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WO2006110961A2 - Nouveaux materiaux inhibiteurs de corrosion - Google Patents

Nouveaux materiaux inhibiteurs de corrosion Download PDF

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Publication number
WO2006110961A2
WO2006110961A2 PCT/AU2006/000540 AU2006000540W WO2006110961A2 WO 2006110961 A2 WO2006110961 A2 WO 2006110961A2 AU 2006000540 W AU2006000540 W AU 2006000540W WO 2006110961 A2 WO2006110961 A2 WO 2006110961A2
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Prior art keywords
corrosion inhibiting
inhibiting material
corrosion
acid
trans
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PCT/AU2006/000540
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English (en)
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WO2006110961A3 (fr
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Andrew Joseph Koplick
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A J Scientific Pty Ltd
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Priority claimed from AU2005902014A external-priority patent/AU2005902014A0/en
Application filed by A J Scientific Pty Ltd filed Critical A J Scientific Pty Ltd
Publication of WO2006110961A2 publication Critical patent/WO2006110961A2/fr
Publication of WO2006110961A3 publication Critical patent/WO2006110961A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors
    • 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
    • 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/145—Amides; N-substituted amides
    • 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
    • C23F11/18—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 inorganic inhibitors
    • C23F11/187—Mixtures of inorganic inhibitors

Definitions

  • This invention relates to methods and materials for the protection of metals from corrosion, more particularly - to corrosion inhibiting materials, including those materials that are suitable for water- and vapour- phase corrosion inhibition, to the incorporation of the corrosion inhibiting materials in polymers, and attachment to various substrates.
  • the invention relates to polymers incorporating vapour-phase corrosion inhibitors and vapour-phase corrosion-inhibiting materials that are capable of releasing corrosion inhibitors as vapour and to methods of producing such polymers incorporating these vapour phase corrosion inhibitors.
  • the metal-corrosion inhibitors are used in protecting metals from flash rusting, protecting metals exposed to corrosive environments in composite materials (e. g. cement); protecting electrical and electronic components as vapour-phase corrosion inhibitors; in fluids contained in various receptacles both aqueous (e. g. boilers, pipes) and non-aqueous (e. g. oil wells) and in humid atmospheres particularly during the transport of ferruginous metals; in coolant fluids for car radiators and industrial water coolers; in aqueous fluids for metal polishing and buffing; in aqueous fluids as metal chelates.
  • composite materials e. g. cement
  • protecting electrical and electronic components as vapour-phase corrosion inhibitors
  • in fluids contained in various receptacles both aqueous (e. g. boilers, pipes) and non-aqueous (e. g. oil wells) and in humid atmospheres particularly during the transport of ferruginous metals in coolant fluids for car radiators and
  • 'Metal' refers to any conventional metal and also alloys of metals such as carbon steel and metal alloys containing iron (mild steel) as well as zinc, aluminium, copper, brass, bronze.
  • the metals can be in such diverse forms as rolls, sheets, tubes, coils, piano wire or guitar strings and various electrical and electronic devices, their electrical terminals and internal electrical connections.
  • Mannich bases derived from either mono- or polyhydroxy aromatic compounds.
  • Mannich bases from monohvdroxyaromatic compounds Mannich bases derived from phenols with three dialkylaminomethyl groups in the 2, 4, 6-positions of the aromatic ring were synthesised by Bruson and Macmullen (U.S. Pat. No. 2,220,834; 1940) and were claimed as being soluble in water and noted as being useful as corrosion inhibitors. Also, phenols such as 2,4,6 tris(dimethylaminomethyl)phenol and 2,4-bis(dimethylaminomethyl)phenol that are soluble in mineral oil were disclosed as corrosion inhibitors for lubricating oils after tests in oil/water mixtures ( East German Pat. No.146754).
  • Bis(disubstituted-aminomethyl) phenols such as 2-(dialkylaminomethyl)-4- alkyiaminophenol and 2-(dialkylaminomethyl)-4-dialkylaminophenol have been disclosed as stablisers in cracked gasoline (U.S. Pat. No. 2,401 ,957) and several bis (disubstituted-aminomethyl)alkyl phenols (U.S. Pat. No. 4,322,304) have been reported as important additives for hydrocarbon fuel and lubricating compositions.
  • Mono-molecular Mannich bases derived from polyhydroxybenzenes such as hydroquinone were disclosed by Chenicek (U. S. Patent No. 2,553,441) as materials that prevent edible fats and oils of animal or vegetable origin from becoming rancid.
  • Compounds such as 2, 5-bis(dialkylaminomethyl)-1 ,4- dihydroxybenzene (where the alkyl group can designate methyl, ethyl or morpholino) as well as 2-dimethylaminomethyl-4-methoxyphenol were claimed to inhibit oxidative deterioration of fats and oils.
  • Mannich bases such as bis- ((dihydroxyalkyl)aminomethyl) hydroquinone were disclosed by Donovan and Bean (U.S. Patent No.
