EP0562062A1 - Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissage - Google Patents
Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissageInfo
- Publication number
- EP0562062A1 EP0562062A1 EP92918231A EP92918231A EP0562062A1 EP 0562062 A1 EP0562062 A1 EP 0562062A1 EP 92918231 A EP92918231 A EP 92918231A EP 92918231 A EP92918231 A EP 92918231A EP 0562062 A1 EP0562062 A1 EP 0562062A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- borated
- carbon atoms
- aromatic polyol
- oil
- aromatic
- 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.)
- Granted
Links
- 239000000654 additive Substances 0.000 title claims abstract description 36
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims description 25
- 238000005461 lubrication Methods 0.000 title abstract description 4
- 239000003921 oil Substances 0.000 title description 48
- 230000001681 protective effect Effects 0.000 title description 2
- -1 aromatic polyols Chemical class 0.000 claims abstract description 84
- 239000010687 lubricating oil Substances 0.000 claims abstract description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920005862 polyol Polymers 0.000 claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 77
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 229960002317 succinimide Drugs 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 229920000768 polyamine Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229940079877 pyrogallol Drugs 0.000 claims description 3
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims 2
- 150000002830 nitrogen compounds Chemical class 0.000 claims 2
- 229920001083 polybutene Polymers 0.000 claims 1
- 230000003381 solubilizing effect Effects 0.000 claims 1
- SCWWDULYYDFWQV-UHFFFAOYSA-N (2-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1O SCWWDULYYDFWQV-UHFFFAOYSA-N 0.000 abstract description 23
- 238000012360 testing method Methods 0.000 description 28
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 21
- 239000002199 base oil Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000002270 dispersing agent Substances 0.000 description 15
- 238000009472 formulation Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- 229910052796 boron Inorganic materials 0.000 description 12
- 239000000806 elastomer Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 10
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 description 10
- 229940014800 succinic anhydride Drugs 0.000 description 10
- 150000003871 sulfonates Chemical class 0.000 description 10
- 229920002367 Polyisobutene Polymers 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 229920001281 polyalkylene Polymers 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001342 alkaline earth metals Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 235000016804 zinc Nutrition 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 238000005885 boration reaction Methods 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000003244 pro-oxidative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229920002449 FKM Polymers 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- TTZGACSBMSVUOJ-UHFFFAOYSA-N benzene-1,2-diol;boric acid Chemical compound OB(O)O.OC1=CC=CC=C1O TTZGACSBMSVUOJ-UHFFFAOYSA-N 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical class [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WJECKFZULSWXPN-UHFFFAOYSA-N 1,2-didodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCCCCCCCCCCC WJECKFZULSWXPN-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 1
- 229910015444 B(OH)3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- AOZDHFFNBZAHJF-UHFFFAOYSA-N [3-hexanoyloxy-2,2-bis(hexanoyloxymethyl)propyl] hexanoate Chemical compound CCCCCC(=O)OCC(COC(=O)CCCCC)(COC(=O)CCCCC)COC(=O)CCCCC AOZDHFFNBZAHJF-UHFFFAOYSA-N 0.000 description 1
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- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical group C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GHKVUVOPHDYRJC-UHFFFAOYSA-N didodecyl hexanedioate Chemical compound CCCCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCCCC GHKVUVOPHDYRJC-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
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- 239000005060 rubber Substances 0.000 description 1
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- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 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
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol-fuelled engines
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
Definitions
- This invention relates to a discovery that a borated aromatic polyol having at least one aromatic ring and at least two hydroxyl groups and wherein at least two of the hydroxy1 groups are on adjacent carbpn atoms on the
- aromatic ring can serve to inhibit fluorocarbon engine seal deterioration in the presence of basic nitrogen.
- R is a polyisobutylene
- polyamine such as tetraethylenepentamine (TEPA) or
- TETA triethylenetetramine
- TBN Total Base Number
- Additive is also concerned, in part, with the use of succinimides as lube oil additives.
- Anderson recognizes in Col. 2, lines 28 et seq. that lube additives prepared from "long chain aliphatic polyamines", i.e., succinimides "are excellent lube oil additives.”
- succinimides are "inferior to additives where the alkylene polyamine is hydroxylated” (Col.2, lines 31 - 32).
- Such hydroxylated polyamine based succinimides "have the drawback that they tend to attack engine seals particularly those of the fluorocarbon polymer type" (Col. 2, lines 35-37).
