CA1103699A - Alkylates and sulphonic acids and sulphonates produced therefrom - Google Patents
Alkylates and sulphonic acids and sulphonates produced therefromInfo
- Publication number
- CA1103699A CA1103699A CA295,829A CA295829A CA1103699A CA 1103699 A CA1103699 A CA 1103699A CA 295829 A CA295829 A CA 295829A CA 1103699 A CA1103699 A CA 1103699A
- Authority
- CA
- Canada
- Prior art keywords
- cation
- sulphonates
- alkylate
- olefine
- sulfonates
- 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
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 title description 25
- 239000002253 acid Substances 0.000 title description 12
- 150000007513 acids Chemical class 0.000 title description 12
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims description 31
- 229910052791 calcium Inorganic materials 0.000 claims description 19
- 239000011575 calcium Substances 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 12
- 150000001491 aromatic compounds Chemical class 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000002152 alkylating effect Effects 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 150000003871 sulfonates Chemical class 0.000 claims 7
- 150000003460 sulfonic acids Chemical class 0.000 claims 6
- 238000006277 sulfonation reaction Methods 0.000 claims 2
- 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 abstract description 19
- 238000005187 foaming Methods 0.000 abstract description 12
- 125000000217 alkyl group Chemical group 0.000 abstract description 7
- 238000005804 alkylation reaction Methods 0.000 abstract description 6
- 239000003995 emulsifying agent Substances 0.000 abstract description 6
- 230000029936 alkylation Effects 0.000 abstract description 5
- 239000003879 lubricant additive Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 239000000314 lubricant Substances 0.000 description 9
- -1 alkyl aromatic compounds Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 6
- 239000002518 antifoaming agent Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 239000002585 base Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical group NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/12—Sulfonates of aromatic or alkylated aromatic 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
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
- C07C2/70—Catalytic processes with acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
Alkyl aromatics are prepared by alkylation with a mixture of straight and branched chain olefines. The alkylates may be sulphonated to yield low viscosity sulphonate emulsifiers and are raw materials for producing low foaming overbased sulphonate lubricant additives.
Alkyl aromatics are prepared by alkylation with a mixture of straight and branched chain olefines. The alkylates may be sulphonated to yield low viscosity sulphonate emulsifiers and are raw materials for producing low foaming overbased sulphonate lubricant additives.
Description
il~3f~gg The present invention relates to improved alkyl aromatic compounds, known as alkylates, and their preparation, and to oil soluble sulphonic acids and sulphonates produced from the alkylates in particular the inventlon is concerned with alkylates from which overbased sulphonates especially overbased calcium sulphonates which have a reduced tendency to cause foaming when they are used as lubricant additives may be obtained.
Sulphonates, particularly calcium, barium or magnesium overbased sulphonates are widely used as additives for lubricating oils. The term overbased is used to describe sulphonates containing an amount of metal in excess of that required to react with the sulphonic acid from which the sulphonate is obtained.
Frequently the excess metal is in the form of its carbonate in which case the overbased sulphonate consists of a colloidal dispersion of the metal carbonate in the metal sulphonate as dispersant. These overbased sulphonates are used as - dispersants in the lubricating oil where their high basicity neutralises acids which develop in crank cases during engine operation thus reducing corrosin.
Sulphonic acids and sulphonates are generally obtained from mono-alkylates of aromatics the alkyl chain being either branched or straight chain. Oil soluble sulphonîc acids are obtained from alkylates containing an alkyl group of more than 16 generally more than 20, carbon atoms, the group is usually branched chain since branched chain olefines are more readily available and cheaper than the corresponding straight chain olefines.
However, one problem associated with the use of overbased sulphonates particularly overbased sulphonates obtained from branched chain alkylates is that despite the inclusion of an antifoam agent in the oil after a short period of use they tend to cause foaming of the lubricant during operation of the engine which is, of course, undesirable. This problem is particularly marked with overbased calcium sulphonates. It has been proposed in British Patent Sp~cification 1390951 to overcome this problem by preparing the sulphonic ac ds from mixtures of straight and branched chain alkylates.
1~36g9 Whilst this technique has proved successful it requires significant amounts of the straight chain alkylate which increases costs since the straight chain olefines from which these alkylates are made are more expensive than the branched chain olefins that we used. We have found that the same effect may be achieved using considerably less of the straight chain olefine if the alkylates from which the sulphonic acids are produced are obtained by alkylating an aromatic compound with a mixture of branched and straight chain olefines.
