EP0235929B1 - Overbased additives - Google Patents
Overbased additives Download PDFInfo
- Publication number
- EP0235929B1 EP0235929B1 EP19870300761 EP87300761A EP0235929B1 EP 0235929 B1 EP0235929 B1 EP 0235929B1 EP 19870300761 EP19870300761 EP 19870300761 EP 87300761 A EP87300761 A EP 87300761A EP 0235929 B1 EP0235929 B1 EP 0235929B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- sodium hydroxide
- moles
- sodium
- alkoxyalkanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000654 additive Substances 0.000 title description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 157
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 25
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 21
- 229910052708 sodium Inorganic materials 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 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 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- -1 amine salt Chemical class 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 150000008064 anhydrides Chemical class 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 239000010687 lubricating oil Substances 0.000 claims description 9
- 238000010533 azeotropic distillation Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000004703 alkoxides Chemical class 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 150000003388 sodium compounds Chemical class 0.000 claims description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- 239000002199 base oil Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- 230000001050 lubricating effect Effects 0.000 claims 2
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 235000019198 oils Nutrition 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 8
- 229940093475 2-ethoxyethanol Drugs 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 125000001183 hydrocarbyl group Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000158728 Meliaceae Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical class CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical class CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- OAAZUWWNSYWWHG-UHFFFAOYSA-N 1-phenoxypropan-1-ol Chemical class CCC(O)OC1=CC=CC=C1 OAAZUWWNSYWWHG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KDUGNDDZXPJVCS-UHFFFAOYSA-N 6-oxo-6-tridecoxyhexanoic acid Chemical compound CCCCCCCCCCCCCOC(=O)CCCCC(O)=O KDUGNDDZXPJVCS-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- AEVBUGHMKXBGBL-UHFFFAOYSA-N didecyl butanedioate Chemical compound CCCCCCCCCCOC(=O)CCC(=O)OCCCCCCCCCC AEVBUGHMKXBGBL-UHFFFAOYSA-N 0.000 description 1
- WMDDQWGAOSOSAB-UHFFFAOYSA-N didecyl nonanedioate Chemical compound CCCCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCCCC WMDDQWGAOSOSAB-UHFFFAOYSA-N 0.000 description 1
- FFPZYKQFAKXVSW-UHFFFAOYSA-N didecyl pentanedioate Chemical compound CCCCCCCCCCOC(=O)CCCC(=O)OCCCCCCCCCC FFPZYKQFAKXVSW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RRLWYLINGKISHN-UHFFFAOYSA-N ethoxymethanol Chemical compound CCOCO RRLWYLINGKISHN-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 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
- 150000002334 glycols Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VHWYCFISAQVCCP-UHFFFAOYSA-N methoxymethanol Chemical compound COCO VHWYCFISAQVCCP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- CZMAXQOXGAWNDO-UHFFFAOYSA-N propane-1,1,2-triol Chemical compound CC(O)C(O)O CZMAXQOXGAWNDO-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- PWCSGRFTKCPNJK-UHFFFAOYSA-N sodium;1-ethoxyethanolate Chemical compound [Na+].CCOC(C)[O-] PWCSGRFTKCPNJK-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
- C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
Definitions
- This invention relates to overbased additives containing sodium sulphonate.
- Lubricants often need the presence of detergents and there is an increasing need for detergent additives which have high basicity, especially automotive lubricants where their high basicity neutralises acids formed during operation of the engine.
- This invention relates to such high basicity or "overbased" additives which contain colloidally dispersed carbonates and include the presence of sodium sulphonate.
- an oil solution of a highly basic sodium sulphonate is prepared by a process which comprises:
- step (a) in the case when the alkoxyalkanol and sulphonic acid are the only species present capable of reacting with sodium hydroxide to form water in steps (a) and (b) the azeotrope is removed in step (a) until the sum of number of moles of sodium hydroxide in excess of that reacted in step (a) plus the number of moles of organic sulphonic acid to be added to step (b) is not more than the number of moles of sodium hydroxide reacted in step (a).
- a + C ⁇ B (wherein A is the number of moles of sodium hydroxide in excess of that reacted with alkoxyalkanol in step (a), B is the number of moles of sodium hydroxide reacted with alkoxyalkanol in step (a) and C is the number of moles of sulphonic acid added in step (b)).
- a + C ⁇ B and sufficient water is not formed to hydrolyse the formed sodium alkoxyalkoxide, then more water, preferably as an alkoxyalkanol/water mixture, is added after step (c) and before step (d) to hydrolyse any remaining alkoxyalkoxide.
- additional reactants such as further surfactants may be added to the process, and in the event that these additional reactants are capable of reacting with sodium hydroxide to form water the azeotrope may be carried further to form more alkoxide provided that : where D n is the number of moles of additional reactant of which 1 mole is capable of reacting with sodium hydroxide to form n moles of water in excess of the amount of water produced if that sodium hydroxide were carbonated.
- n y-x/2 where x moles of sodium hydroxide react with one mole of the additional reactant to produce y moles of water.
- TBN total base numbers
- One of the starting materials is sodium hydroxide and the normal commercial grade can be used.
- the solvent can be, for example, any aliphatic, naphthenic or aromatic solvent provided it forms an azeotrope with water; in particular, n-hexane, n-heptane, n-octane, n-dodecane, benzene, xylene, toluene, white spirit, naphtha or isoparaffins.
- hydrocarbon solvent usually, it is a hydrocarbon solvent but it could be a halogenated hydrocarbon, e.g. chlorobenzene.
