Patent GB-1044148-A (GB)
Title: Carbonated calcium sulfonate complexes
IPC: B01J13/00
Filed: 1964-08-27
Abstract: A paint drier comprises a substantially neutral, carbonated calcium sulphonate complex having a metal ratio of at least 10, which is prepared by mixing a mass in which at 50 DEG  C. at least 50% of the components are in the liquid state, and in which mass the active components are:  (A) a carbonated calcium sulphonate complex having a metal ratio of from 1.1 to 8.0; (B) an oil-soluble calcium phenate; the ratio of equivalents of A : B being from 20 : 1 to 2 : 1; (C) at least 5% by weight of (A) of an aliphatic monohydric alcohol; (D) a calcium base, in an amount such that there is present in the mass a total of at least 10 equivalents of calcium per equivalent of (A); and then treating the mass with CO2 until the base number thereof is less than 20 and heating it to drive off substantially all the alcohol and any water present.  Numerous examples are given of the component A, those preferred being complexes of carbonated calcium petroleum sulphonate, carbonated calcium mahogany sulphonate, carbonated calcium alkaryl sulphonate and carbonated calcium tridecyl benzene bottoms sulphonate.  Principally useful as component (B) are the calcium phenates of alkylphenols and alkylphenolaldehyde condensation products in which the alkyl substituent or substituents contain a total of at least 6 carbon atoms to impart oil solubility, e.g. a calcium phenate of a heptylphenol - formaldehyde condensation product. The component (C) is preferably an alkanol containing from 1 to 12 carbon atoms. A mixture of methyl, isobutyl and primary amyl alcohols is particularly suitable.  Component (D), the calcium base, is generally calcium oxide or calcium hydroxide.  An example describes a composition of a rutile-base house paint and a substantially neutral carbonated calcium sulphonate complex of the invention.  A lubricant comprises a major proportion of a lubricating oil and a minor proportion of a substantially neutral carbonated calcium sulphonate complex having a metal ratio of at least 10 which is prepared by mixing a mass in which at 50 DEG  C. at least 50% of the components are in the liquid state, and in which mass the active components are:  (A) a carbonated calcium sulphonate complex having a metal ratio of from 1.1 to 8.0; (B) an oil-soluble calcium phenate; the ratio of equivalents of A : B being from 20 : 1 to 2 : 1; (C) at least 5% by weight of (A) of an aliphatic monohydric alcohol; (D) a calcium base, in an amount such that there is present in the mass a total of at least 10 equivalents of calcium per equivalent of (A); and then treating the mass with CO2 until the base number thereof is less than 20 and heating it to drive off substantially all the alcohol and any water present. Numerous examples are given of the component (A) those preferred being complexes of carbonated calcium petroleum sulphonate, carbonated calcium mahogany sulphonate, carbonated calcium alkaryl sulphonate and carbonated calcium tridecyl benzene bottoms sulphonate.  Principally useful as component (B) are the calcium phenates of alkylphenols and alkylphenol-aldehyde condensation products in which the alkyl substituent or substituents contain a total of at least 6 carbon atoms to impart oil solubility, e g a calcium phenate of a heptylphenol-formaldehyde condensation product.  The component (C) is preferably an alkanol containing from 1 to 12 carbon atoms. A mixture of methyl, isobutyl and primary amyl alcohols is particularly suitable.  Component (D), the calcium base, is generally calcium oxide or calcium hydroxide. The lubricating oil is generally a mineral oil having a Saybolt viscosity of from 75 seconds at 100 DEG  F. to 250 seconds at 210 DEG  F.  Synthetic oils, such as polymerized polyisobutene, polymerized cracked paraffin waxes, dioctyl adipate or dioctyl sebacate or naturally occurring vegetable or animal oils may also be used. Numerous lubricant additives are mentioned those particularly useful with the sulphonate complexes being zinc dihydrocarbyl phosphorodithioates, phosphorus pentasulphide treated terpenes or alkaline earth metal alkylphenate sulphides.ALSO:A substantially neutral, carbonated calcium sulphonate complex having a metal ratio of at least 10 is prepared by mixing a mass in which, at 50 DEG  C. at least 50% of the components are in the liquid state, and in which mass the active components consist of (A) a carbonated calcium sulphonate complex having a metal ratio of from 1.1 to 8.0; (B) an oil-soluble calcium phenate; the ratio of equivalents of A:B being from 20: 1 to 2: 1; (C) an aliphatic monohydric alcohol, in an amount of at least 5% by weight of (A); (D) a calcium base, in an amount such that there is present in the mass a total of at least 10 equivalents of calcium per equivalent of (A); and then treating the mass with carbon dioxide until the base number thereof is less than 20 and heating it to drive off substantially all the alcohol and any water present.  