US3192159A - Water-in-oil emulsion lubricant and hydraulic fluid - Google Patents
Water-in-oil emulsion lubricant and hydraulic fluid Download PDFInfo
- Publication number
- US3192159A US3192159A US145766A US14576661A US3192159A US 3192159 A US3192159 A US 3192159A US 145766 A US145766 A US 145766A US 14576661 A US14576661 A US 14576661A US 3192159 A US3192159 A US 3192159A
- Authority
- US
- United States
- Prior art keywords
- oil
- water
- dithiocarbamate
- composition
- sodium
- 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
- 239000012530 fluid Substances 0.000 title claims description 17
- 239000007762 w/o emulsion Substances 0.000 title claims description 14
- 239000000314 lubricant Substances 0.000 title claims description 10
- 239000000203 mixture Chemical class 0.000 claims description 57
- 239000012990 dithiocarbamate Substances 0.000 claims description 31
- 239000003921 oil Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002480 mineral oil Substances 0.000 claims description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 235000010446 mineral oil Nutrition 0.000 claims description 15
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 14
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical class O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 claims 1
- -1 phosphate ester Chemical class 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000010688 mineral lubricating oil Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000001593 sorbitan monooleate Substances 0.000 description 9
- 235000011069 sorbitan monooleate Nutrition 0.000 description 9
- 229940035049 sorbitan monooleate Drugs 0.000 description 9
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 239000002585 base Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000009970 fire resistant effect Effects 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- VLDHWMAJBNWALQ-UHFFFAOYSA-M sodium;1,3-benzothiazol-3-ide-2-thione Chemical compound [Na+].C1=CC=C2SC([S-])=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-M 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000000654 additive Substances 0.000 description 5
- KFDMSDGLVCKYOP-UHFFFAOYSA-N 1-ethoxy-4-methyl-2-(2-methylpropyl)-1-phenoxypentan-1-ol Chemical compound C(C(C)C)C(C(O)(OCC)OC1=CC=CC=C1)CC(C)C KFDMSDGLVCKYOP-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NWGKJDSIEKMTRX-MGMRWDBRSA-N [(2R)-2-[(2R,3R,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] (Z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O NWGKJDSIEKMTRX-MGMRWDBRSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- JXLJLMGBTDHWLJ-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;potassium Chemical compound [K].C1=CC=C2SC(=S)NC2=C1 JXLJLMGBTDHWLJ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- IUAIJFLWVIJYQA-UHFFFAOYSA-M sodium;n,n-bis(2-methylpropyl)carbamodithioate Chemical compound [Na+].CC(C)CN(C([S-])=S)CC(C)C IUAIJFLWVIJYQA-UHFFFAOYSA-M 0.000 description 2
- HUMLQUKVJARKRN-UHFFFAOYSA-M sodium;n,n-dibutylcarbamodithioate Chemical compound [Na+].CCCCN(C([S-])=S)CCCC HUMLQUKVJARKRN-UHFFFAOYSA-M 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- JGSUMMPGKPITGK-UHFFFAOYSA-L zinc;n,n-dipentylcarbamodithioate Chemical compound [Zn+2].CCCCCN(C([S-])=S)CCCCC.CCCCCN(C([S-])=S)CCCCC JGSUMMPGKPITGK-UHFFFAOYSA-L 0.000 description 2
- JNYAEWCLZODPBN-KVTDHHQDSA-N (2r,3r,4r)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O JNYAEWCLZODPBN-KVTDHHQDSA-N 0.000 description 1
- RGAGKIRENCJAQY-UHFFFAOYSA-N 1-ethoxy-1-phenoxyethanol Chemical compound CCOC(C)(O)OC1=CC=CC=C1 RGAGKIRENCJAQY-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- HIVBGIWIIXMWOH-UHFFFAOYSA-N 3,5-dipentylphenol Chemical compound CCCCCC1=CC(O)=CC(CCCCC)=C1 HIVBGIWIIXMWOH-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- LWZFANDGMFTDAV-JOCBIADPSA-N [(2r)-2-[(2r,3r,4r)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O LWZFANDGMFTDAV-JOCBIADPSA-N 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- JXXXSUVMLORLHT-UHFFFAOYSA-N bis(3-methylbutyl)carbamodithioic acid Chemical compound CC(C)CCN(C(S)=S)CCC(C)C JXXXSUVMLORLHT-UHFFFAOYSA-N 0.000 description 1
- GAQHRUGINNUYSO-UHFFFAOYSA-L cadmium(2+);n,n-dipentylcarbamodithioate Chemical compound [Cd+2].CCCCCN(C([S-])=S)CCCCC.CCCCCN(C([S-])=S)CCCCC GAQHRUGINNUYSO-UHFFFAOYSA-L 0.000 description 1
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 1
- 229960005286 carbaryl Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- AFCCDDWKHLHPDF-UHFFFAOYSA-M metam-sodium Chemical compound [Na+].CNC([S-])=S AFCCDDWKHLHPDF-UHFFFAOYSA-M 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- CTAGWAHHVKDYTF-UHFFFAOYSA-M potassium;n,n-dibutylcarbamodithioate Chemical compound [K+].CCCCN(C([S-])=S)CCCC CTAGWAHHVKDYTF-UHFFFAOYSA-M 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- DWVJEMMXXKPJTE-UHFFFAOYSA-M sodium;n,n-dipentylcarbamodithioate Chemical compound [Na+].CCCCCN(C([S-])=S)CCCCC DWVJEMMXXKPJTE-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229940022860 xylitan Drugs 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
- C10M173/00—Lubricating compositions containing more than 10% water
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
-
- 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
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Definitions
- This invention relates to improved fire-resistant hydraulic fluids. More particularly, it pertains to water-in-oil colliery hydraulic fluids and lubricants which are fire and, wear-resistant, stable and non-corrosive and to oil concentrates which are readily emulsifiable with large amounts of water.