The present invention therefore provides a process for the production of alkylates comprising alkylating an aromatic compound with a mixture containing l0 up to 95% by weight of a branched chain olefin containing from 15 to 40 carbon atoms and at least 5% by weight of a linear olefin containing from 16 to 30 carbon atoms the lar ratio of said aromatic compound to the olefin mixture being from lO:l to 1:1.
The alkylation reaction may be achieved by any of the well-known alkylation techniques. Our preferred technique being the use of a Friedel Crafts catalyst such as aluminium tricholride preferably together with hydrochloric acid. No special conditions are needed for alkylation, our invention being the composition of the olefine feed and the ratios of the material used. In the aspect of the invention concerned with alkylates for producing overbased sulphonates our 20 techniques are particularly useful when the aromatic compound is benzene since the problems of foaming of lubricants containing the overbased alkyl benzene sulphonates are particularly acute.
We find that the olefine mixture used as the feed should contain at least 5 wt.~ of the linear olefine since mixtures containing less than 5 wt.% do not give the improved sulphonic acids and sulphonates. We have also found that there is no further improvement in effect if the mixture contains more than 30 ut.%
of the linear olefine. Thus, since linear olefines are more expensive than branched chain olefines we prefer that the mixture contain from 5% to 30%
by weight of the linear olefine although this is not essential. We have found ~36g9 that there is llttle if any reduction of the foaming tendency of the lubricant if the linear olefine from which the sulphonate is derived contains fewer than 16 carbon atoms and we prefer to use olefins containing less than 24 carbon atoms since heavier olefins tend to be unsuitable because they are waxy.
The branched chain olefine should contain from 15 to 40 carbon atoms to ensure the desired oil solubility and viscosity of the sulphonates obtained from the alkylates. Because of their ready availability we prefer to use oligomers of propylene as our branched chain olefines.
The ratio of aromatic compound to the olefine mixture in the reaction of our invention should be from 10:1 to 1:1 by volume so that an excess of the olefine is not used. This ensures that the products formed are essentially mono-alkyl aromatics which we find to be important since dialkyl aromatics containing a branched chain alkyl group are difficult to sulphonate.
The alkylates of our invention may be used themselves for example as synthetic lubricants. The principle use with which we are concerned however is as raw materials in the production of alkylaryl sulphonic acids particularly sulphonic acids that are subsequently converted to overbased sulphonates especially calcium sulphonates or to neutral sulphonates such as sodium sul-phonates which are used as emulsifiers.
As a further aspect the present invention therefore provides a process for the production of sulphonic acids comprising sulphonating an alkyl aromatic compound that has been obtained by alkylating an aromatic compound with a mixture containing up to 95% by weight of a branched chain olefine containing from 15 to 40 carbon atoms and at least 5% by weight of a linear olefine con-taining from 16 to 30 carbon atoms the mole ratio of said aromatic compound to the olefine mixture being from 10:1 to 1:1.
~i~13699 Any of the well-known sulphonation techniques may be used. For example the alkylate may be solphonated with concentrated sulphuric acid, with oleum or with sulphur trioxide dissolved in sulphur dioxide, this latter technique being preferred. After sulphonation the sulphonic acid is purified by standard techniques or purifying aids such as the addition of olefines and optionally water as described in our Belgian patent 851516 and the ether containing compounds as described in British patent 1469203 may be included.
The sulphonic acids produced according to this further aspect of our invention may be neutralised to form sulphonates which may be used as detergents dispersants and emulsifiers. The choice of cation will depend upon the use to which the sulphonate is to be put. For use as an emulsifier or in oil recovery the cation will generally be an alkali metal or a quaternary nitrogenous cation, whilst for use as lubricant additives the cation will usually be calcium, barium or magnesium and the sulphonate is often overbased.
The present invention therefore further provides a sulphonate in which the anion is derived from a sulphonic acid obtained by sulphonating an alkyl aromatic compound that has been obtained by alkylating from 1 to 10 moles of an aromatic compound with one mole of a mixture containing up to 95% by weight of a branched chain olefin containing from 15 to 40 carbon atoms and at least 5% by weight of a linear olefine containing from 16 to 30 carbon atoms and the cation is an alkali metal, a quaternary nitrogenous group or calcium, magnesium or barium.