- Anderson solves his fluorocarbon polymer seal compatibility problem by directly borating his hydroxylated polyamine based succinimides. Anderson fails to teach or suggest any solution to the fluorocarbon seal compatibility problem when using unhydroxylated polyamine based succinimides. In fact, Anderson teaches that boration of the unhydroxylated succinimides failed to solve the problem (Col. 3, lines 3 to 5). What is desired and needed is a separate additive to use with other lube oil additives containing basic nitrogen which will serve to inhibit the deterioration of engine seals of the fluorocarbon polymer type.
- an additive comprising a borated aromatic polyol having at least one aromatic ring and at least two hydroxyl groups and wherein at least two of said hydroxyl groups are on adjacent carbon atoms on said aromatic ring, has been discovered for use in lubricating oils containing basic nitrogen, the borated aromatic polyol being used at an effective amount to improve the compatibility of the lubricating oil towards fluorocarbon engine seals.
- this invention relates to a
- lubricating oil composition suitable for use in engines containing fluorocarbon seals comprising a major amount of an oil of lubricating viscosity which has basic nitrogen and an effective amount to compatibilize the oil and the fluorocarbon seals of a borated aromatic polyol having at least one aromatic ring and at least two hydroxyl groups on adjacent carbon atoms on said aromatic ring.
- a borated aromatic polyol having at least one aromatic ring and at least two hydroxyl groups on adjacent carbon atoms on said aromatic ring.
- the borated aromatic polyol such as borated catechol, is believed to complex with the basic nitrogen.
- the borated alkyl catechols of Liston are those where the alkyl group has from 10 to 30 carbon atoms (Col. 2, lines 22 et seq.).
- a method for improving the compatibility of a lubricating oil containing basic nitrogen to fluorocarbon seals in engines which comprises adding to said lubricating oil a compatibilizing amount of the borated aromatic polyols of this invention.
- the Figure is a graphic representation of the change in dispersion units of a reference oil containing a alkylcatechol borate versus the number of carbon atoms inthe alkyl group of the alkylcatechol borate.
- the additive for use in the compositions of this invention is a borated aromatic polyol having at least one aromatic ring and at least two hydroxyl groups and wherein at least two of said hydroxyl groups are on adjacent carbon atoms on an aromatic ring.
- the aromatic polyol is a single ring aromatic having from 2 to 3 hydroxyl groups and wherein two of the hydroxyl groups are on adjacent carbon atoms on the aromatic ring. More preferably the aromatic polyol has the following formula:
- R' and R" can be the same or different and are selected from the group consisting of -OH; hydrogen; alkyl group having from 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms.
- One subclass of preferred aromatic polyols are those having the formula: where R"' is selected from the group consisting of H; OH; or an alkyl group having from 1 to 8, preferably 1 to 6 and more preferably 1 to 4 carbon atoms. While all catechol borates, as the data later show, can be expected to compatibilize the oil with the fluorocarbon polymer seals, catechol borates without any alkyl groups, or those carrying a short chain alkyl group of 1-8 carbons, were unexpectedly found by the dispersancy blotter spot test, to be discussed later, to be effective in enhancing the overall dispersancy, while alkylcatechol borates carrying long alkyl groups surprisingly showed a loss in the overall dispersancy.
- mixtures of aromatic polyols as described above can be employed, the higher carbon number alkylated catechols tending to solubilize the lower molecular weight catechols in the lubricating oil.
- alkylcatechol borates having an alkyl group of ten carbon atoms or longer can be used effectively to enhance the solubility of catechol borate in a reference oil, and the overall loss in dispersancy of the higher alkylcatechol borates can be offset by the addition of the lower alkylcatechol borate or catechol borate which has a positive effect on the overall dispersancy.
- the most effective ratio to use for optimum results is a matter of simple experimentation.
- aromatic polyols which can be used to prepare the borated aromatic polyols for use in this invention include, but are not limited to: Catechol
- Dialkyl (C 18 -C 2 4) catechol The aromatic polyols useful in preparing the additives of this invention are well known in the art and many are commercially available.
- the alkyl catechols may be prepared, for example, as described in U.S.P. 4,629,578 whose teachings are incorporated herein by reference.
- aromatic polyols are borated by methods well known in the art, see for example U.S.P. 4,975,211 and U.S.P.
- the preferred boron compound to employ in the boration reaction is boric acid.