- a variety of so-called fire-resistant ,fluids are commercially available such as phosphate ester base fluids, but these have been found to possess poor lowtemperature viscosity-temperature properties, andthey are toxic.
- Water-glycol solution or various water-oil" emulsions have been found to have a tendency to form deposits and cause sistant to deterioration, inhibits corrosion and not cause wear.
- Still another object of this invention is to provide a water-mineral oil emulsion usable as lubricants and fire resistant hydraulic fluids for various equipment used in colliery hydraulic equipment.
- Oil concentrates of this invention are readily emulsified with large amounts of water (20-45%) to form a stable, fire resistant water-in-oil emulsion, particularly usefulin colliery hydraulic equipment.
- the highly aromatic mineral oil base should be one having a viscosity index (Dean Davis) of at least 80, preferably between 90 and 100.
- Mineral oil fraction should also be in the lubricating oil range and have a viscosity, as determined at 100 F., of from 75 to 250 "ice SUS, preferably between and and an aromatic content of from about 10% to about 30%.
- a typical mineral oil base is a high viscosity index highly solvent refined mineral lubricating oil having the following properties.
- Pentaaromatics Other sulfur compounds 1.3
- the two non-ionic surface agents and the metal com pounds defined above may be added to the mineral oil and these compounds are (1) a monoester of a long chain fatty acid having at least 3 carbon atoms and an inner ether of aliphatic polyhydric alcohols such as hexahydric alcohols and (2) a polyalkylenoxy phenoxy alkanol, and (3) an alkali metal dithio'carbomate or a mixture of (a) alkali metal thiocarbamate and (b) alkali metal mercaptobenzothiazole.
- each of these additives must be present in critical amounts of which the monoester (1) be used in amounts ranging from 1% to 4%, preferably from 1.5% to 3% and the polyalkylenoxy phenoxy alkanol (2) is used in amounts ranging from 0.5% to 3%, preferably from 1% to 2%, and (3) isused in amount of from 0.01% to 1.0%, each by weight.
- the inner ether alcohol is prepared by partially dehydrating polyhydric alcohols which results in the conversion of the polyhydric alcohol to inner ether polyhdric compounds having 1 or 2 ethers and 4 to 6 hydroxyl groups in the molecule in the manner described in US. Patent 2,322,820.
- Compounds of this type are exemplified by sorbitan, mannitan, xylitan, dulcitan, etc.
- Fatty acids which are used to form the monoesters of the inner ether polyalcohols are saturated and unsaturated fatty acids having at least 8 carbon atoms, preferably from 12 to 18 carbon atoms, such as lauric, stearic, oleic, linoleic, ricinoleic acids and the like.
- Monoesters of this type include sorbitan monolaurate, sorbitan rnonostearate, sorbitan monooleate, sorbitan monoricinoleate, mannitan monolaurate, mannitan monooleate, and mixtures thereof. Compounds of this type are available commercially as Span 20, 60, or 80 from the Atlas Powder Company.
- the second essential additive is an oil-soluble alkyl potassium mercaptobenzothiazole.
- phenoxy polyalkylene glycol having the formula R-phenyl (OR') OR"OH, wherein n is an integer of from 2 to 6, preferably 3 to 4, R is an alkyl radical of 4 to 20 carbon atoms, preferably 4 to 12, and R and R are the same or different alkylene groups such as ethylene or propylene groups, they are preferably the same, and preferably ethylene;
- Compounds of this type are C alkyl phenoxy(alkoxy) alkanols exemplified by isobutylphenoxy tetraethyleneoxy ethanol, diisobutylphenoxy tetraethyleneoxy ethanol, nonylphenoxy tetraethyleneoxy ethanol, octylphenoxy hexaethyleneoxy ethanol, diisobutylphenoxy tripropyleneoxy propanol, and mixtures I thereof.
- both R radicals are alkyl radicals'from 1 to 16 carbon atoms in which the alkyl radicals'can be of same di'lferent chain length and structure, and it is preferred that the Rs are C alkyl radicals of the samechain length but different structure.
- salts are sodium and/ or potassium dimethyl, dibutyl, diamyl, dihexyl, diisobutyl, dioctyl, dicyclohexyl, dicresyl, dithiocarbamates of which the preferred are sodium dimethyl dithiocarbamate, sodium dibu-tyl dithiocarbamate, sodium diisobutyl dithiocarbamate and sodium diamyl dithiocarbamate.
- the other portion of mixture (3) includes sodium or Preferred mixture of (3) includes 90-l0tmixtures of sodium methyl dithio carbamate and sodium mercaptobenzothiazole, sodium dibutyl dithiocarbamate and sodium mercaptobenzothiazole, sodium diaryl dithiocarbamate and sodium mercaptobenzothiazole, sodium diisobutyl dithiocarbamate and sodium mercaptobenzothiazole, potassium dibutyl dithiocarbamate and potassium mercaptobenzothiazole, andpotassium. diamyl dithiocarbamate and potassium mercaptobenzothiazole.
- stability I and emulsifiability can be improved by addition of small amounts (0.010.5% each) ofpolyvalent metal dithiocarbamate and alkylene glycol or its ether derivatives.
- the .polyvalent metal dithiocarbamates includes the zinc, cadmium or lead salts of N- or N,N'-C alkyl substituted dithiocarbamic. acid such as zinc, cadmium, or lead clipropyl mono and dithiocarbamate, dibutyl mono anddithiocarbamate, diamyl mono and dithiocarbamate,
- the alkylene glycols and the ether derivatives thereof includes ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol,- hexylene glycol and mixtures thereof.
- the antioxidants include phenolic and aromatic soluble antioxidants.
- the antioxidants includes phenolic and aromatic amine compounds.
- the phenolic compounds are illustrated by the alkyl phenols, e.g., diand trialkyl phenols, for instance 2,4-, 2,3-, 3,4-, 2,6- and 3,5-diamyl phenol, 2,4-dirnethyl- 6-ter t. butylphenol, 2,6-ditert.butyl-4-methylphenol,j as well as bisphenols such as 4,4'rnethylene-bis(2,6-ditert. butylphenol).