  • Dialkylaminomethyl resorcinol derivatives are disclosed in U.S. Patent No's: 3,798,051 ; 4,089,902 to Morita and in U.S. Patent No's 3,462,382; 3,504,040; 3,609.108 to Kolka, Tai and Moult.
  • the tris-substituted resorcinol compounds referred to in the above-mentioned patent were claimed to impart increased adhesive properties to rubber.
  • Vapour-phase corrosion inhibitors have been used for many years and many attempts to incorporate them into polymer melts used for extrusion or moulding have been made.
  • the basic problem is that known VPCIs have high volatility and reactivity at processing temperatures resulting in large losses of the VPCI material, chemical breakdown of the VPCIs and blistering or disfiguring of the extruded or moulded plastic. Since many VPCIs and their breakdown products are very toxic to humans their copious release during processing presents serious problems.
  • these materials are either in direct contact with metal parts or closely envelope these metal parts; and there remains a need to protect the metal parts from corrosion by using corrosion inhibitors incorporated in these materials and subsequently releasable form these materials when the metal parts are exposed to moisture.
  • the invention provides for novel corrosion inhibiting materials obtained by a chemical reaction between a Mannich base and other suitable reactants.
  • the Mannich bases of this invention are derived from hydroxyaromatic compounds, secondary amines or cyclic secondary amines and aldehydes.
  • the other reactants include:
  • organo-metallic compounds • metal oxides
  • the invention also provides for modified corrosion inhibiting materials obtained from an admixture of the corrosion inhibiting materials mentioned above and other complementary substances, wherein the complementary substances include:
  • the invention teaches that the predetermined chemical and physical properties of the corrosion inhibiting materials and of the modified corrosion inhibiting materials are achieved by variations in the structure of the hydroxyaromatic compounds, secondary amines and aldehydes.
  • the preparation of Mannich bases from the hydroxyaromatic compounds, aldehydes and amines is well documented in the chemical literature, however, this invention provides Mannich base compounds that have a range of suitable vapour pressures and solubility in aqueous fluids.
  • This invention provides Mannich bases as corrosion inhibiting materials for the purposes of protecting metal surfaces from corrosive attack either in the vapour phase or in aqueous fluids.
  • the gamut of chemical and physical properties required of such corrosion inhibiting materials is fulfilled by varying the chemical composition of the three main components that make up the Mannich bases, namely, hydroxyaromatic compounds, secondary amines and aldehydes.
  • This invention provides Mannich bases derived from the following: mono- and polyhydroxyaromatic compounds, secondary amines with saturated and unsaturated substituents, cyclic secondary amines in 5- or 6-membered ring compounds, cyclic secondary amines in azamacrocyclic rings having at least three nitrogen atoms; aldehydes both saturated and unsaturated.
  • Mannich bases prepared from monohydroxyaromatic comounds such as phenol, dimethylamine and formaldehyde to afford 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol and 2,6-bis(dimethylaminomethyI)phenol were found to be good corrosion inhibitors in both the water- and vapour-phase.
  • the properties of the above-mentioned Mannich bases namely, high water solubility and high volatility, are ideally suited for applications in humid atmospheres and in confined spaces where there is considerable condensation occurring on the surface of the metal articles to be protected.
  • the polar dialkylaminomethyl and phenolic OH groups confer water solubility whereas the dialkylaminomethyl groups adjacent to the phenolic OH group in the ortho position confer volatility because of intramolecular H-bonding of the phenolic hydrogen to the nitrogen atom of the dialkylaminomethyl moiety.
  • R is methyl
  • the highly volatile Mannich bases mentioned above required modification before they could be incorporated successfully into sachets, cardboard or polyolefinic films as water- and/or vapour-phase corrosion inhibitors.
  • the present invention provides Mannich bases as well as other homologue derivatives in which the alkyl substituents on the nitrogen atom can be varied to adjust their physical and chemical properties for specific applications. This aspect is important when the designated inhibitors are intended for use in polymeric films as vapour- phase corrosion inhibitors, since the rate of exudation and release of inhibitor from the surface of the film can be more easily controlled.
  • alkyl substituents are included on the hydroxyaromatic compound in the para position.
  • Alkyl substituents (C1 to C20) replaced the dimethylaminomethyl moiety on the aromatic ring of the hydroxyaromatic compound in para position so that it would be less volatile and more compatible with the polyolefinic film, polyisobutene (low-, medium- and high-molecular weight) or hydrocarbon solvent.
  • alkyl substitution in the para position of the Mannich bases, 2,6 bis(dimethylaminomethyl)phenol and 2-mono(dimethylaminomethyl)phenol affords inhibitors of less volatility and compatibility with polyolefinic substrates allowing for a sustained and controlled migration from the bulk of the substrates to the surface.
  • the alkyl substituents can vary in length from C1 -C20 but preferably from C1 -C9 and they may be straight-chained, branched and/or unsaturated. For instance, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert.-butyl, octyl, nonyl, allyl, vinyl.
