Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/26—Carboxylic acids; Salts thereof
  • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
  • C10M129/42—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms polycarboxylic
• • 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
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• • 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
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
  • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
• • 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
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
  • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
• • 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
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains 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
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/22—Acids obtained from polymerised unsaturated acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

Definitions

• This invention concerns corrosion inhibiting compositions which are useful as light duty or temporary corrosion preventatives and heavy duty or permanent corrosion preventatives.
• the invention relates to coatings which may be applied to metal for protection during storage between fabrication and use.
• coatings are generally applied from oil solution by spraying or dipping and must adhere to the metal sufficiently to give the desired anti-­corrosion effect during the storage period which can be up to 6 months whilst at the same time being readily removable generally by washing with aqueous alkaline detergent to enable the metal to be painted. It is therefore important that the coatings have adequate light stability to ensure they are not converted to a laquer during storage which cannot then be easily removed.
• Corrosion inhibiting compositions based on alkali or alkaline earth metal salts are known.
• US Patent No. 3 453 124 relates to a product for inhibiting the corrosion of metal surfaces prepared by the reaction of (A) a non-Newtonian colloidal dispersed system comprising alkali or alkaline earth metal carbonates predispersed in dispersing medium and, as a third essential component, an alkali or alkaline earth metal salt of a carboxylic or sulphonic acid with (B) an acidic ester of a phosphoric acid.
• A a non-Newtonian colloidal dispersed system comprising alkali or alkaline earth metal carbonates predispersed in dispersing medium and, as a third essential component, an alkali or alkaline earth metal salt of a carboxylic or sulphonic acid with (B) an acidic ester of a phosphoric acid.
• US Patent No. 3 730 895 concerns greases thickened with conventional grease thickeners and containing a cloudy type overbased alkali metal or alkaline earth metal sulphonate or carboxylate dispersant and a water-soluble corrosion inhibiting salt, that is an alkali metal nitrite or an alkali metal chromate.
• US Patent No. 3 850 823 discloses a method for producing corrosion inhibiting compositions comprising lubricating oil, a cloudy type overbased alkali metal and/or alkaline earth metal dispersant and at least one water-soluble salt effective as a corrosion inhibitor, that is an alkali metal nitrite or an alkali metal chromate.
• US Patent No. 3 897 350 relates to anti-rust lubricating and hydraulic oil compositions containing a naphthtol, a metal sulphonate selected from neutral alkali metal sulphonate, neutral alkaline earth metal sulphonate, neutral zinc sulphonate, overbased alkali metal sulphonate, overbased alkaline earth metal sulphonate, and overbased zinc sulphonate, and a detergent selected from alkenyl succinimides, alkenyl succinic esters, alkyl lactone amides, alkyl lactam amides, and Mannich bases.
• PCT Application WO 86/03513 concerns corrosion inhibiting compositions comprising a mixture of (A) an oil-soluble neutral or basic alkali metal or alkaline earth metal salt or complex of an organic acid, and (B) a nitrogen- and boron- containing composition which is the reaction product of an amino alcohol, a boric acid or boron trioxide, and an organic carboxylic acid.
• US Patent No 3 714 042 discloses a composition prepared by a process comprising mixing (A) a basic metal complex selected from sulphonate, sulphonate-carboxylate and carboxylate complexes with up to an amount equivalent to the total basicity thereof of (B) a high molecular weight aliphatic carboxylic acid or anhydride wherein there are at least about 25 aliphatic carbon atoms per carboxy group in (B), such mixing is generally effected at temperatures that will cause the products to react.
• A a basic metal complex selected from sulphonate, sulphonate-carboxylate and carboxylate complexes with up to an amount equivalent to the total basicity thereof of (B) a high molecular weight aliphatic carboxylic acid or anhydride wherein there are at least about 25 aliphatic carbon atoms per carboxy group in (B), such mixing is generally effected at temperatures that will cause the products to react.
• Oxidation can be prevented or at least in large measure inhibited, by relatively impermeable coatings which have the effect of excluding moisture and/or oxygen from contact with the metal surface.
• coatings are often exposed to high humidity, corrosive atmosphere, etc, and to the extent that these coatings are penetrated or otherwise harmed by such influences they become ineffective for the desired purpose.