- the amines are illustrated by 'arylamines such as phenyl-alpha-naphthylamine or phenyl-betanaphthylamine.
- mineral oil bases of this invention which are emulsified .with from about20% to about 45%, preferably from about 30% to about 40% of Water to form a stable fire-resistant hydraulic fluid are presented below. Percent Wt.
- Composition A A:
- Sorbitan mono-cleats 2 Diisobutylphenoxy-(ethoxy) ethanol 1 Sodium dimethyl dithiocarbamate-sodium mercaptobenzothiazole, /10% mixture 0.5 Mineral lubricating oil (X) Balance Composition Bz) Sorbitan mono-oleate 2 Diisobutylphenoxy(eth-oxy) ethanol 1 Sodium dibutyl dithiocarbamate-sodium mercaptobenzothiazole, 50% mixture 0.5 Miner-a1 lubricating oil (X) Balance Composition C:
- Sorbitan mono-oleate 2 Diisobutylphenoxy(ethoxy) ethanol 1 Sodium dimethyl dithiocarbamate-sodium mercaptobenzothiazole, 50% mixture 0.5 2,6-ditert.butyl-4-methyl phenol 0.2 Phenyl-alpha-naphthylamine 0.1 Cadmium diamyl dithiocarbamate 0.025 Mineral lubricating oil (X) Balance Composition H:
- Sorbitan mono-oleate 2 Diisobutylphenoxy(et-hoxy) ethanol 1 Sodium dimethyl dithiocarbamate 0.01 2,6-ditert.butyl-4-methyl phenol 0.2 Phenyl-alpha-naphthylamine 0.1 Zinc diamyl dithiocarbamate 0.025 Ethylene, glycol 0.2
- the finished emulsion fluid is prepared by slowly adding to the oil base composition such as A, B, C, D, E, F,'G
- an aqueous base such as water which may or may not contain 0.1% to 1% of a corrosion or wear inhibitor such as water-soluble inorganic nitrites, nitrates, chromates, phosphates or watersoluble low molecular weight salts such as alkali metal-or alkaline earth metal (Na, K, Ca, Ba) acetate or propionate.
- a corrosion or wear inhibitor such as water-soluble inorganic nitrites, nitrates, chromates, phosphates or watersoluble low molecular weight salts such as alkali metal-or alkaline earth metal (Na, K, Ca, Ba) acetate or propionate.
- the water-in-oil emulsion can be mixed by any suitable means such as by air agitation, propeller agitation orby passing through a colloid mill until a homogeneous stable water-in-oil emulsion is formed;
- the water is added to the oil in desired amounts at the time the emulsion is to be used, although a stable water-in-oil emulsion can be prepared and stored for :a moderate period.
- composition I A finished water-in-oil emulsion (Composition I) was prepared by admixing 60% of composition D with 40% Water and the mixture was passed through a colloid mill until a stable homogeneous water-irr-oil emulsion was formed.
- compositions include:
- compositions I and V in Table 1 in comparison with composition W* which does not contain a metal carbamate.
- the stability was determined by measuring the amount of oil and water separation at 140 F. from a 100 ml. sample. Also in a Vickers Hydraulic Pump Test similar to that described in Lubrication Engineering, February 1949, pages 16-17, negligible wear was noted using compositions I and V after 1000 hours testing, whereas compositions X* and Y* resulted in phase separation in from about 1 to 2 days.
- compositions of the present invention are fire-resistant passing over 50 cycles as determined by the Pipe Cleaner Test described in Lubricating Engineering, March-April 1955, pages 86- 87 while a neat mineral oil or a mineral oil containing 4% *Composition W: [water-in-oil emulsion comprising 40% water plus 60% mineral oil composition containing 2% sorbitan monooleate (Span 80)+1% diisobutylphenoxflothoxyh ethanol+0.2% 2,6-ditertiarybutyl- 4-methyl phenol+0.l% phenyl alphanephthylamine].
- composition X [water-in-oil emulsion comprising 40% water+60% mineral oil composition containing +15% polyethylene substituted sorbitan monooleate (Tween 81)+0.15% glycerol monoo1eate+0.12% sulfurized oleic acid].
- composition Y [oil-in-water emulsion comprising 50% water-+50% mineral oil composition containing 20% Ne petroleum sulfonate, 1% ricinoleic acid, 1% hexylene glycol, 1% lard oil, 2% water, 0.3% Dowicide- O, 0.1% sodium hydroxide and the balance mineral oil].
- each of Ca petroleum sulfonate and/or Ca C1242 alkyl salicylate ignited after 5 cycles.
- a water-in-oil emulsion lubricant and hydraulic fluid which is fromabout 20% to about 45 water'phase and from about 55% to 80% oil phase, the oil phase being essentially a 80-100 VI mineral oil having a viscosity in the range of from 75 to 250 SUS at 100 F.
- a water-in-oil emulsion lubricant and hydraulic fluid which is from about 20% to about 45 Water phase and from about 55% to about 80% oil phase, the oil phase being essentially a 80-100 VI mineral oil having a viscosity in the range of from 75 to 250 SUS at 100 F.
- a water-in-oil emulsion lubricant and hydraulic fluid which is from about 20% to about 45% water phase and from about 55 to about oil phase, the oil phase being essentially a 80-100 VI mineral lubricating oil having a viscosity in the range of from to SUS at 100 F. containing from about 1.5% to about 3% .of a sorbitan monooleate, from about 1% to about 2% of an alkyl mixture of phenoxy(ethoxy) ethanol and from about 0.01 to about 1% of a mixture of 10-90% of sodium dimethyldithiocarbamate and 90-10% of sodium mercaptobenzothiazole.