  • the unsaturated substituents in the para position will allow the modified bases to be co-polymerised with acrylic or methacrylic acids to form water-dispersible polymers for use as corrosion inhibiting coatings.
  • the secondary amines as a group is the second component that can be varied to achieve desirable properties of the Mannich bases.
  • the secondary amines with saturated and unsaturated substituents in which the alkyl substituents on the N atom of the dialkylaminoalkyl moiety were lengthened to decrease the volatility of the Mannich base.
  • the alkyl substituents on the nitrogen atom can vary in length from C1-C20 but preferably from C1 -C12 and they may be straight-chained, branched and/or unsaturated, for instance, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert.-butyl, octyl, nonyl, decyl, neodecyl, hexadecyl and allyl.
  • the unsaturated substituents will allow the modified Mannich bases to be co- polymerised with acrylic or methacrylic acid to form water-dispersible polymers for use in coatings.
  • the long-chained alkyl substituents for instance decyl and hexadecyl confer compatibility and increase the residence time in the polymeric substrates.
  • the preferred amines utilised in the invention are secondary amines of the formula HN(RR') wherein R,R' are equivalent or different alkyl groups and may be linear, branched, saturated or unsaturated with C1-C12 carbon atoms, for example, R, R' may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.- butyl, decyl, allyl, sorbyl.
  • Cyclic secondary amines in 5- or 6-membered ring compounds may also be used to prepare the Mannich bases, for example, pyrrole, pyrrolidine, piperidine, piperazine, methylpiperazine, N- hydroxyethylpiperazine, imidazole, benzimidazole, morpholine.
  • Mannich bases for example, pyrrole, pyrrolidine, piperidine, piperazine, methylpiperazine, N- hydroxyethylpiperazine, imidazole, benzimidazole, morpholine.
  • the polymeric Mannich base compounds are obtained by reaction between either a 4-alkylsubstituted phenol or resorcinol with the following cyclic secondary amines: hexahydropyrimidine, tetrahydroimidazole, imidazolidenone, imidazolidenethione in the presence of an aldehyde such as formaldehyde.
  • a novel corrosion-inhibiting and metal-chelating Mannich-base polymeric/cyclic compound is described.
  • the compound is prepared by allowing either a para-substituted phenol or resorcinol to react with formaldehyde and hexahydropyrimidine.
  • the compound is prepared by allowing para-alkylated dimethylolphenol to react with the hexahydropyrimidine.
  • the compound is prepared by allowing N, N'-bis(hydroxymethyl) pyrimidine to react with a para-alkylated phenol.
  • the Mannich bases are derived from cyclic secondary amines in azamacrocyclic rings having at least three nitrogen atoms.
  • the reaction of the cyclic secondary amines for example, tri- and tetra-azamacrocycles
  • 2,4- dialkylsubstituted phenol in the presence of formaldehyde affords Mannich base chelating agents.
  • the macrocyclic chelates that act as corrosion inhibitors also have other uses such as in X-ray imaging, magnetic resonance imaging (MRI) and heavy metal detoxification.
  • the macrocyclic chelates may be prepared from the following cyclic secondary amines in azamacrocyclic rings: 1 ,4,8,11 - tetraazacyclotetradecane, 1 ,5,9,13-tetraazacyclohexadecane, 1 ,4,8,12- tetraazacyclopentadecane, 1 , 4,7,10-tetraazacyclododecane. 1 , 4, 7- triazacyclononane and cross-bridged 1 , 4, 7, 10- tetraazacyclododecane
  • Mannich bases derived from polyhydroxyaromatic compounds have out-standing corrosion- inhibiting properties both in the vapour- and aqueous-phase.
  • the Mannich bases derived from polyhydroxyaromatic compounds display the requisite range of vapour pressures under ambient conditions enabling them to be suitable VPCIs when incorporated as mixtures of VPCIs in various substrates.
  • Implementing a mixture of the Mannich bases, each with differing vapour pressure enables a continual supply of corrosion inhibiting vapours to be maintained over prolonged periods.
  • the invention provides novel low-molecular-weight Mannich bases derived from polyhydroxybenzenes, hydroxybenzoic and polyhydroxybenzoic acids or their derivatives as well as novel metal-corrosion inhibitors.
  • the Mannich bases of the invention are preferably prepared under the usual Mannich reaction conditions by heating under reflux in an inert solvent, adding stoichiometric amounts of amines, formaldehyde and the corresponding polyhydroxybenzenes, hydroxybenzoic and polyhydroxybenzoic acids or their derivatives, while continually removing the water of reaction as it forms.
  • the final product is obtained by distilling the solvent and residual reactants.
  • the reactants are heated under reflux at low temperatures as an aqueous mixture without solvent and the Mannich bases are extracted with ether, the ether dried, distilled and the product recrystallised from an alcohol such as methanol.
  • the corresponding Mannich bases of polyhydroxyaromatic compounds that were found to be suitable for use as corrosion inhibitors in the present invention include:
  • mono-cyclic six-membered-ring aromatic compounds having at least one hydroxy group in the ring with at least one other group in the ring being a carboxylic acid group or its derivatives.
