barium sulfate ash content of 9.3%, a phosphorus con tent of 1.7%, a sulfur content of 1.8%, and a metal ratio of 1.3.
EXAMPLE 7 A neutral barium salt is obtained by reacting at 130- 135 C. stoichiometric amounts of the hydrolyzed acid of Example 4, water, and barium oxide in the presence of mineral oil. The product is diluted further with mineral oil to give an oil solution having an oil content of 85%. The solution is found to have a barium content of 0.94%, a phosphorus content of 0.3%, and a sulfur content of 0.34%.
EXAMPLE 8 A polyisobutene having a molecular weight of 1000 is phosphosulfurized by heating a mixture of 750 parts of the polyisobutene with 110 parts of phosphorus pentasuL 150 C. for 1 hour and filtering the mixture. The filtrate is found to have a barium sulfate ash content of 11.6%, a phosphorus content of 2%, a sulfur content of 0.8%, and a metal ratio of 1.
EXAMPLE 9 A neutral barium salt is prepared by the reaction of stoichiometric amounts of barium hydroxide and thehydrolyzed acid of Example 8 (Without air blowing) and the reaction production is diluted with mineral oil to a solution having a barium sulfate ash content of 9.3%, a phosphorus content of 2.1% and a sulfur content of 1%.
EXAMPLE 10 A basic barium salt is prepared from the hydrolyzed acid of Example 8 (without airblowing) and diluted with mineral oil to a solution having a barium sulfate ash content of 14%, a phosphorus content of 1.5%, a sulfur content of 1.3%, and a metal ratio of 2.
EXAMPLE 11 A neutral barium salt is prepared from the hydrolyzed acid of Example 8 (without air blowing) and diluted with mineral oil to a solution having a barium sulfate ash con tent of 6.9%, a phosphorus content of 1.3%, and a sulfur content of 1.1%.
As indicated previously, the relative proportions of the two types of metal salts in the basic mixtures of this invention are of critical importance to the effectiveness of such mixtures as additives in oils. The ratio of the metal salt (A), i.e., the highly basic metal salt, to the metal salt (B), i.e., the slightly basic or neutral metal salt, should be at least about :60 (by weight). The preferred ratio of (A) :(B) is withinthe range from :50 to 70:30, respectively such as 60:40. Onthe other hand, mixtures in which the ratio of (A) (B) is 80:20 or 90:10 or, as high as 95:5 have been found to be equally effective. This ratio, i.e., 95:5, appears to represent a practical upper limit of the relative amounts of the two types of metal salts..
It will be noted further that another critical feature of this invention is that the basic mixture must be characterized by a metal ratio of at least about 2.5. Thus, for a mixture having a particular metal ratio, less of a highly basic (A) is required than of a less basic (A). To illustrate, a basic mixture containing 50 parts of a highly basic salt having a metal ratio of 10 and 50 parts of a neutral metal salt has a resultant metal ratio of 5.5; another basic mixture containing 70 parts of a highly basic metal salt having a metal ratio of 7.4 and 30 parts of a neutral metal salt likewise has a resultant metal ratio of 5.5.
The concentration of the basic mixtures of this invention as additives in oils may vary within wide ranges, depending upon the type of the oils and the nature of the service to Which ;the oils are to be subjected. The optimum concentrations usually range from about 0.001% to about 20% by weight. To illustrate, lubricants for use in gasoline internal combustion engines may contain from 1about0.5% to about 10% of the additive, lubricants for use in gears and diesel engines may contain more than 10% of the additive, and hydrocarbon fuels may contain as little as 0.01% or even less of the additive. For instance, a lubricating composition may comprise from about 99 to about parts by weight of a mineral lubricating oil and from about 1 to about .20 parts by Weight of the basic mixture.
The lubricating oils in which the compositions of this invention are useful as additives may be of synthetic, animal, vegetable, or mineral origin. Ordinarily mineral 7 lubricating oils are preferred by reason of their availability, general excellence, and low cost. For certain applications, oils belonging to one of the other three groups may be preferred. For instance, synthetic polyhibitors, load-carrying additive-s, anti-foam additives, pour point depressants, viscosity index improving agents, additives to improve the frictional characteristics, etc.