- the borated compounds used in the working examples in this application were either prepared via published procedures in U.S.P. 4,975,211; and U.S.P. 4,629,578, or were
- Z can be hydrogen or an alkyl group having 1 to 20 carbon atoms, preferably 1 to 8.
- Preferred is boric acid (B(OH) 3 ).
- compositions of this invention is catechol borate.
- Catechol borate is a general term which has been used in the literature to describe any catechol-boric acid complex or reaction product.
- the exact structure of the product, however, is dictated largely by stoichiometry (charge molar ratio of reactants).
- the extent of the reaction is most conveniently followed by the amount of water of reaction collected in a Dean-Stark trap using some appropriate organic azeotroping solvent such as toluene, o-xylene, m- xylene, p-xylene, xylene mixture, and etc. All of
- the amount of the borated aromatic polyol to use in the compositions of this invention is that amount which is sufficient to improve the compatibility of the basic nitrogen containing additives in the lube oil base stock towards fluorocarbon engine seals.
- the amount of borated aromatic polyol to add is at least the stoichiometric amount required to react or to passivate the basic nitrogen atoms present, although depending on the circumstances, the amount of boron added can be greater or less than the stoichiometric amount of available basic nitrogen. When less than the
- the weight percent of said borated aromatic polyol is at least about 0.15 weight percent of the lube oil composition, more usually 0.5 to 5 weight percent although amounts to 10 weight percent or more can be used.
- the borated aromatic polyols of this invention are useful in complexing with basic nitrogen in the lubricating oil so as to compatibilize the lubricating oil with the
- the oil soluble alkenyl or alkyl mono- or bis-succinimides which are employed in this invention are generally known as lubricating oil detergents and are described in U.S. Pat Nos. 2,992,708, 3,018,291, 3,024,237, 3,100,673, 3,219,666, 3,172,892 and 3,272,746, the disclosures of which are incorporated herein by reference.
- the alkenyl succinimides are the reaction product of a polyolefin polymer- substituted succinic anhydride with an amine, preferably a polyalkylene polyamine.
- the polyolefin polymer-substituted succinic anhydrides are obtained by reaction of a
- a product comprising predominantly mono- or bis-succinimide can be prepared by controlling the molar ratios of the reactants.
- a predominantly mono- succinimide product will be prepared.
- two moles of the succinic anhydride are reacted per mole of polyamine, a bis-succinimide will be prepared.
- compositions of this invention are obtained when the alkenyl succinimide is a mono- or a bis-succinimide prepared from a polyisobutene-substituted succinic
- the polyisobutene (from which the polyisobutene-substituted succinic anhydride is prepared) is obtained by polymerizing isobutene and can vary widely in its composition.
- the average number of carbon atoms can range from 30 or less to 250 or more, with a resulting number average molecular weight of about 400 or less to 3,000 or more.
- the average number of carbon atoms per polyisobutene molecule will range from about 50 to about 100 with the polyisobutene having a number average molecular weight of about 600 to about 1,500.
- the average number of carbon atoms per polyisobutene molecule ranges from about 60 to about 90, and the number average molecular weight ranges from about 800 to 1,300.
- the polyisobutene is reacted with maleic anhydride according to well-known procedures to yield the polyisobutene-substituted succinic anhydride. See, for example, U.S. Pat. Nos. 4,388,471 and 4,450,281.
- the substituted succinic anhydride is reacted with a polyalkylene polyamine to yield the corresponding succinimide.
- Each alkylene radical of the polyalkylene polyamine usually has up to about 8 carbon atoms.
- the number of alkylene radicals can range up to about 8.
- the alkylene radical is exemplified by ethylene, propylene, butylene, trimethylene,
- the number of amino groups generally, but not necessarily, is one greater than the number of alkylene radicals present in the amine, i.e., if a
- polyalkylene polyamine contains 3 alkylene radicals, it will usually contain 4 amino
- the number of amino radicals can range up to about 9.
- the alkylene radical contains from about 2 to about 4 carbon atoms and all amine groups are primary or secondary. In this case, the number of amine groups exceeds the number of alkylene groups by 1.
- the polyalkylene polyamine contains from 3 to 5 amine groups.
- Specific examples of the polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine,
- tripropylenetetramine tetraethylenepentamine
- trimethylenediamine pentaethylenehexamine, di- (trimethylene)triamine, tri(hexamethylene)tetramine, etc.