  • the carboxylic acid groups are usually converted to an ester functional group with C1 to C8 that may be linear, branched, saturated or unsaturated.
  • 2-hydroxybenzoic acid salicylic acid
  • 3-hydroxybenzoic acid 3-hydroxybenzoic acid
  • 4-hydroxybenzoic acid 4- hydroxyallylbenzoate.
  • mono-cyclic six-membered-ring aromatic compounds having two hydroxy groups in the ring such as 1 ,2-dihydroxybenzene (catechol), 1 ,3- dihydroxybenzene (resorcinol) and 1 ,4-dihydroxybenzene (hydroquinone).
  • alkyl groups may be linear, branched, saturated or unsaturated and containing from C1 to C20, whereas the carboxylic acid group is usually converted to an ester functional group with C1 to C8 that may be linear, branched, saturated or unsaturated.
  • alkyl and alkoxy groups may be saturated or unsaturated, linear or branched and contain from C1 -C20 carbon atoms (e.g. eugenol).
  • alkoxy groups may be saturated or unsaturated, linear or branched and contain from C1-C20 carbon atoms (e.g. guaicol (2-methoxyphenol), 2- methoxyhydroquinone, 4-methoxyphenol.
  • formaldehyde, metaldehyde and paraldehyde are the aldehydes used in the synthesis of the Mannich bases in this invention.
  • Unsaturated aldehydes such as alpha-methylacrylaldehyde, trans,trans-2,4- hexadienal, fra/7s,frans-2,4-hepadienaUrans,fra/7s- octadienal, trans,trans- nonadienal and frans-cinnamaldehyde may be incorporated into the molecular structure so that volatility as well as the chemical nature can be modified with the presence of conjugated double bonds.
  • the preferred aldehydes are those of the formula RCHO wherein R is H or C1 -C!2 hydrocarbyl both saturated and unsaturated.
  • the main formaldehyde producing precursors include paraformaldehyde, trioxane or aqueous formaldehyde solutions.
  • Other aldehydes include acetaldehyde, propionaldehyde, butyraldehyde, crotonaldehyde and benzaldehyde.
  • the reactant is an organo-metallic compound.
  • the invention provides for the reaction products resulting from the interaction of metal alkoxides and other metal derivatives with the following:
  • FIG.2 A scheme depicting the formation of corrosion inhibiting materials from Mannich base, amino alcohols and carboxylic acid is presented in Fig.2. The scheme also demonstrates steps of attaching the organo-metallic compound to a metal oxide carrier or polymeric substrate and final liberation of the corrosion inhibitors upon hydrolysis.
  • the Mannich base is bonded to the metal centre of the organometallic compound as a nucleating ligand with or without other ligands such as amino alcohols and carboxylic acids.
  • the invention provides for a wide range of the organo-metallic compounds, including, but not limited to the following substances: metal alkoxides and other metal derivatives such as, alkoxometal carboxylates, oxometal carboxylates or metal carboxylates, for example, Ti(OPr) 4 , Zr(OR) 4 , Sn(OR) 4 ,WO(OR) 4 , MoO(OR) 4 , H 2 WO 4 , H 2 MoO 4 , B(OR) 3 , B(OH) 3 , RB(OH) 2 , P(OR) 3 , PO(OR) 3 , RPO(OH) 2 , AI(OI Pr) 3 , OAIOOCR, Si(OR) 4 ,RSi(OR) 4 where R is an alkyl substituent f
  • Mannich bases derived from mono- and polyhydroxyaromatic compounds bond to metal centres of organo-metallic compounds either as mono- or bidentate- ligands forming complexes that are designated in this invention as corrosion inhibiting precursors.
  • the organo-metallic compounds may simultaneously form reaction products with the above-mentioned Mannich bases, long-chained aliphatic acids both saturated and unsaturated (e.g.
  • This introduction of long-chained aliphatic carboxylic acids into the organo-metallic precursors allows for an increased solubility in the polymeric olefinic material and a delayed diffusion/migration from the bulk of the material.
  • the bonding of the long-chained aliphatic carboxylic acid to the organo-metallic precursor affects only the solubility and diffusion of the precursor in the polymeric olefinic material but not the volatility of the actual corrosion inhibitive materials such as the Mannich bases, carboxylic acids (e.g. sorbic acid) and amino alcohols that are also bonded to the same organo-metallic compound.
  • these precursors are involatile at ambient temperatures (20-30° C) and stable if kept in moisture-free atmospheres.
  • the latent corrosion inhibitors bound as precursors remain dormant until moisture hydrolyses the organo-metallic bond and releases the corrosion inhibitor as vapour.
  • the precursors are stable at melt temperatures in excess of 200 0 C on hot metallic surfaces during extrusion of polymeric material, enabling them to be easily incorporated into polymeric films without rupture. It has been found that following the preparation of polymeric films, these precursors migrate or diffuse through the polymeric material to its surface, where, upon hydrolysis, the volatile corrosion- inhibiting Mannich base and other volatile corrosion inhibiting substances such as amino alcohols or carboxylic acids are released.
