CA2993333A1 - Use of polyclycerin esters as friction modifiers in lubricant formulations - Google Patents
Use of polyclycerin esters as friction modifiers in lubricant formulations Download PDFInfo
- Publication number
- CA2993333A1 CA2993333A1 CA2993333A CA2993333A CA2993333A1 CA 2993333 A1 CA2993333 A1 CA 2993333A1 CA 2993333 A CA2993333 A CA 2993333A CA 2993333 A CA2993333 A CA 2993333A CA 2993333 A1 CA2993333 A1 CA 2993333A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- lubricating oil
- oil composition
- acids
- composition according
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 150000002148 esters Chemical class 0.000 title claims abstract description 40
- 239000003607 modifier Substances 0.000 title claims description 17
- 239000000314 lubricant Substances 0.000 title description 12
- 238000009472 formulation Methods 0.000 title description 8
- 229920000223 polyglycerol Polymers 0.000 claims abstract description 56
- -1 poly(hydroxystearic acid) Polymers 0.000 claims abstract description 34
- 239000010687 lubricating oil Substances 0.000 claims abstract description 31
- 239000000194 fatty acid Substances 0.000 claims abstract description 21
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 19
- 229930195729 fatty acid Natural products 0.000 claims abstract description 19
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 19
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims description 40
- 150000007513 acids Chemical class 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 14
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007866 anti-wear additive Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims description 4
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 claims description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 4
- 230000001050 lubricating effect Effects 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 claims description 4
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 3
- 239000005069 Extreme pressure additive Substances 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 239000010696 ester oil Substances 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229960003656 ricinoleic acid Drugs 0.000 claims description 3
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- GBURUDXSBYGPBL-UHFFFAOYSA-N 2,2,3-trimethylhexanedioic acid Chemical compound OC(=O)C(C)(C)C(C)CCC(O)=O GBURUDXSBYGPBL-UHFFFAOYSA-N 0.000 claims description 2
- BTUDGPVTCYNYLK-UHFFFAOYSA-N 2,2-dimethylglutaric acid Chemical compound OC(=O)C(C)(C)CCC(O)=O BTUDGPVTCYNYLK-UHFFFAOYSA-N 0.000 claims description 2
- 235000021357 Behenic acid Nutrition 0.000 claims description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 229940116226 behenic acid Drugs 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- ZVRMGCSSSYZGSM-UHFFFAOYSA-N hexadec-2-enoic acid Chemical class CCCCCCCCCCCCCC=CC(O)=O ZVRMGCSSSYZGSM-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims 2
- 235000003441 saturated fatty acids Nutrition 0.000 claims 1
- 239000002585 base Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 230000009467 reduction Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000000539 dimer Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 239000010705 motor oil Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 2
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-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
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000011158 quantitative evaluation Methods 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
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- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- DPUOLQHDNGRHBS-MDZDMXLPSA-N trans-Brassidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-MDZDMXLPSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZJVATSUMFCZSKA-QZOPMXJLSA-N (z)-docos-13-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O ZJVATSUMFCZSKA-QZOPMXJLSA-N 0.000 description 1
- YZAZXIUFBCPZGB-QZOPMXJLSA-N (z)-octadec-9-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O YZAZXIUFBCPZGB-QZOPMXJLSA-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
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-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
- GSOYMOAPJZYXTB-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3,5-ditert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 GSOYMOAPJZYXTB-UHFFFAOYSA-N 0.000 description 1
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- NISAHDHKGPWBEM-UHFFFAOYSA-N 2-(4-nonylphenoxy)acetic acid Chemical compound CCCCCCCCCC1=CC=C(OCC(O)=O)C=C1 NISAHDHKGPWBEM-UHFFFAOYSA-N 0.000 description 1
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- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-UHFFFAOYSA-N 0.000 description 1
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
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- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- HBEMHMNHYDTVRE-UHFFFAOYSA-N ClC(CCCCCCCCCCCCCCCCC(=O)OC)(Cl)Cl Chemical compound ClC(CCCCCCCCCCCCCCCCC(=O)OC)(Cl)Cl HBEMHMNHYDTVRE-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- VBIGULIJWJPALH-UHFFFAOYSA-L calcium;2-carboxyphenolate Chemical class [Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O VBIGULIJWJPALH-UHFFFAOYSA-L 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- LMODBLQHQHXPEI-UHFFFAOYSA-N dibutylcarbamothioylsulfanylmethyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SCSC(=S)N(CCCC)CCCC LMODBLQHQHXPEI-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229940113162 oleylamide Drugs 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/78—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids, hydroxy carboxylic acids
-
- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
-
- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
-
- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
-
- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Lubricants (AREA)
Abstract
The present invention relates to a lubricating oil composition comprising polyglycerol partial esters of polyfunctional carboxylic acids and saturated or unsaturated, linear or branched fatty acids and/or poly(hydroxystearic acid) and the use thereof to lubricate an engine and reduce friction.
Description
Use of polyclycerin esters as friction modifiers in lubricant formulations The present invention relates to a lubricating oil composition comprising polyglycerol partial esters of polyfunctional carboxylic acids and saturated or unsaturated, linear or branched fatty acids and/or poly(hydroxystearic acid) and the use thereof to lubricate an engine and reduce friction.
Energy losses due to friction in lubricated contacts can be reduced by adding friction modifiers to the lubricant formulation. Friction modifiers are used especially in gear and engine oil formulations where lower viscosity formulations are applied in order to save energy. While reducing the energy losses in the fluid, lubricants with low viscosities struggle to keep the sliding surfaces completely apart from each other and require a friction modifier to maintain a lubricant film on the surfaces.
Friction modifiers work by forming adsorption layers on the metal surface.
They are of high importance under mixed lubrication conditions when the sliding surfaces are not always separated by a lubricant film of sufficient thickness. Such conditions can be simulated with a mini traction machine (MTM) that is able to measure the friction coefficient over a broad range of conditions.
Friction reducing additives that have been used to improve fuel economy fall into three main chemically-defined categories, which are organic, metal organic and oil insoluble. The organic friction reducing additives themselves fall within four main categories which are (i) carboxylic acids or their derivatives, including partial esters, (ii) nitrogen-containing compounds such as amides, imides, amines and their derivatives, (iii) phosphoric or phosphonic acid derivatives and (iv) organic polymers.
In current commercial practice examples of friction reducing additives are glycerol monooleate and oleylamide, which are both derived from unsaturated fatty acids, or molybdenum dialkyldithiocarbamate. Also used are copolymers with blocks of polyethyleneglycol (WO
2011/107739 and WO 2015/065801) or other alkoxide polymers (WO 2014/139935).
It is further known that polyglycerol solubilized by a long alkyl chain attached via an ether function (US
7,803,745) or an ester function (WO 2015/044639) can be applied as a friction modifier.
It was now surprisingly found that polyglycerol partial esters of polyfunctional carboxylic acids and saturated or unsaturated, linear or branched fatty acids and/or poly(hydroxystearic acid) show superior performance as friction modifiers for lubricants. Superior means a larger reduction of the friction coefficient and/or more efficient friction reduction due to a lower treat rate and/or a better combination of oil compatibility and friction reducing performance.
Energy losses due to friction in lubricated contacts can be reduced by adding friction modifiers to the lubricant formulation. Friction modifiers are used especially in gear and engine oil formulations where lower viscosity formulations are applied in order to save energy. While reducing the energy losses in the fluid, lubricants with low viscosities struggle to keep the sliding surfaces completely apart from each other and require a friction modifier to maintain a lubricant film on the surfaces.
Friction modifiers work by forming adsorption layers on the metal surface.
They are of high importance under mixed lubrication conditions when the sliding surfaces are not always separated by a lubricant film of sufficient thickness. Such conditions can be simulated with a mini traction machine (MTM) that is able to measure the friction coefficient over a broad range of conditions.
Friction reducing additives that have been used to improve fuel economy fall into three main chemically-defined categories, which are organic, metal organic and oil insoluble. The organic friction reducing additives themselves fall within four main categories which are (i) carboxylic acids or their derivatives, including partial esters, (ii) nitrogen-containing compounds such as amides, imides, amines and their derivatives, (iii) phosphoric or phosphonic acid derivatives and (iv) organic polymers.