- Other amines suitable for preparing the alkenyl succinimide useful in this invention include the cyclic amines such as piperazine, morpholine and dipiperazines.
- alkenyl succinimides used in the alkenyl succinimides used in the alkenyl succinimides
- compositions of this invention have the following formula:
- R 1 represents an alkenyl group, preferably a
- substantially saturated hydrocarbon prepared by polymerizing aliphatic monoolefins and preferably R 1 is prepared from isobutene and has an average number of carbon atoms and a number average molecular weight as described above;
- the "Alkylene" radical represents a substantially straight chain hydrocarbyl group containing up to about 8 carbon atoms and preferably containing from about 2 to 4 carbon atoms as described hereinabove;
- A represents a hydrocarbyl group, an amine- substituted hydrocarbyl group, or hydrogen; the hydrocarbyl group and the amine-substituted hydrocarbyl groups are generally the alkyl and amino-substituted alkyl analogs of the alkylene radicals described above; and preferably "A” represents hydrogen; and d.
- n represents an integer of from about 1 to 10, and preferably from about 3 to 5 inclusive.
- the alkenyl succinimide is present in the lubricating oil compositions useful in this invention in an amount
- the weight percent succinimide is from 1 to 20 weight percent of the finished lubricating oil, usually from 2 to 15 weight percent and preferably from 1 to 10 weight percent of the total composition.
- the complex may be formed by reacting the borated alkyl catechol and the succinimide together neat at a temperature above the melting point of the mixture of reactants and below the decomposition temperature, or in a diluent in which both reactants are soluble.
- the borated alkyl catechol and the succinimide together neat at a temperature above the melting point of the mixture of reactants and below the decomposition temperature, or in a diluent in which both reactants are soluble.
- reactants may be combined in the proper ratio in the absence of a solvent to form a homogeneous product which may be added to the oil or the reactants may be combined in the proper ratio in a solvent such as toluene or
- the complex may be prepared in a lubricating oil as a concentrate containing from about 20 to 90% by weight of the complex, which concentrate may be added in appropriate amounts to the lubricating oil in which it is to be used or the complex may be prepared directly in the lubricating oil in which it is to be used.
- the diluent is preferably inert to the reactants and products formed and is used in an amount sufficient to ensure solubility of the reactants and to enable the mixture to be efficiently stirred.
- Temperatures for preparing the complex may be in the range of from 25°C to 200°C and preferably 25°C to 100°C
- the complexes of this invention may also be used in combination with other additive systems in
- the base composition described above will be formulated with supplementary additives to provide the necessary stability, detergency, dispersancy, anti-wear and anti-corrosion properties.
- reacting the borated alkyl catechols and succinimides may contain an alkali or alkaline earth metal phenate, and Group II metal salt dihydrocarbyl dithiophosphate.
- succinimides act as excellent dispersants
- additional succinimide may be added to the lubricating oil compositions, above the amounts added in the form of the complex with the borated alkyl catechols.
- the amount of succinimides can range up to about 20% by weight of the total lubricating oil compositions.
- the alkali or alkaline earth metal hydrocarbyl sulfonates may be either petroleum sulfonate, synthetically alkylated aromatic sulfonates, or aliphatic sulfonates such as those derived from polyisobutylene.
- One of the more important functions of the sulfonates is to act as a detergent and dispersant.
- the sulfonates are well known in the art.
- hydrocarbyl group must have a sufficient number of carbon atoms to render the sulfonate molecule oil soluble.
- the hydrocarbyl portion has at least 20 carbon atoms and may be aromatic or aliphatic, but is usually alkylaromatic. Most preferred for use are calcium, magnesium or barium sulfonates which are aromatic in character.
- Certain sulfonates are typically prepared by sulfonating a petroleum fraction having aromatic groups, usually mono- or dialkylbenzene groups, and then forming the metal salt of the sulfonic acid material.
- Other feedstocks used for preparing these sulfonates include synthetically alkylated benzenes and aliphatic hydrocarbons prepared by
- polyisobutenyl group prepared by polymerizing isobutene.
- the metallic salts are formed directly or by metathesis using well-known procedures.
- the sulfonates may be neutral or overbased having base numbers up to about 44 or more. Carbon dioxide and calcium hydroxide or oxide are the most commonly used material to produce the basic or overbased sulfonates. Mixtures of neutral and overbased sulfonates may be used.
