USRE32295E - Hindered phenyl esters of cyclic borates and lubricants containing same - Google Patents
Hindered phenyl esters of cyclic borates and lubricants containing same Download PDFInfo
- Publication number
- USRE32295E USRE32295E US06/679,517 US67951784A USRE32295E US RE32295 E USRE32295 E US RE32295E US 67951784 A US67951784 A US 67951784A US RE32295 E USRE32295 E US RE32295E
- Authority
- US
- United States
- Prior art keywords
- sub
- phenol
- boron compound
- group
- carbon atoms
- 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 - Fee Related
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- 239000000314 lubricant Substances 0.000 title claims abstract description 26
- -1 cyclic borates Chemical class 0.000 title description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 48
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 230000001050 lubricating effect Effects 0.000 claims abstract description 5
- 238000002485 combustion reaction Methods 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000004519 grease Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 9
- 239000010687 lubricating oil Substances 0.000 claims description 8
- BITAPBDLHJQAID-KTKRTIGZSA-N 2-[2-hydroxyethyl-[(z)-octadec-9-enyl]amino]ethanol Chemical group CCCCCCCC\C=C/CCCCCCCCN(CCO)CCO BITAPBDLHJQAID-KTKRTIGZSA-N 0.000 claims description 7
- 239000002480 mineral oil Substances 0.000 claims description 7
- 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 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 235000010446 mineral oil Nutrition 0.000 claims description 4
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 4
- 239000010689 synthetic lubricating oil Substances 0.000 claims 4
- 239000010688 mineral lubricating oil Substances 0.000 claims 3
- 101150108015 STR6 gene Proteins 0.000 claims 1
- 150000003871 sulfonates Chemical class 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002562 thickening agent Substances 0.000 description 8
- 239000002199 base oil Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- PIWWRTXEDNNIJH-UHFFFAOYSA-N (2,6-ditert-butyl-4-methylphenoxy)boronic acid Chemical compound CC1=CC(C(C)(C)C)=C(OB(O)O)C(C(C)(C)C)=C1 PIWWRTXEDNNIJH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NDLNTMNRNCENRZ-UHFFFAOYSA-N 2-[2-hydroxyethyl(octadecyl)amino]ethanol Chemical compound CCCCCCCCCCCCCCCCCCN(CCO)CCO NDLNTMNRNCENRZ-UHFFFAOYSA-N 0.000 description 2
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000004010 onium ions Chemical class 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- MUBGWEHIJABTPP-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pentyl 2,2-dimethylpropanoate Chemical compound CCCCC(OC(=O)C(C)(C)C)C1=CC=C(O)C=C1 MUBGWEHIJABTPP-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical class CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical class CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- WTHCRRXOPUNKAA-UHFFFAOYSA-N 16-methylheptadecan-1-amine Chemical compound CC(C)CCCCCCCCCCCCCCCN WTHCRRXOPUNKAA-UHFFFAOYSA-N 0.000 description 1
- PUUNYSPCIIYXRW-UHFFFAOYSA-N 2,6-bis[(2-methylpropan-2-yl)oxy]phenol Chemical compound CC(C)(C)OC1=CC=CC(OC(C)(C)C)=C1O PUUNYSPCIIYXRW-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
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Chemical class CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- YSDGSQDHXJAHIA-UHFFFAOYSA-N 2-[decyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCCCCCN(CCO)CCO YSDGSQDHXJAHIA-UHFFFAOYSA-N 0.000 description 1
- NKFNBVMJTSYZDV-UHFFFAOYSA-N 2-[dodecyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCCCCCCCN(CCO)CCO NKFNBVMJTSYZDV-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-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
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Chemical class CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- VAWGWGFDTNSNGL-UHFFFAOYSA-L barium(2+);octadecanoate;acetate Chemical compound [Ba+2].CC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O VAWGWGFDTNSNGL-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- KWGASIUWELSTHP-UHFFFAOYSA-N boron;phenol Chemical compound [B].OC1=CC=CC=C1 KWGASIUWELSTHP-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 1
- YCOWPKCEXHRGBW-UHFFFAOYSA-N butyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 YCOWPKCEXHRGBW-UHFFFAOYSA-N 0.000 description 1
- HRPZQBIESQCGRM-UHFFFAOYSA-L calcium octadecanoic acid octanoate acetate Chemical class C(C)(=O)[O-].C(CCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCCCC)(=O)O.[Ca+2] HRPZQBIESQCGRM-UHFFFAOYSA-L 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- VMHDCBGLCDWDMQ-UHFFFAOYSA-L calcium;octadecanoate;acetate Chemical compound [Ca+2].CC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O VMHDCBGLCDWDMQ-UHFFFAOYSA-L 0.000 description 1
- JHVJHCOGRSPCSN-UHFFFAOYSA-L calcium;octanoate;acetate Chemical compound [Ca+2].CC([O-])=O.CCCCCCCC([O-])=O JHVJHCOGRSPCSN-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Chemical class 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- LCXAARCEIWRIMU-UHFFFAOYSA-M dibenzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C[N+](C)(C)CC1=CC=CC=C1 LCXAARCEIWRIMU-UHFFFAOYSA-M 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 235000019488 nut oil Nutrition 0.000 description 1
- 239000010466 nut oil Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical class C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
- C10L1/303—Organic compounds compounds not mentioned before (complexes) derived from metals boron compounds
-
- 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
-
- 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
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
-
- 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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
-
- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
-
- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
- C10M2227/062—Cyclic esters
-
- 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
- C10M2290/00—Mixtures of base materials or thickeners or additives
- C10M2290/02—Mineral base oils; Mixtures of fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- the invention is concerned with a novel group of compounds and their use as friction reducing and antioxidant additives in lubricants, i.e. lubricant compositions containing same.
- Friction is also a problem any time two surfaces are in sliding or rubbing contact. It is of especial significance in an internal combustion engine, because loss of a substantial amount of the theoretical mileage possible from a gallon of fuel is traceable directly to friction.
- 3,359,298 disclose lubricants containing a product made by reacting a 2,6-tertiary alkyl phenol with a boron compound (e.g., an alkyl borate) to produce a hindered phenol borate ester.