In current commercial practice examples of friction reducing additives are glycerol monooleate and oleylamide, which are both derived from unsaturated fatty acids, or molybdenum dialkyldithiocarbamate. Also used are copolymers with blocks of polyethyleneglycol (WO
2011/107739 and WO 2015/065801) or other alkoxide polymers (WO 2014/139935).
It is further known that polyglycerol solubilized by a long alkyl chain attached via an ether function (US
7,803,745) or an ester function (WO 2015/044639) can be applied as a friction modifier.
It was now surprisingly found that polyglycerol partial esters of polyfunctional carboxylic acids and saturated or unsaturated, linear or branched fatty acids and/or poly(hydroxystearic acid) show superior performance as friction modifiers for lubricants. Superior means a larger reduction of the friction coefficient and/or more efficient friction reduction due to a lower treat rate and/or a better combination of oil compatibility and friction reducing performance.
2 In a first embodiment, the present invention is directed to a lubricating oil composition comprising a lubricating base oil and polyglycerol partial esters, characterized in that the polyglycerol partial esters are obtainable by esterification of a polyglycerol mixture with (i) polyfunctional carboxylic acids and (ii) saturated or unsaturated, linear or branched fatty acids and/or (ii) poly(hydroxystearic acid).
Polyglycerol esters were found to work especially in apolar formulations containing mainly API
Group II, Ill and/or IV as lubricating base oils.
The American Petroleum Institute (API) currently defines five groups of lubricant base stocks (API
Publication 1509). Groups I, ll and III are mineral oils which are classified by the amount of saturates and sulphur they contain and by their viscosity indices. The table below illustrates these API classifications for Groups I, ll and III.
Group Saturates Sulphur content Viscosity Index (VI) <90% > 0.03% 80-120 II at least 90% not more than 0.03% 80-120 Ill at least 90% not more than 0.03% at least 120 Group I base stocks are solvent refined mineral oils, which are the least expensive base stock to produce, and currently account for the majority of base stock sales. They provide satisfactory oxidation stability, volatility, low temperature performance and traction properties and have very good solvency for additives and contaminants.
Group ll base stocks are mostly hydroprocessed mineral oils, which typically provide improved volatility and oxidation stability as compared to Group I base stocks.
Group III base stocks are severely hydroprocessed mineral oils or they can be produced via wax or paraffin isomerisation. They are known to have better oxidation stability and volatility than Group I
and ll base stocks but have a limited range of commercially available viscosities.
Group IV base stocks differ from Groups I, II and III in that they are synthetic base stocks comprising e.g. polyalphaolefins (PA05). PAOs have good oxidative stability, volatility and low pour points. Disadvantages include moderate solubility of polar additives, for example antiwear additives.
Group II, II and IV oils are known for their exceptional stability towards oxidation and high temperatures, but they provide only limited solubility for polar additives such as friction modifiers.
For this reason the lubricating oil compositions according the present invention may contain up to 10% of an ester base oil according to API Group V as solubilizer.
Polyglycerol esters were found to work especially in apolar formulations containing mainly API
Group II, Ill and/or IV as lubricating base oils.
The American Petroleum Institute (API) currently defines five groups of lubricant base stocks (API
Publication 1509). Groups I, ll and III are mineral oils which are classified by the amount of saturates and sulphur they contain and by their viscosity indices. The table below illustrates these API classifications for Groups I, ll and III.
Group Saturates Sulphur content Viscosity Index (VI) <90% > 0.03% 80-120 II at least 90% not more than 0.03% 80-120 Ill at least 90% not more than 0.03% at least 120 Group I base stocks are solvent refined mineral oils, which are the least expensive base stock to produce, and currently account for the majority of base stock sales. They provide satisfactory oxidation stability, volatility, low temperature performance and traction properties and have very good solvency for additives and contaminants.
Group ll base stocks are mostly hydroprocessed mineral oils, which typically provide improved volatility and oxidation stability as compared to Group I base stocks.
Group III base stocks are severely hydroprocessed mineral oils or they can be produced via wax or paraffin isomerisation. They are known to have better oxidation stability and volatility than Group I
and ll base stocks but have a limited range of commercially available viscosities.
Group IV base stocks differ from Groups I, II and III in that they are synthetic base stocks comprising e.g. polyalphaolefins (PA05). PAOs have good oxidative stability, volatility and low pour points. Disadvantages include moderate solubility of polar additives, for example antiwear additives.
Group II, II and IV oils are known for their exceptional stability towards oxidation and high temperatures, but they provide only limited solubility for polar additives such as friction modifiers.
For this reason the lubricating oil compositions according the present invention may contain up to 10% of an ester base oil according to API Group V as solubilizer.
3 Group V base stocks are all base stocks that are not included in the other Groups. Examples include alkyl naphthalenes, alkyl aromatics, vegetable oils, esters (including polyol esters, diesters and monoesters), polycarbonates, silicone oils and polyalkylene glycols.
The friction modifier performance of polyglycerol partial esters according to the present invention can be achieved in formulations with and without the additional ester base stock.
In a preferred embodiment, the lubricating oil compositions according to the present invention are characterized in that they comprise (a) 90-100% by weight of an apolar oil selected from the group consisting of API Group II, Ill and IV and/or mixtures thereof and (b) 0-10% of a polar ester oil of Group V according to the definition of the American Petroleum Institute (API), based on the total weight of the lubricating oil composition.
Polyglycerol partial esters of poly(hydroxystearic acid) and polyfunctional carboxylic acids are known as W/O emulsifiers in cosmetic or pharmaceutical formulations and as auxiliaries for dispersing inorganic micropigments in oily dispersions (EP 1 500 427 B1 and EP
1 683 781 B1).
For best performance as friction modifiers the parameters surface activity or polarity and oil solubility have to be balanced and adjusted to the polarity of the respective oil mixture used as base stock. The balance of polar and apolar parts in the polymer is described by the HLB value that is calculated. This can be done by selection of a polyglycerol characterized by a certain degree of polymerization and selection of carboxylic acids and polycarboxylic acids.
Especially the amount of polycarboxylic acids has a major influence on the molecular weight (measured by SEC) of the resulting component. The ratio of acid and alcohol functions is important as it determines the degree of esterification and thus the amount of unreacted OH-functions (described by the OH-number determined by titration). Free acid functions are unwanted and should be kept at a minimum level (described by the acid value, determined by titration).
The superior performance relative to other friction modifiers is attributed to the high polarity of the polyglycerol moieties, the free OH-functions due to the partial esterification and the polymeric nature of the substances which provides multiple interaction sites between the surface and the friction reducing component. The polymeric nature of the described friction modifiers is especially important for the solubility of the component as very polar moieties in the molecule have to be kept in solution.
These polyglycerol partial esters of polyfunctional carboxylic acids and saturated or unsaturated, linear or branched fatty acids and/or poly(hydroxystearic acid) are obtainable by esterification of a polyglycerol mixture with saturated or unsaturated, linear or branched fatty acids having 8 to 22
The friction modifier performance of polyglycerol partial esters according to the present invention can be achieved in formulations with and without the additional ester base stock.
In a preferred embodiment, the lubricating oil compositions according to the present invention are characterized in that they comprise (a) 90-100% by weight of an apolar oil selected from the group consisting of API Group II, Ill and IV and/or mixtures thereof and (b) 0-10% of a polar ester oil of Group V according to the definition of the American Petroleum Institute (API), based on the total weight of the lubricating oil composition.
Polyglycerol partial esters of poly(hydroxystearic acid) and polyfunctional carboxylic acids are known as W/O emulsifiers in cosmetic or pharmaceutical formulations and as auxiliaries for dispersing inorganic micropigments in oily dispersions (EP 1 500 427 B1 and EP
1 683 781 B1).
For best performance as friction modifiers the parameters surface activity or polarity and oil solubility have to be balanced and adjusted to the polarity of the respective oil mixture used as base stock. The balance of polar and apolar parts in the polymer is described by the HLB value that is calculated. This can be done by selection of a polyglycerol characterized by a certain degree of polymerization and selection of carboxylic acids and polycarboxylic acids.