We have found that overbased sulphonates according to this further feature of our invention have reduced foaming tendency and neutral sulphonates which may be used as emulsifiers have improved stability and these improvements are achieved with most aromatic compounds. Since the greatest foaming problems occur with alkyl benzenes our technique is particularly useful with benzene although an improvement is also achieved with toluene and xylene. We find in particular that neutral sulphonates of this invention particularly alkali metal or nitrogenous base salts may 11~3699 be used as the higher molecular sulphonate of the emulsifier compositions of British Patent 1476891 and that resulting oil in water emulsions have especially good emulsion stability and are most useful as metal working fluids.
~r - 5a -~i~3699 Where the cation of the sulphonate of the present invention is an al~ali metal it lS generally sodium, where it is a quaternary nitrogenous group it may be an ammonium cation although we find quaternary amino, particularly ethoxylated quaternary amino sulphonates to be especially useful surfactants. The principle benefits of the use of the mixed olefine feedstock is in the production of overbased alkaline earth metal sulphonates which are used as lubricant additives. In particular the invention is useful in producing overbased calcium sulphonates which when used as lubricant additives have a reduced tendency to cause foaming of an automobile crankcase lubricant during operation of the motor. We have found that using overbased calcium sulphonates based on our alkylates acceptable foam levels may be obtained using the conventional antifoam additives which is not the situation with overbased additives based on other alkylates and that furthermore in some instances the antifoam additives may not be needed.
The calcium sulphonate may be a neutral sulphonate or an overbased sulphonate athough since it is the overbased sulphonates that pose the greatest foaming problems it is here our techniques have the greatest use. These materials are generally produced by the neutralisation of the sulphonic acid with lime in the presence of reaction promoters and then carbonating the reaction mixture to convert the excess calcium present to colloidal calcium carbonate. Various techniques have 20 been proposed for controlling the viscosity and speed of reaction and the alkylates of our invention may be used in the production of sulphonic acids by any of these techniques. Although primarily directed at overcoming the foaming problems of overbased calcium sulphonates the alkylates may also be used in the preparation of neutral and overbased magnesium and barium sulphonates.
The calcium, magnesium and barium sulphonates are useful as additives for lubricating oil where they may be used in the amounts traditionally used and in combination with other well-known additives such as the polyamine dispersants, viscosity index modifiers and antiwear sdditives. We have found that the use of : sulphonates derived from the alkylates of this invention yields lubricating oils with reduced foaming tendency as compared with oils containing currently available sulphonates and also that less straight chain component is required to achieve this than with oils containing sulphonates based on a mixture of alkyl benze:~s some carrying branched chain alkyl group and others carrying linear alkyl groups, the two types of alkylate having been prepared separately.
The present invention is illustrated but in no way limited by the following Examples.
Example 1 85 wt.% of a C24 average branched chain propylene oligomer was blended with i5 wt.% of C24 linear olefine. 839 parts by weight of this olefine mixture were added to 1360 parts by weight of benzene in an alkylation vessel at 0C containing 17 parts by weight of aluminium trichloride and 4 parts by weight of hydrochloric acid. The vessel was held at that temperature for half an hour, the temperature then raised to 20 C for 3 hours while the alkylate settled and the alkylate finally washed with sodium hydroxide and water and purified by distillation.
The alkylate thus obtained had a specific gravity at 15C of 0.860 (as measured by ASTM D 1298), a flash point of 185 (As measured by ASTM D 92), a viscosity at 100 F of 75 centistokes (as measured by ASTM D 445) and a molecular weight of about 42 The alkylate was sulphonated with sulphur trioxide dissolved in sulphur dioxide and the resulting sulphonic acid separated, purified and converted into ~ ~0t~ n~
300 T~I~ overbased calcium sulphonate by the process described in French Patent No. 1526400.
Example 2 The process of Example 1 was repeated except that the starting olefine mixture contained 80 wt.% of the branched chain olefine and 20 wt.% of the linear olefine.
69g Example 3 For the sake of comparison benzene was separately alkylated with the linear olefine and the branched chain olefine used in Example 1 using exactly the same alkylation conditions as used in Exa~ple 1.
The blends of the alkylates so obtained were prepared containing 85 wt.% of the branched chain alkylate and 15 wt.% of the linear chain alkylate and the other containing 80 wt.% of the branched chain alkylate and 20 wt.%
of the llnear chain alkylate.
Both these blends were sulphonated and converted into a 300 TBN overbased calcium sulphonates by the techniques described in Example l.
Example 4 5 wt.% of the 300 TBN Calcium high base number sulphonates of Examples 1 to 3 were-incorporated into a standard reference oil (SIS 3453) and the oils subjected to the standard ASTM D 892 foam test. The materials were also compared with the same oil containing 5 wt.% of the 300 TBN calcium sulphonate obtained from C24 branched chain alkyl benzene. The lubricants tested also contained equal amounts of a conventionsl antifoam agent.