The ashless detergents include the neutralization prodester oils such as didodecyl adipate and di-2-ethylhexyl 5 nets of an alkenyl-substituted succinic anhydride having sebacate are often preferred as jet engine lubricants. 50 or more carbon atoms in the alkenyl-substituent with Normally the lubricating oils preferred will be fluid oils, an amine, preferably an alkylene amine such as ethylene ranging in viscosity from about 40 Saybol't Universal diamine, diethylene triamine, tetraethylene pent-amine, Seconds at 100 F. to about 200 Saybolt Universal Secpentaethylene hexamine, hexamethylene diamine, dionds at 210 F. triethylene diamine, piperazine, or aminoethyl morpho- To prepare the oil compositions containing the basic line; the copolymer of a long chain alkyl (e.g., dodecyl) mixtures of this invention, the two types of metal salts acrylate or methacrylate with from 2% to 10% (by 'may be added separately to the oil or they may be Weight) of a polar-substituted acrylate or methacrylate mixed first and the resulting mixture added to the oil. (e.g., beta-diethylaminoethyl acrylate). A convenient method is'to prepare a concentrate of the The metal-containing detergents may be normal or the mixture by dissolving the mixture in a limited amount of basic alkali metal salts or alkaline earth metal salts of the oil and then diluting the concentrate with additional oil soluble sulfonic acids such as petroleum sulfonic acids amounts of the oil to prepare the final oil composition. or sulfonic acids obtained by the sul'fonation of an The unusual effectiveness of the basic mixtures of the alkyla-ted aromatic compound (e.g., didodecyl benzene). metal salts of this invention as additives in oils to inhibit Oxidation inhibitors include, for example, hindered the formation of harmful deposits is shown by the rephenols, such as 2,6-ditert-butyl-4-methylphenol, 2,2',6, sults (Table I) of a deposit-inhibition test. In this test 6 tetra tert butyl 4,4 methylene bisphenol, a 350-cc. sample of a lubricating oil containing the and Z-tert-pentyl-6-isohexylphenol; metal phenates such additive is placed in a 2" x 15" borosilicate tube. A as barium octylphenate, calcium didodecylphenate, stronsteel panel is immersed in the oil. The sample is heated tium salt of the product obtained by the condensation of at 300 F. for 96 hours while air is bubbled through the a 2:1 molar mixture of heptylphenol and formaldeoil at the rate of 10 liters per hour. The oxidized sample hyde, barium salt of bis(hydroxyphenyl)sulfide, and calis cooled to 120 F., mixed with 0.5% of water, homogcium salt of the product obtained by the condensation of enized, allowed to stand at room temperature for 24 a 2:1 molar mixture of heptylphenol and formaldehours, and then filtered through two layers of No. 1 such as phenylene diamine, N,N-dibutyl phenylene diwhatman filter paper at 20 mm. mercury pressure. The amine, naphthyl amine, N-beta-phenyl naphthylamine, weight of the precipitate, washed with naphtha and dried, o-aminobenzoic acid, p-aminobenzoic acid, methyl ester is taken as a measure of the eiiectiveness of the additive, of o-aminobenzoic acid, and diphenylamine; carbam-ates i.e., the greater the weight of the precipitate the less and xanthates such as methyl N-octylcarbamate, dodecyl eifective the additive. The lubricating oil used in the N-phenyldithiocarbamate, and cyclohexy-l N,N'-dibutyltest is a Mid-Continent conventional-1y refined petroleum carbamate. oil having a viscosity of about 200 SUS at 100 F. Load-carrying additives include, e.g., chlorinated par- The basic mixtures of this invention are suitable for afiin oils containing from 20% to 70% of chlorine, use in oil compositions containing other additives such chlorinated eicosane wax containing from to of as ashless detergents, supplemental metal-containing de- 0 chlorine, hexachlorodiphenyl ether, polychloro-diphenyl, tergents, corosion inhibitors, rust inhibitors, oxidation inetc. Additives to improve the frictional characteristics Table 1 Metal salt(s) in the lubricant Weight ratio Resulting Test result Lubricant tested A. Salt having metal ratio greater B. Salt having metal ratio less of AzB in metal ratio (mg. of sludge (*Denotes baseline) than 4 than 2 mixture of mixture per ml. of