Especially the amount of polycarboxylic acids has a major influence on the molecular weight (measured by SEC) of the resulting component. The ratio of acid and alcohol functions is important as it determines the degree of esterification and thus the amount of unreacted OH-functions (described by the OH-number determined by titration). Free acid functions are unwanted and should be kept at a minimum level (described by the acid value, determined by titration).
The superior performance relative to other friction modifiers is attributed to the high polarity of the polyglycerol moieties, the free OH-functions due to the partial esterification and the polymeric nature of the substances which provides multiple interaction sites between the surface and the friction reducing component. The polymeric nature of the described friction modifiers is especially important for the solubility of the component as very polar moieties in the molecule have to be kept in solution.
These polyglycerol partial esters of polyfunctional carboxylic acids and saturated or unsaturated, linear or branched fatty acids and/or poly(hydroxystearic acid) are obtainable by esterification of a polyglycerol mixture with saturated or unsaturated, linear or branched fatty acids having 8 to 22
4 carbon atoms, preferably 12 to 18 carbon atoms, and polyfunctional carboxylic acids having 4 to 54 carbon atoms, preferably 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms and even more preferably 6 to 12 carbon atoms, and a mean functionality of from 2 to 4, preferably 2 to 3 and more preferably 2 to 2.5, the degree of esterification of the polyglycerol mixture being between 30 and 75% of the OH groups.
The mean functionality of a mixture of polyfunctional carboxylic acids can be determined using the following formula:
= 1x, ¨ = N with = mean functionality of a mixture of polyfunctional 100 carboxylic acids = mass fraction [ia] of individual polyfunctional carboxylic acid i N, = functionality of individual polyfunctional carboxylic acid i Particularly suitable linear or branched saturated fatty acid components are selected from the group consisting of caprylic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, arachidic acid, behenic acid and mixtures thereof.
A suitable saturated fatty acid is also 12-hydroxy stearic acid. Naturally occurring mixtures are, for example, the coconut fatty acids, which contain lauric acid as the main constituent and also contain saturated C14 - to C18 -fatty acids and possibly small amounts of saturated C8 - to C18 -fatty acids and unsaturated fatty acids, and tallow fatty acids, which are essentially a mixture of palmitic acid and stearic acid.
Suitable unsaturated fatty acid components are monoolefinically unsaturated acids, for example hexadecenoic acids, octadecenoic acids, such as oleic acid (cis-9-octadecenoic acid) or eladidic acid (trans-9-octadecenoic acid), eicosenoic acids and docosenoic acids, such as erucic acid (cis-13-docosenoic acid) or brassidic acid (trans-13-docosenoic acid), poly-unsaturated fatty acids, for example octadecadienoic acids and octadecatrienoic acids, such as linoleic acid and linolenic acid, ricinoleic acid and mixtures thereof.
The liquid fatty acids which contain 18 to 22 carbon atoms, namely oleic, ricinoleic, erucic and isostearic acids, are particularly suitable. Because of branching solidification points are below 35 DEG C. It is also possible to use fatty acid mixtures, which can also contain wax-like components, such as hydrogenated ricinoleic acid.
The poly(hydroxystearic acids) co-used according to the invention are prepared, for example, by polycondensation of hydroxystearic acid, preferably 12-hydroxystearic acid, which is obtained by hardening of ricinoleic acid or technical-grade castor oil fatty acid, by known processes. They have
The mean functionality of a mixture of polyfunctional carboxylic acids can be determined using the following formula:
= 1x, ¨ = N with = mean functionality of a mixture of polyfunctional 100 carboxylic acids = mass fraction [ia] of individual polyfunctional carboxylic acid i N, = functionality of individual polyfunctional carboxylic acid i Particularly suitable linear or branched saturated fatty acid components are selected from the group consisting of caprylic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, arachidic acid, behenic acid and mixtures thereof.
A suitable saturated fatty acid is also 12-hydroxy stearic acid. Naturally occurring mixtures are, for example, the coconut fatty acids, which contain lauric acid as the main constituent and also contain saturated C14 - to C18 -fatty acids and possibly small amounts of saturated C8 - to C18 -fatty acids and unsaturated fatty acids, and tallow fatty acids, which are essentially a mixture of palmitic acid and stearic acid.
Suitable unsaturated fatty acid components are monoolefinically unsaturated acids, for example hexadecenoic acids, octadecenoic acids, such as oleic acid (cis-9-octadecenoic acid) or eladidic acid (trans-9-octadecenoic acid), eicosenoic acids and docosenoic acids, such as erucic acid (cis-13-docosenoic acid) or brassidic acid (trans-13-docosenoic acid), poly-unsaturated fatty acids, for example octadecadienoic acids and octadecatrienoic acids, such as linoleic acid and linolenic acid, ricinoleic acid and mixtures thereof.
The liquid fatty acids which contain 18 to 22 carbon atoms, namely oleic, ricinoleic, erucic and isostearic acids, are particularly suitable. Because of branching solidification points are below 35 DEG C. It is also possible to use fatty acid mixtures, which can also contain wax-like components, such as hydrogenated ricinoleic acid.
The poly(hydroxystearic acids) co-used according to the invention are prepared, for example, by polycondensation of hydroxystearic acid, preferably 12-hydroxystearic acid, which is obtained by hardening of ricinoleic acid or technical-grade castor oil fatty acid, by known processes. They have
5 PCT/EP2016/065904 a mean degree of polymerization of 1 to 10 units, preferably 2 to 8 units and in particular 2 to 5 units.
The polyfunctional carboxylic acids can be dicarboxylic acids, tricarboxylic acids or polycarboxylic 5 acids. The polyfunctional carboxylic acids may be unsubstituted or optionally substituted by one, two or three hydroxyl groups, preferably by one hydroxyl group.
The aliphatic dicarboxylic acids used for the esterification should have a chain length of 3 to 18 carbon atoms. They can be straight-chain or branched, such as, for example, malonic acid, succinic acid, fumaric acid, maleic acid, dimethylglutaric acid, adipic acid, trimethyladipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hecadecanedioic acid, octadecanedioic and their anhydrides.
The dicarboxylic acids used can also be dimeric fatty acids. As is known, these are mixtures of acyclic and cyclic dicarboxylic acids which are obtained by a catalyzed dimerization reaction of unsaturated fatty acids having 12 to 22 carbon atoms.
For the preparation and use of dimer acids and their physical and chemical properties, reference is made to the publication "The Dimer Acids: The chemical and physical properties, reactions and applications", Ed. E. C. Leonard; Humko Sheffield Chemical, 1975, Memphis, Tenn.
The dicarboxylic acids can also contain, to a lesser extent, tri-and polyfunctional carboxylic acids.
The functionality of the mixture should not exceed a value of 2 to 2.5 molar average.
Furthermore, as polyfunctional carboxylic acids can be used phthalic acid, trimellitic acid and pyromellitic acid.
Under the term "polyglycerol" according to the present invention encompasses a polyglycerol comprising glycerol. Therefore, for the calculation of amounts, masses etc.
the glycerol content has to be taken into account. The term glycerol oligomers or polyglycerol(s) encompasses linear as well as cyclic structures.
Suitable polyglycerols are in particular those having a mean degree of condensation of >2, preferably from 3 to 6. These are technical-grade polyglycerol mixtures which are obtained, for example, by alkali-catalyzed condensation of glycerol at elevated temperatures and from which fractions with the desired degree of condensation can be obtained if desired by distillation methods.
Also suitable are polyglycerols obtained by other methods, e.g. from epichlorohydrin or glycidol.
Commercial polyglycerols can be obtained from companies like Solvay, Spiga Nord, Daicel or Lonza.
The polyfunctional carboxylic acids can be dicarboxylic acids, tricarboxylic acids or polycarboxylic 5 acids. The polyfunctional carboxylic acids may be unsubstituted or optionally substituted by one, two or three hydroxyl groups, preferably by one hydroxyl group.