The ~esults of the tests were as follows:
Sulphonates Derived From Te~t Result -Example 1 40/o Example 2 T/0 Example 3 (î) 240/0 (ii) 20/0 G24 Alkyl Benzene 650/500 T indicates that only a trace of foam was formed.
Example 5 The foaming properties of a lubricant containing the product of Example l were also compared with those of a lubricant containing the calcium sulphonate obtained from the C24 branch~d chain alkyl benzene. In this instance 11~336~9 the lubricants contained no antifoam agent. The results were as follows:
Product of Example 1 410/320 C24 Alkyl Benzene 650/500 Example 6 The sodium salt of the sulphonic acid of Example 1 was prepared by neutrali-sation with sodium hydroxide and the viscosity of a 70 wt.% active ingredient solution of the sodium sulphonate in a diluent oil was measured at 98.9 C. The ~ viscosity of solutions containing increasing amounts of water was determined and - compared with similar solutions containing a branched chain C24 alkyl benzene sulphonate.
The results of these tests are set out in the graph which is attached hereto as Figure l.
Sulphonates, particularly calcium, barium or magnesium overbased sulphonates are widely used as additives for lubricating oils. The term overbased is used to describe sulphonates containing an amount of metal in excess of that required to react with the sulphonic acid from which the sulphonate is obtained.
Frequently the excess metal is in the form of its carbonate in which case the overbased sulphonate consists of a colloidal dispersion of the metal carbonate in the metal sulphonate as dispersant. These overbased sulphonates are used as - dispersants in the lubricating oil where their high basicity neutralises acids which develop in crank cases during engine operation thus reducing corrosin.
Sulphonic acids and sulphonates are generally obtained from mono-alkylates of aromatics the alkyl chain being either branched or straight chain. Oil soluble sulphonîc acids are obtained from alkylates containing an alkyl group of more than 16 generally more than 20, carbon atoms, the group is usually branched chain since branched chain olefines are more readily available and cheaper than the corresponding straight chain olefines.
However, one problem associated with the use of overbased sulphonates particularly overbased sulphonates obtained from branched chain alkylates is that despite the inclusion of an antifoam agent in the oil after a short period of use they tend to cause foaming of the lubricant during operation of the engine which is, of course, undesirable. This problem is particularly marked with overbased calcium sulphonates. It has been proposed in British Patent Sp~cification 1390951 to overcome this problem by preparing the sulphonic ac ds from mixtures of straight and branched chain alkylates.
1~36g9 Whilst this technique has proved successful it requires significant amounts of the straight chain alkylate which increases costs since the straight chain olefines from which these alkylates are made are more expensive than the branched chain olefins that we used. We have found that the same effect may be achieved using considerably less of the straight chain olefine if the alkylates from which the sulphonic acids are produced are obtained by alkylating an aromatic compound with a mixture of branched and straight chain olefines.
The present invention therefore provides a process for the production of alkylates comprising alkylating an aromatic compound with a mixture containing l0 up to 95% by weight of a branched chain olefin containing from 15 to 40 carbon atoms and at least 5% by weight of a linear olefin containing from 16 to 30 carbon atoms the lar ratio of said aromatic compound to the olefin mixture being from lO:l to 1:1.
The alkylation reaction may be achieved by any of the well-known alkylation techniques. Our preferred technique being the use of a Friedel Crafts catalyst such as aluminium tricholride preferably together with hydrochloric acid. No special conditions are needed for alkylation, our invention being the composition of the olefine feed and the ratios of the material used. In the aspect of the invention concerned with alkylates for producing overbased sulphonates our 20 techniques are particularly useful when the aromatic compound is benzene since the problems of foaming of lubricants containing the overbased alkyl benzene sulphonates are particularly acute.
We find that the olefine mixture used as the feed should contain at least 5 wt.~ of the linear olefine since mixtures containing less than 5 wt.% do not give the improved sulphonic acids and sulphonates. We have also found that there is no further improvement in effect if the mixture contains more than 30 ut.%
of the linear olefine. Thus, since linear olefines are more expensive than branched chain olefines we prefer that the mixture contain from 5% to 30%
by weight of the linear olefine although this is not essential. We have found ~36g9 that there is llttle if any reduction of the foaming tendency of the lubricant if the linear olefine from which the sulphonate is derived contains fewer than 16 carbon atoms and we prefer to use olefins containing less than 24 carbon atoms since heavier olefins tend to be unsuitable because they are waxy.