- a boron compound e.g., an alkyl borate
- the additives are taught to be hydrolytically stable and to possess antioxidant properties.
- the hindered phenyl borate esters of this invention are believed to be unknown.
- a reaction product prepared by reacting a hindered phenol, a boron compound and an N,N-di-(2-hydroxyalkyl)-N-hydrocarbyl amine.
- the invention also provides a lubricant composition comprising a major proportion of lubricant and a minor, antifriction, fuel consumption reducing or antioxidant or high temperature stabilizing amount of said reaction product.
- the hindered phenyl borate esters of this invention provide a significant combination of benefits not present in prior art compositions.
- the additives of this invention combine hydrolytic stability with friction reducing, fuel consumption reducing and oxidative stability properties unattainable using either hindered phenyl borates or alkoxylated amine borates alone.
- the minor amounts of additive in the lubricant provide a method for hardening lubricated contacting metal surfaces.
- reaction products of this invention are made by reacting a boron compound, a hindered phenol and an N,N-di-(2-hydroxyalkyl)-N-hydrocarbyl amine to yield a hindered phenyl borate ester.
- the reaction to form the product will take place in two stages, the first of which is a reaction of the boron compound with one of the other two reactants to form a product in which at least one of the elements of the boron compound is an ester.
- the useful boron compounds include boric oxides and compounds of the general structure
- R, Y and Z are hydrogen or alkyl groups containing 1 to 6 carbon atoms, p, n and r are 0 to 2 and q is 1 to 3. Included within the formula are boric acid, metaboric acid, the alkyl metaborates, the alkyl boroxines, boroxine, boroxides and the like.
- the hindered phenols that are contemplated have the formula ##STR1## where R 2 and R 3 are the same or different alkyl group containing 4 to 18 carbon atoms, preferably a tertiary alkyl group.
- the carbon atoms of the alkyl group can be in any isomeric arrangement provided that the carbon atom bonded to the phenyl group is itself bonded to at least two other carbon atoms or chain segments, and R 1 is a C 1 to C 30 hydrocarbyl group, i.e., an alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group which may have substituted thereon other groups, e.g., an alkoxy group, an alkylthio group or the like.
- the hindered phenols include 2,6-di-t butyl phenol, 2,6-di-t-butoxyphenol, 2,6-di-t-butyl-4-carbobutoxyphenol and 3,5-t butyl-4-hydroxybenzyl pivalate and the like.
- the temperature of reaction of phenol and boron compound can be from about 125° C. to about 250° C., preferably about 140° C. to about 225° C., the precise temperature being selected on the basis of the particular reactants used.
- a wide range of reactant proportions is contemplated, but will generally and preferably range from a mole ratio of boron containing compound to phenol of from .[.0.1:1 to about 1:15.]. .Iadd.about 0.1 to 1.Iaddend..
- the amine to be used in the practice of this invention is one coming within the formula
- R 4 is a hydrocarbyl group (as defined hereinabove) containing 4 to 30 carbon atoms and R 5 is an alkylene or substituted alkylene group containing 1 to 12 carbon atoms.
- R 4 is a hydrocarbyl group (as defined hereinabove) containing 4 to 30 carbon atoms and R 5 is an alkylene or substituted alkylene group containing 1 to 12 carbon atoms.
- These hydroxyamines can be produced by conventional methods through the reaction of alkylamines with hydrocarbyl oxides, such as ethylene oxide, propylene oxide, butylene oxide and the like as well as the substituted members thereof.
- Useful amines within the stated formula include bis (2-hydroxyethyl) oleylamine, bis (2-hydroxyethyl)cocoamine, bis (2-hydroxyethyl) octadecylamine, bis (2-hydroxyethyl) stearylamine, bis (2-hydroxyethyl) decylamine, bis (2-hydroxyethyl) tallowamine, bis (2-hydroxyethyl) isostearylamine and bis (2-hydroxyethyl) dodecylamine. Mixtures of these can also be used.
- reaction of the amine with the boron-phenol product if this intermediate is made first, will preferably be carried out at from about 75° C. to about 250° C. using from about 1 mole to about 2 mole per mole of the intermediate.
- the intermediate product must have at least one boron ester group, although diesters and coordinate diesters may also be initially present.
- the boron compound can initially be reacted with either the hindered phenol or with the defined amine.
- a mono hindered phenyl borate can be convented to the additive of this invention by reaction with the amine. The sequence of reactions can be reversed, so that the amine and the boron compound are reacted first, followed by reaction of the resulting borate ester with the hindered phenol reactant.
- a suitable stoichiometric mixture of the hindered phenol, amine and boron compound can be subjected to suitable reaction conditions to produce the products of this invention.
- reaction product whether obtained by (1)reacting the hindered phenol with alkyl borate, followed by reaction of the product thus obtained with a hydroxyamine or by (2) reacting amine and borate followed by reaction of hindered phenol, is believed to be ##STR2## While the reaction product may not consist solely of the structure represented, it is believed that there are substantial quantities of such product present in the subject lubricant and fuel additives.
- mineral oils both paraffinic, naphthenic oils and mixtures thereof, employed as the lubricating oil or grease vehicle, may be of any suitable lubricating viscosity range.
- they may range in viscosities of from about 45 SSU at 100° F. to about 6000 SSU at 100° F., and preferably, from about 50 to about 250 SSU at 210° F.
- These oils may have viscosity indexes ranging to about 100 or higher. Viscosity indexes from about 70 to about 95 are preferred.
- the average molecular weights of these oils may range from about 250 to about 800.
- Typical synthetic vehicles include polyisobutylene, polybutenes, hydrogenated polyolefins, polypropylene glycol, polyethylene glycol, trimethylol propane esters, neopentyl and pentaerythritol esters, di(2-ethylhexyl) sebacate, di(2-ethylhexyl)adipate, dibutyl phthalate, fluorocarbons, silicate esters, silanes, esters of phosphorus-containing acids, liquid ureas, ferrocene derivatives, hydrogenated mineral oils, chain-type polyphenyls, siloxanes and silicones (polysiloxanes), alkyl-substituted diphenyl ethers typified by a butyl-substituted bis(p-phenoxy phenol) ether, phenoxy phenylethers.