The aliphatic dicarboxylic acids used for the esterification should have a chain length of 3 to 18 carbon atoms. They can be straight-chain or branched, such as, for example, malonic acid, succinic acid, fumaric acid, maleic acid, dimethylglutaric acid, adipic acid, trimethyladipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hecadecanedioic acid, octadecanedioic and their anhydrides.
The dicarboxylic acids used can also be dimeric fatty acids. As is known, these are mixtures of acyclic and cyclic dicarboxylic acids which are obtained by a catalyzed dimerization reaction of unsaturated fatty acids having 12 to 22 carbon atoms.
For the preparation and use of dimer acids and their physical and chemical properties, reference is made to the publication "The Dimer Acids: The chemical and physical properties, reactions and applications", Ed. E. C. Leonard; Humko Sheffield Chemical, 1975, Memphis, Tenn.
The dicarboxylic acids can also contain, to a lesser extent, tri-and polyfunctional carboxylic acids.
The functionality of the mixture should not exceed a value of 2 to 2.5 molar average.
Furthermore, as polyfunctional carboxylic acids can be used phthalic acid, trimellitic acid and pyromellitic acid.
Under the term "polyglycerol" according to the present invention encompasses a polyglycerol comprising glycerol. Therefore, for the calculation of amounts, masses etc.
the glycerol content has to be taken into account. The term glycerol oligomers or polyglycerol(s) encompasses linear as well as cyclic structures.
Suitable polyglycerols are in particular those having a mean degree of condensation of >2, preferably from 3 to 6. These are technical-grade polyglycerol mixtures which are obtained, for example, by alkali-catalyzed condensation of glycerol at elevated temperatures and from which fractions with the desired degree of condensation can be obtained if desired by distillation methods.
Also suitable are polyglycerols obtained by other methods, e.g. from epichlorohydrin or glycidol.
Commercial polyglycerols can be obtained from companies like Solvay, Spiga Nord, Daicel or Lonza.
6 In the polyglycerol partial esters according to the invention, from 30 to 75%, preferably from 50 to 65%, of the hydroxyl groups of the polyglycerol are esterified. They are initially esterified to a degree of esterification of from 25 to 60%, preferably from 35 to 50%, using fatty acid and in a second step, using dicarboxylic acids to an overall degree of esterification of from 30 to 75%, preferably from 50 to 65%. Through suitable selection of the hydrophilic and lipophilic molecular proportions, an HLB value of from 3 to 7 is aimed at in order to obtain favorable products.
The HLB value is a measure of the degree to which the molecule is hydrophilic or lipophilic, determined by calculating values for the different regions of the molecule.
For the purpose of the present invention, the HLB value of the polyglycerol partial esters is calculated as follows:
HLB = (mp/ (mp+ma))*20, where mp is the mass of polyglycerol, and ma is the mass of carboxylic acid mixture comprising mono-, di- and polycarboxylic acids as well as polyhydroxy fatty acids used in the synthesis of the polyglycerol ester. For example, esterification of 100 g polyglycerol with 90 g mono-carboxylic acid and 10 g dicarboxylic acid would result in an HLB of (100 g 1(90 g + 10 g +
100 g) )*20 = 10, independent of the degree of polymerization of the polyglycerol and the type of carboxylic acids used.
For the present invention it is essential that the polyglycerol backbone of the polyglycerol partial ester comprises an average degree of polymerization of from 2 to 8, preferred from 2.5 to 6, particularly preferred from 3 to 4.5. A suitable method for determining the oligomer distribution of the polyglycerol in a given polyglycerol partial ester comprises hydrolysis or alcoholysis of the partial ester, separation of the resulting polyglycerol from the formed carboxylic acid compounds, and analysis by gas chromatography after derivatization.
The polyglycerol partial esters according to the invention can be prepared in a manner known per se by heating the reaction components and removing the resultant water of reaction by distillation.
The reaction can be accelerated by means of acidic catalysts such as sulfonic acids, phosphoric acid or phosphorous acid or basic catalysts such as alkali metal or alkaline earth metal oxides or hydroxides, alcoholates or salts, or Lewis acids, such as tin salts,. However, the addition of a catalyst is not absolutely necessary. The polyglycerol partial esters are preferably prepared in a two-step process, which again is carried out in a manner known per se. In a first step, the polyglycerol is esterified using the monofunctional fatty acid or some of the fatty acid. After most, or all, of the fatty acid has reacted, the polyfunctional carboxylic acid is then added and the esterification reaction is continued. The progress of the reaction can be monitored, for example, via the water of reaction removed, by measuring the acid number or by infrared spectroscopy. In general, an acid number in the end product of <20, preferably <10, is desired.
Products with an acid number of <5 are particularly preferred. The acid number is measured according to DIN EN
ISO 2114.
The HLB value is a measure of the degree to which the molecule is hydrophilic or lipophilic, determined by calculating values for the different regions of the molecule.
For the purpose of the present invention, the HLB value of the polyglycerol partial esters is calculated as follows:
HLB = (mp/ (mp+ma))*20, where mp is the mass of polyglycerol, and ma is the mass of carboxylic acid mixture comprising mono-, di- and polycarboxylic acids as well as polyhydroxy fatty acids used in the synthesis of the polyglycerol ester. For example, esterification of 100 g polyglycerol with 90 g mono-carboxylic acid and 10 g dicarboxylic acid would result in an HLB of (100 g 1(90 g + 10 g +
100 g) )*20 = 10, independent of the degree of polymerization of the polyglycerol and the type of carboxylic acids used.
For the present invention it is essential that the polyglycerol backbone of the polyglycerol partial ester comprises an average degree of polymerization of from 2 to 8, preferred from 2.5 to 6, particularly preferred from 3 to 4.5. A suitable method for determining the oligomer distribution of the polyglycerol in a given polyglycerol partial ester comprises hydrolysis or alcoholysis of the partial ester, separation of the resulting polyglycerol from the formed carboxylic acid compounds, and analysis by gas chromatography after derivatization.
The polyglycerol partial esters according to the invention can be prepared in a manner known per se by heating the reaction components and removing the resultant water of reaction by distillation.
The reaction can be accelerated by means of acidic catalysts such as sulfonic acids, phosphoric acid or phosphorous acid or basic catalysts such as alkali metal or alkaline earth metal oxides or hydroxides, alcoholates or salts, or Lewis acids, such as tin salts,. However, the addition of a catalyst is not absolutely necessary. The polyglycerol partial esters are preferably prepared in a two-step process, which again is carried out in a manner known per se. In a first step, the polyglycerol is esterified using the monofunctional fatty acid or some of the fatty acid. After most, or all, of the fatty acid has reacted, the polyfunctional carboxylic acid is then added and the esterification reaction is continued. The progress of the reaction can be monitored, for example, via the water of reaction removed, by measuring the acid number or by infrared spectroscopy. In general, an acid number in the end product of <20, preferably <10, is desired.
Products with an acid number of <5 are particularly preferred. The acid number is measured according to DIN EN
ISO 2114.
7 The weight average molecular weight Mw of the claimed polyglycerol partial esters determined via SEC versus polymethylmethacrylate (PMMA) standard is in the range of 2,000 to 15,000 g/mol, preferably in the range of 4,000 to 10,000 g/mol, with a polydispersity index of 1.5 to 5, preferably 2 to 4.
The OH-number of the polyglycerol partial esters according to the present invention is in the range of 50 to 180 mg KOH/g, preferably 80 to 170 mg KOH/g and most preferred in the range of 110 to 150 mg KOH/g. The OH-number is measured according to DIN 53240-2.
For engine oils the organic polymeric friction reducing additive is present at levels of 0.2 to 5% by weight, preferably 0.3 to 3% by weight, and even more preferably 0.5 to 2% by weight in an automotive engine oil, based on the total weight of the lubricating oil composition.