- halogenated hydrocarbon e.g. chlorobenzene.
- the most preferred solvents are toluene and xylene.
- aromatic substituted alkoxyalkanols could be used, it is preferable to use an aliphatic alkoxyalkanol, expecially those containing 2 to 10 carbon atoms per molecule.
- Suitable examples of aliphatic alkoxyalkanols are methoxy methanol, methoxy ethanol, methoxy isopropanol, ethoxy methanol, 2-ethoxy ethanol, 2-butoxy-ethanol or propylene glycol ethers, e.g. methoxy propanols, butoxy propanols or phenoxy propanols.
- the amount of alkoxyalkanol employed in the process per mole of sodium hydroxide will usually be in the range of 0.5 to 50, preferably 0.75 to 2.
- the organic sulphonic acids are usually obtained from the sulphonation of natural hydrocarbons or synthetic hydrocarbons; e.g. a mahogany or petroleum alkyl sulphonic acid; an alkyl sulphonic acid or an alkaryl sulphonic acid.
- Such sulphonic acids are obtained by treating lubricating oil basestocks with concentrated or fuming sulphuric acid to produce oil-soluble "mahogany" acids or by sulphonating alkylated aromatic hydrocarbons.
- Sulphonates derived from synthetic hydrocarbons include those prepared by the alkylation of aromatic hydrocarbons with olefins or olefin polymers; e.g. C15-C30 polypropenes or polybutenes.
- sulphonic acids of alkyl benzenes, alkyl toluenes or alkyl xylenes which may have one or more alkyl groups wherein each group, which may be straight or branched, preferably contains at least 12 carbon atoms.
- the preferred sulphonic acids have molecular weights of from 300 to 1000, for example, between 400 and 800, e.g. about 500. Mixture of these sulphonic acids may also be used.
- the mole ratio of sulphonic acid to sodium hyroxide is usually between 1:5 and 1:36, preferably 1:10 to 1:25.
- a sulphonic acid e.g. an alkyl benzene sulphonic acid
- an alkyl benzene sulphonic acid may be sufficient to act as the surfactant for the overbased material of the invention, especially when it has a relatively high molecular weight aliphatic chain e.g. of molecular weight more than about 400, very often it is desirable to include another surfactant having a long aliphatic chain usually with a molecular weight of 700 or greater, for example about 900, in the reaction mixture.
- This additional surfactant is a dicarboxylic acid or anhydride, or an ester, amide imide, amine salt or ammonium salt of a dicarboxylic acid and as such include those represented by the formulae: where R1 and R2 are hydrogen or optionally-substituted hydrocarbyl groups of at least 30 carbon atoms provided they are not both hydrogen, m and n are zero or integers, R3 and R4 are hydrogen or hydrocarbyl groups and R5 and R6 are hydrocarbyl groups.
- R2 be hydrogen and that m and n be zero or a small integer, e.g. 1 or 2.
- acids or anhydrides are the preferred surfactant.
- R3, R4, R5 and R6 are alkyl groups, especially a C1 to C5 alkyl group, for example, methyl, ethyl or propyl.
- the ester could be derived from a glycol, in which case R3 and R4 would not be separate hydrocarbyl groups, but instead, the residue of a glycol, for example, ethylene glycol or propylene glycol.
- the most preferred compounds are those where R1 contains 40 to 200 carbon atoms and where R1 has no atoms other than carbon, hydrogen and halogen, and especially when it only contains carbon and hydrogen atoms, i.e., it is a hydrocarbyl group.
- R1 contains 40 to 200 carbon atoms and where R1 has no atoms other than carbon, hydrogen and halogen, and especially when it only contains carbon and hydrogen atoms, i.e., it is a hydrocarbyl group.
- Preferred hydrocarbyl groups are aliphatic groups.
- the acid, anhydride, ester, amide, imide, amine salt or ammonium salt is preferably substantially saturated, but the substituent group, for example, the group R1, may be unsaturated.
- the substituent group be a polymer of a monolefin, for example, a C2 to C5 monolefin, such as polyethylene, polypropylene or polyisobutene. Such polymers will usually have only one double bond so that they could be regarded as predominantly saturated, especially since they must have at least 30 carbon atoms.
- the most preferred acid or anhydride is one of the formula: especially where R1 is polyisobutenyl, i.e. a polyisobutenyl succinic acid or anhydride, preferably where R1 has 30 to 200 carbon atoms, especially 45 to 60 carbon atoms.
- Such anhydrides are frequently known as PIBSA.
- the molar ratio of organic sulphonic acid to the acid, amide, imide, amine salt, ammonium salt, anhydride or ester can vary but is usually between 20:1 and 2:1, e.g. between 15:1 and 4:1.
- the first step of the process is the addition of sodium hydroxide to the mixture of alkoxyalkanol and solvent and reaction of a part of the sodium hydroxide to form the sodium alkoxyalkoxide.
- the reaction mixture is heated so that the temperature is slowly increased and the water formed by the reaction to form sodium alkoxyalkoxide is removed as an azeotrope with the solvent and the alkoxyalkanol. Little solvent is normally removed in the azeotrope, and the reaction vessel may be equipped with a condenser so that substantially all solvent is returned to the reaction vessel.
- the recovered azeotrope then comprises water and alkoxyalkanol with substantially no solvent.
- This heating which in effect is azeotropic distillation effectively controls the amount of sodium hydroxide converted to alkoxyalkoxide since the removal of water drives the alkoxyalkoxide-forming reaction.