- compositions contemplated herein can also contain other materials.
- corrosion inhibitors e.g. calcium or magnesium alkyl phenates
- metal sulfonates e.g. calcium or magnesium aryl sulfonates
- zinc phosphorodithioates i.e. zinc dihydrocarbyl phosphorodithioates.
- the preformed adducts of the present invention may be employed in any amount which is effective for imparting the desired degree of friction reduction anti-corrosion or anti-wear activity. In many applications, however, the adduct is effectively employed in amounts from about 0.1% to about 10% by weight, and preferable from about 0.5 to about 5% of the total weight of the composition.
- thickening agents can be used to prepare them. Included among the useful thickening agents are alkali and alkaline earth metal soaps of fatty acids and fatty materials having from about 12 to about 30 carbon atoms per molecule.
- the metals are typified by sodium, lithium, calcium and barium.
- Fatty materials are illustrated by stearic acid, hydroxystearic acid, stearin, cottonseed oil acids, oleic acid, palmitic acid, myristic acid and hydrogenated fish oils.
- thickening agents include salt and salt-soap complexes as calcium stearate-acetate (U.S. Pat. No. 2,197,263), barium stearate acetate (U.S. Pat. No. 2,564,561), calcium stearate-caprylate-acetate complexes (U.S. Pat. No. 2,999,065) calcium caprylate-acetate (U.S. Pat. No. 2,999,066), and calcium salts and soaps of low-, intermediate- and high-molecular weight acids and of nut oil acids.
- Another group of thickening agents comprises substituted ureas, phthalocyanines, indanthrene, pigments such as perylimides, pyromellitdiimides, and ammeline.
- the preferred thickening gelling agents employed in the grease compositions are essentially hydrophobic clays.
- Such thickening agents can be prepared from clays which are initially hydrophilic in character, but which have been converted into a hydrophobic condition by the introduction of long chain hydrocarbon radicals into the surface of the clay particles; prior to their use as a component of a grease composition, as, for example, by being subjected to a preliminary treatment with an organic cationic surface active agent, such as an onium compound.
- Typical onium compounds are tetraalkylammonium chlorides, such as dimethyl dioctadecyl ammonium chloride, dimethyl dibenzyl ammonium chloride and mixtures thereof.
- the clays which are useful as starting materials in forming the thickening agents to be employed in the grease compositions can comprise the naturally occurring chemically unmodified clays.
- These clays are crystalline complex silicates, the exact composition of which is not subject to precise description, since they vary widely from one natural source to another.
- These clays can be described as complex inorganicsilicates such as aluminum silicates, magnesium silicates, barium silicates, and the like, containing, in addition to the silicate lattice, varying amount of catio-exchangeable groups such as sodium.
- Hydrophilic clays which are particularly useful for conversion to desired thickening agents include montmorillonite clays, such as bentonite, attapulgite hectorite, illite, saponite, sepiolite, biotite, vermiculite, zeolite clays, and the like.
- the thickening agent is employed in an amount from about 0.5 to about 30, and preferably from 3 percent to 15, percent by weight of the total grease composition.
- liquid fuels contemplated include liquid hydrocarbon fuels such as fuel oils, diesel oils and gasolines and alcohol fuels such as methanol and ethanol or mixtures of these fuels.
- the effective amount of additive therein for fuel usage reduction will range from about 5 pounds to about 1,000 pounds thereof per 1000 barrels of fuel, preferably from about 20 pounds to about 50 pounds per 1000 barrels.
- the compounds were evaluated in a low velocity friction apparatus (LVFA) in a fully formulated 5W-20 oil containing 20% by weight of an additive package including antioxidant, dispersant and detergent.
- the friction reducing compound was 1-5% of the total weight of oil.
- Base oil had the following general characteristics:
- the Low Velocity Friction Apparatus is used to measure the coefficient of friction of test lubricants under various loads, temperatures, and sliding speeds.
- the LVFA consists of a flat SAE 1020 steel surface (diam. 1.5 in.) which is attached to a drive shaft and rotated over a stationary, raised, narrow ringed SAE 1020 steel surface (area 0.08 in. 2 ). Both surfaces are submerged in the test lubricant. Friction between the steel surfaces is measured as a function of the sliding speed at a lubricant temperature of 250° F. The friction between the rubbing surfaces is measured using a torque arm-strain gauge system.
- the strain gauge output which is calibrated to be equal to the coefficient of friction, is fed to the Y axis of an X-Y plotter.
- the speed signal from the tachometer-generator is fed to the X-axis.
- the piston is supported by an air bearing.
- the normal force loading the rubbing surfaces is regulated by air pressure on the bottom of the piston.
- the drive system consists of an infinitely variable-speed hydraulic transmission driven by a 1/2 HP electric motor. To vary the sliding speed, the output speed of the transmission is regulated by a lever-cam-motor arrangement.
- test lubricants 5W/20 fully formulated base synthetic oil containing a detergent/dispersant/inhibitor package
- a 240 psi load is applied, and the sliding speed is maintained at 40 fpm at ambient temperature for a few minutes.
- a minimum of three measurements is obtained for each test lubricant.
- the test lubricant and specimens are heated to 250° F., 240 psi, and 40 fpm sliding speed. Afterward, measurements of U k vs.
- test lubricant a 150 second paraffinic neutral mineral oil containing the product
- test lubricant a 150 second paraffinic neutral mineral oil containing the product
- a stream of air which is bubbled through at the rate of 5 liters per hour at 325° F. for 40 hours.
- metals commonly used in engine construction namely, iron, copper, aluminum and lead. See U.S. Pat. No. 3,682,980, incorporated herein by reference, for further details of the test. Improvement in viscosity index or neutralization number (or both) shows effective control. See the results in Table 2.