The branched chain olefine should contain from 15 to 40 carbon atoms to ensure the desired oil solubility and viscosity of the sulphonates obtained from the alkylates. Because of their ready availability we prefer to use oligomers of propylene as our branched chain olefines.
The ratio of aromatic compound to the olefine mixture in the reaction of our invention should be from 10:1 to 1:1 by volume so that an excess of the olefine is not used. This ensures that the products formed are essentially mono-alkyl aromatics which we find to be important since dialkyl aromatics containing a branched chain alkyl group are difficult to sulphonate.
The alkylates of our invention may be used themselves for example as synthetic lubricants. The principle use with which we are concerned however is as raw materials in the production of alkylaryl sulphonic acids particularly sulphonic acids that are subsequently converted to overbased sulphonates especially calcium sulphonates or to neutral sulphonates such as sodium sul-phonates which are used as emulsifiers.
As a further aspect the present invention therefore provides a process for the production of sulphonic acids comprising sulphonating an alkyl aromatic compound that has been obtained by alkylating an aromatic compound with a mixture containing up to 95% by weight of a branched chain olefine containing from 15 to 40 carbon atoms and at least 5% by weight of a linear olefine con-taining from 16 to 30 carbon atoms the mole ratio of said aromatic compound to the olefine mixture being from 10:1 to 1:1.
~i~13699 Any of the well-known sulphonation techniques may be used. For example the alkylate may be solphonated with concentrated sulphuric acid, with oleum or with sulphur trioxide dissolved in sulphur dioxide, this latter technique being preferred. After sulphonation the sulphonic acid is purified by standard techniques or purifying aids such as the addition of olefines and optionally water as described in our Belgian patent 851516 and the ether containing compounds as described in British patent 1469203 may be included.
The sulphonic acids produced according to this further aspect of our invention may be neutralised to form sulphonates which may be used as detergents dispersants and emulsifiers. The choice of cation will depend upon the use to which the sulphonate is to be put. For use as an emulsifier or in oil recovery the cation will generally be an alkali metal or a quaternary nitrogenous cation, whilst for use as lubricant additives the cation will usually be calcium, barium or magnesium and the sulphonate is often overbased.
The present invention therefore further provides a sulphonate in which the anion is derived from a sulphonic acid obtained by sulphonating an alkyl aromatic compound that has been obtained by alkylating from 1 to 10 moles of an aromatic compound with one mole of a mixture containing up to 95% by weight of a branched chain olefin containing from 15 to 40 carbon atoms and at least 5% by weight of a linear olefine containing from 16 to 30 carbon atoms and the cation is an alkali metal, a quaternary nitrogenous group or calcium, magnesium or barium.
We have found that overbased sulphonates according to this further feature of our invention have reduced foaming tendency and neutral sulphonates which may be used as emulsifiers have improved stability and these improvements are achieved with most aromatic compounds. Since the greatest foaming problems occur with alkyl benzenes our technique is particularly useful with benzene although an improvement is also achieved with toluene and xylene. We find in particular that neutral sulphonates of this invention particularly alkali metal or nitrogenous base salts may 11~3699 be used as the higher molecular sulphonate of the emulsifier compositions of British Patent 1476891 and that resulting oil in water emulsions have especially good emulsion stability and are most useful as metal working fluids.
~r - 5a -~i~3699 Where the cation of the sulphonate of the present invention is an al~ali metal it lS generally sodium, where it is a quaternary nitrogenous group it may be an ammonium cation although we find quaternary amino, particularly ethoxylated quaternary amino sulphonates to be especially useful surfactants. The principle benefits of the use of the mixed olefine feedstock is in the production of overbased alkaline earth metal sulphonates which are used as lubricant additives. In particular the invention is useful in producing overbased calcium sulphonates which when used as lubricant additives have a reduced tendency to cause foaming of an automobile crankcase lubricant during operation of the motor. We have found that using overbased calcium sulphonates based on our alkylates acceptable foam levels may be obtained using the conventional antifoam additives which is not the situation with overbased additives based on other alkylates and that furthermore in some instances the antifoam additives may not be needed.