- the extent to which this reaction is driven and formed water is removed is critical since surprisingly it has been found that excess water in the system tends to result in a hazy and unsatisfactory product.
- a surprising and effective means of preventing this haze formation is by using the alkoxyalkoxide formation and subsequent hydrolysis as a control of the water in the system. By forming alkoxyalkoxide in such an amount that the water required to hydrolyse it is at least equal to the water generated in the remaining steps of the process, effective control over haze may be obtained.
- azeotropic distillation takes at least an hour, and times of from 1.5 to 2 hours are typical for small scale operations.
- the organic sulphonic acid and optionally the dicarboxylic acid, anhydride or ester, amide, imide, amine salt or ammonium salt are added preferably at 50°C to 70°C to the reaction mixture which may then be heat-soaked, e.g. at a temperature of about 80°C to 100°C.
- the sulphonic acid and dicarboxylic acid, anhydride, ester, amide, imine, amine salt or ammonium salt are usually introduced as solutions in diluent oil, e.g. an aliphatic or aromatic hydrocarbon.
- the purpose of this heat soaking is to effect neutralisation of the organic sulphonic acid, and if used, the dicarboxylic acid, anhydride, monoamine salt or monoammonium salt by the sodium hydroxide.
- the time taken for this heat soaking is usually from 10 to 30 minutes, e.g. about 20 minutes.
- the amount of sodium hydroxide and organic sulphonic acid are related and dependent on the degree of reaction with alkoxyalkanol in step (a) as discussed above.
- a part of the sodium hydroxide reacts with the alkoxyalkanol according to the equation NaOH + ROH ----> NaOR + H2O (where R is an alkoxyalkyl group).
- B moles of sodium hydroxide react with alkoxyalkanol in step (a) in this and B moles of water are formed and removed as azeotrope, while there is an excess of A moles of sodium hydroxide unreacted in step (a).
- step (b) If C moles of organic sulphonic acid are introduced in step (b) to react with a further part of the sodium hydroxide then C moles of water are formed and A + C ⁇ B to ensure that excess water is not formed which would give rise to haze.
- the reaction of sulphonic acids with sodium hydroxide may be represented: R ⁇ SO2OH + NaOH ----> R ⁇ SO2ONa + H2O (where R ⁇ is the organic group of the sulphonic acid). If a further surfactant is used, such as dicarboxylic acid or anhydride which also reacts with sodium hydroxide to form water than an appropriate adjustment must be made such that:
- n 1 and A + C + 2D2 ⁇ B where D2 is the number of moles of dicarboxylic acid, mono-amine or salt.
- n 0 and A + C ⁇ B, that is independent of the number of moles (D0) of the anhydride present.
- carbon dioxide is introduced to react with the basic sodium compounds in the reaction mixture which is preferably maintained at a temperature from ambient to the reflux temperature of the mixture, typically 120°C, more preferably between 80°C and 100°C, for example, about 90°C.
- the preferred amount of carbon dioxide which is blown into or injected into the reaction mixture is 90% to 115%, e.g. about 105% of the theoretical amount required to react with available basic sodium compounds.
- carbon dioxide is blown in until no more carbon dioxide is absorbed, e.g. when the gas inlet and exit rates, as measured on gas rotameters are the same. Rates are usually chosen to introduce the carbon dioxide over 2 to 4 hours, e.g. about 3 hours.
- the basic sodium compounds which will react with the carbon dioxide include the previously unreacted sodium hydroxide which will react: 2 NaOH + CO2 ----> Na2CO3 + H2O to form the desired overbased product.
- sodium alkoxyalkoxide formed in step (a) will be hydrolysed and carbonated to form additional sodium carbonate in the product according to the overall reaction: 2 NaOR + H2O + CO2 ----> Na2CO3 + 2 ROH in which the water for the hydrolysis (on the left hand side of the reaction) is obtained from the reaction of sulphonic acid with sodium hydroxide, the reaction of carbon dioxide with sodium hydroxide and, if present, the reaction of additional materials such as further surfactants with sodium hydroxide.
- This overall carbonation and hydrolysis may taken place in stages.
- Either the alkoxyalkoxide may be first hydrolysed: RONa + H2O ----> ROH + Na OH for example in step (b) and then the formed sodium hydroxide subsequently carbonated, or the alkoxyalkoxide may be carbonated in step (c) according to the reaction: RONa + CO2 ----> RO-COONa and the carbonated alkoxyalkoxide subsequently hydrolysed: 2 RO-COONa + H2O ----> 2 ROH + CO2 + Na2CO3 or a combination of these steps may take place giving the overall reaction set out above.
- water may be added, preferably as a mixture of water and alkoxyalkanol, to convert the residual carbonated sodium alkoxyalkoxide to sodium carbonate.
- Water or any mixture of water and alkoxyalkanol can be used preferably between 1:6 and 1:2 water:alkoxyalkanol (by weight).
- the water/alkoxyalkanol mixture is usually slowly added to the reaction mixture to convert the residual carbonated sodium alkoxyalkoxide to sodium carbonate, alkoxyalkanol and carbon dioxide and this addition continues until the evolution of carbon dioxide ceases.
- the next step in the process is to remove the alkoyalkanol and solvent by distillation. Usually, this takes place by atmospheric distillation typically at a temperature of about 180°C, optionally followed by distillation under reduced pressure whence the residual solvent and alkoxyalkanol will be removed.
- solid contaminants may be removed from the product preferably by filtration or centrifuging.
- the desired product is the filtrate or centrifugate.