• a satisfactory corrosion-proof coating must have the ability to resist weathering, high humidity and corrosive atmospheres, such as air contaminated with industrial waste, so that a uniform protective film is maintained on all or most of the metal surface.
• a corrosion inhibiting composition comprises a mixture of (A) at least one basic metal sulphonate and (B) at least one aliphatic dicarboxylic acid or anhydride containing no more than 38 carbon atoms excluding the carbon atoms in the carboxylic acid or anhydride groups or a metal salt thereof.
• the metal salts of component (A) may be a group I or group II metal such as lithium, sodium, potassium, magnesium, calcium, strontium or barium.
• An alkaline earth metal and especially calcium is preferred, sodium salts are less preferred since their light resistance is inferior.
• Component (A) may be the salt of a natural or synthetic sulphonate and is preferably a metal salt of an alkyl substituted aromatic sulphonic acid.
• the product should have a residual basicity and we prefer it have a TBN of at least 40 preferably greater than 60. Blends of neutral and basic sulphonates may also be used.
• the sulphonic acid is a benzene sulphonic acid having 1-3 alkyl substituents in the meta and para positions of the benzene ring or a naphthalene sulphonic acid. Said alkyl substituents may be branched or linear or cyclic alkyl residues.
• At least one of said alkyl substituents of the benzene sulphonic acid is a "long-chain residue" containing from 12-50 carbon atoms.
• the additional alkyl substituents may also be long-chain residues or they may be short-chain residues containing less than 12 carbon atoms, for example, methyl or ethyl groups.
• Many processes have been described for the production of basic metal salts of such sulphonic acids and the choice of process is not important although the thixotiopic forms of the sulphonates, particularly calcium sulphonate, are not preferred since they can be difficult to remove from the metal.
• component (A) consists of a mixture of different alkyl benzene sulphonates which mainly differ in the size of their long-chain alkyl substituents. It is especially preferred that an even distribution of alkyl substituents continuously increasing in size is present in component (A). The substituents may increase in size over a range of 20 carbon atoms, especially from C10 to C30. Compositions according to this invention containing such mixtures of alkyl benzene sulphonates yield films on metal surfaces which are especially resistant to weathering and humidity.
• Component (B) is preferably an alkyl or alkenyl succinic acid or anhydride or a salt therefore preferred salts are the alkyl or alkenyl succinic acids or anhydrides containing from 6-32 aliphatic carbon atoms particularly those 10 to 24 especially 10 to 14 carbon atoms excluding those in the carboxylic acid groups or their salts.
• component (B) be present as the free acid or anhydride rather than the salt prior to application to the metal protected since it is believed that the presence of the free acid or anhydride can give improved adhesion to the metal.
• composition according to the present invention may further comprise a minor amount of a monocarboxylic metal salt, for example a formic acid salt.
• a monocarboxylic metal salt for example a formic acid salt.
• the mixture contains from 95% to 75% by weight of the basic metal sulphonate and from 5% to 25% by weight of the component B although the relative amounts will depend upon the use to which the composition is put. It is especially preferred that component (B) makes up 10-50 wt% of the total amount of components (A) and (B). It is preferred that the composition have residual basicity.
• the corrosion inhibiting compositions are employed as coating compositions which are solutions in a liquid vehicle.
• liquid vehicles are hydrocarbon oils and the various petroleum distillates which generally contain up to 15 wt% of the corrosion inhibiting composition, particularly up to 10 wt% generally between 0.5 and 5 wt% active ingredient content of the composition of the invention.
• the composition contains a non-polar vehicle there may additionally be present some metal in solid (colloidal) form associated with components (A) and (B) action as dispersants.
• the vehicle may also be a water-based system, for example a mixture of polyisobutylene, wax and water.
• the coating composition including the vehicle is usually grease-like material having a consistency from fluid to semi-solid.
• the corrosion inhibiting films of this invention may be applied to metal surfaces by any of the ordinary methods such as brushing, spraying, dip-coating, flow-coating, roller coating and the like.
• the viscosity of the corrosion inhibiting coating composition may be adjusted for the particular method of application selected by adding a suitable amount of diluent.
• the corrosion inhibiting compositions according to the present invention may be prepared in different ways, for example, by preparing the metal salts independently and mixing them subsequently. Alternatively a solution of an overbased metal sulphonate complex can be prepared to which an aliphatic dicarboxylic acid or its anhydride is added.