Accordingly, a preferred embodiment of the present invention is directed to a lubricating oil composition, comprising (a) 0.2 to 5% by weight, preferably 0.3 to 3% by weight, even more preferably 0.5 to 2% by weight, of a polyglycerol partial ester, based on the total weight of the lubricating oil composition, (b) 85 to 99.8% by weight, preferably 87 to 99.7% by weight, even more preferably 88 to 99.5% by weight, of an apolar base stock selected from the group consisting of API Group II, Ill and IV and/or mixtures thereof, based on the total weight of the lubricating oil composition, and (c) 0 to 10% by weight of a polar ester oil of Group V according to the definition of the American Petroleum Institute (API), based on the total weight of the lubricating oil composition.
In a preferred embodiment (a), (b) and (c) add up to 100% by weight.
In addition to the polyglycerol partial esters in accordance with the invention, the lubricant oil compositions detailed herein may also comprise one or more further additive(s). These additives include viscosity index (VI) improvers, pour point depressants and dispersant inhibitor (DI) additives selected from the group consisting of dispersants, detergents, defoamers, corrosion inhibitors, antioxidants, antiwear and extreme pressure additives and further friction modifiers.
Suitable viscosity index improvers are, for example, polyalkyl(meth)acrylate polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrogenated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improvers.
The OH-number of the polyglycerol partial esters according to the present invention is in the range of 50 to 180 mg KOH/g, preferably 80 to 170 mg KOH/g and most preferred in the range of 110 to 150 mg KOH/g. The OH-number is measured according to DIN 53240-2.
For engine oils the organic polymeric friction reducing additive is present at levels of 0.2 to 5% by weight, preferably 0.3 to 3% by weight, and even more preferably 0.5 to 2% by weight in an automotive engine oil, based on the total weight of the lubricating oil composition.
Accordingly, a preferred embodiment of the present invention is directed to a lubricating oil composition, comprising (a) 0.2 to 5% by weight, preferably 0.3 to 3% by weight, even more preferably 0.5 to 2% by weight, of a polyglycerol partial ester, based on the total weight of the lubricating oil composition, (b) 85 to 99.8% by weight, preferably 87 to 99.7% by weight, even more preferably 88 to 99.5% by weight, of an apolar base stock selected from the group consisting of API Group II, Ill and IV and/or mixtures thereof, based on the total weight of the lubricating oil composition, and (c) 0 to 10% by weight of a polar ester oil of Group V according to the definition of the American Petroleum Institute (API), based on the total weight of the lubricating oil composition.
In a preferred embodiment (a), (b) and (c) add up to 100% by weight.
In addition to the polyglycerol partial esters in accordance with the invention, the lubricant oil compositions detailed herein may also comprise one or more further additive(s). These additives include viscosity index (VI) improvers, pour point depressants and dispersant inhibitor (DI) additives selected from the group consisting of dispersants, detergents, defoamers, corrosion inhibitors, antioxidants, antiwear and extreme pressure additives and further friction modifiers.
Suitable viscosity index improvers are, for example, polyalkyl(meth)acrylate polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrogenated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improvers.
8 Suitable pour point depressants are, for example, polyalkyl(meth)acrylate polymers.
Suitable dispersants are, for example, alkenyl succinimides, alkenyl succinate esters, alkenyl succinimides modified with other organic compounds, alkenyl succinimides modified by post-treatment with ethylene carbonate or boric acid, pentaerythritols, phenatesalicylates and their post-treated analogs, alkali metal or mixed alkali metal, alkaline earth metal borates, dispersions of hydrated alkali metal borates, dispersions of alkaline-earth metal borates, polyamide ashless dispersants and the like or mixtures of such dispersants.
Suitable detergents are, for example, metal detergents which include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, as for example barium, sodium, potassium, lithium, calcium, and magnesium. The most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from 20 to 450, neutral and overbased calcium phenates and sulfurized phenates having TBN of from 50 to 450 and neutral and overbased magnesium or calcium salicylates having a TBN of from 20 to 450.
Combinations of detergents, whether overbased or neutral or both, may be used as well.
Suitable defoamers are, for example, selected from the group consisting of alkyl (meth)acrylate polymers, silicone oil and dimethyl silicone polymers.
Suitable corrosion inhibitors are, in many cases, divided into antirust additives and metal passivators/deactivators. The antirust additives used may, inter alia, be sulphonates, for example petroleumsulphonates or (in many cases overbased) synthetic alkylbenzenesulphonates, e.g.
dinonylnaphthenesulphonates; carboxylic acid derivatives, for example lanolin (wool fat), oxidized paraffins, zinc naphthenates, alkylated succinic acids, 4-nonylphenoxy-acetic acid, amides and imides (N-acylsarcosine, imidazoline derivatives); amine-neutralized mono- and dialkyl phosphates;
morpholine, dicyclohexylamine or diethanolamine. The metal passivators/deactivators include benzotriazole, tolyltriazole, tolutriazole (such as Vanlube 887 or 887E), 2-mercaptobenzothiazole, dialkyl-2,5-dimercapto-1,3,4-thiadiazole; N,N'-disalicylideneethylenediamine, N,N'-disalicylidenepropylenediamine; zinc dialkyldithiophosphates and dialkyl dithiocarbamates.
Suitable anti-oxidants are, for example, phenol type (phenolic) oxidation inhibitors, such as 4,4'-methylene-bis(2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4'-bis(2-methy1-6-tert-butylphenol), 2,2'-methylene-bis( 4-methyl-6-tert-butyl-phenol), 4,4'butylidene-bis(3-methy1-6-tert-butylphenol), 4,4'-isopropylidene-bis(2,6-di-tertbutylphenol), 2,2'-methylene-bis(4-methy1-6-nonylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2,2'-methylene-bis(4-methy1-6-
Suitable dispersants are, for example, alkenyl succinimides, alkenyl succinate esters, alkenyl succinimides modified with other organic compounds, alkenyl succinimides modified by post-treatment with ethylene carbonate or boric acid, pentaerythritols, phenatesalicylates and their post-treated analogs, alkali metal or mixed alkali metal, alkaline earth metal borates, dispersions of hydrated alkali metal borates, dispersions of alkaline-earth metal borates, polyamide ashless dispersants and the like or mixtures of such dispersants.
Suitable detergents are, for example, metal detergents which include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, as for example barium, sodium, potassium, lithium, calcium, and magnesium. The most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from 20 to 450, neutral and overbased calcium phenates and sulfurized phenates having TBN of from 50 to 450 and neutral and overbased magnesium or calcium salicylates having a TBN of from 20 to 450.
Combinations of detergents, whether overbased or neutral or both, may be used as well.
Suitable defoamers are, for example, selected from the group consisting of alkyl (meth)acrylate polymers, silicone oil and dimethyl silicone polymers.
Suitable corrosion inhibitors are, in many cases, divided into antirust additives and metal passivators/deactivators. The antirust additives used may, inter alia, be sulphonates, for example petroleumsulphonates or (in many cases overbased) synthetic alkylbenzenesulphonates, e.g.
dinonylnaphthenesulphonates; carboxylic acid derivatives, for example lanolin (wool fat), oxidized paraffins, zinc naphthenates, alkylated succinic acids, 4-nonylphenoxy-acetic acid, amides and imides (N-acylsarcosine, imidazoline derivatives); amine-neutralized mono- and dialkyl phosphates;
morpholine, dicyclohexylamine or diethanolamine. The metal passivators/deactivators include benzotriazole, tolyltriazole, tolutriazole (such as Vanlube 887 or 887E), 2-mercaptobenzothiazole, dialkyl-2,5-dimercapto-1,3,4-thiadiazole; N,N'-disalicylideneethylenediamine, N,N'-disalicylidenepropylenediamine; zinc dialkyldithiophosphates and dialkyl dithiocarbamates.
Suitable anti-oxidants are, for example, phenol type (phenolic) oxidation inhibitors, such as 4,4'-methylene-bis(2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4'-bis(2-methy1-6-tert-butylphenol), 2,2'-methylene-bis( 4-methyl-6-tert-butyl-phenol), 4,4'butylidene-bis(3-methy1-6-tert-butylphenol), 4,4'-isopropylidene-bis(2,6-di-tertbutylphenol), 2,2'-methylene-bis(4-methy1-6-nonylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2,2'-methylene-bis(4-methy1-6-
9 cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butylphenol, 2,4-dimethy1-6-tert-butyl-phenol, 2,6-di-tert-1-dimethylamino-p-cresol, 2,6-di-tert-4-(N,N'dimethylamino-methylphenol), 4,4'-thiobis(2-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methy1-6-tert-butylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzy1)-sulfide, and bis(3,5-di-tert-buty1-4-hydroxybenzyl). Other types of oxidation inhibitors include alkylated diphenylamines (e.g., Irganox L-57 from BASF), metal dithiocarbamate (e.g., zinc dithiocarbamate) and methylenebis(dibutyldithiocarbamate).