- sulfonates are ordinarily used so as to provide from 0.3% to 10% by weight of the total composition.
- the neutral sulfonates are present from 0.4% to 5% by weight of the total composition and the overbased sulfonates are present from 0.3% to 33% by weight of the total
- the phenates for use in this invention are those
- the phenates functions of the phenates is to act as a detergent and dispersant. Among other things, it prevents the deposit of contaminants formed during high temperature operation of the engine.
- the phenols may be mono- or polyalkylated.
- the alkyl portion of the alkyl phenate is present to lend oil solubility to the phenate.
- the alkyl portion can be obtained from naturally occurring or synthetic sources. Naturally occurring sources include petroleum hydrocarbons such as white oil and wax. Being derived from petroleum, the hydrocarbon moiety is a mixture of different
- hydrocarbyl groups the specific composition of which depends upon the particular oil stock which was used as a starting material.
- Suitable synthetic sources include various commercially available alkenes and alkane
- Suitable radicals obtained include butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl,
- alkyl radical examples include olefin polymers such as polypropylene, polybutylene, polyisobutylene and the like.
- the alkyl group can be straight-chained or branch-chained, saturated or unsaturated (if unsaturated, preferably containing not more than 2 and generally not more than 1 site of olefinic unsaturation).
- the alkyl radicals will generally contain from 4 to 30 carbon atoms. Generally when the phenol is monoalkyl-substituted, the alkyl radical should contain at least 8 carbon atoms.
- the phenate may be sulfurized if desired. It may be either neutral or
- overbased and if overbased will have a base number of up to 200 to 300 or more. Mixtures of neutral and overbased phenates may be used.
- the phenates are ordinarily present in the oil to provide from 0.2% to 27% by weight of the total composition.
- the neutral phenates are present from 0.2% to 9% by weight of the total composition and the overbased phenates are present from 0.2 to 13% by weight of the total composition. Most preferably, the overbased phenates are present from 0.2% to 5% by weight of the total composition.
- Preferred metals are calcium, magnesium, strontium or barium.
- the sulfurized alkaline earth metal alkyl phenates are preferred. These salts are obtained by a variety of processes such as treating the neutralization product of an alkaline earth metal base and an alkylphenol with sulfur. Conveniently the sulfur, in elemental form, is added to the neutralization product and reacted at elevated temperatures to produce the sulfurized alkaline earth metal alkyl phenate.
- basicity can be obtained by adding carbon dioxide to the basic sulfurized alkaline earth metal alkyl phenate.
- the excess alkaline earth metal base can be added subsequent to the sulfurization step but is conveniently added at the same time as the alkaline earth metal base is added to neutralize the phenol.
- Carbon dioxide and calcium hydroxide or oxide are the most commonly used materials to produce the basic or "overbased" phenates.
- a process wherein basic sulfurized alkaline earth metal alkylphenates are produced by adding carbon dioxide is shown in Hanneman, U.S. Pat. No. 3,178,368.
- the Group II metal salts of dihydrocarbyl dithiophosphoric acids exhibit wear, antioxidant and thermal stability properties.
- Group II metal salts of phosphorodithioic acids have been described previously. See, for example, U.S. Pat. No. 3,390,080, columns 6 and 7, wherein these compounds and their preparation are described generally.
- the Group II metal salts of the dihydrocarbyl dithiophosphoric acids useful in the lubricating oil composition of this invention contain from about 4 to about 12 carbon atoms in each of the hydrocarbyl radicals and may be the same or different and may be aromatic, alkyl or cycloalkyl.
- Preferred hydrocarbyl groups are alkyl groups containing from 4 to 8 carbon atoms and are represented by butyl, isobutyl, sec-butyl, hexyl, isohexyl, octyl, 2-ethylhexyl and the like.
- the metals suitable for forming these salts include barium, calcium, strontium, zinc and cadmium, of which zinc is preferred.
- the Group II metal salt of a dihydrocarbyl dithiophosphoric acid has the following formula:
- R 2 and R 3 each independently represent hydrocarbyl radicals as described immediately above, and f. M 1 represents a Group II metal cation as described above.
- the dithiophosphoric salt is present in the lubricating oil compositions of this invention in an amount effective to inhibit wear and oxidation of the lubricating oil.