  • the Mannich bases derived from polyhydroxybenzenes of this invention enable the use of corrosion inhibitors with a wide range of vapour pressures effecting an extended service period of the substrate by the continual supply of vapours.
  • the reaction product with alkoxides, such as, B(OR) 3 is not easily hydrolysed but is an excellent corrosion inhibitor in the aqueous phase.
  • vapour pressure in the range from 0.002 Pa to 2 Pa.
  • the invention therefore provides for the corrosion inhibiting materials that are derived as stated above to release two or more vapour phase corrosion inhibitors of different molecular weight and volatility.
  • the corrosion inhibitors with low volatility have low vapour pressure, whereas high volatility results in high vapour pressure.
  • the low volatility inhibitors are included to effect a rapid inhibition of corrosion.
  • the rapidity with which the volatile inhibitors are liberated is proportional to the concentration of water in the environment and their high volatility results in minimising the time lag between changes in corrosive conditions and the coverage of metal surface by the inhibitor that protects the metal from corrosion.
  • the low vapour pressure components are essential to maintain this protection over a longer period.
  • the invention provides for materials wherein the volatility can be varied within a family of chemically similar substances. Members of one family react with and are liberated from, for example, organo-metallic compounds in a similar fashion.
  • N 1 N dimethylethanolamine when allowed to react with titanium tetraisopropoxide formed a stable compound that was successfully incorporated into low-density polyethylene from which a film was blown.
  • N, N dimethylethanolamine was released from a sample of the film as a vapour-phase corrosion inhibitor and prevented the corrosion of a metal surface.
  • the corrosion inhibiting materials were formed in which both the Mannich base and the amino alcohol are covalently bonded to the metal centre of the organometallic compound.
  • this invention provides mixed organo-metallic species as corrosion inhibiting materials (precursors) that can be easily incorporated into polyolefinic substrates and release simutaneously corrosion inhibitors of varying volatility.
  • the amino alcohols include: 2- methylaminoethanol, 2-dimethylaminoethanol, 1-amino-2-propanol, 1 , 1 1 -2-propanol,diethanolamine and triethanolamine.
  • the corrosion inhibiting material resulting from sequential chemical reactions of an organometallic compound with the Mannich base and the carboxylic acid such that both the Mannich base and carboxylic acid are covalently bonded to the metal centre of the organometallic compound.
  • corrosion-inhibiting volatile and unsaturated carboxylic acids such as frans-cinnamic acid, trans, frans-2,4-hexadienoic acid and trans,trans- ⁇ ,3- butadiene-1 ,4-dicarboxylic acids can be efficiently incorporated into polyolefinic substrates.
  • the reaction with the given organo-metallic conpound is carried out sequentially.
  • the molar ratio of the Mannich base and carboxylic acid to the organo-metallic compound has to be such that allows both to bond to the metal centre.
  • the other reactant is a metal oxide, including: calcium oxide or zinc oxide.
  • Corrosion inhibiting materials derived from the Mannich bases and the metal oxides are used as corrosion inhibiting additives in admixture with polyisobutene because of their tacky and adhesive properties. Application of such blends on tapes made from textiles or polymers as pipe-wraps provides good corrosion protection for metal surfaces.
  • the present invention discloses that the tertiary-N atoms of the Mannich bases may be easily converted to quaternary ammonium centres by reaction with inorganic acids, inorganic acid derivatives, or alkyl halides (e.g. HCI, HNO 2 , H 3 PO 4, , H 2 MoO 4 , H 2 WO 4 , phosphonic acids, alkylphosphonic acids, RCI, where R may be alkyl ) giving rise to salts with the corresponding anions and through subsequent reactions the anions may be substituted by corrosion-inhibiting anions such as , for example, MoO 4 2' , Mo x Oy 2" , NO 2 ' .
  • alkyl halides e.g. HCI, HNO 2 , H 3 PO 4, , H 2 MoO 4 , H 2 WO 4 , phosphonic acids, alkylphosphonic acids, RCI, where R may be alkyl
  • alkyl halide or acid halide is attached to the remaining tertiary-N centre.
  • the alkyl moiety may be straight-chained branched and/or unsaturated from C1-C20.
  • the acids may be myristric, octanoic, propionic, isostearic, frans-cinnamic acid, frans, fra/7s-2,4-hexadienoic acid and trans,transA ,3-butadiene-1 ,4-dicarboxylic acid.
  • Polyhydroxy acids such as gallic acid are useful as oxygen scavengers and were able to be incorporated into polyethylene through the use of these quatemerised Mannich bases.
  • the reaction products such as those mentioned above provide a means of introducing corrosion imhibiting anions into polyolefinic substrates which in turn diffuse and migrate to the surface of the polymer together with the Mannich base.