The calcium sulphonate may be a neutral sulphonate or an overbased sulphonate athough since it is the overbased sulphonates that pose the greatest foaming problems it is here our techniques have the greatest use. These materials are generally produced by the neutralisation of the sulphonic acid with lime in the presence of reaction promoters and then carbonating the reaction mixture to convert the excess calcium present to colloidal calcium carbonate. Various techniques have 20 been proposed for controlling the viscosity and speed of reaction and the alkylates of our invention may be used in the production of sulphonic acids by any of these techniques. Although primarily directed at overcoming the foaming problems of overbased calcium sulphonates the alkylates may also be used in the preparation of neutral and overbased magnesium and barium sulphonates.
The calcium, magnesium and barium sulphonates are useful as additives for lubricating oil where they may be used in the amounts traditionally used and in combination with other well-known additives such as the polyamine dispersants, viscosity index modifiers and antiwear sdditives. We have found that the use of : sulphonates derived from the alkylates of this invention yields lubricating oils with reduced foaming tendency as compared with oils containing currently available sulphonates and also that less straight chain component is required to achieve this than with oils containing sulphonates based on a mixture of alkyl benze:~s some carrying branched chain alkyl group and others carrying linear alkyl groups, the two types of alkylate having been prepared separately.
The present invention is illustrated but in no way limited by the following Examples.
Example 1 85 wt.% of a C24 average branched chain propylene oligomer was blended with i5 wt.% of C24 linear olefine. 839 parts by weight of this olefine mixture were added to 1360 parts by weight of benzene in an alkylation vessel at 0C containing 17 parts by weight of aluminium trichloride and 4 parts by weight of hydrochloric acid. The vessel was held at that temperature for half an hour, the temperature then raised to 20 C for 3 hours while the alkylate settled and the alkylate finally washed with sodium hydroxide and water and purified by distillation.
The alkylate thus obtained had a specific gravity at 15C of 0.860 (as measured by ASTM D 1298), a flash point of 185 (As measured by ASTM D 92), a viscosity at 100 F of 75 centistokes (as measured by ASTM D 445) and a molecular weight of about 42 The alkylate was sulphonated with sulphur trioxide dissolved in sulphur dioxide and the resulting sulphonic acid separated, purified and converted into ~ ~0t~ n~
300 T~I~ overbased calcium sulphonate by the process described in French Patent No. 1526400.
Example 2 The process of Example 1 was repeated except that the starting olefine mixture contained 80 wt.% of the branched chain olefine and 20 wt.% of the linear olefine.
69g Example 3 For the sake of comparison benzene was separately alkylated with the linear olefine and the branched chain olefine used in Example 1 using exactly the same alkylation conditions as used in Exa~ple 1.
The blends of the alkylates so obtained were prepared containing 85 wt.% of the branched chain alkylate and 15 wt.% of the linear chain alkylate and the other containing 80 wt.% of the branched chain alkylate and 20 wt.%
of the llnear chain alkylate.
Both these blends were sulphonated and converted into a 300 TBN overbased calcium sulphonates by the techniques described in Example l.
Example 4 5 wt.% of the 300 TBN Calcium high base number sulphonates of Examples 1 to 3 were-incorporated into a standard reference oil (SIS 3453) and the oils subjected to the standard ASTM D 892 foam test. The materials were also compared with the same oil containing 5 wt.% of the 300 TBN calcium sulphonate obtained from C24 branched chain alkyl benzene. The lubricants tested also contained equal amounts of a conventionsl antifoam agent.
The ~esults of the tests were as follows:
Sulphonates Derived From Te~t Result -Example 1 40/o Example 2 T/0 Example 3 (î) 240/0 (ii) 20/0 G24 Alkyl Benzene 650/500 T indicates that only a trace of foam was formed.
Example 5 The foaming properties of a lubricant containing the product of Example l were also compared with those of a lubricant containing the calcium sulphonate obtained from the C24 branch~d chain alkyl benzene. In this instance 11~336~9 the lubricants contained no antifoam agent. The results were as follows:
Product of Example 1 410/320 C24 Alkyl Benzene 650/500 Example 6 The sodium salt of the sulphonic acid of Example 1 was prepared by neutrali-sation with sodium hydroxide and the viscosity of a 70 wt.% active ingredient solution of the sodium sulphonate in a diluent oil was measured at 98.9 C. The ~ viscosity of solutions containing increasing amounts of water was determined and - compared with similar solutions containing a branched chain C24 alkyl benzene sulphonate.
The results of these tests are set out in the graph which is attached hereto as Figure l.