Suitable antiwear additives are, for example, phosphates, phosphites, carbamates, esters, sulfur containing compounds and molybdenum complexes.
Suitable extreme pressure additives are, for example, zinc dialkyldithiophosphate (primary alkyl, secondary alkyl, and aryl type), sulfurized oils, diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, fluoroalkylpolysiloxane and lead naphthenate.
A second embodiment of the present invention is directed to an engine oil comprising the lubricating oil composition as described hereinbefore.
A third embodiment of the present invention is directed to a method of lubricating an engine using the lubricating oil composition as described hereinbefore.
A fourth embodiment of the present invention is directed to a method of reducing friction in an engine by applying/by the addition of the lubricating oil composition as described hereinbefore.
The invention has been illustrated by the following non-limiting examples.
Experimental Part Example 1: Polycarboxylic acid ester prepared from polyglycerol, isostearic acid, sebacic acid and poly(hydroxystearic acid) according to synthesis example 2 of EP 1 500 427 A mixture of isostearic acid (91.1 g, 0.320 mol) and poly(hydroxystearic acid) (141.7 g, 0.120 mol, acid number of 47 mg KOH/g) was esterified with polyglycerol (61.9 g, 0.121 mol, hydroxyl value of 950 mg KOH/g) at 240 C while nitrogen flowing through. After 2 h at this temperature, the acid number of the reaction mixture was <10. Then, the mixture was cooled to 130 C, sebacic acid (20.2 g, 0.100 mol) was added and the mixture was heated again to 240 C.
After 3 h at this temperature, a viscous product having an acid number of <5 was obtained.
Comparative Example 1: Polycarboxylic acid ester prepared from ethoxylated soybean oil, oleic acid and dimer acid A mixture of epoxidized soybean oil (300 g, 0.302 mol) with an oxirane-[0]
content of 6.3%, oleic acid (331 g, 1.18 mol) and dimer acid (57.5 g; 0.101 mol, comprising about 2%
monobasic acids, 5 about 96% dimer acids and about 2% trimer acids and higher polyacids) was heated to 240 C until the acid value was <10 mg KOH/g.
The structure of this polymer is different to polyglycerol partial ester according to the present invention and therefore not encompassed by the present invention.
Suitable antiwear additives are, for example, phosphates, phosphites, carbamates, esters, sulfur containing compounds and molybdenum complexes.
Suitable extreme pressure additives are, for example, zinc dialkyldithiophosphate (primary alkyl, secondary alkyl, and aryl type), sulfurized oils, diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, fluoroalkylpolysiloxane and lead naphthenate.
A second embodiment of the present invention is directed to an engine oil comprising the lubricating oil composition as described hereinbefore.
A third embodiment of the present invention is directed to a method of lubricating an engine using the lubricating oil composition as described hereinbefore.
A fourth embodiment of the present invention is directed to a method of reducing friction in an engine by applying/by the addition of the lubricating oil composition as described hereinbefore.
The invention has been illustrated by the following non-limiting examples.
Experimental Part Example 1: Polycarboxylic acid ester prepared from polyglycerol, isostearic acid, sebacic acid and poly(hydroxystearic acid) according to synthesis example 2 of EP 1 500 427 A mixture of isostearic acid (91.1 g, 0.320 mol) and poly(hydroxystearic acid) (141.7 g, 0.120 mol, acid number of 47 mg KOH/g) was esterified with polyglycerol (61.9 g, 0.121 mol, hydroxyl value of 950 mg KOH/g) at 240 C while nitrogen flowing through. After 2 h at this temperature, the acid number of the reaction mixture was <10. Then, the mixture was cooled to 130 C, sebacic acid (20.2 g, 0.100 mol) was added and the mixture was heated again to 240 C.
After 3 h at this temperature, a viscous product having an acid number of <5 was obtained.
Comparative Example 1: Polycarboxylic acid ester prepared from ethoxylated soybean oil, oleic acid and dimer acid A mixture of epoxidized soybean oil (300 g, 0.302 mol) with an oxirane-[0]
content of 6.3%, oleic acid (331 g, 1.18 mol) and dimer acid (57.5 g; 0.101 mol, comprising about 2%
monobasic acids, 5 about 96% dimer acids and about 2% trimer acids and higher polyacids) was heated to 240 C until the acid value was <10 mg KOH/g.
The structure of this polymer is different to polyglycerol partial ester according to the present invention and therefore not encompassed by the present invention.
10 Comparative Example 2: Polycarboxylic acid ester prepared from polyglycerol, isostearic acid and sebacic acid A mixture of 72 g isostearic acid and 11 g sebacic acid was esterified with 17 g polyglycerol (average degree of polymerization = 3) at 240 C while nitrogen flowing through. Reaction was cooled down when an acid number of 12 was reached.
The OH-value of this polymer is much lower than the favorable range according to the present invention.
Comparative Example 3:
Polymeric friction modifier Perfad TM 3006, which is commercially available by Croda Inc. (see US
2013/0079536, WO 2011/107739 Al for structure and Lube Magazine No. 120, April 2014, page 27 for physical properties).
The structure of this polymer is different to polyglycerol partial ester according to the present invention and therefore not encompassed by the present invention.
Comparative Example 4:
Polymeric friction modifier Perfad TM 3057, diluted form of Perfad TM 3050, which is commercially available by Croda Sucursal Colombia (see US 2013/0079536, WO 2011/107739 Al for structure and Lube Magazine No. 120, April 2014, page 27 for physical properties).
The structure of this polymer is different to polyglycerol partial ester according to the present invention and therefore not encompassed by the present invention.
Table 1: physical data of examples and comparative examples HLB value acid number OH-number Mn Mw [mg KOH/g] [mg KOH/g] [g/mol] [g/mol]
Ex 1 ¨5 <5 125-145 2600 6100 Comp. Ex 1 9 24 4600 16000 Comp. Ex. 2 - 12 10-20 3200 10600 Comp. Ex. 3 - 1.2 Comp. Ex. 4 - 4*)
The OH-value of this polymer is much lower than the favorable range according to the present invention.
Comparative Example 3:
Polymeric friction modifier Perfad TM 3006, which is commercially available by Croda Inc. (see US
2013/0079536, WO 2011/107739 Al for structure and Lube Magazine No. 120, April 2014, page 27 for physical properties).
The structure of this polymer is different to polyglycerol partial ester according to the present invention and therefore not encompassed by the present invention.
Comparative Example 4:
Polymeric friction modifier Perfad TM 3057, diluted form of Perfad TM 3050, which is commercially available by Croda Sucursal Colombia (see US 2013/0079536, WO 2011/107739 Al for structure and Lube Magazine No. 120, April 2014, page 27 for physical properties).
The structure of this polymer is different to polyglycerol partial ester according to the present invention and therefore not encompassed by the present invention.
Table 1: physical data of examples and comparative examples HLB value acid number OH-number Mn Mw [mg KOH/g] [mg KOH/g] [g/mol] [g/mol]
Ex 1 ¨5 <5 125-145 2600 6100 Comp. Ex 1 9 24 4600 16000 Comp. Ex. 2 - 12 10-20 3200 10600 Comp. Ex. 3 - 1.2 Comp. Ex. 4 - 4*)
11 Mn and Mw are measured via GPC using PMMA (polymethyl methacrylate) as standard *) value given for Perfad TM 3050; Perfad TM 3057 is a diluted form of Perfad All polymers were diluted in Nexbase 3043 which is a Group III oil according to the American Petroleum Institute (API). The final blends have a similar kinematic viscosity at 100 C (KVioo) of about 4.45 cSt.