- the hindered phenyl esters of this invention substantially improve the gasoline fuel economy of lubricating oils in engine tests and significantly reduce the observed coefficients of friction when evaluated in bench-scale evaluations. Improvements in energy efficiency are expected in a wide variety of automotive and industrial lubricants containing additive concentrations of these non-metallic, non-phosphorus containing compositions. In addition, they are multifunctional additives which provide significant antioxidation and high temperature stabilizing properties not available in some other friction reducing additives. Other beneficial properties provided by these esters may include substantial antirust, dispersant/detergent, and antifatigue/metal hardening and related antiwear activity.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Lubricants (AREA)
Abstract
New reaction products obtained by reacting (1) a hindered phenol, (2) a boron compound and (3) an amine together are described. Preferred reaction sequences are:
(a)(2)+(1), then this product with (3); and
(b)(2)+(3), then this product with (1).
Also described are lubricant compositions containing the reaction products and a method of reducing fuel consumption in an internal combustion engine by lubricating the engine with a lubricant containing the reaction product.
Description
1. Field of the Invention
The invention is concerned with a novel group of compounds and their use as friction reducing and antioxidant additives in lubricants, i.e. lubricant compositions containing same.
2. Description of the Prior Art
It is known that sliding or rubbing metal or other solid surfaces are subject to wear under conditions of extreme pressure. Wearing is particularly acute in modern engines in which high temperatures and contact pressures are prevalent. Under such conditions, severe erosion of metal surfaces can take place even with present generation lubricants unless a load carrying or antiwear additive is present therein.
Friction is also a problem any time two surfaces are in sliding or rubbing contact. It is of especial significance in an internal combustion engine, because loss of a substantial amount of the theoretical mileage possible from a gallon of fuel is traceable directly to friction.
Borate esters of hindered phenols, i.e. phenols in which both ring positions ortho to the hydroxy group have been substituted by bulky hydrocarbyl groups, are known in the art. U.S. Pat. No. 3,347,793, for example, discloses lubricants containing compounds made by reacting a hindered phenol, e.g., 2,6-di-tert-butyl-p-cresol, with a borate ester. Similarly, U.S. Pat. No. 3,356,707 and U.S. Pat. No. 3,359,298 disclose lubricants containing a product made by reacting a 2,6-tertiary alkyl phenol with a boron compound (e.g., an alkyl borate) to produce a hindered phenol borate ester. The additives are taught to be hydrolytically stable and to possess antioxidant properties. The hindered phenyl borate esters of this invention are believed to be unknown.
In accordance with this invention, there is provided a reaction product prepared by reacting a hindered phenol, a boron compound and an N,N-di-(2-hydroxyalkyl)-N-hydrocarbyl amine. The invention also provides a lubricant composition comprising a major proportion of lubricant and a minor, antifriction, fuel consumption reducing or antioxidant or high temperature stabilizing amount of said reaction product.
The hindered phenyl borate esters of this invention provide a significant combination of benefits not present in prior art compositions. The additives of this invention combine hydrolytic stability with friction reducing, fuel consumption reducing and oxidative stability properties unattainable using either hindered phenyl borates or alkoxylated amine borates alone. Furthermore, the minor amounts of additive in the lubricant provide a method for hardening lubricated contacting metal surfaces.
The reaction products of this invention, as has been noted, are made by reacting a boron compound, a hindered phenol and an N,N-di-(2-hydroxyalkyl)-N-hydrocarbyl amine to yield a hindered phenyl borate ester. Preferably the reaction to form the product will take place in two stages, the first of which is a reaction of the boron compound with one of the other two reactants to form a product in which at least one of the elements of the boron compound is an ester. The useful boron compounds include boric oxides and compounds of the general structure
.[.(RO).sub.p (BO.sub.2).sub.q Yn Zr .]. (.Iadd.RO).sub.p (BO.sub.2).sub.q Y.sub.n Z.sub.r.Iaddend.
wherein R, Y and Z are hydrogen or alkyl groups containing 1 to 6 carbon atoms, p, n and r are 0 to 2 and q is 1 to 3. Included within the formula are boric acid, metaboric acid, the alkyl metaborates, the alkyl boroxines, boroxine, boroxides and the like.
The hindered phenols that are contemplated have the formula ##STR1## where R2 and R3 are the same or different alkyl group containing 4 to 18 carbon atoms, preferably a tertiary alkyl group. Broadly, the carbon atoms of the alkyl group can be in any isomeric arrangement provided that the carbon atom bonded to the phenyl group is itself bonded to at least two other carbon atoms or chain segments, and R1 is a C1 to C30 hydrocarbyl group, i.e., an alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group which may have substituted thereon other groups, e.g., an alkoxy group, an alkylthio group or the like.
The hindered phenols include 2,6-di-t butyl phenol, 2,6-di-t-butoxyphenol, 2,6-di-t-butyl-4-carbobutoxyphenol and 3,5-t butyl-4-hydroxybenzyl pivalate and the like.
The temperature of reaction of phenol and boron compound can be from about 125° C. to about 250° C., preferably about 140° C. to about 225° C., the precise temperature being selected on the basis of the particular reactants used. A wide range of reactant proportions is contemplated, but will generally and preferably range from a mole ratio of boron containing compound to phenol of from .[.0.1:1 to about 1:15.]. .Iadd.about 0.1 to 1.Iaddend.. The amine to be used in the practice of this invention is one coming within the formula
R.sup.4 N(R.sup.5 OH).sub.2
wherein R4 is a hydrocarbyl group (as defined hereinabove) containing 4 to 30 carbon atoms and R5 is an alkylene or substituted alkylene group containing 1 to 12 carbon atoms. These hydroxyamines can be produced by conventional methods through the reaction of alkylamines with hydrocarbyl oxides, such as ethylene oxide, propylene oxide, butylene oxide and the like as well as the substituted members thereof. Useful amines within the stated formula include bis (2-hydroxyethyl) oleylamine, bis (2-hydroxyethyl)cocoamine, bis (2-hydroxyethyl) octadecylamine, bis (2-hydroxyethyl) stearylamine, bis (2-hydroxyethyl) decylamine, bis (2-hydroxyethyl) tallowamine, bis (2-hydroxyethyl) isostearylamine and bis (2-hydroxyethyl) dodecylamine. Mixtures of these can also be used.
The reaction of the amine with the boron-phenol product, if this intermediate is made first, will preferably be carried out at from about 75° C. to about 250° C. using from about 1 mole to about 2 mole per mole of the intermediate.