- composition of claim 2 containing in the emulsion from 0.01% to 2% of an oil-soluble antioxidant selected from the group consisting of alkyl substituted simple phenol and phenyl-alpha-naphthylamine and mixtures thereof.
- composition of claim 2 containing in the emulsion from about 0.01% to about 1% of an oil-soluble polyvalent metal N,N'-C alkyl substituted dithiocarbamate, the metal being selected from the group consisting of zinc, cadmium and lead.
- composition of claim 3 containing in the emulsion from 0.01% to 2% of an oil-soluble antioxidant selected from the group consisting of alkyl substituted simple phenol and phenyl-alpharnaphthylamine and mixtures thereof.
- composition of claim 3 containing in the emulsion from about 0.01% to about 1% of an oil-soluble polyvalent metal N,N-C alkyl substituted dithiocarbamate, the metal being selected from the group consisting of zinc, cadmium and lead.
- a Water-in-oil emulsion lubricant and hydraulic fluid which is from about 30% to about 40% Water phase and from about 70% to about 60% oil phase, the oil phase being essentially a 80-100 VI mineral lubricating oil containing from about 1.5% to about 3% of sorbitan monooleate, from about 1% to about 2% of an oil-soluble diisobutylphenoxy(ethoxy) ethanol and from about 0.01% to about 1% of a 50-50 mixture of sodium dimethyl dithiocarbamate and sodium mercaptobenzothiazole.
- composition of claim 8 containing in the emul: butylA-methylphenol, phenyl-alphanapthylamine and eth- Sion from about 0.01% to about 1% each of an oil-soluble 3 1 116 glycol.
- alkylphenol, an oil-soluble ar'ylamine and polyvalent metal N,N'-,C alkyl substituted dithiocarbamate the metal be- References Cited by theiExammer ing selected frorn'the group consisting of zinc, cadmium UNITED STATES A E T and lead; 2,625,509 1/53 Lang 252-495 10.1
- Thecom-position of claim 8 containing in the emul- 5 1 6/54 3 F 25275 sion from about"0.01% to about 1% each of 2,6-ditert.-
- composition of claim 8 containing in the emul- JOSEPH LIBERMAN ALBERT '11 MEYERS sion from about 0.01%v to about 1% each of 2,6-ditert.- 1 E in
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Description
United States Patent O WATER-IN-OIL EMULSION LUBRICANT AND HYDRAULIC FLUID Charles E. Francis,,Martinez, Califi, assignor to Shell Oil Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Oct. 17, 1961, Ser. No. 145,766
a I 11 Claims. (Cl. 252-336) This invention relates to improved fire-resistant hydraulic fluids. More particularly, it pertains to water-in-oil colliery hydraulic fluids and lubricants which are fire and, wear-resistant, stable and non-corrosive and to oil concentrates which are readily emulsifiable with large amounts of water.
Although it is known in the art that certain emulsions are useful as coolants and lubricants in metal working operations, the use of emulsions in hydraulic systems has been limited because of their inability to resist wear, their poor stability and their inability to pass. fire-resistant requirements for which such fluids are primarily used.
In colliery equipment such as various hydraulic machinery, e.g., winder brake mechanism and wagon tipper to hydraulic. jacks, pit props and roof bar straighteners, mechanical loaders and various other fluid drive mechanisms which are subject to load, shock and vibration, it is essential that the hydraulic fluid employed therein function properly and efliciently without the danger of being flammable or toxic.
A variety of so-called fire-resistant ,fluids are commercially available such as phosphate ester base fluids, but these have been found to possess poor lowtemperature viscosity-temperature properties, andthey are toxic. Water-glycol solution or various water-oil" emulsions have been found to have a tendency to form deposits and cause sistant to deterioration, inhibits corrosion and not cause wear. Still another object of this invention is to provide a water-mineral oil emulsion usable as lubricants and fire resistant hydraulic fluids for various equipment used in colliery hydraulic equipment.
These and other objectsare accomplished in accordance. with this invention by providing a highly aromatic high viscosity indeX mineral oil base concentrate which is readily emulsifiable with a large amount of water, and which contains two particular types of dissimilar nonionic surface active agents and an alkali metal dithiocarbamate or a mixture of alkali metal dithiocarbamate and alkali metal mercaptobenzothiazole, the metal portion being selected from the group consisting of sodium and potassium, all of the'additives being present in critical.
amounts. Oil concentrates of this invention are readily emulsified with large amounts of water (20-45%) to form a stable, fire resistant water-in-oil emulsion, particularly usefulin colliery hydraulic equipment.
If desired small amounts of polyvalent metal dithiocarbamates, the
7 metal portion of the compound beingselected from the group consisting of zinc, cadmium and/ or lead and an alkylene glycol or ether derivative thereofcan be added to the oil concentrate to improve emulsification and cold storagestability of the finished Water-in-oil' emulsion.
The highly aromatic mineral oil base should be one having a viscosity index (Dean Davis) of at least 80, preferably between 90 and 100. Mineral oil fraction should also be in the lubricating oil range and have a viscosity, as determined at 100 F., of from 75 to 250 "ice SUS, preferably between and and an aromatic content of from about 10% to about 30%.
A typical mineral oil base is a high viscosity index highly solvent refined mineral lubricating oil having the following properties.