lubricant) Identity Metal Ratio Identity Metal Ratio 900 100 60 Example 3. 220 Example 4. 88 None l 635 1.3 805 1 600 1 700 2 1 220 1 300 8.3 1 7.6 19 8.3 1 6.1 9 8.3 do 1 4.7 s 7.2 ExampleG 1.3 6.6 5 7.2 do 1.3 5.4 5 7.2 1.3 4.3 4 12.8 1 11.6 19 12.8 1 9.3 3 12.8 1 6.9 4 7.6 1 6.9 47 7.6 1 5.6 70 7.6 1 4.3 66 12.8 Examples l 6.9 15 12.8 Example 6 1.3 5.9 20 12.8 Example 9.-. 1 3.4 250 12.8 do. 1 8.9 19 12.8 do 1 10.4 34 12.8 do 1 12.1 32 8.3 Example 11 1 4.7 4 8.3 do 1 6.1 5 8.3 do 1 7.6 10 12.8 Example 10 2 7. 1 3 12.8 -416 2 9.6 12 12.8 1o 2 11.7 34
are illustrated by methyl oleate, oleic acid, stearic acid, s'uliurized sperm oil, sperm oil, corn oil, mono-stearyl ester of glycerol, and quionid-ine dioleate. Pour point depressing agents are, e.g., wax-alkylated naphthylenes, copolymers of butyl methacrylate with decyl methacry-late, etc.
The iollowing examples illustrate the oil compositions containing the basic mixtures of this invention. (All parts are by weight.)
COMPOSITION A (LUBRICANT) Parts SAE 10W30 mineral oil 90 Basic salt of Example 1 8 Neutral salt of Example 5 2 COMPOSITION B (FUEL OIL) Catalytically cracked No. 2 light petroleum fuel oil 99 Basic salt of Example 1 0.5 Neutral salt of Example 6 0.5
COMPOSITION C (LUBRICANT) SAE 30 mineral oil 85 Basic salt of Example 4 10 Slightly basic salt of Example 10 5 COMPOSITION D (LUBRICANT CONCENTRATE) SAE 20 mineral oil 50 Basic salt of Example 3 30 Neutral salt of Example 9 20 COMPOSITION E (LUBRICANT CONCENTRATE) SAE 10lW30 mineral oil 20 Basic salt of Example 3 60 Neutral salt of Example 11 30 Zinc dioctylphosphorodithioate 20 COMPOSITION F (LUBRICANT) SAE 90 mineral oil 85 Basic salt of Example 2 8 Neutral salt of Example 7 4 Dibutyl tetrasulfide 4 2,6-ditert-butyl-4-methylphenol "4 COMPOSITION G (LUBRICANT) SAE 10W30 mineral oil 85 Basic salt of Example 2 8 Neutral salt of Example 8 4 Zinc di-primary-pentyl phosphorodithioate 4 Poly(alkylmethacrylate) viscosity index improving agent COMPOSI'Ill'ON H (LUBRICANT) SAE 10W30 mineral oil Q. 75 Basic salt of Example 2 l Neutral salt of Example 9 Barium dinonyl phosphorodithioate 5 Acylated product obtained by the reaction at 150 C. of tetraethylene pentamine (1 equivalent) \With an alkenyl-substituted succinic .anhydride having 75 carbon atoms in the alkenyl-substituent (1 equivalent) 5 What is claimed is:
1. A basic mixture of alkaline earth metal salts of acidic phosphorized olefin polymers having molecular weights ranging from about 150 to about 48,000 and prepared by the reaction of a polymeric reactant selected from the class consisting of olefin polymers and chlorinated olefin polymers with a phosphorizing agent selected from the class consisting of phosphorus sulfides, phosphorus thiohalides, phosphorus oxyhalides, chlorine and a phosphorus trihalide, sulfur and a phosphorus trihalide, yellow phosphorus and a sulfur halide, yellow phosphorus and sulfur, and phosphorus .trihalides; said mixture being characterized by a metal ratio greater than 10 about 2.5 and comprising (A) from parts to 95 parts by weight of a said metal salt having a metal rat-i0 greater than 4 and (B) from 5 parts to 60 parts by weight of a said metal salt having a meta-l ratio less than 2.
2. The basic mixture of claim 1 characterized further in that the acidic phosphorized olefin polymers are acidic phosphosul furized olefin polymers.