Claims (16)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A process comprising alkylating an aromatic compound with a mixture containing up to 95% by weight of a branched chain olefine containing from 15 to 40 carbon atoms and at least 5% by weight of a linear olefin containing from 16 to 30 carbon atoms the molar ratio of said aromatic compound to the olefine mixture being from 10:1 to 1:1 to produce an alkylate, and where required converting said alkylate to sulfonic acids by sulfonation and then if required converting said sulfonic acids to sulfonates by reaction with a cation. - 2. A process according to claim 1 in which the mixture con-tains from 5% to 30% by weight of the linear olefine.
- 3. A process according to claim 1 or claim 2 in which the linear olefine contains less than 24 carbon atoms.
- 4. A process as claimed in claim 1 for the production of an alkylate.
- 5. A process as claimed in claim 1 wherein the alkylate is converted to sulfonic acids by sulfonation.
- 6. A process as claimed in claim 5 wherein the sulfonic acids are reacted with a cation to form the corresponding sulfonates.
- 7. A process as claimed in claim 6 wherein the cation is used in excess to produce overbased sulfonates.
- 8. A process as claimed in claim 6 wherein the cation is an alkali metal or quaternary nitrogenous group.
- 9. A process as claimed in claim 8 wherein the cation is calcium, magnesium or barium.
- 10. A process as claimed in claim 9 wherein the cation is calcium.
- 11. A process as claimed in claim 9 wherein the cation is used in excess to produce overbased sulfonates.
- 12. The product of the process of claim 1 of the group of an alkylate, sulfonic acids thereof and sulfonates thereof.
- 13. The product alkylate of the process of claim 4.
- 14. The product sulfonic acids of the process of claim 5.
- 15. The product sulfonates of the process of claim 6, 7 or 8.
- 16. The product sulfonates of the process of claim 9, 10 or 11.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB3557/77 | 1977-01-28 | ||
GB355777 | 1977-01-28 | ||
GB32726/77 | 1977-08-04 | ||
GB3272677 | 1977-08-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1103699A true CA1103699A (en) | 1981-06-23 |
Family
ID=26238417
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA295,829A Expired CA1103699A (en) | 1977-01-28 | 1978-01-27 | Alkylates and sulphonic acids and sulphonates produced therefrom |
Country Status (5)
Country | Link |
---|---|
JP (1) | JPS5395924A (en) |
CA (1) | CA1103699A (en) |
DE (1) | DE2803420A1 (en) |
FR (2) | FR2381004A1 (en) |
IT (1) | IT1091965B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5071576A (en) * | 1987-10-12 | 1991-12-10 | Exxon Chemical Patents Inc. | Lubricant oil additive |
US5089155A (en) * | 1987-10-12 | 1992-02-18 | Exxon Chemical Patents Inc. | Overbased magnesium sulphonate composition |
US5112506A (en) * | 1987-10-12 | 1992-05-12 | Exxon Chemical Patents Inc. | Overbased metal sulphonate composition |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63168792U (en) * | 1987-04-20 | 1988-11-02 | ||
CA2204461C (en) * | 1996-05-14 | 2006-07-04 | Thomas V. Harris | Process for producing an alkylated, non-oxygen-containing aromatic hydrocarbon |
JP4632465B2 (en) * | 1997-05-30 | 2011-02-16 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
US6392109B1 (en) * | 2000-02-29 | 2002-05-21 | Chevron U.S.A. Inc. | Synthesis of alkybenzenes and synlubes from Fischer-Tropsch products |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2712530A (en) * | 1950-03-31 | 1955-07-05 | Exxon Research Engineering Co | Sulfonate detergent blend |
GB749737A (en) * | 1953-12-30 | 1956-05-30 | Exxon Research Engineering Co | Sulfonate detergent blend |
US2806875A (en) * | 1954-06-21 | 1957-09-17 | Continental Oil Co | Preparation of alkaryl sulfonic acids |
NL102417C (en) * | 1957-02-15 | |||
US3410925A (en) * | 1964-05-14 | 1968-11-12 | Continental Oil Co | Dimerization of c3 to c18 olefins |
GB1093359A (en) * | 1965-08-12 | 1967-11-29 | Grange Chemicals Ltd | Production of heavy alkylate |
US3681442A (en) | 1968-12-26 | 1972-08-01 | Universal Oil Prod Co | Alkylaromatic sulfonate detergent process of preparation |