Gr. API, 60 C. Color, ASTM 1 Pour point, F. 5 Flash, F., COC 370 Fire, F. 435 Viscosity, SUS at 100 F 103 Viscosity index 93 Neutralization No. 0.01 Components, percent w.:
n-Alkanes 21.8
Isoalkenes 11.8 Noncondensed cycloalkanes 24.9 Condensed cycloalkanes 12.4- Total saturates 70.9 Monoaromatics 13.6 Diaromatics 5.8 Triaromatics 4.0
Teteraaromatics 1.6 Pentaaromatics 0.2 Hexaaromatics Total sulfur compounds 3.9
Total 100.0
Sulfur analysis, percent w.:
Thiopenes Benzo- 1.7
Triaromatics 0.5
Teteraaromatics 0.4
Pentaaromatics Other sulfur compounds 1.3
Total 3.9
The two non-ionic surface agents and the metal com pounds defined above may be added to the mineral oil and these compounds are (1) a monoester of a long chain fatty acid having at least 3 carbon atoms and an inner ether of aliphatic polyhydric alcohols such as hexahydric alcohols and (2) a polyalkylenoxy phenoxy alkanol, and (3) an alkali metal dithio'carbomate or a mixture of (a) alkali metal thiocarbamate and (b) alkali metal mercaptobenzothiazole. Each of these additives must be present in critical amounts of which the monoester (1) be used in amounts ranging from 1% to 4%, preferably from 1.5% to 3% and the polyalkylenoxy phenoxy alkanol (2) is used in amounts ranging from 0.5% to 3%, preferably from 1% to 2%, and (3) isused in amount of from 0.01% to 1.0%, each by weight.
In themonoester non-ionic surface agent the inner ether alcohol is prepared by partially dehydrating polyhydric alcohols which results in the conversion of the polyhydric alcohol to inner ether polyhdric compounds having 1 or 2 ethers and 4 to 6 hydroxyl groups in the molecule in the manner described in US. Patent 2,322,820. Compounds of this type are exemplified by sorbitan, mannitan, xylitan, dulcitan, etc. Fatty acids which are used to form the monoesters of the inner ether polyalcohols are saturated and unsaturated fatty acids having at least 8 carbon atoms, preferably from 12 to 18 carbon atoms, such as lauric, stearic, oleic, linoleic, ricinoleic acids and the like. Monoesters of this type include sorbitan monolaurate, sorbitan rnonostearate, sorbitan monooleate, sorbitan monoricinoleate, mannitan monolaurate, mannitan monooleate, and mixtures thereof. Compounds of this type are available commercially as Span 20, 60, or 80 from the Atlas Powder Company.
The second essential additive is an oil-soluble alkyl potassium mercaptobenzothiazole.
phenoxy polyalkylene glycol having the formula R-phenyl (OR') OR"OH, wherein n is an integer of from 2 to 6, preferably 3 to 4, R is an alkyl radical of 4 to 20 carbon atoms, preferably 4 to 12, and R and R are the same or different alkylene groups such as ethylene or propylene groups, they are preferably the same, and preferably ethylene; Compounds of this type are C alkyl phenoxy(alkoxy) alkanols exemplified by isobutylphenoxy tetraethyleneoxy ethanol, diisobutylphenoxy tetraethyleneoxy ethanol, nonylphenoxy tetraethyleneoxy ethanol, octylphenoxy hexaethyleneoxy ethanol, diisobutylphenoxy tripropyleneoxy propanol, and mixtures I thereof.
' it can be hydrogen; it is desirable that both R radicals are alkyl radicals'from 1 to 16 carbon atoms in which the alkyl radicals'can be of same di'lferent chain length and structure, and it is preferred that the Rs are C alkyl radicals of the samechain length but different structure.
Examples of such salts are sodium and/ or potassium dimethyl, dibutyl, diamyl, dihexyl, diisobutyl, dioctyl, dicyclohexyl, dicresyl, dithiocarbamates of which the preferred are sodium dimethyl dithiocarbamate, sodium dibu-tyl dithiocarbamate, sodium diisobutyl dithiocarbamate and sodium diamyl dithiocarbamate.
The other portion of mixture (3) includes sodium or Preferred mixture of (3) includes 90-l0tmixtures of sodium methyl dithio carbamate and sodium mercaptobenzothiazole, sodium dibutyl dithiocarbamate and sodium mercaptobenzothiazole, sodium diaryl dithiocarbamate and sodium mercaptobenzothiazole, sodium diisobutyl dithiocarbamate and sodium mercaptobenzothiazole, potassium dibutyl dithiocarbamate and potassium mercaptobenzothiazole, andpotassium. diamyl dithiocarbamate and potassium mercaptobenzothiazole. I
In addition tothe above essential additives, stability I and emulsifiability can be improved by addition of small amounts (0.010.5% each) ofpolyvalent metal dithiocarbamate and alkylene glycol or its ether derivatives.
The .polyvalent metal dithiocarbamates includes the zinc, cadmium or lead salts of N- or N,N'-C alkyl substituted dithiocarbamic. acid such as zinc, cadmium, or lead clipropyl mono and dithiocarbamate, dibutyl mono anddithiocarbamate, diamyl mono and dithiocarbamate,
.dihexyl Emono and dithiocarbamate, dioctyl mono and dithiocarbamate, di-2-ethylhexy1 mono and dithiocarbamate, di-isobutylmono and .dithio-carbamate, diisoamyldithiocarbamate mono and N-amyl-N-methyl mono and dithiocarbamate, N-methyl-N-octyl mono and dithiocarbamate, N-octyl-N-butyl mono and dithiocarbamate, N-n-amyl-N-2-methylbutyl dithiocarbamate, N-n-amyl- N"-3-methylbutyl dithiocarbam-ate, N-ootyl-N'-2-ethyl- -hexyl dithiocarbamate, N-ethyl-N phenyl mono and dithiocarbamate, dicyclohexyl mono and dithiocarbamate, diphenyl mono and dithiocarbamate, and the like.
The alkylene glycols and the ether derivatives thereof includes ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol,- hexylene glycol and mixtures thereof.
In addition to the above essential additives it is preferred to use in such compositions small amounts of from about 0.01% to about 2%, preferably from about 0.2% to about 1% of oil soluble antioxidants. The antioxidants include phenolic and aromatic soluble antioxidants. The antioxidants includes phenolic and aromatic amine compounds. The phenolic compounds are illustrated by the alkyl phenols, e.g., diand trialkyl phenols, for instance 2,4-, 2,3-, 3,4-, 2,6- and 3,5-diamyl phenol, 2,4-dirnethyl- 6-ter t. butylphenol, 2,6-ditert.butyl-4-methylphenol,j as well as bisphenols such as 4,4'rnethylene-bis(2,6-ditert. butylphenol). The amines are illustrated by 'arylamines such as phenyl-alpha-naphthylamine or phenyl-betanaphthylamine.