  • reaction products useful as corrosion inhibitors, obtained from the reaction between the phenolic hydroxyl group of the Mannich base and quaternary ammonium derivatives, metal cations and silanes containing reactive groups such as isocyanate or epoxy, for example, isocyanatopropyltrimethoxysilane or glycidoxypropyltrimethoxysilane.
  • the quaternary ammonium group is selected from the following: alkyltrimethylammonium wherein the alkyl group is a C8 to C18-substituent; dialkyldimethylammonium wherein the alkyl groups are C8 to C18-substituent or a mixture of the above; alkyltrihydroxyethylammonium wherein the alkyl group is a C8 to C18-substituent.
  • the quaternary ammonium phenolates of this invention are oil soluble and can be incorporated into hydrocarbon polymeric films such as polyethylene, polypropylene, polyisobutene or into hydrocarbon oils over a wide range of concentrations.
  • Metal salts e.g.
  • Sorbic acid ⁇ trans, trans-2, 4-hexadienoic acid was found to have sufficient vapour pressure at ca. 18-20° C to inhibit corrosion of a nail suspended in moist vapour. Contrary to the disclosures of the prior art, potassium sorbate at the same concentrations as for sorbic acid of this invention, displayed poor vapour-corrosion inhibition.
  • a significant advantage of having sorbic acid or its salts as a complementary substance in admixture with Mannich bases or corrosion inhibitive materials is that it is non-toxic and is readily incorporated into polyolefinic substrates.
  • reaction products of Mannich bases with organo-metallic compounds can be formulated in admixtures with the acids described above.
  • Other related conjugated systems such as the aldehydes trans, trans-2, 4-hexadienal transjrans -2,4-hepadienal, trans, fra ⁇ s-2,4-octanal and trans,trans- 2,4-nonadienal as well as fra/is-cinnamaldehyde, may also be incorporated into polyethylene for use as vapour-phase corrosion inhibitors as admixtures or be further modified by reaction with aminosilanes or epoxy silanes respectively, to afford materials that are exemplary aqueous corrosion inhibitors for metal surfaces.
  • VPCI precursors bonded to inorganic carriers and grafted to organic polymeric substrates
  • this invention provides:
  • inorganic substances by covalent bonding of VPCI precursors to inorganic metal oxide carriers such as silica, alumina, talc, mica, hydrotalcite or clay minerals such as montmorillonite or metakaolin from which VPCI can either be released by hydrolysis under neutral or alkaline conditions (pH 8-9);
  • the modified substrates (or carriers) are useful as fillers for cement, epoxide, polyesters and acrylic coatings as well as for polyolefinic substrates and the like.
  • the modified substances or carriers are grafted to the organic polymers such as polyethylene vinyl alcohols (EVOH) through the use of unsaturated bonds present in the precursors and radical graft initiators; these composites are then incorporated into polyolefinic substrates. 4.
  • VPCI precursors through the formation of metal- oxygen bonds to organic polymeric materials with abundant carboxylic acid and /or hydroxyl groups such as polyacrylic, polymethacrylic acids, polyvinyl alcohol (PVOH) and polyethylene vinyl alcohol (EVOH); these composites may then be incorporated into other organic polymers e.g. polyolefinic substrates or used as such to release VPCI on hydrolysis.
  • organic polymeric materials with abundant carboxylic acid and /or hydroxyl groups
  • PVOH polyvinyl alcohol
  • EVOH polyethylene vinyl alcohol
  • the present invention discloses the reaction of vapour-phase corrosion-inhibiting precursors (VPCI precursors) with active hydroxyl groups on various substrates such as zeolites, silica, alumina, talc, hydrotalcite and clays such as montmorillanite or metakaolin.
  • VPCI precursors vapour-phase corrosion-inhibiting precursors
  • the inorganic substrates are particulate carriers.
  • these particulate carriers comprise nano-particles.
  • the nano-particles are attached to a microparticle.
  • the nano- particles and micro-particles of the particulate carrier are of differing chemical composition.
  • the corrosion inhibiting materials were made from the Mannich bases, amino alcohols, both saturated and unsaturated carboxylic acids and organometallic compounds (for example metal alkoxides, oxometal carboxylates) in varying ratios so that some reactive alkoxy groups of the organometallic compounds were free to interact with hydroxyl groups on the inorganic substrates forming covalent metal- oxygen bonds.
  • organometallic compounds for example metal alkoxides, oxometal carboxylates
  • modified carriers were useful in enabling corrosion inhibitors to be incorporated into various composites such as cement, polyester, epoxide and acrylic coatings as well as polyolefinic substrates.
  • Unsaturated acid groups allow the VPCI attached to the inorganic substrates as well as the VPCI themselves to be grafted to various polymeric substances, e. g.
  • polyethylene vinyl alcohols EVOH
  • polyolefinic materials polyethylene, polypropylene, polyisobutene
  • the organo-metallic compounds comprise trialkyl borates with saturated and unsaturated substituents, tetraethylorthosilicate, aluminium triisopropoxide, oxoaluminium carboxylates and titanium tetraisopropoxide.