- the amount ranges from about 0.1 to about 4 percent by weight of the total composition, preferably the salt is present in an amount ranging from about 0.2 to about 2.5 percent by weight of the total lubricating oil composition.
- the final lubricating oil composition will ordinarily contain 0.025 to 0.25% by weight phosphorus and preferably 0.05 to 0.15% by weight.
- the finished lubricating oil may be single or multigrade.
- Multigrade lubricating oils are prepared by adding
- VI improvers viscosity index improvers.
- Typical viscosity index improvers are polyalkyl methacrylates, ethylene-propylene copolymers, styrene-diene copolymers and the like. So-called decorated VI improvers having both viscosity index and dispersant properties are also suitable for use in the formulations of this invention.
- the lubricating oil used in the compositions of this invention may be a mineral oil or a synthetic oil of lubricating viscosity, preferably suitable for use in the crankcase of an internal combustion engine.
- Crankcase lubricating oils ordinarily have a viscosity of about 1300 cSt at 0°F. (-18°C.) to 22.7 cSt at 210°F. (99°C).
- the lubricating oils may be derived from synthetic or natural sources.
- Mineral oil for use as the base oil in this invention includes paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions. Synthetic oils include both hydrocarbon synthetic oils and synthetic esters.
- Useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C 6-12 alpha olefins such as 1-decene trimer, tetramer, and higher oligomers. Likewise, alkyl benzenes of proper viscosity, such as didodecyl benzene, can be used.
- Useful synthetic esters include the esters of both monocarboxylie acid and polycarboxylic acids as well as monohydroxy alkanols and polyols.
- Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2- ethylhexyl adipate, dilaurylsebacate and the like.
- Complex esters prepared from mixtures of mono and dicarboxylic acid and mono and dihydroxy alkanols can also be used.
- Blends of hydrocarbon oils with synthetic oils are also useful. For example, blends of 10 to 25 weight percent hydrogenated 1-decene trimer with 75 to 90 weight percent 33 cSt at 100°F. (38°C.) mineral oil gives an excellent lubricating oil base.
- Other additives which may be present in the formulation include rust inhibitors, foam inhibitors, corrosion
- the candidate additives were tested for their compatibility in a bench test (PV3334) by suspending a fluorocarbon coupon (AK6) in an oil solution heated at 150°C for 96 hours (4 days) followed by measuring a change in the physical properties of the specimen, particularly the tensile strength (TS), and the percent elongation to break (EL) in accordance with DIN53504 procedure, and observing whether any cracks had developed at 120% elongation (CR).
- a passing test criteria included the following: no
- the baseline formulation used for testing a fluorocarbon coupon contained a dispersant (6% by weight), i.e., either a mono- or bis-succinimide; an overbased calcium
- hydrocarbyl sulfonate (30 mmol/kg); an overbased calcium phenate (20 mmol/kg); mixed primary and secondary zinc dialkyl dithiophosphates (22.5 mmol/kg); and ethylene-propylene copolymer viscosity index improver (13% by weight) in 150N Exxon base oil.
- borated additives were tested, these were added in appropriate percentages as top treats on top of the baseline formulation above.
- Examples 1-4 are base runs and show that the presence of mono- or bis-succinimides alone in the formulation without borated aromatic polyols, lack
- borated t-butyl catechol results in passivation of the basic nitrogen (Ex 13) using bis-succinimides but fails using the mono-succinimides (Ex 14).
- Examples 27 and 28 in Table 2 below show that increasing the concentration of the borated t-butyl catechol to 2% results in a "PASS" with the mono-succinimide.
- Examples 15-19 show that using only 1 weight percent of several different alkylated borated catechols within the scope of the invention is insufficient to passivate the fluorocarbon elastomers. Examples in Table 2 below show that increasing the concentrations of such catechols results in a PASS.
- aromatic polyol as defined in this invention is observed.
- borating the bis-succinimide (Ex 36) is not successful, confirming the teachings of Anderson in Column 3, lines 3-5 of his U.S.P. 4,873,009 referred to above.
- the boration and use of other hydroxy containing structures also fails as seen in Examples 37 through 45.
- Examples 5, 46 and 47 show that the aromatic polyol can be a single (Ex 5) or condensed ring (Ex 47) aromatic as long as two hydroxy groups are present on adjacent aromatic ring carbon atoms (Compare Examples 5 and 46, which were
- Example 45 which was unsuccessful due to the hydroxy groups being on non-adjacent aromatic ring carbon atoms).