• the products are mixed in a manner that they do not react, i.e. the temperature is maintained below about 50°C although reaction products of components (A) and (B) are within the scope of the invention.
• the amount of the aliphatic dicarboxylic acid or its anhydride added to the overbased metal sulphonate complex should be such that the resulting mixture is overbased. Such overbased mixtures are also useful as corrosion inhibiting compositions.
• composition may be supplied as a concentrate preferably a solution of the mixture of (A) and (B) in oil in which case it is preferred that the solution contains from 20% to 60% active ingredient.
• the components may be supplied separately for incorporation into the final coating medium.
• the corrosion coatings of the present invention have improved weather resistance particularly resistance to light and can be readily removed from the metal to enable painting etc.
• the coatings may be used on metal sheets to be used for automobile manufacture, constructional steelwork in building and bridge building etc.
• compositions may also contain other additives such as antioxidants, antifoams, etc.
• additives such as antioxidants, antifoams, etc.
• the invention is further illustrated by the following examples.
• compositions according to the present invention and comparative compositions were prepared and their corrosion inhibiting effects were determined according to the methods of DIN 51 386 and DIN 50 017.
• Each cycle consisted of an eight hour period at a temperature of 40 ⁇ 3°C and a relative humidity of 100% followed by a 16 hour period at a temperature in the range of from 18-28°C and a relative humidity of less than 75%.
• compositions tested were based on mineral oil. They consisted of 94 wt.% mineral oil and 6 wt.% active ingredient (that is anything different from mineral oil). All compositions tested had a total base number in the range of from 6-10 milligram KOH/gram.
• a composition was prepared containing 94 wt.% of mineral oil (130 neutral base stock) and 6 wt.% of a mixture of calcium sulphonates.
• the calcium sulphonates employed were the neutral salt of 4-(C12-alkyl)-3,5-dimethyl benzene sulphonic acid and the basic salt of 4-(C24-alkyl) benzene sulphonic acid having a TOTAL BASE NUMBER (TBN) of 250 to give a blend of TBN 60 .
• TBN TOTAL BASE NUMBER
• a composition was prepared containing 94 wt.% of mineral oil (130 neutral base stock), 5.5 wt.% of a mixture of calcium sulphonates and 0.5 wt.% of solid calcium carbonate in colloidal form.
• the calcium sulphonates employed were salts of 4-(C12 -alkyl)-3,5-dimethyl benzene sulphonic acid, 4-(C18-alkyl) benzene sulphonic acid and 4-(C24-alkyl) benzene sulphonic acid of TBN 250 to provide the colloidal calcium carbonate.
• C12, C18 and C24 indicate the average number of carbon atoms in the long chain residue of the respective benzene sulphonic acid.
• a composition was prepared containing 94 wt.% of mineral oil (130 neutral base stock), 3.1 wt.% of a mixture of sodium sulphonates, 1.0 wt.% of a mixture of calcium sulphonates, and 1.9 wt.% of a calcium carboxylate.
• the sodium sulphonates employed were salts of 4-(C12 alkyl) -3,5-dimethyl benzene sulphonic acid and 4-(C24 alkyl) benzene sulphonic acid.
• the calcium sulphonates were the same as in Example 2.
• the calcium carboxylate was a salt prepared from an alkenyl succinic anhydride with an average number of 12 carbon atoms in the alkenyl residue.
• a composition was prepared containing 94 wt.% of mineral oil (130 neutral base stock), 4.0 wt.% of a mixture of calcium sulphonates used as in Example 3, and 2.0 wt.% of calcium carboxylate used in Example 4.
• Example 5 demonstrates the improved resistance to weathering and humidity of a composition according to the present invention.
• a comparison of Example 5 with Examples 2 and 3 shows the synergism between calcium sulphonates and calcium carboxylate.
• the products of the invention were compared with a similar composition containing the calcium salt of an C68 Alkenyl succinic acid, the products tested were prepared by adding the following formulations to oil (130 neutral base stock) to give the total active ingredient levels set out in Table 1.
• the formulations were tested as metal anti-corrosion coatings in the humidity cabinet (ASTM D 1748) and salt spray cabinet (ASTM B117) tests with the following results

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Paints Or Removers (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)
• Lubricants (AREA)

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Publications (2)

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Cited By (10)

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Citations (7)

• 1987
  • 1987-06-10 GB GB878713549A patent/GB8713549D0/en active Pending
• 1988
  • 1988-06-09 ES ES88305292T patent/ES2024024B3/es not_active Expired - Lifetime
  • 1988-06-09 DE DE8888305292T patent/DE3863848D1/de not_active Expired - Lifetime
  • 1988-06-09 AT AT88305292T patent/ATE65554T1/de not_active IP Right Cessation
  • 1988-06-09 EP EP88305292A patent/EP0295108B1/fr not_active Expired - Lifetime
  • 1988-06-10 WO PCT/GB1988/000450 patent/WO1988009831A1/fr unknown
  • 1988-06-10 JP JP63504723A patent/JP2728708B2/ja not_active Expired - Fee Related

Patent Citations (7)

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