As has already been stated, the intermediate product must have at least one boron ester group, although diesters and coordinate diesters may also be initially present. Thus, the boron compound can initially be reacted with either the hindered phenol or with the defined amine. A mono hindered phenyl borate can be convented to the additive of this invention by reaction with the amine. The sequence of reactions can be reversed, so that the amine and the boron compound are reacted first, followed by reaction of the resulting borate ester with the hindered phenol reactant. Alternatively, a suitable stoichiometric mixture of the hindered phenol, amine and boron compound can be subjected to suitable reaction conditions to produce the products of this invention.
Thus a variety of methods are available for use in making the additives. As has been noted the reactions can be carried out over a wide range of temperatures, i.e., from about 75° C. to about 250° C. When using methods other than the preferred one (reaction of phenol and boron compound followed by reaction with amine), the same relative proportions of reactants are to be used as already stated.
The reaction product, whether obtained by (1)reacting the hindered phenol with alkyl borate, followed by reaction of the product thus obtained with a hydroxyamine or by (2) reacting amine and borate followed by reaction of hindered phenol, is believed to be ##STR2## While the reaction product may not consist solely of the structure represented, it is believed that there are substantial quantities of such product present in the subject lubricant and fuel additives.
Of particular significance, in accordance with the present invention, is the ability to improve the fuel use, friction, and oxidation and high temperature stabilizing properties of oleaginous materials such as lubricating media which may comprise either a mineral oil or a synthetic oil or mixtures thereof, or a grease therefrom. In general, mineral oils, both paraffinic, naphthenic oils and mixtures thereof, employed as the lubricating oil or grease vehicle, may be of any suitable lubricating viscosity range. For example, they may range in viscosities of from about 45 SSU at 100° F. to about 6000 SSU at 100° F., and preferably, from about 50 to about 250 SSU at 210° F. These oils may have viscosity indexes ranging to about 100 or higher. Viscosity indexes from about 70 to about 95 are preferred. The average molecular weights of these oils may range from about 250 to about 800.
In instances where synthetic oils or combinations thereof with mineral oils are preferred, various compounds of this type may be successfully utilized. Typical synthetic vehicles include polyisobutylene, polybutenes, hydrogenated polyolefins, polypropylene glycol, polyethylene glycol, trimethylol propane esters, neopentyl and pentaerythritol esters, di(2-ethylhexyl) sebacate, di(2-ethylhexyl)adipate, dibutyl phthalate, fluorocarbons, silicate esters, silanes, esters of phosphorus-containing acids, liquid ureas, ferrocene derivatives, hydrogenated mineral oils, chain-type polyphenyls, siloxanes and silicones (polysiloxanes), alkyl-substituted diphenyl ethers typified by a butyl-substituted bis(p-phenoxy phenol) ether, phenoxy phenylethers. It is to be understood, however, that the compositions contemplated herein can also contain other materials. For example, corrosion inhibitors, extreme pressure agents, viscosity index improvers, co-antioxidants, anti-wear agents and the like can be used, including metal phenates, e.g. calcium or magnesium alkyl phenates, metal sulfonates, e.g. calcium or magnesium aryl sulfonates and zinc phosphorodithioates, i.e. zinc dihydrocarbyl phosphorodithioates. These can be used in amounts in total of from about 0.1% to about 5% by weight, preferably from about 0.5 to about 2% by weight. These materials do not detract from the value of the compositions of this invention, but rather they serve to impart their customary properties to the particular compositions in which they are incorporated. In general, the preformed adducts of the present invention may be employed in any amount which is effective for imparting the desired degree of friction reduction anti-corrosion or anti-wear activity. In many applications, however, the adduct is effectively employed in amounts from about 0.1% to about 10% by weight, and preferable from about 0.5 to about 5% of the total weight of the composition.
With respect to the greases of the invention, a wide variety of thickening agents can be used to prepare them. Included among the useful thickening agents are alkali and alkaline earth metal soaps of fatty acids and fatty materials having from about 12 to about 30 carbon atoms per molecule. The metals are typified by sodium, lithium, calcium and barium. Fatty materials are illustrated by stearic acid, hydroxystearic acid, stearin, cottonseed oil acids, oleic acid, palmitic acid, myristic acid and hydrogenated fish oils.
Other thickening agents include salt and salt-soap complexes as calcium stearate-acetate (U.S. Pat. No. 2,197,263), barium stearate acetate (U.S. Pat. No. 2,564,561), calcium stearate-caprylate-acetate complexes (U.S. Pat. No. 2,999,065) calcium caprylate-acetate (U.S. Pat. No. 2,999,066), and calcium salts and soaps of low-, intermediate- and high-molecular weight acids and of nut oil acids.
Another group of thickening agents comprises substituted ureas, phthalocyanines, indanthrene, pigments such as perylimides, pyromellitdiimides, and ammeline.
The preferred thickening gelling agents employed in the grease compositions are essentially hydrophobic clays. Such thickening agents can be prepared from clays which are initially hydrophilic in character, but which have been converted into a hydrophobic condition by the introduction of long chain hydrocarbon radicals into the surface of the clay particles; prior to their use as a component of a grease composition, as, for example, by being subjected to a preliminary treatment with an organic cationic surface active agent, such as an onium compound. Typical onium compounds are tetraalkylammonium chlorides, such as dimethyl dioctadecyl ammonium chloride, dimethyl dibenzyl ammonium chloride and mixtures thereof. This method of conversion, being well known to those skilled in the art, is believed to require no further discussion, and does not form a part of the present invention. More specifically, the clays which are useful as starting materials in forming the thickening agents to be employed in the grease compositions, can comprise the naturally occurring chemically unmodified clays. These clays are crystalline complex silicates, the exact composition of which is not subject to precise description, since they vary widely from one natural source to another. These clays can be described as complex inorganicsilicates such as aluminum silicates, magnesium silicates, barium silicates, and the like, containing, in addition to the silicate lattice, varying amount of catio-exchangeable groups such as sodium. Hydrophilic clays which are particularly useful for conversion to desired thickening agents include montmorillonite clays, such as bentonite, attapulgite hectorite, illite, saponite, sepiolite, biotite, vermiculite, zeolite clays, and the like. The thickening agent is employed in an amount from about 0.5 to about 30, and preferably from 3 percent to 15, percent by weight of the total grease composition.