- the presence of an additional hydroxy group on the ring is acceptable (See Example 46).
- the reference oil formulation contained 3.5% dispersant, 50 mmol/kg calcium as hydrocarbyl sulfonates, 17 mmol/kg zinc dialkyl dithiophosphate, and 6.8% viscosity index improver in Chevron 100N base oil.
- the oxidation test employed herein measures the resistance of the test sample to oxidation using pure oxygen with a Dornte-type oxygen absorption apparatus [R. W. Dornte, "Oxidation of White Oils," Industrial and Engineering Chemistry. 28 p. 26 (1936)].
- the conditions are: an atmosphere of pure oxygen exposed to the test oil, an oil temperature of 340° F.
- Example 4 of U.S. Patent 4,199,462 Column 7, lines 13 et seq.
- the Test set forth in Example 4 of the '462 Patent has been modified for the seventh series of runs to be discussed below.
- the hot spots are made as soon as the tube is removed from the bath at 200°C.
- the “spot” consists of an inner darker circle of diameter "d” surrounded by a translucent area soaked with basic oil and forming a larger circle of diameter "D.”
- d:D For each spot, the ratio d:D is calculated and multiplied by 100. The "best" dispersion would be where d:D equals 1 for each spot to give a combined maximum of 600
- the purpose of the seventh series of runs was to compare the dispersive properties of (1) catechol borate (2) butyl catechol borate and (3) a long-chain (average C 22 ) alkyl catechol borate with the reference SAE30 oil containing the sludge.
- Catechol borate showed a gain of about 50 units over the reference value of 396.
- t-Butyl catechol borate showed a gain of about 18 units while the long chain alkyl catechol borate showed a loss of about 25 units.
- Figure is a plot of these data with the carbon number of the alkyl group on the x-axis and a loss or gain in
- alkylcatechol borates with alkyl groups below 10 carbon i.e., 8 or 9 should not only provide passing results in the VW Bench Test, but also offer no loss in the overall dispersancy, a quite unexpected result.
- catechol borate has the advantages set forth above, it and the lower alkyl catechol borates have low solubility in base oils.
- catechol borate was soluble only to the extent of about 0.3 weight percent or less.
- catechol borate was soluble only to the extent of about ⁇ 0.3%, but this value was exceeded by adding an alkylcatechol containing a long (avg C22) alkyl group.
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Abstract
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US772821 | 1985-09-05 | ||
US77282191A | 1991-10-08 | 1991-10-08 | |
PCT/US1992/007141 WO1993007242A1 (fr) | 1991-10-08 | 1992-08-25 | Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissage |
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EP (1) | EP0562062B1 (fr) |
JP (1) | JP3231322B2 (fr) |
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US8993496B2 (en) | 2010-03-31 | 2015-03-31 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
US9150811B2 (en) | 2010-03-31 | 2015-10-06 | Cherron Oronite Company LLC | Method for improving copper corrosion performance |
CN111718778A (zh) * | 2020-06-23 | 2020-09-29 | 长沙众城石油化工有限责任公司 | 一种复合钙基润滑脂及其制备方法 |
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US5569644A (en) * | 1995-05-18 | 1996-10-29 | The Lubrizol Corporation | Additive combinations for lubricants and functional fluids |
US5962380A (en) * | 1995-06-06 | 1999-10-05 | Chevron Chemical Company Llc | Fluorocarbon elastomer compatibility improving agent having wear inhibition effect |
FR2762848B1 (fr) * | 1997-05-05 | 2000-02-04 | Chevron Res & Tech | Utilisation de composes borates pour ameliorer la compatibilite d'huiles lubrifiantes avec des elastomeres fluorocarbones |
US6010986A (en) * | 1998-07-31 | 2000-01-04 | The Lubrizol Corporation | Alcohol borate esters to improve bearing corrosion in engine oils |
US20040171501A1 (en) * | 2003-02-27 | 2004-09-02 | Leeuwen Jeroen Van | Method for improving elastomer compatibility |