3. The basic mixture oi claim 1 characterized further in that the acidic phosphorized olefin polymers are derived from the reaction of phosphorus pentasulfide with a polyisobutene having a molecular weight within the range from about 500 to 5000.
4. The basic mixture of claim 1 characterized further in that the alkaline earth metal salts are barium salts.
5. A basic mixture of barium salt of an acidic phos phosul'rturized olefin polymer having a molecular weight from about 500 to 5000, said mixture being characterized by a metal rat-i0 within the range from about 3 to about 7 and comprising (A) from parts to 90 parts by weight of a said barium salt having a metal ratio greater than 6 and prepared by carbonating a said acidic phosphosulfurized olefin polymer with an excess of barium oxide in the presence of a phenolic promoting agent, and (B) from 10 parts to 50 parts by weight of a said barium salt having a metal ratio less than 1.5.
6. The basic mixture of claim 5 characterized further in that the acidic phosphosulfurized olefin polymer is derived from the reaction of phosphorus pentasulfide with a polyisobutene having a molecular weight: of about 1000.
7. A basic mixture of barium salt of an acidic phosphosul-furized polyisobutene having a molecular Weight of about 1000, said mixture being characterized by a metal ratio of about 5 and comprising (A) about parts by Weight of said barium salt having a metal ratio of about 10 and prepared by .carbonating a said acid phosphosulfurized polyisobu-tene with at least 10 equivalents of barium oxide in the presence of a phenolic promoting agent and (B) about 40 parts by Weight of a said barium salt having a metal ratio of about 1.
8. A concentrate comprising from about 95 to about 20 parts by weight of tthe basic mixture of claim 1 and from about to about 5 parts by weight of a hydrocarbon oil.
9. A concentrate consisting essentially of from about to about 20 parts by Weight of the basic mixture of claim 7 and from about 80 to about 5 parts by Weight of a hydrocarbon oil.
10. A lubricating composition comprising a major proportion of a mineral lubricating oil and a minor proportion suificien-t to inhibit the formation of deposits of the basic mixture of claim 1.
11. A lubricating composition comprising from about '99 to about '80 parts by Weight of a mineral lubricating oil and from about 1 to about 20 parts by weight of the basic mixture of claim 7.
References Cited by the Examiner UNITED STATES PATENTS 2,316,088 4/1943 Loane et al. 252-32.7 2,606,872 8/ 1952 Gasser et al 25233 2,800,450 7/1957 Bondi et al. 25232.7 2,895,913 7/ 1959 Carlyle et al. 25233 2,906,709 9/1959 Lemmon et al. 25232.7 2,931,773 4/1960 Thompson et al. 252-33 2,943,052 6/1960 Carlyle et al. 25233 3,003,959 10/ 1961 Wilson et al. 25232.7
DANIEL E. WYMAN, Primary Examiner.
JULIUS GREENWALD, Examiner.
Claims (2)
1. A BASIC MIXTURE OF ALKALINE EARTH METAL SALTS OF ACIDIC PHOSPHORIZED OLEFIN POLYMERS HAVING MOLECULAR WEIGHTS RANGING FROM ABOUT 150 TO ABOUT 48,000 AND PREPARED BY THE REACTION OF A POLYMERIC REACTANT SELECTED FROM THE CLASS CONSISTING OF OLEFIN POLYMERS AND CHLORNATED OLEFIN POLYMERS WITH A PHOSPHORIZING AGENT SELECTED FROM THE CLASS CONSISTING OF PHOSPHORUS SULFIDES, PHOSPHORUS THIOHALIDES, PHOSPHORUS OXYHALIDES, CHLORINE AND A PHOSPHORUS TRIHALIDE, SULFRU AND PHOSPHORUS TRIHALIDE, YELLOW PHOSPHORUS AND A SULFUR HALIDE, YELLOW PHOSPHORUS AND SULFUR, AND PHOSPHORUS TRIHALIDES; SAID MIXTURE BEING CHARACTERIZED BY A METAL RATIO GREATER THAN ABOUT 2.5 AND COMPRISING (A) FROM 40 PARTS TO 95 PARTS BY WEIGHT OF A SAID METAL SALT HAVING A METAL RATIO GREATER THAN 4 AND (B) FROM 5 PARTS TO 60 PARTS BY WEIGHT OF A SAID METAL SALT HAVING A METAL RATIO LESS THAN 2.