- the desired product is a solution in oil and therefore base oil is added to the process in step (b), (c) or (d). Most preferably the oil is added with the sulphonic acid in step (b).
- Base oils used in the process are preferably lubricating oils as described hereinafter.
- the process of the invention enables a high quality, high TBN sodium sulphonate product to be obtained in good yields (e.g. 95% + of theoretical) with reduced amounts of material losses in sludge and/or sediment and reduced problems in waste disposal which can arise when large amounts of sludge or flocculent material are produced.
- the process of the invention in particular provides a means of preparing a preferred product with a TBN of at least 250, preferably 250 to 600 mg (KOH)/g, more preferably 350 to 500, specifically in the region of 400 mg (KOH)/g.
- the overbased additive of this invention is suitable for use in oleaginous compositions such as fuels or lubricating oils for gasoline or diesel engines, both mineral and synthetic.
- the lubricating oil may be an animal, vegetable or mineral oil, for example, petroleum oil fractions ranging from naphthas or spindle oil to SAE 30, 40 or 50 lubricating oil grades, castor oil, fish oils or oxidised mineral oil.
- Suitable synthetic ester lubricating oils include diesters such as dioctyl adipate, dioctyl sebacate, didecyl azelate, tridecyl adipate, didecyl succinate, didecyl glutarate and mixtures thereof.
- the synthetic ester can be a polyester such as that prepared by reacting polyhydric alcohols such as trimethylolpropane and pentaerythritol with monocarboxylic acids such as butyric acid, caproic acid, caprylic acid and pelargonic acid to give the corresponding tri- and tetra-ester.
- complex esters may be used as base oils such as those formed by esterification reactions between a dicarboxylic acid, a glycol and an alcohol and/or a monocarboxylic acid.
- Blends of diesters with minor proportions of one or more thickening agents may also be used as lubricants.
- the amount of overbased detergent added to the lubricating oil should be a minor proporton, e.g. between 0.01% and 10% by weight, preferably between 0.1% and 5% by weight.
- the final lubricating oil may contain other additives according to the particular use for the oil.
- viscosity index improvers such as ethylene-propylene copolymers may be present as may ashless dispersants such as substituted succinic acid based dispersants, other metal containing dispersant additives, well known zinc dialkyldithio-phosphate antiwear additives, antioxidants, demulsifiers, corrosion inhibitors, extreme pressure additives and friction modifiers.
- the oils of the invention may contain ashless dispersant, a zinc dialkyl dithiophosphate and copper in an oil soluble form (preferably in an amount of 5 to 500 ppm copper) as antioxidant.
- the invention also includes an additive concentrate comprising an oil solution of an overbased sodium sulphonate of the invention comprising 10 to 90 wt %, preferably 40 to 60 wt % overbased sodium sulphonate (active matter) based on the weight of oil.
- the overbased material When used in fuels as a detergent or combustion improver the overbased material is used in minor proportions, e.g. between 0.01 and 10% by weight of the fuel.
- Example H This is a repeat of Example H except that only 20 grams of hydrolysis water is used and thus all the carbonated alkoxide was not converted to the carbonate. The product was very viscous and skinned on exposure to air, but Example H shows that by addition of the appropriate amount of water an excellent product may be prepared.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Lubricants (AREA)
Description
- This invention relates to overbased additives containing sodium sulphonate.
- Lubricants often need the presence of detergents and there is an increasing need for detergent additives which have high basicity, especially automotive lubricants where their high basicity neutralises acids formed during operation of the engine. This invention relates to such high basicity or "overbased" additives which contain colloidally dispersed carbonates and include the presence of sodium sulphonate.
- Various patents disclose processes for making overbased additives including those containing sodium sulphonates such as US 3489682, US4326972 and GB1481553 but few teach the necessity of using an alkoxyalkanol or of hydrolysing after the addition of carbon dioxide. Examples of prior art processes are found in GB1388021, GB1551820, GB2055885, GB2055886, US5346493, US3428561, US3437465, US3471403, and US3488284 which include references to alkoxide formation or the use of alkoxyalcohols in preparing overbased additives. Prior art processes tend to form sodium sulphonate products which are hazy due to instability of the colloid. We have surprisingly found that a careful balance of water in relation to the amount of sodium hydroxide used, which was not appreciated by the prior art, provides an excellent route to overbased sodium sulphonate suitable as fuel or lubricant additives.
- In accordance with this invention, an oil solution of a highly basic sodium sulphonate is prepared by a process which comprises:
- (a) heating sodium hydroxide with an alkoxyalkanol and a solvent to remove as an azeotrope with said alkyoxyalkanol and solvent a controlled amount of water formed in the reaction of a part of the sodium hydroxide with the alkoxyalkanol so as to form a mixture comprising unreacted sodium hydroxide and sodium alkoxyalkoxide
- (b) adding to the mixture an organic sulphonic acid so as to react with a part of basic sodium compounds therein and form the sodium salt of the sulphonic acid and water;
- (c) thereafter introducing carbon dioxide into the reaction mixture so as to react with the basic sodium compounds therein;
- (d) removing solvent by distillation; and
- (e) adding base oil to the process during one of steps (b), (c) and (d) so that the desired product is obtained,
- Thus, in the process of the invention in the case when the alkoxyalkanol and sulphonic acid are the only species present capable of reacting with sodium hydroxide to form water in steps (a) and (b) the azeotrope is removed in step (a) until the sum of number of moles of sodium hydroxide in excess of that reacted in step (a) plus the number of moles of organic sulphonic acid to be added to step (b) is not more than the number of moles of sodium hydroxide reacted in step (a). That is, A + C ≦ B (wherein A is the number of moles of sodium hydroxide in excess of that reacted with alkoxyalkanol in step (a), B is the number of moles of sodium hydroxide reacted with alkoxyalkanol in step (a) and C is the number of moles of sulphonic acid added in step (b)). In the case where A + C < B and sufficient water is not formed to hydrolyse the formed sodium alkoxyalkoxide, then more water, preferably as an alkoxyalkanol/water mixture, is added after step (c) and before step (d) to hydrolyse any remaining alkoxyalkoxide.