US8933001B2 (en) | 2010-03-31 | 2015-01-13 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
US9388362B2 (en) * | 2012-10-30 | 2016-07-12 | Chevron Oronite Company Llc | Friction modifiers and a method of making the same |
KR102608828B1 (ko) | 2015-02-26 | 2023-11-30 | 더루브리졸코오퍼레이션 | 방향족 세제 및 이의 윤활 조성물 |
DE102020117671B4 (de) | 2020-07-03 | 2022-06-09 | Fuchs Petrolub Se | Schmierstellen aufweisend eine Polyharnstoff-Schmierfett-Zusammensetzung und eine Dichtung umfassend ein Dichtmaterial aus fluorierten Elastomeren und die Verwendung der Polyharnstoff-Schmierfett-Zusammensetzung für eine Schmierstelle umfassend eine derartige Dichtung |
DE102020008047A1 (de) | 2020-07-03 | 2022-01-05 | Fuchs Petrolub Se | Polyharnstoff-Schmierfette enthaltend Carbonate und deren Verwendung |
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EP0136185A2 (fr) * | 1983-09-29 | 1985-04-03 | Edwin Cooper, Inc. | Procédé pour borer des dispersants, dispersants borés et compositions fluides les contenant |
WO1991004312A1 (fr) * | 1989-09-15 | 1991-04-04 | Chevron Research And Technology Company | Complexes alkylamines de pyrocatechines d'alkyle boratees et composition d'huiles lubrifiantes les contenant |
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US4482464A (en) * | 1983-02-14 | 1984-11-13 | Texaco Inc. | Hydrocarbyl-substituted mono- and bis-succinimide having polyamine chain linked hydroxyacyl radicals and mineral oil compositions containing same |
US4629577A (en) * | 1985-06-17 | 1986-12-16 | Chevron Research Company | Method for improving fuel economy of internal combustion engines |
US4629578A (en) * | 1985-06-17 | 1986-12-16 | Chevron Research Company | Succinimide complexes of borated alkyl catechols and lubricating oil compositions containing same |
US4713190A (en) * | 1985-10-23 | 1987-12-15 | Chevron Research Company | Modified carboxylic amide dispersants |
US5061390A (en) * | 1989-07-05 | 1991-10-29 | Chevron Research And Technology Company | Diethylamine complexes of borated alkyl catechols and lubricating oil compositions containing the same |
-
1992
- 1992-08-25 SG SG1996007816A patent/SG48193A1/en unknown
- 1992-08-25 EP EP92918231A patent/EP0562062B1/fr not_active Expired - Lifetime
- 1992-08-25 WO PCT/US1992/007141 patent/WO1993007242A1/fr active IP Right Grant
- 1992-08-25 JP JP50688293A patent/JP3231322B2/ja not_active Expired - Fee Related
- 1992-08-25 DE DE69223942T patent/DE69223942T2/de not_active Expired - Lifetime
- 1992-08-25 CA CA002097828A patent/CA2097828C/fr not_active Expired - Fee Related
Patent Citations (3)
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US2795548A (en) * | 1954-06-29 | 1957-06-11 | California Research Corp | Lubricant compositions |
EP0136185A2 (fr) * | 1983-09-29 | 1985-04-03 | Edwin Cooper, Inc. | Procédé pour borer des dispersants, dispersants borés et compositions fluides les contenant |
WO1991004312A1 (fr) * | 1989-09-15 | 1991-04-04 | Chevron Research And Technology Company | Complexes alkylamines de pyrocatechines d'alkyle boratees et composition d'huiles lubrifiantes les contenant |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8901050B2 (en) | 2010-03-31 | 2014-12-02 | Chevron Oronite Company Llc | Method for improving copper corrosion performance |
US8993496B2 (en) | 2010-03-31 | 2015-03-31 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
US9150811B2 (en) | 2010-03-31 | 2015-10-06 | Cherron Oronite Company LLC | Method for improving copper corrosion performance |
US8716202B2 (en) | 2010-12-14 | 2014-05-06 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
CN111718778A (zh) * | 2020-06-23 | 2020-09-29 | 长沙众城石油化工有限责任公司 | 一种复合钙基润滑脂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2097828A1 (fr) | 1993-04-09 |
EP0562062A4 (fr) | 1994-04-27 |
JPH06505526A (ja) | 1994-06-23 |
CA2097828C (fr) | 2003-07-08 |
EP0562062B1 (fr) | 1998-01-07 |
SG48193A1 (en) | 1998-04-17 |
WO1993007242A1 (fr) | 1993-04-15 |
JP3231322B2 (ja) | 2001-11-19 |
DE69223942T2 (de) | 1998-06-18 |
DE69223942D1 (de) | 1998-02-12 |
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