Illustrative examples of mineral oil bases of this invention which are emulsified .with from about20% to about 45%, preferably from about 30% to about 40% of Water to form a stable fire-resistant hydraulic fluid are presented below. Percent Wt.
Composition A:
Sorbitan mono-cleats 2 Diisobutylphenoxy-(ethoxy) ethanol 1 Sodium dimethyl dithiocarbamate-sodium mercaptobenzothiazole, /10% mixture 0.5 Mineral lubricating oil (X) Balance Composition Bz) Sorbitan mono-oleate 2 Diisobutylphenoxy(eth-oxy) ethanol 1 Sodium dibutyl dithiocarbamate-sodium mercaptobenzothiazole, 50% mixture 0.5 Miner-a1 lubricating oil (X) Balance Composition C:
Sorbitan mono-Oleate 2 -Diisobutylphenoxy(ethoxy) ethanol 1 Sodium diamyl dithiocarbamatesodium' mercaptobenzothiazole, 50% mixture 0.5 Mineral lubricating oil (X) Balanc Composition D:
. Sorbitan mono-oleate 2 Diisobutylphenoxy(ethoxy) ethanol 1 Sodium dimethyl dithiocarbamate 0.01 2,6-ditertbutyl-4-methyl phenol 0.2 Phenyl-alpha-naphthylamine 0.1 Mineral lubricating oil (X) Balance Composition E:
Mannitan mono-oleate 2 Diisobutyl-phenoxy(ethoxy) ethanol 1 Sodium dimethyl dithiocarbamatesodium mercaptobenzothiazole', 90/10% mixture 0.5 2,6-ditert.butyl-4-methyl phenol 0.2 Phenyl-alpha-naphthylamine 0.1 Mineral lubricating oil (X) Balance Composition F:
Mannitan mono-oleate 2 Nonylphenoxy(ethoxy) ethanol 1 Sodium dimethyl dithiocarbamate-sodium mercaptobenzothiazole, 90/10% mixture 0.5 4,4-methylene (2,6-ditert.butylpheno-l) 0.2 Phenyl-alpha-naphthylamine 0.1 Mineral lubricating oil (X) Balance Composition G:
Sorbitan mono-oleate 2 Diisobutylphenoxy(ethoxy) ethanol 1 Sodium dimethyl dithiocarbamate-sodium mercaptobenzothiazole, 50% mixture 0.5 2,6-ditert.butyl-4-methyl phenol 0.2 Phenyl-alpha-naphthylamine 0.1 Cadmium diamyl dithiocarbamate 0.025 Mineral lubricating oil (X) Balance Composition H:
Sorbitan mono-oleate 2 Diisobutylphenoxy(et-hoxy) ethanol 1 Sodium dimethyl dithiocarbamate 0.01 2,6-ditert.butyl-4-methyl phenol 0.2 Phenyl-alpha-naphthylamine 0.1 Zinc diamyl dithiocarbamate 0.025 Ethylene, glycol 0.2
Mineral lubricating oil (X) Balance The finished emulsion fluid is prepared by slowly adding to the oil base composition such as A, B, C, D, E, F,'G
or H from 20% to 45% based on the total composition,
an aqueous base, such as water which may or may not contain 0.1% to 1% of a corrosion or wear inhibitor such as water-soluble inorganic nitrites, nitrates, chromates, phosphates or watersoluble low molecular weight salts such as alkali metal-or alkaline earth metal (Na, K, Ca, Ba) acetate or propionate. The water-in-oil emulsion can be mixed by any suitable means such as by air agitation, propeller agitation orby passing through a colloid mill until a homogeneous stable water-in-oil emulsion is formed; For economical reasons, the water is added to the oil in desired amounts at the time the emulsion is to be used, although a stable water-in-oil emulsion can be prepared and stored for :a moderate period.
A finished water-in-oil emulsion (Composition I) was prepared by admixing 60% of composition D with 40% Water and the mixture was passed through a colloid mill until a stable homogeneous water-irr-oil emulsion was formed.
Other finished compositions include:
Percent Composition 11-- 'Water 30 Composition A 70 Composition III-.-
Water containing 0.1% Ca acetate 4'0 Composition G 60 Composition IV- Water containing 0.1% NaNO 35 Composition C 65 Composition V Water 40 Composition H 60 The outstanding emulsion stability properties of these compositions is demonstrated by compositions I and V in Table 1 in comparison with composition W* which does not contain a metal carbamate. The stability was determined by measuring the amount of oil and water separation at 140 F. from a 100 ml. sample. Also in a Vickers Hydraulic Pump Test similar to that described in Lubrication Engineering, February 1949, pages 16-17, negligible wear was noted using compositions I and V after 1000 hours testing, whereas compositions X* and Y* resulted in phase separation in from about 1 to 2 days.
Compositions of the present invention such as compositions I through V are fire-resistant passing over 50 cycles as determined by the Pipe Cleaner Test described in Lubricating Engineering, March-April 1955, pages 86- 87 while a neat mineral oil or a mineral oil containing 4% *Composition W: [water-in-oil emulsion comprising 40% water plus 60% mineral oil composition containing 2% sorbitan monooleate (Span 80)+1% diisobutylphenoxflothoxyh ethanol+0.2% 2,6-ditertiarybutyl- 4-methyl phenol+0.l% phenyl alphanephthylamine].
*Composition X: [water-in-oil emulsion comprising 40% water+60% mineral oil composition containing +15% polyethylene substituted sorbitan monooleate (Tween 81)+0.15% glycerol monoo1eate+0.12% sulfurized oleic acid].