10. A LUBRICATING COMPOSITION COMPRISING A MAJOR PROPORTION OF A MINERAL LUBRICATING OIL AND A MINOR PROPORTION SUFFICIENT TO INHIBIT THE FORMATION OF DEPOSITS OF THE BASIC MIXTURE OF CLAIM 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US162956A US3232883A (en) | 1961-12-28 | 1961-12-28 | Basic mixtures of metal salts and lubricants containing them |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US162956A US3232883A (en) | 1961-12-28 | 1961-12-28 | Basic mixtures of metal salts and lubricants containing them |
Publications (1)
Publication Number | Publication Date |
---|---|
US3232883A true US3232883A (en) | 1966-02-01 |
Family
ID=22587826
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US162956A Expired - Lifetime US3232883A (en) | 1961-12-28 | 1961-12-28 | Basic mixtures of metal salts and lubricants containing them |
Country Status (1)
Country | Link |
---|---|
US (1) | US3232883A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3272743A (en) * | 1964-08-05 | 1966-09-13 | Lubrizol Corp | Lubricants containing metal-free dispersants and metallic dispersants |
US3397219A (en) * | 1963-03-29 | 1968-08-13 | British Petroleum Co | Preparation of phosphorus-containing olefin polymers and salts thereof |
US3764571A (en) * | 1971-02-18 | 1973-10-09 | Dart Ind Inc | Organotin stabilizer systems |
US4468339A (en) * | 1982-01-21 | 1984-08-28 | The Lubrizol Corporation | Aqueous compositions containing overbased materials |
EP0695798A2 (en) | 1994-08-03 | 1996-02-07 | The Lubrizol Corporation | Lubricating compositions, concentrates, and greases containing the combination of an organic polysulfide and an overbased composition or a phosphorus or boron compound |
US5767044A (en) * | 1993-08-20 | 1998-06-16 | The Lubrizol Corporation | Lubricating compositions with improved thermal stability and limited slip performance |
US5858929A (en) * | 1995-06-09 | 1999-01-12 | The Lubrizol Corporation | Composition for providing anti-shudder friction durability performance for automatic transmissions |
US20050242328A1 (en) * | 2004-04-29 | 2005-11-03 | Crompton Corporation | Method for the preparation of a hydroxyalkyl hindered phenolic antioxidant |
US20080064616A1 (en) * | 2004-10-25 | 2008-03-13 | Huntsman Petrochemical Corporation | Fuel And Oil Detergents |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2316088A (en) * | 1941-11-27 | 1943-04-06 | Standard Oil Co | Lubricant |
US2606872A (en) * | 1948-12-06 | 1952-08-12 | Shell Dev | Lubricating composition |
US2800450A (en) * | 1954-05-10 | 1957-07-23 | Shell Dev | Lubricating compositions |
US2895913A (en) * | 1957-05-28 | 1959-07-21 | Continental Oil Co | Magnesium containing organic compositions and method of preparing the same |
US2906709A (en) * | 1956-05-31 | 1959-09-29 | Standard Oil Co | Lubricant additive of high metal content |
US2931773A (en) * | 1956-10-18 | 1960-04-05 | Continental Oil Co | Method of dispersing calcium carbonate in lubricating oil |
US2943052A (en) * | 1955-12-08 | 1960-06-28 | Continental Oil Co | Lubricating composition |
US3003959A (en) * | 1959-12-21 | 1961-10-10 | Union Oil Co | Lubricating oil additives and lubricating oils containing the same |
-
1961
- 1961-12-28 US US162956A patent/US3232883A/en not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2316088A (en) * | 1941-11-27 | 1943-04-06 | Standard Oil Co | Lubricant |
US2606872A (en) * | 1948-12-06 | 1952-08-12 | Shell Dev | Lubricating composition |
US2800450A (en) * | 1954-05-10 | 1957-07-23 | Shell Dev | Lubricating compositions |
US2943052A (en) * | 1955-12-08 | 1960-06-28 | Continental Oil Co | Lubricating composition |
US2906709A (en) * | 1956-05-31 | 1959-09-29 | Standard Oil Co | Lubricant additive of high metal content |
US2931773A (en) * | 1956-10-18 | 1960-04-05 | Continental Oil Co | Method of dispersing calcium carbonate in lubricating oil |
US2895913A (en) * | 1957-05-28 | 1959-07-21 | Continental Oil Co | Magnesium containing organic compositions and method of preparing the same |
