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
  • C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
  • C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
  • C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
  • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
  • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
  • C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/40—Fatty vegetable or animal oils
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/40—Fatty vegetable or animal oils
  • C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/10—Semi-solids; greasy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2070/00—Specific manufacturing methods for lubricant compositions
  • C10N2070/02—Concentrating of additives

Definitions

• Alkylsalicylic acids having a high degree of para-substitution and having the alkyl group attached to the benzene nucleus by a quaternary carbon atom are prepared from tertiary alkylating agents and in particular 'by a two stage alkylation of phenol using a straight chain monoolefin in the first stage and a branched monoolefin 'm the second stage.
• the polyvalent metal salts of said acids are excellent lubricant and fuel additives characterized by improved high temperature performance, the ability .to keep the interior of engine cylinders clean and to counteract deposition of carbonaceous matter on pistons and piston ring grooves.
• This invention relates to alkylsalicyclic acids and their polyvalent metal salts as novel compounds and to processes to prepare these compounds.
• the invention particularly relates to the application of basic polyvalent compounds as additives in lubricants and fuels.
• British Pat. 1,146,925 relates to lubricant compositions with improved dispersant properties at high temperatures, comprising one or more lubricants and one or more salts of polyvalent metals and alkylsalicylic acids, which alkylsalicylic acids contain at least one alkyl group having more than 12 carbon atoms and of which more than 60% m. consists of acids with an alkyl group that is attached to the benzene nucleus in para-position relative to the hydroxyl group.
• alkylsalicylic acids of which 88% m. contains an alkyl group that is attached to the benzene nucleus in para-position-relative to the hydroxyl group. These acids can be converted via conventional methods into the .desired salts.
• Etforts to find a suitable way to decrease the quantity of 2-al-kylphenol in the alkylate have heretofore failed.
• the quantity of 2,4-dialkylphenol was increased at the cost of the quantity of 2-alkylphenol, formed during alkylation by applying more severe alkylation conditions (higher alkylation temperature and large excess of olefins).
• this only led to an increase in the percentage of noncarboxylatable 2,4,6-trialkylphenol in the alkylate, while the yield of.2,4-dialkylphenol hardly increased.
• Another possibility investigated was the separation of the Z-alkylphenol from the mixture of alkylphenols.
• the invention therefore, relates to salts of polyvalent metals and alkylsalicylic acids containing at least one alkyl group having more than 12 carbon atoms and having an alkyl group in the para position relative to the hydroxyl group, the para positioned alkyl group being attached to the benzene nucleus by a quaternary carbon atom.
• Alkylation agents having such a structure that the alkyl group which attaches to the benzene nucleus is attached to it with a quaternary carbon atom, will for the sake of brevity be indicated hereinafter as tertiary alkylation agents.
• tertiary alkylation agents Generally at least 25% m. and preferably 30% in. of the para-positioned alkyl groups are attached- .polyisobutenes, triisopentene and higher polyisopentenes,
• diisooctenes and higher polyisooctenes etc. or precursors for these olefins such as monohydroxyalkanes in which the hydroxyl group is attached to a tertiary carbon atom or occurs in an a-position relative to a tertiary carbon atom in the molecule.
• the alkylation of phenol is preferably carried out in two stages using a different alkylation agent in each stage,
• a-tertiary alkylation agent having from 4 to 12 carbon atoms-in the molecule and the other an alkylation agent containing a hydrocarbon group having from 12 to 30 carbon atoms.
• suitable tertiary alkylation agents are in this case monoolefins having from 4 to 12 carbon atoms in the molecule which are branched at one or both of the carbon atoms adjacent to the double bond, or precursors'for these olefins.
• R represents an alkyl group having from 1 to 9 carbon atoms.
• monoolefins are isobutene, isopentene and isohexene. Particularly suitable is isobutene.
• suitable alkylation agents which can be used in combination with the above-mentioned tertiary alkylation agents are straight-chain olefins having from 12 to 30 carbon atoms in the molecule, for example tridecene, tetradecene, pentadecene, etc. Mixtures of such straight-chain monoolefins are very suitable, in particular such olefin mixtures obtained in cracking straight-chain paratl'ins, e.g. straight-chain'parafiins obtained by means of urea extraction or by selective separation by means of molecular sieves.