US3732324A (en) * | 1971-04-02 | 1973-05-08 | Continental Oil Co | Process for producing oil-soluble sulfonate feedstock |
US3772198A (en) | 1971-06-07 | 1973-11-13 | Continental Oil Co | Method for preparing overbased oil soluble compositions |
FR2264011B1 (en) | 1974-03-13 | 1978-01-06 | Exxon Research Engineering Co | |
GB1572496A (en) | 1976-02-20 | 1980-07-30 | Exxon Research Engineering Co | Stabilisation of alkylaryl sulphonic acids and sulphonates |
-
1978
- 1978-01-12 IT IT19220/78A patent/IT1091965B/en active
- 1978-01-13 JP JP259878A patent/JPS5395924A/en active Granted
- 1978-01-26 DE DE19782803420 patent/DE2803420A1/en active Granted
- 1978-01-27 CA CA295,829A patent/CA1103699A/en not_active Expired
- 1978-01-27 FR FR7802401A patent/FR2381004A1/en active Granted
- 1978-06-01 FR FR7816457A patent/FR2381026A1/en active Granted
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5071576A (en) * | 1987-10-12 | 1991-12-10 | Exxon Chemical Patents Inc. | Lubricant oil additive |
US5089155A (en) * | 1987-10-12 | 1992-02-18 | Exxon Chemical Patents Inc. | Overbased magnesium sulphonate composition |
US5112506A (en) * | 1987-10-12 | 1992-05-12 | Exxon Chemical Patents Inc. | Overbased metal sulphonate composition |
US5137648A (en) * | 1987-10-12 | 1992-08-11 | Exxon Chemical Patents Inc. | Overbased metal sulphonate composition |
Also Published As
Publication number | Publication date |
---|---|
FR2381004A1 (en) | 1978-09-15 |
IT1091965B (en) | 1985-07-06 |
FR2381026A1 (en) | 1978-09-15 |
JPS5395924A (en) | 1978-08-22 |
JPS629093B2 (en) | 1987-02-26 |
FR2381004B1 (en) | 1981-06-12 |
DE2803420A1 (en) | 1978-08-31 |
IT7819220A0 (en) | 1978-01-12 |
FR2381026B1 (en) | 1983-09-30 |
DE2803420C2 (en) | 1992-10-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4259193A (en) | Overbased sulphonates | |
US4235810A (en) | Alkylates and sulphonic acids and sulphonates produced therefrom | |
CA2236318C (en) | Mixture of earth-alkaline metal alkyl-aryl-sulphonates, its use as additive for lubricating oil and method of preparation | |
US3764533A (en) | Oil soluble dialkaryl sulfonate compositions | |
CA2171357C (en) | Superalkalinized isomerized linear alkylaryl sulfonates of alkaline earth metals and useful as detergent/dispersant additives for lubricating oils, processes for their preparationand intermediate alkylaryl hydrocarbon | |
CA1103699A (en) | Alkylates and sulphonic acids and sulphonates produced therefrom | |
US4165291A (en) | Overbasing calcium petroleum sulfonates in lubricating oils employing monoalkylbenzene | |
US8293698B2 (en) | Alkylaryl sulfonate detergent mixture derived from linear olefins | |
US3422161A (en) | Unsymmetrical dialkylbenzene mixtures | |
US3933201A (en) | Method using overbased branched-chain alkylaromatic sulfonates as waterflood additives | |
US4153627A (en) | Sulphonic acids and sulphonates | |
CA1270260A (en) | Process for the preparation of a low viscosity alkyl toluene or alkyl xylene sulfonate | |
US4618458A (en) | Sulphonic acids and sulphonates | |
US3367865A (en) | Oil-soluble metal sulfonates and lubricants containing them | |
US3703475A (en) | Preparation of oil soluble sulfonic acids useful as dispersant additives | |
JPS6340781B2 (en) | ||
GB2232665A (en) | Sulphonic acid derivatives and their use as emulsifiers | |
EP0354621A1 (en) | Overbased sulphonates and their use as additives | |
US3661780A (en) | Hydrocarbon composition containing polyalkyl-substituted tetrahydro-naphthalenes and di-n-c10-c15-alkaryl hydrocarbons and process for preparing same | |
US3816354A (en) | Alkyl aromatic polysulfonate surfactants | |
US3476800A (en) | Oil-soluble sulfonic acids and process for manufacture thereof | |
SU759576A1 (en) | Method of producing sulfonate additive to lubricating oils | |
SU759577A1 (en) | Method of producing sulfonate additive to lubricating oils | |
CS256600B1 (en) | Method of oil-soluble aromatic sulphoacids and aromatic sulphonates production | |
CN105829281A (en) | Process for preparing a para-linear alkyl-substituted hydroxyaromatic compound |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEX | Expiry |