US3003959A (en) * | 1959-12-21 | 1961-10-10 | Union Oil Co | Lubricating oil additives and lubricating oils containing the same |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3397219A (en) * | 1963-03-29 | 1968-08-13 | British Petroleum Co | Preparation of phosphorus-containing olefin polymers and salts thereof |
US3484373A (en) * | 1963-03-29 | 1969-12-16 | British Petroleum Co | Reaction product of olefin and phosphorus halide in the presence of friedel-crafts catalysts |
US3272743A (en) * | 1964-08-05 | 1966-09-13 | Lubrizol Corp | Lubricants containing metal-free dispersants and metallic dispersants |
US3764571A (en) * | 1971-02-18 | 1973-10-09 | Dart Ind Inc | Organotin stabilizer systems |
US4468339A (en) * | 1982-01-21 | 1984-08-28 | The Lubrizol Corporation | Aqueous compositions containing overbased materials |
US5767044A (en) * | 1993-08-20 | 1998-06-16 | The Lubrizol Corporation | Lubricating compositions with improved thermal stability and limited slip performance |
EP0695798A2 (en) | 1994-08-03 | 1996-02-07 | The Lubrizol Corporation | Lubricating compositions, concentrates, and greases containing the combination of an organic polysulfide and an overbased composition or a phosphorus or boron compound |
US5858929A (en) * | 1995-06-09 | 1999-01-12 | The Lubrizol Corporation | Composition for providing anti-shudder friction durability performance for automatic transmissions |
US20050242328A1 (en) * | 2004-04-29 | 2005-11-03 | Crompton Corporation | Method for the preparation of a hydroxyalkyl hindered phenolic antioxidant |
US7329772B2 (en) | 2004-04-29 | 2008-02-12 | Crompton Corporation | Method for the preparation of a hydroxyalkyl hindered phenolic antioxidant |
US20080064616A1 (en) * | 2004-10-25 | 2008-03-13 | Huntsman Petrochemical Corporation | Fuel And Oil Detergents |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3346493A (en) | Lubricants containing metal complexes of alkenyl succinic acid-amine reaction product | |
US3271310A (en) | Metal salts of alkenyl succinic acid | |
US3338832A (en) | Lubricating oil containing reaction product of certain acylated nitrogen containing intermediates and a boron compound | |
US3347790A (en) | Lubricating compositions containing metal salts of acids of phosphorus | |
US3562159A (en) | Synthetic lubricants | |
US3344069A (en) | Lubricant additive and lubricant containing same | |
US3306908A (en) | Reaction products of high molecular weight hydrocarbon succinic compounds, amines and heavy metal compounds | |
US3200107A (en) | Process for preparing acylated amine-cs2 compositions and products | |
US3256185A (en) | Lubricant containing acylated aminecarbon disulfide product | |
US3281428A (en) | Reaction product of certain acylated nitrogen containing intermediates and a boron compound | |
US4328111A (en) | Modified overbased sulfonates and phenates | |
US3632510A (en) | Mixed ester-metal salts and lubricants and fuels containing the same | |
US3216936A (en) | Process of preparing lubricant additives | |
US3372116A (en) | Preparation of basic metal phenates and salicylates | |
US3282955A (en) | Reaction products of acylated nitrogen intermediates and a boron compound | |
US3254025A (en) | Boron-containing acylated amine and lubricating compositions containing the same | |
US3373111A (en) | Reaction products of an organic epoxide and an acylated polyamine | |
US3444170A (en) | Process which comprises reacting a carboxylic intermediate with an amine | |
US4034038A (en) | Boron-containing esters | |
US3480548A (en) | Alkaline earth metal polyborate carbonate overbased alkaline earth metal sulfonate lube oil composition | |
US3542678A (en) | Lubricant and fuel compositions containing esters | |
JPH0241395A (en) | Lubricating oil composition and concentrate | |
US3232883A (en) | Basic mixtures of metal salts and lubricants containing them | |
US3182019A (en) | Process for preparing petroleum oil additives | |
US3256183A (en) | Lubricant having improved oxidation resistance |