• Alkyl groups attached with a quaternary carbon atom to the benzene nucleus show the tendency to shift under the prevailing alkylation conditions (for example a shift from the para to the ortho position). This shift is proportionally greater the longer the alkylate is in contact with the alkylation catalyst. Since the two-stage alkylation of phenol has as its primary purpose a maximum yield of para-substituted material,
• the contact between the para-tert-alkylphenol and the alkylation catalyst should be as short as possible.
• the two-stage alkylation of phenol as hereinbefore described is preferably carried out in such a way that the tertiary alkylation agent is applied in the second kinds of clays.
• the most frequently used clay catalysts come from naturally occurring sources, such as bentonites composed of montmorillonite, from halloysites, and from kaolinite clays.
• the specific type of clay used is not very critical if the clay selected is low in iron content and substantially free from various elements such as heavy metals which would favor either poisoning of the catalyst or the production of undesired products. Both pellet or fluid powder forms can be used.
• the clays are usually activated by treatment with a mineral acid, such as sulfuric, at
• the *alkylphenols are converted into the corresponding alkylphenates, which 7 are then treated with CO at about 140 C. and'a pressure of 10 to 30 atm.
• the alkylsalicylic acids are obtained from the alkylsalicylates by using, for example, a 30% sulphuric acid solution.
• the salts according to the invention are suitable for use as additives in lubricants and fuels. They are of special importance as additives in lubricating oils, because they are capable of keeping the interior of engine cylinders, in particular diesel engine cylinders, clean, and of counteracting deposition of carbonaceous products on pistons and in piston ring grooves.
• salts according to the invention are used as .lubricant additives
• basic salts are preferable because these salts, in addition to their dispersant action, are capable of neutralizing acid compounds formed during the combustion process in the engine.
• a basicity up 'to about 250% is in most cases suflicient.
• Favorable results can, however, be obtained by using polyvalent metal salts of the present type with a basicity between 25 and 225%, e.g. polyvalent metal salts with a basicity of about 50% or of about 200%.
• Particularly eligible among the salts of polyvalent metals and alkylsalicylic acids as lubricant oils additives are the salts of bivalent metals. Preference is given to salts of Group II metals, particularly alkaline earth metals and most particularly to calcium salts.
• alkylsalibelonging to S.A.E. grades from SWto 70W are accep'table.
• Suitable oils can also be derived from highly paraflinic or highly napthenic oils with substantial amounts or aromatics. Chemical or selective solvent treatment can be used if desired.
• Mixed base crudes and highly aromatic crudes containing parafiinic hydrocarbons are also suitable base'stocks after refining.
• the mineral oil bases can be blends of distillate lubricating oils and bright stocks or they can be mixed with, or even entirely replaced by, synthetic lubricants or polymerized olefins such as polyisobutylene.
• the polyvalents salts of the invention can also be added to lubricating greases.
• the salts of the polyvalent metals and the alkylsalicylic acids can be incorporated as suchin the lubricant or in the form of a concentrate that has been obtained, for example, by mixing the salts withasmall quantity of oil.
• Example A and B are prior art methods.
• Examples I and II are examples according to the present invention.
• the C -C olefin mixtures used in Example B, I and II was a mixture of straight-chain monoolefins with 15-18 carbon atoms, in the molecule, obtained in cracking straight-chain paraflins obtained by means of urea extraction.
• Example 11 Phenol was alkylated at 200 C. with a mixture of C -C olefins (molar ratio 13:1) with 5% w. of acid clay as catalyst.
• the alkyl-phenols thus obtained were subsequently alkylated at C. with isobutene (molar ratio 1:1.1), again with 5% w. of acid clay as catalyst.
• the alkylphenols obtained in this second alkylation were converted into the corresponding alkylsalicylic acids by phenation, carboxylation and hydrolysis. In this way 1 mole of C -C olefins yielded 0.5 mole of alkylsalicylic acids with the following composition:
• the catalyst was prepared as in Example I and the phenols were alkylated, converted into the corresponding alkylsalicylic acids and the basic calcium salts were prepared and recovered under conditions similar to those given in Example I.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Lubricants (AREA)

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Cited By (18)

Families Citing this family (13)

• 1968
  • 1968-12-19 GB GB60355/68A patent/GB1184020A/en not_active Expired
• 1969
  • 1969-12-17 BE BE743261D patent/BE743261A/xx unknown
  • 1969-12-17 NL NLAANVRAGE6918900,A patent/NL169730C/xx not_active IP Right Cessation
  • 1969-12-17 SE SE17379/69A patent/SE359537B/xx unknown
  • 1969-12-17 DE DE1963320A patent/DE1963320C3/de not_active Expired
  • 1969-12-17 FR FR6943706A patent/FR2026542A1/fr not_active Withdrawn
  • 1969-12-17 US US885982A patent/US3704315A/en not_active Expired - Lifetime

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