- As discussed in more detail hereinafter additional reactants, such as further surfactants may be added to the process, and in the event that these additional reactants are capable of reacting with sodium hydroxide to form water the azeotrope may be carried further to form more alkoxide provided that :
where Dn is the number of moles of additional reactant of which 1 mole is capable of reacting with sodium hydroxide to form n moles of water in excess of the amount of water produced if that sodium hydroxide were carbonated. Thus n = y-x/2 where x moles of sodium hydroxide react with one mole of the additional reactant to produce y moles of water. As indicated where more than one reactant is present the product 2n.Dn is summed for all the reactants, thus - This process enables one to obtain highly basic sodium sulphonates having relatively high total base numbers (TBN) of at least 250 mg KOH/g. TBN is a measure of basicity of a product and is measured by the method laid down in ASTM D2896.
- One of the starting materials is sodium hydroxide and the normal commercial grade can be used.
- The solvent can be, for example, any aliphatic, naphthenic or aromatic solvent provided it forms an azeotrope with water; in particular, n-hexane, n-heptane, n-octane, n-dodecane, benzene, xylene, toluene, white spirit, naphtha or isoparaffins.
- Usually, it is a hydrocarbon solvent but it could be a halogenated hydrocarbon, e.g. chlorobenzene. The most preferred solvents are toluene and xylene.
- Although aromatic substituted alkoxyalkanols, could be used, it is preferable to use an aliphatic alkoxyalkanol, expecially those containing 2 to 10 carbon atoms per molecule. Suitable examples of aliphatic alkoxyalkanols are methoxy methanol, methoxy ethanol, methoxy isopropanol, ethoxy methanol, 2-ethoxy ethanol, 2-butoxy-ethanol or propylene glycol ethers, e.g. methoxy propanols, butoxy propanols or phenoxy propanols.
- The amount of alkoxyalkanol employed in the process per mole of sodium hydroxide will usually be in the range of 0.5 to 50, preferably 0.75 to 2.
- The organic sulphonic acids are usually obtained from the sulphonation of natural hydrocarbons or synthetic hydrocarbons; e.g. a mahogany or petroleum alkyl sulphonic acid; an alkyl sulphonic acid or an alkaryl sulphonic acid. Such sulphonic acids are obtained by treating lubricating oil basestocks with concentrated or fuming sulphuric acid to produce oil-soluble "mahogany" acids or by sulphonating alkylated aromatic hydrocarbons. Sulphonates derived from synthetic hydrocarbons include those prepared by the alkylation of aromatic hydrocarbons with olefins or olefin polymers; e.g. C₁₅-C₃₀ polypropenes or polybutenes. Also suitable are the sulphonic acids of alkyl benzenes, alkyl toluenes or alkyl xylenes, which may have one or more alkyl groups wherein each group, which may be straight or branched, preferably contains at least 12 carbon atoms. The preferred sulphonic acids have molecular weights of from 300 to 1000, for example, between 400 and 800, e.g. about 500. Mixture of these sulphonic acids may also be used.
- The mole ratio of sulphonic acid to sodium hyroxide is usually between 1:5 and 1:36, preferably 1:10 to 1:25.
- Although a sulphonic acid, e.g. an alkyl benzene sulphonic acid, may be sufficient to act as the surfactant for the overbased material of the invention, especially when it has a relatively high molecular weight aliphatic chain e.g. of molecular weight more than about 400, very often it is desirable to include another surfactant having a long aliphatic chain usually with a molecular weight of 700 or greater, for example about 900, in the reaction mixture.
- This additional surfactant is a dicarboxylic acid or anhydride, or an ester, amide imide, amine salt or ammonium salt of a dicarboxylic acid and as such include those represented by the formulae:
- It is preferred that R² be hydrogen and that m and n be zero or a small integer, e.g. 1 or 2. In general, acids or anhydrides are the preferred surfactant. However, if an ester, monoamide or ammonium salt is used, it is preferred that R³, R⁴, R⁵ and R⁶ are alkyl groups, especially a C₁ to C₅ alkyl group, for example, methyl, ethyl or propyl. If desired, however, the ester could be derived from a glycol, in which case R³ and R⁴ would not be separate hydrocarbyl groups, but instead, the residue of a glycol, for example, ethylene glycol or propylene glycol.
- The most preferred compounds are those where R¹ contains 40 to 200 carbon atoms and where R¹ has no atoms other than carbon, hydrogen and halogen, and especially when it only contains carbon and hydrogen atoms, i.e., it is a hydrocarbyl group. Preferred hydrocarbyl groups are aliphatic groups.
- The acid, anhydride, ester, amide, imide, amine salt or ammonium salt is preferably substantially saturated, but the substituent group, for example, the group R¹, may be unsaturated. In practice, it is preferred that the substituent group be a polymer of a monolefin, for example, a C₂ to C₅ monolefin, such as polyethylene, polypropylene or polyisobutene. Such polymers will usually have only one double bond so that they could be regarded as predominantly saturated, especially since they must have at least 30 carbon atoms.