  • Graft polymers can be produced by activating the dissolved, suspended or melted polyolefinic polymer (e.g. polyethylene, polypropylene, polyisobutene or polyethylene vinyl alcohol (EVOH) with a radical initiator, adding either the corrosion inhibitor with ethylenically unsaturated carboxylic acid groups themselves or the corrosion inhibiting material that includes the corrosion inhibitors attached to the inorganic substrate.
  • polyolefinic polymer e.g. polyethylene, polypropylene, polyisobutene or polyethylene vinyl alcohol (EVOH)
  • a radical initiator e.g. polyethylene, polypropylene, polyisobutene or polyethylene vinyl alcohol (EVOH)
  • a radical initiator e.g. polyethylene, polypropylene, polyisobutene or polyethylene vinyl alcohol (EVOH)
  • a radical initiator e.g. polyethylene, polypropylene, polyisobutene or polyethylene vinyl alcohol (EVOH)
  • a radical initiator e.
  • VPCI covalent bonding of VPCI through the formation of metal-oxygen bonds to carboxylic acid groups and /or hydroxyl groups of the polymers such as polyacrylic, polymethacrylic acids, polyvinyl alcohol (PVOH) and polyethylene vinyl alcohol (EVOH) affords composites; these composites are incorporated into other organic polymeric substances e.g. polyolefinic substrates or used as such to release VPCI on hydrolysis.
  • PVOH polyvinyl alcohol
  • EVOH polyethylene vinyl alcohol
  • the present invention provides novel dendrimers resulting from the reaction of Mannich bases derived from certain poly-hydroxyaromatic compounds (such as hydroquinone, resorcinol or phloroglucinol (1 ,3,5-trihydroxybenzene)) with metallo- organic compounds (such as metal alkoxides, alkoxometal carboxylates, alkylmetal oxides, oxometal carboxylates or metal carboxylates,
  • metallo- organic compounds such as metal alkoxides, alkoxometal carboxylates, alkylmetal oxides, oxometal carboxylates or metal carboxylates,
  • the dendrimers produced form the above materials are generally unstable under corrosion causing conditions.
  • the dendrimers formed from some organo-metallic compounds e.g. B(OR) 3 , ) however, are not easily hydrolysed under neutral conditions and are good corrosion inhibitors in the aqueous phase.
  • the present invention allows for various types of multi-functional Mannich base corrosion inhibitors to be incorporated into protective coatings as dendrimers, preferably at concentrations sufficient to inhibit corrosion without affecting the physical properties of the coating. Hydrolysis by hydroxide ion formed under corrosion causing conditions would allow the slow release of corrosion inhibiting Mannich bases and nano-sized metal hydroxides/oxides.
  • the protective coatings may be any of the known types of protective coatings based on film forming polymers of resins, in particular, epoxy resins, vinyl resins or alkyd resins.
  • the physical and chemical properties of the highly branched macromolecules formed by successive reactions of these polyfunctional monomeric Mannich bases with metallo-organic derivatives depend on the initial core molecules and the subsequent number of iterative steps.
  • the 3 rd generation of dendritic Mannich base corrosion inhibitors with an initial core of phloroglucinol may have up to 12 peripheral boric acid moieties
  • the 3 rd generation of dendrimers with an initial core of boric acid may have up to 12 peripheral phioroglucinol Mannich bases groups. It is not necessary to bond with all the pendant hydroxyl groups on the periphery to form an effective corrosion inhibitive dendrimer.
  • peripheral hydroxyl groups may be allowed to react with such reactants as epoxy-or isocyanate-functionalised silanes, to give enhanced adhesion to metal surfaces. Interaction of the pendant hydroxyl groups with metallo-organic derivatives such as oxoalumimium carboxylates would provide compatibility with hydrocarbon polymers. Depending on the type of alkyl group in the dialkylaminomethyl groups of the Mannich base the secondary structure of the dendritic molecule could display either hydrophobic or hydrophilic behaviour.
  • the present invention provides new cost-effective corrosion inhibiting material used to protect buried conduits made of iron, steel or concrete reinforced with steel by incorporating the corrosion inhibiting materials into a textile or polymer wrap that provides a conduit contacting layer with the corrosion-inhibiting material impregnated therein.
  • the corrosion-inhibiting material may be selected from Mannich bases or their reaction products with organo-metallic compounds.
  • the slow release of the corrosion-inhibiting Mannich bases is achieved by modifying the structure of the Mannich bases through the use of various amines, aldehydes or hydroxy aromatic compounds.
  • high-density cross-laminated polyethylene provides an outer layer of the wrap whilst a low-density polyethylene allows the slow migration of the corrosion-inhibiting material towards the surface of the conduit.
  • a layer of medium density polyethylene is interposed between the outer and inner later to prevent migration of the corrosion inhibiting materials away from the metal surface.