Numerous examples are given of the component A which may be prepared by carbonating a mixture of calcium sulphonate and/or sulphonic acids, calcium base and a promoting agent which is an active hydrogen compound such as water or alcohol water mixtures.  Those preferred are complexes of carbonated calcium petroleum sulphonate, carbonated calcium mahogany sulphonate, carbonated calcium alkaryl sulphonate and carbonated calcium tridecyl benzene bottoms sulphonate.  Principally useful as component (B) are the calcium phenates of alkylphenols and alkylphenolaldehyde condensation products, in which the alkyl substituent or substituents contain a total of at least 6 carbon atoms to impart oil solubility, e.g. a calcium phenate of a heptylphenol-formaldehyde condensation product.  The component (C) is preferably an alkanol containing from 1 to 12 carbon atoms.  A mixture of methyl, isobutyl and primary aryl alcohols is particularly suitable. Component D, the calcium base, may be calcium oxide, calcium hydroxide, calcium sulphide, calcium hydrosulphide, calcium amide, calcium carbide, calcium hydride, calcium peroxide, calcium nitride or a calcium alcoholate such as calcium methoxide or calcium ethoxide or a calcium alkyl carbonate such as calcium methyl carbonate.  The complexes are particularly useful in lubricants (see Division C5).ALSO:A stabilizing agent for plastics, particularly halogen-containing plastics, comprises a substantially neutral, carbonated calcium sulphonate complex having a metal ratio of at least 10 which is prepared by mixing a mass in which at 50 DEG  C. at least 50% of the components are in the liquid state, and in which mass the active components are: (A) a carbonated calcium sulphonate complex having a metal ratio of from 1.1 to 8.0; (B) an oil-soluble calcium phenate; the ratio of equivalents of A:B being from 20:1 to 2:1; (C) at least 5% by weight of (A) of an aliphatic monohydric alcohol; (D) a calcium base, in an amount such that there is present in the mass a total of at least 10 equivalents of calcium per equivalent of (A); and then treating the mass with CO2 until the base member thereof is less than 20, and heating it to drive off substantially all the alcohol and any water present. Numerous examples are given of the component A, those preferred being complexes of carbonated calcium petroleum sulphonate, carbonated calcium mahogany sulphonate, carbonated calcium alkaryl sulphonate and carbonated calcium tridecyl benzene bottoms sulphonate. Principally useful as component (B) are the calcium phenates of alkyl-phenols and alkylphenolaldehyde condensation products in which the alkyl substituent or substituents contain a total of at least 6 carbon atoms to impart oil solubility e.g. a calcium phenate of a heptylphenol - formaldehyd condensation product. The component (C) is preferably an alkanol containing from 1 to 12 carbon atoms.  A mixture of methyl, isobutyl, and primary amyl alcohols is particularly suitable.  Component (D), the calcium base, is generally calcium oxide or calcium hydroxide.  An example describes a composition of polyvinyl chloride, dioctyl phthalate and a substantially neutral carbonated calcium sulphonate complex of the invention.  Calcium phenates of alkylphenolaldehyde condensation products may be prepared by (a) condensation of the alkylphenol and aldehyde in a mole ratio of 4:1 to 1:4 at 50-200 DEG  C. in the presence of a basic or acidic catalyst followed by reaction with a calcium base; (b) as in (a) but using the calcium base as a catalyst for the condensation reaction and for supplying the calcium necessary for phenate formation; or (c) preparing the calcium phenole by heating the alkylphenol and calcium base and then condensing this product with an aldehyde. Examples describe the preparation in mineral oil of the calcium phenate of (i) a heptylphenolformaldehyde resin; (ii) a polyisobutene-substituted phenol - formaldehyde resin; (iii) a C15 alkyl substituted phenol-formaldehyde resin and (N) tertiary octylphenol formaldehyde resin.