-
- When such an acid, anhydride or ester is used, the molar ratio of organic sulphonic acid to the acid, amide, imide, amine salt, ammonium salt, anhydride or ester can vary but is usually between 20:1 and 2:1, e.g. between 15:1 and 4:1.
- The first step of the process is the addition of sodium hydroxide to the mixture of alkoxyalkanol and solvent and reaction of a part of the sodium hydroxide to form the sodium alkoxyalkoxide. The reaction mixture is heated so that the temperature is slowly increased and the water formed by the reaction to form sodium alkoxyalkoxide is removed as an azeotrope with the solvent and the alkoxyalkanol. Little solvent is normally removed in the azeotrope, and the reaction vessel may be equipped with a condenser so that substantially all solvent is returned to the reaction vessel. The recovered azeotrope then comprises water and alkoxyalkanol with substantially no solvent. This heating which in effect is azeotropic distillation effectively controls the amount of sodium hydroxide converted to alkoxyalkoxide since the removal of water drives the alkoxyalkoxide-forming reaction. The extent to which this reaction is driven and formed water is removed is critical since surprisingly it has been found that excess water in the system tends to result in a hazy and unsatisfactory product. It has further been discovered that a surprising and effective means of preventing this haze formation is by using the alkoxyalkoxide formation and subsequent hydrolysis as a control of the water in the system. By forming alkoxyalkoxide in such an amount that the water required to hydrolyse it is at least equal to the water generated in the remaining steps of the process, effective control over haze may be obtained.
- Usually the azeotropic distillation takes at least an hour, and times of from 1.5 to 2 hours are typical for small scale operations.
- In the next step the organic sulphonic acid and optionally the dicarboxylic acid, anhydride or ester, amide, imide, amine salt or ammonium salt are added preferably at 50°C to 70°C to the reaction mixture which may then be heat-soaked, e.g. at a temperature of about 80°C to 100°C. The sulphonic acid and dicarboxylic acid, anhydride, ester, amide, imine, amine salt or ammonium salt are usually introduced as solutions in diluent oil, e.g. an aliphatic or aromatic hydrocarbon. The purpose of this heat soaking is to effect neutralisation of the organic sulphonic acid, and if used, the dicarboxylic acid, anhydride, monoamine salt or monoammonium salt by the sodium hydroxide. The time taken for this heat soaking is usually from 10 to 30 minutes, e.g. about 20 minutes.
- The amount of sodium hydroxide and organic sulphonic acid are related and dependent on the degree of reaction with alkoxyalkanol in step (a) as discussed above. A part of the sodium hydroxide reacts with the alkoxyalkanol according to the equation
- Thus, if a dicarboxylic acid or a mono-amine or mono-ammonium salt of a dicarboxylic acid is employed as surfactant (where 1 mole of the surfactant reacts with 2 moles of sodium hydroxide to form 2 moles of water in total or 1 mole in excess of the 1 mole of water formed by carbonating 2 moles of sodium hydroxide) then n = 1 and A + C + 2D₂ ≦ B where D₂ is the number of moles of dicarboxylic acid, mono-amine or salt.
-
-
-
- It is preferred that: A + C + Σ 2n.Dn = B
since the step of adding additional water to the carbonated reaction mixture is then unnecessary. - After this heat soaking step, carbon dioxide is introduced to react with the basic sodium compounds in the reaction mixture which is preferably maintained at a temperature from ambient to the reflux temperature of the mixture, typically 120°C, more preferably between 80°C and 100°C, for example, about 90°C. The preferred amount of carbon dioxide which is blown into or injected into the reaction mixture is 90% to 115%, e.g. about 105% of the theoretical amount required to react with available basic sodium compounds.
- In practice, carbon dioxide is blown in until no more carbon dioxide is absorbed, e.g. when the gas inlet and exit rates, as measured on gas rotameters are the same. Rates are usually chosen to introduce the carbon dioxide over 2 to 4 hours, e.g. about 3 hours.
- The basic sodium compounds which will react with the carbon dioxide include the previously unreacted sodium hydroxide which will react:
- Water or any mixture of water and alkoxyalkanol can be used preferably between 1:6 and 1:2 water:alkoxyalkanol (by weight). The water/alkoxyalkanol mixture is usually slowly added to the reaction mixture to convert the residual carbonated sodium alkoxyalkoxide to sodium carbonate, alkoxyalkanol and carbon dioxide and this addition continues until the evolution of carbon dioxide ceases.
- The next step in the process is to remove the alkoyalkanol and solvent by distillation. Usually, this takes place by atmospheric distillation typically at a temperature of about 180°C, optionally followed by distillation under reduced pressure whence the residual solvent and alkoxyalkanol will be removed.
- Following this distillation step, solid contaminants may be removed from the product preferably by filtration or centrifuging. The desired product is the filtrate or centrifugate.
- The desired product is a solution in oil and therefore base oil is added to the process in step (b), (c) or (d). Most preferably the oil is added with the sulphonic acid in step (b). Base oils used in the process are preferably lubricating oils as described hereinafter.
- The process of the invention enables a high quality, high TBN sodium sulphonate product to be obtained in good yields (e.g. 95% + of theoretical) with reduced amounts of material losses in sludge and/or sediment and reduced problems in waste disposal which can arise when large amounts of sludge or flocculent material are produced. The process of the invention in particular provides a means of preparing a preferred product with a TBN of at least 250, preferably 250 to 600 mg (KOH)/g, more preferably 350 to 500, specifically in the region of 400 mg (KOH)/g.