The liquid fuels contemplated include liquid hydrocarbon fuels such as fuel oils, diesel oils and gasolines and alcohol fuels such as methanol and ethanol or mixtures of these fuels. The effective amount of additive therein for fuel usage reduction will range from about 5 pounds to about 1,000 pounds thereof per 1000 barrels of fuel, preferably from about 20 pounds to about 50 pounds per 1000 barrels.
The following Examples will present illustrations of the invention. They are illustrative only, and are not meant to limit the invention. Parts are by weight.
A mixture of 2,6-Di-tert-butyl-4-methylphenol (1980 g.), boric acid (93 g.) and xylene (200 ml) was heated while stirring vigorously at 145°-175° C. for 3.5 hours and water (28 ml) was collected by azeotropic stillation. During the next 12 hour three increments of xylene (200 ml each) were periodically added, the temperature was raised to 200° C., and water (63 ml total) was collected. Solvent and unreacted alkylated phenol were removed by reduced pressure distillation, leaving the product, 2,6-Di-tert-butyl-4-methylphenyl borate, a tan solid.
A mixture of 2,6-di-tert-butyl-4-methylphenyl borate prepared by the method of Example 1 (31.5 g.) and bis(2-hydroxyethyl) oleylamine, Armak Chemicals Ethomeen 0/12, (39.2 g) was heated to a temperature of 138° C. for 2.5 hours. Removal of unreacted amine by distillation to a pot temperature of 100° C. at a pressure of less than 0.1 mm of mercury left the product as a clear brown viscous liquid.
A mixture of 2,6-di-tert-butyl-4-methylphenyl borate prepared by the method of Example 1 (815.2 g) and bis(2-hydroxyethyl) oleylamine, Armak Chemicals Ethomeen 0/12, (962 g) was heated under a nitrogen atmosphere for 3.5 hours at a temperature of 130°-138° C. while water produced in the reaction was collected as distillate. The reaction mixture was then stripped to a pot temperature of 138° C. at less than 0.1 mm of mercury pressure with only a minor amount of distillate collected. The product was a dark viscous oil.
The compounds were evaluated in a low velocity friction apparatus (LVFA) in a fully formulated 5W-20 oil containing 20% by weight of an additive package including antioxidant, dispersant and detergent. The friction reducing compound was 1-5% of the total weight of oil. Base oil had the following general characteristics:
______________________________________ Kinematic Viscosity @ 100° C. - 6.8 cs @ 40° C. - 36.9 cs Viscosity Index 143 ______________________________________
The Low Velocity Friction Apparatus (LVFA) is used to measure the coefficient of friction of test lubricants under various loads, temperatures, and sliding speeds. The LVFA consists of a flat SAE 1020 steel surface (diam. 1.5 in.) which is attached to a drive shaft and rotated over a stationary, raised, narrow ringed SAE 1020 steel surface (area 0.08 in.2). Both surfaces are submerged in the test lubricant. Friction between the steel surfaces is measured as a function of the sliding speed at a lubricant temperature of 250° F. The friction between the rubbing surfaces is measured using a torque arm-strain gauge system. The strain gauge output, which is calibrated to be equal to the coefficient of friction, is fed to the Y axis of an X-Y plotter. The speed signal from the tachometer-generator is fed to the X-axis. To minimize external friction, the piston is supported by an air bearing. The normal force loading the rubbing surfaces is regulated by air pressure on the bottom of the piston. The drive system consists of an infinitely variable-speed hydraulic transmission driven by a 1/2 HP electric motor. To vary the sliding speed, the output speed of the transmission is regulated by a lever-cam-motor arrangement.
The rubbing surfaces and 12-13 ml. of test lubricants (5W/20 fully formulated base synthetic oil containing a detergent/dispersant/inhibitor package) are placed on the LVFA. A 240 psi load is applied, and the sliding speed is maintained at 40 fpm at ambient temperature for a few minutes. A plot of coefficients of friction (Uk) over the range of sliding speeds, 5 to 40 fpm (25-195 rpm), is obtained. A minimum of three measurements is obtained for each test lubricant. Then, the test lubricant and specimens are heated to 250° F., 240 psi, and 40 fpm sliding speed. Afterward, measurements of Uk vs. speed were taken at 240, 300, 400, and 500 psi. Freshly polished steel specimens are used for each run. The surface of the steel specimens are used for each run. The surface of the steel is parallel ground to 4 to 8 microinches. The results in Table 1 refer to percent reduction in friction compared to the unmodified oil. That is, the formulation mentioned above was tested without the compound of this invention and this became the basis for comparison. The results were obtained at 250° F. and 500 psi.
TABLE 1 ______________________________________ FRICTION CHARACTERISTICS Additive Conc., % Reduction in Coefficient of Friction Composition Wt. % 5 Ft./Min. 30 Ft./Min. ______________________________________ Base Oil 0 0.sup.(b) 0.sup.(b) Base Oil Plus 4 41 37 Example 1 Base Oil Plus 4 37 33 Example 2 ______________________________________ .sup.(b) Result for base oil taken as zero.
The products were also evaluated for their oxidative stability. In most cases improvements in oxidative stability over the base oil were observed. Basically the test lubricant (a 150 second paraffinic neutral mineral oil containing the product) is subjected to a stream of air which is bubbled through at the rate of 5 liters per hour at 325° F. for 40 hours. Present in the composition are samples of metals commonly used in engine construction, namely, iron, copper, aluminum and lead. See U.S. Pat. No. 3,682,980, incorporated herein by reference, for further details of the test. Improvement in viscosity index or neutralization number (or both) shows effective control. See the results in Table 2.
TABLE 2 ______________________________________ Additive KV, Additive Conc., Wt. % NN % Increase ______________________________________ Base Oil 0 17 334 Di-tert-butyl-p- 1 6.2 75 p-cresol 0.5 6.9 79 Example 2 1 4.7 69 0.5 5.2 73 ______________________________________
The hindered phenyl esters of this invention substantially improve the gasoline fuel economy of lubricating oils in engine tests and significantly reduce the observed coefficients of friction when evaluated in bench-scale evaluations. Improvements in energy efficiency are expected in a wide variety of automotive and industrial lubricants containing additive concentrations of these non-metallic, non-phosphorus containing compositions. In addition, they are multifunctional additives which provide significant antioxidation and high temperature stabilizing properties not available in some other friction reducing additives. Other beneficial properties provided by these esters may include substantial antirust, dispersant/detergent, and antifatigue/metal hardening and related antiwear activity.