*Composition Y: [oil-in-water emulsion comprising 50% water-+50% mineral oil composition containing 20% Ne petroleum sulfonate, 1% ricinoleic acid, 1% hexylene glycol, 1% lard oil, 2% water, 0.3% Dowicide- O, 0.1% sodium hydroxide and the balance mineral oil].
each of Ca petroleum sulfonate and/or Ca C1242 alkyl salicylate ignited after 5 cycles.
I claim as my invention:
1. A water-in-oil emulsion lubricant and hydraulic fluid which is fromabout 20% to about 45 water'phase and from about 55% to 80% oil phase, the oil phase being essentially a 80-100 VI mineral oil having a viscosity in the range of from 75 to 250 SUS at 100 F. containing (1) from about 1% to about 4% of a monoester of a long chain fatty acid having from 8 to 18 carbon atoms and an inner ether of an aliphatic polyhydric alcohol having 1-2 ether and 4-6 hydroxyl groups, (2) from about 0.5% to about 3% of an 0ilsoluble C alkyl'phenoxy(C alkoxy) C alkanol, and (3) from about 0.01% to about 1% of a material selected from the group consisting of alkali metal C alkyl substituted dithiocarbamate and a mixture of 10-90% of an alkali metal C alkyl substituted dithiocarbamate and 90-10% alkali metal mercaptobenzothiazole.
2. A water-in-oil emulsion lubricant and hydraulic fluid which is from about 20% to about 45 Water phase and from about 55% to about 80% oil phase, the oil phase being essentially a 80-100 VI mineral oil having a viscosity in the range of from 75 to 250 SUS at 100 F. containing 1) from about 1.5% to about 3% of a monoester of a fatty acid having from 12 to 18 carbon atoms and an inner other of an aliphatic hexahydric alcohol having 1-2 ether and 4-6 hydroxyl groups, (2) from about 1% to about 2% of an oil-soluble C alkyl phenoxy(ethoxy) ethanol, and (3) from about 0.01% to about 1% of a material selected from the group consisting of an alkali metal C alkyl substituted dithiocarbamate and a mixture of 25-75% of an alkali metal C alkyl substituted dithiocarbamate and -25 of an alkali metal mercaptobenzothiazole.
3. A water-in-oil emulsion lubricant and hydraulic fluid which is from about 20% to about 45% water phase and from about 55 to about oil phase, the oil phase being essentially a 80-100 VI mineral lubricating oil having a viscosity in the range of from to SUS at 100 F. containing from about 1.5% to about 3% .of a sorbitan monooleate, from about 1% to about 2% of an alkyl mixture of phenoxy(ethoxy) ethanol and from about 0.01 to about 1% of a mixture of 10-90% of sodium dimethyldithiocarbamate and 90-10% of sodium mercaptobenzothiazole.
4. The composition of claim 2 containing in the emulsion from 0.01% to 2% of an oil-soluble antioxidant selected from the group consisting of alkyl substituted simple phenol and phenyl-alpha-naphthylamine and mixtures thereof.
5. The composition of claim 2 containing in the emulsion from about 0.01% to about 1% of an oil-soluble polyvalent metal N,N'-C alkyl substituted dithiocarbamate, the metal being selected from the group consisting of zinc, cadmium and lead.
6. The composition of claim 3 containing in the emulsion from 0.01% to 2% of an oil-soluble antioxidant selected from the group consisting of alkyl substituted simple phenol and phenyl-alpharnaphthylamine and mixtures thereof.
7. The composition of claim 3 containing in the emulsion from about 0.01% to about 1% of an oil-soluble polyvalent metal N,N-C alkyl substituted dithiocarbamate, the metal being selected from the group consisting of zinc, cadmium and lead.
8. A Water-in-oil emulsion lubricant and hydraulic fluid which is from about 30% to about 40% Water phase and from about 70% to about 60% oil phase, the oil phase being essentially a 80-100 VI mineral lubricating oil containing from about 1.5% to about 3% of sorbitan monooleate, from about 1% to about 2% of an oil-soluble diisobutylphenoxy(ethoxy) ethanol and from about 0.01% to about 1% of a 50-50 mixture of sodium dimethyl dithiocarbamate and sodium mercaptobenzothiazole.
a '7 8 I 9. The composition of claim 8 containing in the emul: butylA-methylphenol, phenyl-alphanapthylamine and eth- Sion from about 0.01% to about 1% each of an oil-soluble 3 1 116 glycol. alkylphenol, an oil-soluble ar'ylamine and polyvalent metal N,N'-,C alkyl substituted dithiocarbamate, the metal be- References Cited by theiExammer ing selected frorn'the group consisting of zinc, cadmium UNITED STATES A E T and lead; 2,625,509 1/53 Lang 252-495 10.1 Thecom-position of claim 8 containing in the emul- 5 1 6/54 3 F 25275 sion from about"0.01% to about 1% each of 2,6-ditert.-
g 2 5 2 7 buty1-4-methylpheno1, phenyl-alpha-naphthylamine and 10 v mums N 7 X zinc diamyldithiocarbamate. JULIUS GREENWALD; Pimary Examiner.
11. The composition of claim 8 containing in the emul- JOSEPH LIBERMAN ALBERT '11 MEYERS sion from about 0.01%v to about 1% each of 2,6-ditert.- 1 E in
Claims (1)
1. A WATER-IN-OIL EMULSION LUBRICANT AND HYDRAULIC FLUID WHICH IS FROM ABOUT 20% TO ABOUT 45% WATER PHASE AND FROM ABOUT 55% TO 80% OIL PHASE, THE OIL PHASE BEING ESSENTIALLY A 80-100 VI MINERAL OIL HAVING A VISCOSITY IN THE RANGE OF FROM 75 TO 250 SUS AT 100*F. CONTAINING (1) FROM ABOUT 1% TO ABOUT 4% OF A MOOESTER OF A LONG CHAIN FATTY ACID HAVING FROM 8 TO 18 CARBON ATOMS AND AN INNER ETHER OF AN ALIPHATIC POLYHYDRIC ALCOHOL HAVING 1-2 ETHER AND 4-6 HYDROXYL GROUPS, (2) FROM ABOUT 0.5% TO ABOUT 3% OF AN OIL-SOLUBLE C4-20 ALKYL PHENOXY (C2-3 ALKOXYL)4-6 C2-3 ALKANOL, AND (3) FROM ABOUT 0.01% TO ABOUT 1% OF A MATERIAL SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL C1-12 ALKYL SUBSTITUTED DITHIOCARBAMATE AND A MIXTURE OF 10-90% OF AN ALKALI METAL C1-12 ALKYL SUBSTITUTED DITHIOCARBAMATE AND 90-10% ALKALI METAL MERCAPTOBENZOTHIAZOLE.