- The overbased additive of this invention is suitable for use in oleaginous compositions such as fuels or lubricating oils for gasoline or diesel engines, both mineral and synthetic. The lubricating oil may be an animal, vegetable or mineral oil, for example, petroleum oil fractions ranging from naphthas or spindle oil to SAE 30, 40 or 50 lubricating oil grades, castor oil, fish oils or oxidised mineral oil.
- Suitable synthetic ester lubricating oils include diesters such as dioctyl adipate, dioctyl sebacate, didecyl azelate, tridecyl adipate, didecyl succinate, didecyl glutarate and mixtures thereof. Alternatively the synthetic ester can be a polyester such as that prepared by reacting polyhydric alcohols such as trimethylolpropane and pentaerythritol with monocarboxylic acids such as butyric acid, caproic acid, caprylic acid and pelargonic acid to give the corresponding tri- and tetra-ester.
- Also, complex esters may be used as base oils such as those formed by esterification reactions between a dicarboxylic acid, a glycol and an alcohol and/or a monocarboxylic acid.
- Blends of diesters with minor proportions of one or more thickening agents may also be used as lubricants. Thus one may use blends containing up to 50% by volume of one or more water-insoluble polyoxyalkylene glycols, for example, polyethylene or polypropylene glycol, or mixed oxyethylene/oxypropylene glycol.
- The amount of overbased detergent added to the lubricating oil should be a minor proporton, e.g. between 0.01% and 10% by weight, preferably between 0.1% and 5% by weight.
- The final lubricating oil may contain other additives according to the particular use for the oil. For example, viscosity index improvers such as ethylene-propylene copolymers may be present as may ashless dispersants such as substituted succinic acid based dispersants, other metal containing dispersant additives, well known zinc dialkyldithio-phosphate antiwear additives, antioxidants, demulsifiers, corrosion inhibitors, extreme pressure additives and friction modifiers. In particular, the oils of the invention may contain ashless dispersant, a zinc dialkyl dithiophosphate and copper in an oil soluble form (preferably in an amount of 5 to 500 ppm copper) as antioxidant.
- The invention also includes an additive concentrate comprising an oil solution of an overbased sodium sulphonate of the invention comprising 10 to 90 wt %, preferably 40 to 60 wt % overbased sodium sulphonate (active matter) based on the weight of oil.
- When used in fuels as a detergent or combustion improver the overbased material is used in minor proportions, e.g. between 0.01 and 10% by weight of the fuel.
- The invention is now described with reference to the following examples:
-
- The general procedure was as follows:
- 1. 2-Ethoxyethanol and toluene were charged to a 5 litre glass reactor fitted with stirrer, thermocouple, Dean and Stark receiver, condenser and nitrogen purge.
- 2. Sodium hydroxide was added and the temperature slowly increased until azeotropic conditions were attained and water was being steadily removed without losing solvent through the condenser. This condition was continued until the amounts of azeotrope in the attached table were recovered. The azeotrope is predominantely water with 2-ethoxyethanol and minor traces of toluene. Its composition was determined by gas chromatography.
- 3. On reaching the desired level of water removal (i.e. conversion of NaOH to NaOR) a premixture of sulphonic acid, PIBSA and oil at 60°C was added. The contents of the reactor were then stabilised at 90°C and the Dean and Stark receiver replaced by a simple reflux condenser.
- 4. Carbon dioxide was then injected into the solution until no further CO₂ was being absorbed. This point was reached when the gas inlet and exit rates, as measured on gas rotameters, were the same. The CO₂ was then turned off.
- 5. A 1:4 mixture of water and 2-ethoxyethanol was then slowly added from a dropping funnel to convert any residual carbonated sodium ethoxyethoxide to sodium carbonate, 2-ethoxyethanol and carbon dioxide.
When the evolution of CO₂ ceased the water/2-ethoxyethanol addition was stopped and the amount of water added calculated. - 6. The apparatus was then changed from reflux to distillation conditions and a nitrogen purge installed. The temperature was then slowly raised to 180°C and residual solvents (2-ethoxyethanol and toluene) removed. At 180°C a vacuum of 20 inches of mercury was applied to remove the last traces of solvent.
- 7. The product was then filtered through a bed of Dicalite 4200 filter aid in a pressure filter to give the finished product.
- In these Examples D to L are within the scope of the invention with Examples E to G preferred. Examples A, B and C are for comparison purposes.
- No water was removed by azeotropic distillation as described in step 2 above. A mixture of NaOH, 2-ethoxyethanol, toluene, sulphonic acid, PIBSA and oil was carbonated at 90°C. Some CO₂ was absorbed but product gradually hazed as colloid precipitated from solution. The experiment was abandoned.
- 140 cm² of an azeotrope was recovered in step 2. On carbonation the reaction mixture gradually hazed and on distilling colloid precipitation occurred.
- This experiment was carried out on a larger scale and the figures quoted are scaled down to provide a comparison. Water was added at the hydrolysis step but no carbon dioxide was given off - indicating that this was in excess of that reqired for hydrolysis. The product filtered well but was hazy even after passing through the finest filter aid.
- Water was removed to give 58.5% conversion to alkoxide. The finished product was acceptable but with very slight haze appearance.
- All very good preparations. The finished products were all clear and bright with extremely good filtration rates. There was little CO₂ loss during hydrolysis.