Claims (25)
1. A reaction product prepared by reacting (1) a hindered phenol of the formula ##STR3## wherein R1 is a C1 to C30 hydrocarbyl group and R2 and R3 are the same or different alkyl groups containing 4 to 18 carbon atoms, (2) a boron compound of the formula
.[.(RO).sub.p (BO.sub.2).sub.q YnZr.]. (.Iadd.RO).sub.p (BO.sub.2).sub.q Y.sub.n Z.sub.r.Iaddend.
wherein R, Y and Z are selected from the group consisting of hydrogen and a C1 to C6 alkyl group, p, n and r are 0 to 2 and q is 1 to 3 and (3) an amine of the formula
R.sup.4 N(R.sup.5 OH).sub.2
wherein R4 is a hydrocarbyl group containing 4 to 30 carbon atoms and R5 is an alkylene or substituted alkylene group containing 1 to 12 carbon atoms, the reaction being carried out at from about 75° C. to about 250° C. and with proportions of reactants to give a .[.phenol:boron compound.]. .Iadd.boron compound:phenol .Iaddend.ratio of from about .[.0.1:1 to about 1:15.]. .Iadd.0.1 to 1 .Iaddend.and from about 1 to about 2 mole equivalents of amine based on each mole of the phenol:boron compound moiety formed.
2. The product of claim 1 wherein said alkyl groups are tertiary alkyl groups.
3. The product of claim 1 wherein said hydrocarbyl groups are selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, aralkyl and alkaryl.
4. The product of claim 1 wherein the phenol is 2,6-di-tert-butyl-4-methylphenol, the boron compound is boric acid and the amine is bis(2-hydroxyethyl)oleylamine.
5. A lubricant composition comprising a major amount of a lubricating oil or grease therefrom and an antifriction amount of a reaction product prepared by reacting (1) a hindered phenol of the formula ##STR4## wherein R1 is a C1 to C30 hydrocarbyl group and R2 and R3 are the same or different alkyl groups containing 4 to 18 carbon atoms, (2) a boron compound of the formula
.[.(RO).sub.p (BO.sub.2).sub.q YnZr.]. (.Iadd.RO).sub.p (BO.sub.2).sub.q Y.sub.n Z.sub.r.Iaddend.
wherein R, Y and Z are selected from the group consisting of hydrogen and a C1 to C6 alkyl group, p, n and r are 0 to 2 and q is 1 to 3 and (3) an amine of the formula
R.sup.4 N(R.sup.5 OH).sub.2
wherein R4 is a hydrocarbyl group containing 4 to 30 carbon atoms and R5 is an alkylene or substituted alkylene group containing 1 to 12 carbon atoms, the reaction being carried out at from about 75° C. to about 250° C. and with proportions of reactants to give a .[.phenol:boron compound.]. .Iadd.boron compound:phenol .Iaddend.ratio of from about .[.0.1:1 to abut 1:15.]. .Iadd.0.1 to 1 .Iaddend.and from about 1 to about 2 mole equivalents of amine based on each mole of the phenol:boron compound moiety formed.
6. The composition of claim 5 wherein said alkyl groups are tertiary alkyl groups.
7. The composition of claim 5 wherein said hydrocarbyl groups are selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, aralkyl and alkaryl.
8. The composition of claim 5 wherein the phenol is 2,6-di-tert-butyl-4-methylphenol, the boron compound is boric acid and the amine is bis(2-hydroxyethyl)oleylamine.
9. The composition of claim 5 wherein said lubricant is (1) a mineral lubricating oil, (2) a synthetic lubricating oil or mixtures thereof, (3) mixtures of (1) and (2) and (4) a grease from any of (1), (2) and (3).
10. The composition of claim 9 wherein the lubricating oil is a mineral oil.
11. The composition of claim 9 wherein the lubricating oil is a synthetic oil.
12. The composition of claim 11 wherein the synthetic lubricating oil is a mixture of synthetic oils.
13. The composition of claim 9 wherein the lubricating oil is a mixture of (1) a synthetic oil, or a mixture of synthetic oils and (2) a mineral oil.
14. The composition of claim 9 wherein the lubricant is a grease.
15. A method of reducing fuel consumption in an internal combustion engine which comprises lubricating said engine with a lubricant composition comprising a major amount of a lubricating oil and a fuel consumption reducing amount of a reaction product prepared by reacting (1) a hindered phenol of the formula ##STR5## wherein R1 is a C1 to C30 hydrocarbyl group and R2 and R3 are the same or different alkyl groups containing 4 to 18 carbon atoms, (2) a boron compound of the formula
.[.(RO).sub.p (BO.sub.2).sub.q YnZr.]. (.Iadd.RO).sub.p (BO.sub.2).sub.q Y.sub.n Z.sub.r.Iaddend.
wherein R, Y and Z are selected from the group consisting of hydrogen and a C1 to C6 alkyl group, p, n and r are 0 to 2 and q is 1 to 3 and (3) an amine of the formula
R.sup.4 N(R.sup.5 OH).sub.2
wherein R4 is a hydrocarbyl group containing 4 to 30 carbon atoms and R5 is an alkylene or substituted alkylene group containing 1 to 12 carbon atoms, the reaction being carried out at from about 75° C. to about 250° C. and with proportions of reactants to give a .[.phenol:boron compound.]. .Iadd.boron compound:phenol .Iaddend.ratio of from about .[.0.1:1 to abut 1:15.]. .Iadd.0.1 to 1 .Iaddend.and from about 1 to about 2 mole equivalents of amine based on each mole of the phenol:boron compound moiety formed.
16. The method of claim 15 wherein said alkyl groups are tertiary alkyl groups.
17. The method of claim 15 wherein said hydrocarbyl groups are selected from the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl and alkaryl.