For Comparative Examples 3 and 4 treat rates of 0.5% are recommended by the manufacturer.
For Comparative Examples 3 and 4 treat rates of 0.5% are recommended by the manufacturer.
12 Table 1: Viscosity values of the tested blends Comparative Example 1 [%wt] 1 Comparative Example 2 [%wt] 1 Comparative Example 3 [%wt] 0.5 Comparative Example 4 [%wt] 0.5 Example 1 [%wt] 1 Reference Nexbase 3043 [%wt] 99 99 99.5 99.5 99 KVioo mm2/s 4.49 4.45 4.48 4.43 4.48 (KVioo = Kinematic Viscosity @ 100 C) Determination of friction-reducing action:
The measurements of the coefficient of friction at 100 C were performed on a Mini Traction Machine (MTM) from PCS Instruments. The test consist of evaluating the friction level occurring in a lubricated contact formed by a steel ball and a steel disc. The speeds of the ball and the disc are driven independently. The ball is loaded and rubbed in rolling sliding conditions against the steel disc, the contact being fully immersed in oil.
For each sample, the test was performed in two steps:
1) Run In phase For this phase, the conditions described in Table 2 below have been applied, SRR referring to Sliding Roll Ratio. This parameter was maintained constant during the 2 hours testing and is defined as:
it/ Ball¨U Disci where U Ball ¨ U Disc represents the sliding speed and U the entrainment speed, given by U = (U Ball + U Disc)/2
The measurements of the coefficient of friction at 100 C were performed on a Mini Traction Machine (MTM) from PCS Instruments. The test consist of evaluating the friction level occurring in a lubricated contact formed by a steel ball and a steel disc. The speeds of the ball and the disc are driven independently. The ball is loaded and rubbed in rolling sliding conditions against the steel disc, the contact being fully immersed in oil.
For each sample, the test was performed in two steps:
1) Run In phase For this phase, the conditions described in Table 2 below have been applied, SRR referring to Sliding Roll Ratio. This parameter was maintained constant during the 2 hours testing and is defined as:
it/ Ball¨U Disci where U Ball ¨ U Disc represents the sliding speed and U the entrainment speed, given by U = (U Ball + U Disc)/2
13 Table 2: test parameters for run in phase Test Rig MTM 2 von PCS Instruments Disc Highly polished stainless Steel AISI 52100 Disc diameter 46 mm Ball Highly polished stainless Steel AISI 52100 Ball diameter 19.05 mm Mean Speed 100 mm/s Temperature 100 C
Duration 2 hours Load 30N
SRR 50%
2) Stribeck curve evaluation A Stribeck was then obtained by measuring the friction coefficient under the conditions shown in Table 3.
Table 3: conditions for Stribeck curve evaluation Test Rig MTM 2 von PCS Instruments Disc Highly polished stainless Steel AISI 52100 Disc diameter 46 mm Ball Highly polished stainless Steel AISI 52100 Ball diameter 19.05 mm Mean Speed from 5 to 2500 mm/s Temperature 100 C
Load 30N
SRR 50%
The Stribeck curves are plotted in Figure 1. The curve NB3043-Ref refers to the formulation containing 100% of Group III oil named Nexbase 3043.
Figure 1: Stribeck curve measurements after two hours of run in phase To express in % the friction reduction obtained by working Example 1, a quantifiable result can be expressed as a number is obtained as follows:
Integration of the friction value curves in the range of sliding speed 0.005-2.5 m/s using the trapezoidal rule. The area corresponds to the "total friction" over the entire speed range examined.
The smaller the area, the greater the friction-reducing effect of the polymer examined.
Duration 2 hours Load 30N
SRR 50%
2) Stribeck curve evaluation A Stribeck was then obtained by measuring the friction coefficient under the conditions shown in Table 3.
Table 3: conditions for Stribeck curve evaluation Test Rig MTM 2 von PCS Instruments Disc Highly polished stainless Steel AISI 52100 Disc diameter 46 mm Ball Highly polished stainless Steel AISI 52100 Ball diameter 19.05 mm Mean Speed from 5 to 2500 mm/s Temperature 100 C
Load 30N
SRR 50%
The Stribeck curves are plotted in Figure 1. The curve NB3043-Ref refers to the formulation containing 100% of Group III oil named Nexbase 3043.
Figure 1: Stribeck curve measurements after two hours of run in phase To express in % the friction reduction obtained by working Example 1, a quantifiable result can be expressed as a number is obtained as follows:
Integration of the friction value curves in the range of sliding speed 0.005-2.5 m/s using the trapezoidal rule. The area corresponds to the "total friction" over the entire speed range examined.
The smaller the area, the greater the friction-reducing effect of the polymer examined.
14 The percentage friction reductions calculated therefrom in relation to the reference oil are compiled in Table 4 below.
Table 4: Quantitative evaluation of the reduction in friction Comp. Comp. Comp. Comp.
Reference Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Area in 99.239 51.079 62.675 71.354 65.109 86.581 mm/s reduction in friction relative to 0 48.53 36.84 28.10 34.39 12.75 reference [0/0]
The data in Table 4 and Figure 1 show clearly that the inventive polymers have a much better effect with regard to the reduction in friction than the corresponding comparative polymers of the prior art using different chemistry. The effect is even more pronounced in the low speed regime as revealed in Table 5 below.
Since the low speeds are of particular economic interest for the use of the lubricant compositions in accordance with the, Table 5 shows the integration data of the friction value curves within the sliding speed range from 0.005 to 0.090 m/s.
The areas determined and the percentage reductions in friction calculated therefrom in relation to the reference oil are compiled in Table 5 in an analogous manner to Table 4.
Table 5: Quantitative evaluation of the reduction in friction at low frequency (from 0.005 to 0.090 m/s) Comp. Comp. Comp. Comp.
Reference Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Area 7.863 1.855 4.429 5.464 3.405 4.025 [mm/s]
Comp. Comp. Comp. Comp.
Reference Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 reduction in friction relative to reference in 0 76.41 43.67 30.51 56.70 48.81 low speed regime [0/0]
The data in Table 5 show clearly that the inventive polymers have a much better effect once again with regard to the reduction in friction than the corresponding comparative polymers of the prior art.
5 Compared to the results as shown in Table 4, it is found that the friction-increasing action of lubricant composition for use in accordance with the invention is very clearly marked specifically within the range of low sliding speeds.
Table 4: Quantitative evaluation of the reduction in friction Comp. Comp. Comp. Comp.
Reference Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Area in 99.239 51.079 62.675 71.354 65.109 86.581 mm/s reduction in friction relative to 0 48.53 36.84 28.10 34.39 12.75 reference [0/0]
The data in Table 4 and Figure 1 show clearly that the inventive polymers have a much better effect with regard to the reduction in friction than the corresponding comparative polymers of the prior art using different chemistry. The effect is even more pronounced in the low speed regime as revealed in Table 5 below.
Since the low speeds are of particular economic interest for the use of the lubricant compositions in accordance with the, Table 5 shows the integration data of the friction value curves within the sliding speed range from 0.005 to 0.090 m/s.
The areas determined and the percentage reductions in friction calculated therefrom in relation to the reference oil are compiled in Table 5 in an analogous manner to Table 4.
Table 5: Quantitative evaluation of the reduction in friction at low frequency (from 0.005 to 0.090 m/s) Comp. Comp. Comp. Comp.
Reference Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Area 7.863 1.855 4.429 5.464 3.405 4.025 [mm/s]
Comp. Comp. Comp. Comp.
Reference Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 reduction in friction relative to reference in 0 76.41 43.67 30.51 56.70 48.81 low speed regime [0/0]
The data in Table 5 show clearly that the inventive polymers have a much better effect once again with regard to the reduction in friction than the corresponding comparative polymers of the prior art.
5 Compared to the results as shown in Table 4, it is found that the friction-increasing action of lubricant composition for use in accordance with the invention is very clearly marked specifically within the range of low sliding speeds.