- All acceptable but the longer azeotrope step meant that more water was necessary to hydrolyse the carbonated alkoxyalkoxide resulting in greater loss of CO₂ during hydrolysis and poorer filtration.
- This is a repeat of Example H except that only 20 grams of hydrolysis water is used and thus all the carbonated alkoxide was not converted to the carbonate. The product was very viscous and skinned on exposure to air, but Example H shows that by addition of the appropriate amount of water an excellent product may be prepared.
Claims (12)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8601990 | 1986-01-28 | ||
GB868601990A GB8601990D0 (en) | 1986-01-28 | 1986-01-28 | Overbased additives |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0235929A1 EP0235929A1 (en) | 1987-09-09 |
EP0235929B1 true EP0235929B1 (en) | 1991-10-16 |
Family
ID=10592041
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19870300761 Expired EP0235929B1 (en) | 1986-01-28 | 1987-01-28 | Overbased additives |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0235929B1 (en) |
JP (1) | JP2512457B2 (en) |
CA (1) | CA1289547C (en) |
DE (1) | DE3773698D1 (en) |
GB (1) | GB8601990D0 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8621343D0 (en) * | 1986-09-04 | 1986-10-15 | Exxon Chemical Patents Inc | Overbased alkali metal additives |
JP3157830B2 (en) * | 1991-04-19 | 2001-04-16 | ザ ルブリゾル コーポレイション | Overbased alkali metal salt and method for producing the same |
US5449470A (en) * | 1991-04-19 | 1995-09-12 | The Lubrizol Corporation | Overbased alkali salts and methods for making same |
US20080274921A1 (en) | 2007-05-04 | 2008-11-06 | Ian Macpherson | Environmentally-Friendly Lubricant Compositions |
EP2025737A1 (en) | 2007-08-01 | 2009-02-18 | Afton Chemical Corporation | Environmentally-friendly fuel compositions |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2920105A (en) * | 1957-12-13 | 1960-01-05 | Texaco Inc | Preparation of hyperbasic sulfonates |
ZA738848B (en) * | 1973-10-05 | 1975-06-25 | Lubrizol Corp | Basic alkali sulfonate dispersions and processes |
GB1551820A (en) * | 1975-05-23 | 1979-09-05 | Exxon Research Engineering Co | Production of basic magnesium sulphonates |
GB2056482A (en) * | 1979-08-13 | 1981-03-18 | Exxon Research Engineering Co | Lubricating oil compositions |
-
1986
- 1986-01-28 GB GB868601990A patent/GB8601990D0/en active Pending
-
1987
- 1987-01-22 CA CA 527948 patent/CA1289547C/en not_active Expired
- 1987-01-28 EP EP19870300761 patent/EP0235929B1/en not_active Expired
- 1987-01-28 DE DE8787300761T patent/DE3773698D1/en not_active Expired - Lifetime
- 1987-01-28 JP JP1813087A patent/JP2512457B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP2512457B2 (en) | 1996-07-03 |
EP0235929A1 (en) | 1987-09-09 |
GB8601990D0 (en) | 1986-03-05 |
DE3773698D1 (en) | 1991-11-21 |
JPS62190296A (en) | 1987-08-20 |
CA1289547C (en) | 1991-09-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4744921A (en) | Methods for preparing, group II metal overbased sulfurized alkylphenols | |
EP0273588B2 (en) | Sulphurised alkaline earth metal hydrocarbyl phenates, their production and use thereof | |
EP0212922B1 (en) | Overbased additives | |
EP1562887B1 (en) | Method for producing lubricant detergents | |
EP0588824B1 (en) | Preparation of overbased magnesium sulphonates | |
US5024773A (en) | Methods for preparing, group II metal overbased sulfurized alkylphenols | |
US5415792A (en) | Overbased alkylated alkyl salicylates | |
AU660328B2 (en) | Improved overbased carboxylates | |
EP0095322B1 (en) | Process for the production of an overbased sulphurised alkaline earth metal alkyl phenate | |
EP1523540B1 (en) | Engine oil comprising overbased salicylates based on styrenated salicylic acid | |
EP0235929B1 (en) | Overbased additives | |
US4839094A (en) | Overbased alkali metal additives | |
EP0021838B1 (en) | A process for the production of oil-soluble polyol esters of dicarboxylic acid materials in the presence of a metal salt of a hydroxy aromatic compound | |
US5883056A (en) | Magnesium low base number sulphonates | |
WO1993006195A1 (en) | Overbased metal-containing detergents | |
JP3158039B2 (en) | Method for producing orthophenate and overbased phenate | |
US4971710A (en) | Methods for preparing, Group II metal overbased sulfurized alkylphenols | |
EP0259974B2 (en) | Overbased sulfurized alkyl-phenols as lubricating oil additives | |
EP0856043A1 (en) | Overbased magnesium sulphonates | |
MXPA98003036A (en) | Super base magnesium sulphonates |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19870213 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE FR GB IT NL |
|
17Q | First examination report despatched |
Effective date: 19890331 |
|
ITF | It: translation for a ep patent filed | ||
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB IT NL |
|
REF | Corresponds to: |
Ref document number: 3773698 Country of ref document: DE Date of ref document: 19911121 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19980108 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19981211 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19981222 Year of fee payment: 13 Ref country code: GB Payment date: 19981222 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19981223 Year of fee payment: 13 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990131 |
|
BERE | Be: lapsed |
Owner name: EXXON CHEMICAL PATENTS INC. Effective date: 19990131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000128 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000801 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20000128 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000929 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20000801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20001101 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050128 |