18. The method of claim 15 wherein the phenol is 2,6-di-tert-butyl-4-methylphenol, the boron compound is boric acid and the amine is bis(2-hydroxyethyl)oleylamine.
19. The method of claim 15 wherein said lubricant is selected from the group consisting of (1) a mineral lubricating oil, (2) a synthetic lubricating oil, mixtures of synthetic oils and (3) mixtures of (1) and (2).
20. A method of hardening lubricated contacting metal surfaces which comprises lubricating said metal surfaces with a lubricant composition comprising a major amount of a lubricating oil or grease therefrom and an antifriction amount of a reaction product prepared by reacting (1) a hindered phenol of the formula ##STR6## wherein R1 is a C1 to C30 hydrocarbyl group and R2 and R3 are the same or different alkyl groups containing 4 to 18 carbon atoms, (2) a boron compound of the formula
.[.(RO).sub.p (BO.sub.2).sub.q YnZr.]. (.Iadd.RO).sub.p (BO.sub.2).sub.q Y.sub.n Z.sub.r.Iaddend.
wherein R, Y and Z are selected from the group consisting of hydrogen and a C1 to C6 alkyl group, p, n and r are 0 to 2 and q is 1 to 3 and (3) an amine of the formula
R.sup.4 N(R.sup.5 OH).sub.2
wherein R4 is a hydrocarbyl group containing 4 to 30 carbon atoms and R5 is an alkylene or substituted alkylene group containing 1 to 12 carbon atoms, the reaction being carried out at from about 75° C. to about 250° C. and with proportions of reactants to give a .[.phenol:boron compound.]. .Iadd.boron compound:phenol .Iaddend.ratio of from about .[.0.1:1 to about 1:15.]. .Iadd.0.1 to 1 .Iaddend.and from about 1 to about 2 mole equivalents of amine based on each mole of the phenol:boron compound moiety formed.
21. The method of claim 20 wherein said alkyl groups are tertiary alkyl groups.
22. The method of claim 20 wherein said hydrocarbyl groups are selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, aralkyl and alkaryl.
23. The method of claim 20 wherein the phenol is 2,6-di-tert-butyl-4-methylphenol, the boron compound is boric acid and the amine is bis(2-hydroxyethyl)oleylamine.
24. The method of claim 20 wherein said lubricant is selected from the group consisting of (1) a mineral lubricating oil, (2) a synthetic lubricating oil, mixtures of synthetic oils and (3) mixtures of (1) and (2).
25. The composition of claim 5 containing additionally one or more additives selected from the group consisting of metal sulfonates, metal phenates and zinc phosphorodithioates.
Priority Applications (1)
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US06/679,517 USRE32295E (en) | 1983-04-04 | 1984-12-07 | Hindered phenyl esters of cyclic borates and lubricants containing same |
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US06/481,704 US4474670A (en) | 1983-04-04 | 1983-04-04 | Hindered phenyl esters of cyclic borates and lubricants containing same |
US06/679,517 USRE32295E (en) | 1983-04-04 | 1984-12-07 | Hindered phenyl esters of cyclic borates and lubricants containing same |
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US06/481,704 Reissue US4474670A (en) | 1983-04-04 | 1983-04-04 | Hindered phenyl esters of cyclic borates and lubricants containing same |
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US4956105A (en) | 1988-05-31 | 1990-09-11 | Mobil Oil Corporation | Lubricant composition containing phenolic/phosphorodithioate borates as multifunctional additives |
US5698499A (en) * | 1997-02-03 | 1997-12-16 | Uniroyal Chemical Company, Inc. | Phenolic borates and lubricants containing same |
US6363270B1 (en) | 1995-04-11 | 2002-03-26 | Resmed Limited | Monitoring the occurrence of apneic and hypopneic arousals |
US20120088703A1 (en) * | 2010-10-12 | 2012-04-12 | Chevron Oronite Company Llc | Lubricating composition containing multifunctional borated hydroxylated amine salt of a hindered phenolic acid |
US20120088708A1 (en) * | 2010-10-12 | 2012-04-12 | Chevron Oronite Company Llc. | Lubricating composition containing multifunctional hydroxylated amine salt of a hindered phenolic acid |
US20190249777A1 (en) * | 2016-11-01 | 2019-08-15 | Iida Co., Ltd. | Seal structure and manufacturing method thereof |
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US4956105A (en) | 1988-05-31 | 1990-09-11 | Mobil Oil Corporation | Lubricant composition containing phenolic/phosphorodithioate borates as multifunctional additives |
EP0471120A1 (en) * | 1988-05-31 | 1992-02-19 | Mobil Oil Corporation | Lubricant composition containing phenolic/phosphorodithioate borates as multifunctional additives |
US6363270B1 (en) | 1995-04-11 | 2002-03-26 | Resmed Limited | Monitoring the occurrence of apneic and hypopneic arousals |
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WO1998033800A1 (en) * | 1997-02-03 | 1998-08-06 | Uniroyal Chemical Company, Inc. | Phenolic borates and lubricants containing same |
US20120088703A1 (en) * | 2010-10-12 | 2012-04-12 | Chevron Oronite Company Llc | Lubricating composition containing multifunctional borated hydroxylated amine salt of a hindered phenolic acid |
US20120088708A1 (en) * | 2010-10-12 | 2012-04-12 | Chevron Oronite Company Llc. | Lubricating composition containing multifunctional hydroxylated amine salt of a hindered phenolic acid |
US8334242B2 (en) * | 2010-10-12 | 2012-12-18 | Chevron Oronite Company Llc | Lubricating composition containing multifunctional borated hydroxylated amine salt of a hindered phenolic acid |
US8343901B2 (en) * | 2010-10-12 | 2013-01-01 | Chevron Oronite Company Llc | Lubricating composition containing multifunctional hydroxylated amine salt of a hindered phenolic acid |
US20190249777A1 (en) * | 2016-11-01 | 2019-08-15 | Iida Co., Ltd. | Seal structure and manufacturing method thereof |
US10995858B2 (en) * | 2016-11-01 | 2021-05-04 | Iida Co., Ltd. | Seal structure and manufacturing method thereof |
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