Priority Applications (19)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE590388D BE590388A (en) | 1959-05-04 | ||
| NL284362D NL284362A (en) | 1959-05-04 | ||
| NL251182D NL251182A (en) | 1959-05-04 | ||
| NL287079D NL287079A (en) | 1959-05-04 | ||
| BE623612D BE623612A (en) | 1959-05-04 | ||
| BE626342D BE626342A (en) | 1959-05-04 | ||
| FR825981A FR1269611A (en) | 1959-05-04 | 1960-05-02 | Emulsifiable mineral oil compositions |
| DES68328A DE1122656B (en) | 1959-05-04 | 1960-05-02 | Hydraulic fluid and lubricant based on a water-in-oil emulsion |
| GB15336/60D GB882763A (en) | 1959-05-04 | 1960-05-02 | Emulsifiable mineral oil composition |
| CH498760A CH395409A (en) | 1959-05-04 | 1960-05-02 | Emulsifiable mineral oil preparation |
| US145766A US3192159A (en) | 1961-10-17 | 1961-10-17 | Water-in-oil emulsion lubricant and hydraulic fluid |
| CH1209162A CH431778A (en) | 1959-05-04 | 1962-10-15 | Emulsifiable mineral oil preparation |
| GB38993/72A GB960137A (en) | 1959-05-04 | 1962-10-15 | Emulsifiable mineral oil compositions |
| DE19621444898 DE1444898A1 (en) | 1959-05-04 | 1962-10-15 | Hydraulic fluid and lubricant based on a water-in-oil emulsion |
| DK445962AA DK104991C (en) | 1961-10-17 | 1962-10-17 | Water-in-oil emulsion for use as a lubricant or hydraulic fluid and emulsifiable mineral lubricating oil for its manufacture. |
| GB48199/62A GB970680A (en) | 1959-05-04 | 1962-12-20 | Emulsifiable mineral oil composition |
| FR919306A FR83113E (en) | 1959-05-04 | 1962-12-20 | Emulsifiable mineral oil compositions |
| DE19621444899 DE1444899C (en) | 1961-12-22 | 1962-12-20 | Hydraulic fluid and lubricant based on a water in oil emulsion |
| CH1499362A CH434534A (en) | 1959-05-04 | 1962-12-20 | Emulsifiable mineral oil preparation, suitable for the production of hydraulic fluids or lubricants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US145766A US3192159A (en) | 1961-10-17 | 1961-10-17 | Water-in-oil emulsion lubricant and hydraulic fluid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3192159A true US3192159A (en) | 1965-06-29 |
Family
ID=22514442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US145766A Expired - Lifetime US3192159A (en) | 1959-05-04 | 1961-10-17 | Water-in-oil emulsion lubricant and hydraulic fluid |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3192159A (en) |
| DK (1) | DK104991C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040007687A1 (en) * | 2002-07-11 | 2004-01-15 | Hubert Dobbelstein | Formulation of a highly viscous mineral oil for the production of filters for tobacco products |
| US11505499B2 (en) | 2017-12-19 | 2022-11-22 | Corning Incorporated | Green ceramic mixtures comprising a stabilized emulsion and methods for forming a ceramic body |
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|---|---|---|---|---|
| US2625509A (en) * | 1950-03-20 | 1953-01-13 | Soeony Vacuum Oil Company Inc | Cutting fluid and coolant |
| US2681891A (en) * | 1951-11-27 | 1954-06-22 | Texas Co | Hydraulic transmission fluid |
| US3003957A (en) * | 1960-06-23 | 1961-10-10 | Atlantic Refining Co | Fire-resistant lubricating emulsion |
| US3050465A (en) * | 1959-05-04 | 1962-08-21 | Shell Oil Co | Water-in-oil emulsion hydraulic fluids |
-
1961
- 1961-10-17 US US145766A patent/US3192159A/en not_active Expired - Lifetime
-
1962
- 1962-10-17 DK DK445962AA patent/DK104991C/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2625509A (en) * | 1950-03-20 | 1953-01-13 | Soeony Vacuum Oil Company Inc | Cutting fluid and coolant |
| US2681891A (en) * | 1951-11-27 | 1954-06-22 | Texas Co | Hydraulic transmission fluid |
| US3050465A (en) * | 1959-05-04 | 1962-08-21 | Shell Oil Co | Water-in-oil emulsion hydraulic fluids |
| US3003957A (en) * | 1960-06-23 | 1961-10-10 | Atlantic Refining Co | Fire-resistant lubricating emulsion |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040007687A1 (en) * | 2002-07-11 | 2004-01-15 | Hubert Dobbelstein | Formulation of a highly viscous mineral oil for the production of filters for tobacco products |
| US7153447B2 (en) * | 2002-07-11 | 2006-12-26 | Emini Shefqet | Formulation of a highly viscous mineral oil for the production of filters for tobacco products |
| US11505499B2 (en) | 2017-12-19 | 2022-11-22 | Corning Incorporated | Green ceramic mixtures comprising a stabilized emulsion and methods for forming a ceramic body |
Also Published As
| Publication number | Publication date |
|---|---|
| DK104991C (en) | 1966-08-01 |
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