Claims (14)
1. Lubricating oil composition comprising (a) 0.2 to 5% by weight of polyglycerol partial esters, based on the total weight of the lubricating oil composition, characterized in that the polyglycerol partial esters are obtainable by esterification of a polyglycerol mixture with (i) polyfunctional carboxylic acids and (ii) saturated or unsaturated, linear or branched fatty acids and/or (ii) poly(hydroxystearic acid), wherein the degree of esterification of the polyglycerol mixture is between 30 and 75% of the OH groups;
(b) 85 to 99.8% by weight of an apolar base stock selected from the group consisting of API Group II, Ill and IV and/or mixtures thereof, based on the total weight of the lubricating oil composition; and (c) 0 to 10% by weight of a polar ester oil of Group V according to the definition of the American Petroleum Institute (API), based on the total weight of the lubricating oil composition.
(b) 85 to 99.8% by weight of an apolar base stock selected from the group consisting of API Group II, Ill and IV and/or mixtures thereof, based on the total weight of the lubricating oil composition; and (c) 0 to 10% by weight of a polar ester oil of Group V according to the definition of the American Petroleum Institute (API), based on the total weight of the lubricating oil composition.
2. The lubricating oil composition according to claim 1, characterized in that the polyglycerol has a mean degree of condensation of from 3 to 6.
3. The lubricating oil composition according to claim 1 or 2, characterized in that the fatty acids are saturated or unsaturated, linear or branched having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
4. The lubricating oil composition according to claim 1, 2 or 3, characterized in that the saturated fatty acids are selected form the group consisting of caprylic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, arachidic acid, behenic acid, 12-hydroxy stearic acid and mixtures thereof.
5. The lubricating oil composition according to claim 1, 2, 3 or 4, characterized in that the unsaturated fatty acids are selected from the group consisting of hexadecenoic acids, octadecenoic acids, eicosenoic acids, docosenoic acids, octadecadienoic acids, octadecatrienoic acids, ricinoleic acid and mixtures thereof.
6. The lubricating oil composition according to claim 1, 2, 3, 4 or 5, characterized in that the polyfunctional carboxylic acids have 4 to 54 carbon atoms, preferably 6 to 12 carbon atoms, and a mean functionality of from 2 to 2.5.
7. The lubricating oil composition according to claim 1, 2, 3, 4, 5 or 6, characterized in that the polyfunctional carboxylic acids are aliphatic dicarboxylic acids which are selected from the group consisting of malonic acid, succinic acid, fumaric acid, maleic acid, dimethylglutaric acid, adipic acid, trimethyladipic acid, azelaic acid, sebacic acid, dodecanedioic acid and their anhydrides
8. The lubricating oil composition according to claim 1, 2, 3, 4, 5, 6 or 7, characterized in that the polyglycerol partial esters have HLB values of from 3 to 7.
9. The lubricating oil composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8, characterized in that the polyglycerol partial esters have an OH-number in the range of 50 to 180 mg KOH/g.
10. The lubricating oil composition according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9, characterized in that it additionally comprises one or more further additive(s).
11. The lubricating oil composition according to claim 10, characterized in that the one or more additional additive(s) is selected from the group consisting of viscosity index (VI) improvers, pour point depressants, dispersants, detergents, defoamers, corrosion inhibitors, antioxidants, antiwear and extreme pressure additives and friction modifiers.
12. The lubricating oil composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, characterized in that the polyglycerol partial esters have a weight-average molecular weight of 2,000 to 15,000 g/mol, preferably 4,000 to 10,000 g/mol.
13. A method of lubricating an engine using the lubricating oil composition according to any one of claims 1 to 12.
14. A method of reducing friction in an engine by applying the lubricating oil composition according to any one of claims 1 to 12.
Applications Claiming Priority (3)
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EP15178187.9 | 2015-07-24 | ||
EP15178187 | 2015-07-24 | ||
PCT/EP2016/065904 WO2017016825A1 (en) | 2015-07-24 | 2016-07-06 | Use of polyclycerin esters as friction modifiers in lubricant formulations |
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CA2993333A Abandoned CA2993333A1 (en) | 2015-07-24 | 2016-07-06 | Use of polyclycerin esters as friction modifiers in lubricant formulations |
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US (1) | US20180216023A1 (en) |
EP (1) | EP3325582A1 (en) |
JP (1) | JP6761851B2 (en) |
KR (1) | KR20180032622A (en) |
CN (1) | CN107849476A (en) |
BR (1) | BR112018001430A2 (en) |
CA (1) | CA2993333A1 (en) |
MX (1) | MX2018000786A (en) |
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CN109476949B (en) | 2016-07-19 | 2021-06-08 | 赢创运营有限公司 | Use of polyol esters for producing porous plastic coatings |
US11807603B2 (en) | 2016-08-18 | 2023-11-07 | Evonik Operations Gmbh | Cross-linked polyglycerol esters |
DE102017009541A1 (en) | 2017-10-13 | 2019-04-18 | Daimler Ag | Valve drive for an internal combustion engine of a motor vehicle |
EP3914677A2 (en) * | 2019-01-23 | 2021-12-01 | Peter Greven GmbH & Co. KG | Estolide esters and use thereof as a base oil in lubricants |
TWI793346B (en) | 2019-07-10 | 2023-02-21 | 百達精密化學股份有限公司 | Liquid organic wear modifier |
JP2022158116A (en) * | 2021-04-01 | 2022-10-17 | Eneos株式会社 | Lubricant composition |
CN113512460B (en) * | 2021-08-13 | 2022-10-21 | 福建科恩优路润滑油有限公司 | Anti-wear clean type vehicle lubricating oil and preparation process thereof |
CN113801310B (en) * | 2021-09-24 | 2023-03-21 | 广东产品质量监督检验研究院(国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室) | Three-component catalytic initiation system catalyst and application thereof |
CN114106627B (en) * | 2021-12-14 | 2022-05-17 | 广州市印道理印刷有限公司 | Environment-friendly water-based ink and preparation method and application thereof |
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JPS53102307A (en) * | 1977-02-18 | 1978-09-06 | Nippon Oil & Fats Co Ltd | Lubricating oil composition |
US4153464A (en) * | 1977-09-12 | 1979-05-08 | Emery Industries, Inc. | Prevention of water staining of aluminum |
JP2579502B2 (en) * | 1987-11-26 | 1997-02-05 | 日清製油株式会社 | Lubricant |
CA2170503C (en) * | 1994-07-05 | 2005-08-16 | Noriyoshi Tanaka | Engine oil composition |
DE4444137A1 (en) * | 1994-12-12 | 1996-06-13 | Henkel Kgaa | Synthetic esters from alcohols and fatty acid mixtures from oleic acid-rich, low stearic acid vegetable oils |
US5698502A (en) * | 1996-09-11 | 1997-12-16 | Exxon Chemical Patents Inc | Polyol ester compositions with unconverted hydroxyl groups for use as lubricant base stocks |
DE19641604C1 (en) * | 1996-10-09 | 1998-03-12 | Goldschmidt Ag Th | Polyglycerol partial esters of fatty acids and polyfunctional carboxylic acids, their preparation and use |
EP0903399B1 (en) * | 1997-09-18 | 2007-02-14 | Ciba SC Holding AG | Lubricant compositions containing thiophosphoric and dithiophosphoric acid esters |
DE10333443A1 (en) * | 2003-07-23 | 2005-02-10 | Goldschmidt Ag | Emulsifier for low-viscosity W / O emulsions based on partially crosslinked polyglycerol esters of polyhydroxystearic acid |
EP2036963A1 (en) * | 2007-09-14 | 2009-03-18 | Cognis Oleochemicals GmbH | Lubricants for drilling fluids |
US20110237479A1 (en) * | 2008-11-05 | 2011-09-29 | The Lubrizol Corporation | Method of Lubricating an Internal Combustion Engine |
EP2345710A1 (en) * | 2010-01-18 | 2011-07-20 | Cognis IP Management GmbH | Lubricant with enhanced energy efficiency |
UA109139C2 (en) * | 2010-06-25 | 2015-07-27 | APPLICATIONS AND COMPOSITIONS | |
GB201317278D0 (en) * | 2013-09-30 | 2013-11-13 | Croda Int Plc | Gear oil composition |
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