  • the present invention also provides Mannich bases as well as other materials such as amino alcohols and carboxylic acids that are bound to organo-metallic compounds from which corrosion-inhibiting materials are released by hydrolysis after emerging from the bulk to the surface of the polymeric carrier. Diffusion or migration of the corrosion inhibiting materials including both Mannich bases and precursors made from
  • Mannich bases and organo-metallic compounds or other reactants depends heavily on the structure of the Mannich bases.
  • the structure is related to the type of hydroxy aromatic hydrocarbons, amines and aldehydes that are utilised to prepare these Mannich bases.
  • VPCI is only produced in the presence of moisture so that its concentration is directly related to the danger of corrosion and useless losses can be readily prevented by hermetic storage prior to use as a corrosion inhibitor.
  • Corrosion inhibiting materials derived from Mannich bases and metal oxides such as zinc oxide and calcium oxides have shown promise as corrosion inhibiting additives in admixture with polyisobutene because of their tacky and adhesive properties.
  • Application of such blends on tapes made from textiles or polymers as pipe-wraps provides excellent corrosion protection for metal surfaces.
  • Reaction products derived from the reaction of Mannich bases with carboxylic acid containing organo-metallic compounds such as oxoalumiuiumstearate can be conveniently dissolved in low-and medium-weight molecular polyisobutene, thus allowing an easy dosing of polymer melts with polyisobutene containing corrosion-inhibiting material during extrusion to produce films of polyethylene or polypropylene.
  • the polymeric or plastic material can be extrusion or moulding feedstock, such as pellets or beads, as well as extruded or moulded plastic materials and products.
  • commonly available plastics are used, such as polyethylene, polypropylene, polyacrylate, polyester, nylon, ABS, etc.
  • polyolefinic films will be most suitable.
  • Reaction products derived from the reaction of the Mannich bases with carboxylic acid containing organo-metallic compounds such as oxoalumiuiumstearate can be conveniently intermixed in low-and medium-weight molecular polyisobutene and applied as pipe wraps. Any moisture present at the metal surface will release the Mannich base corrosion inhibitor that is attached to the organometallic compound upon hydrolysis.
  • Figure 1 is a scheme depicting formation of chemical compounds of this invention.
  • Figure 2 shows a scheme depicting the formation, attachment to substrates and liberation of corrosion inhibitors of this invention.
  • Figure 3 shows pathways for formation of Mannich base salts in accordance with the examples from 1 to 4 of the invention.
  • Figure 4 depicts a chemical structure of a dendrimer in accordance with the 39 th example of the invention
  • Figure 5 depicts a proposed chemical structure of a polymeric Mannich base prepared in accordance with the 40 th example of the invention.
  • Figure 6 depicts chemical structures and interactions in accordance with the 42 nd example of the invention.
  • Figure 7 depicts chemical structures and interactions in accordance with the 43 rd example of the invention. DESCRIPTION OF EXAMPLES
  • DMP-30 Mannich base derivatives
  • Ancamine K54 Air products & Chemicals
  • DMP-30 and Ancamine K54 have 2,4,6- tris(dimethylaminomethyl)phenol as the main component with lesser amounts of 2,6-bis(dimethylaminomethyl) phenol.
  • a technical grade of DMP-30 containing 2,4,6-tris(dimethylaminomethyl)phenol with up to 30% of 2,6- bis(dimethylaminomethyl) phenol was used throughout in the present specification. Consequently, the average molecular weight was calculated as ca. 245.
  • Examples 1 to 4 illustrate the preparation of ionic salts from 2, 4, 6- tris(dimethylaminomethyl)phenol and 2,6-bis(dimethylaminomethyl) phenol (DMP- 30), sodium molybdate and carboxylic acids.
  • Examples 5 to 13 illustrate the preparation of metal complexes from metal alkoxides or oxymetal carboxylates with 2, 4, 6-tris(dimethylaminomethyl)phenol and 2,6-bis(dimethylaminomethyl) phenol (DMP-30).
  • Examples 14 to 15 illustrate the reaction of various metal oxide/hydroxide substrates with 2, 4, 6-tris(dimethylaminomethyl) phenol and 2,6- bis(dimethylaminomethyl) phenol (DMP-30).
  • Examples 16 to 17 illustrate the preparation of potassium sorbate, sorbic acid and DMP-30 reaction mixtures.
  • Examples 18 to 20 illustrate the preparation of graft corrosion-inhibiting precursors.
  • Example 21 illustrates the attachment of corrosion-inhibiting precursors to metal oxide particles.
  • Example 22 illustrates an admixture of VPCI precursor and polyisobutene.
  • Example 23 illustrates the preparation of corrosion-inhibitive adhesive with polyisobutene for a pipe-wrap.
  • Examples 24 to 35 illustrate the preparation of Mannich bases from various polyhydroxy aromatic compounds and other miscellaneous reactions.
  • Examples 36 to 38 illustrate the preparation of precursors from polyhydroxybenzene Mannich bases.
  • Example 39 illustrates the preparation of a 3 rd generation dendrimer from boric acid and 2, 4, 6- tris(diethylaminomethyl)-1 ,3,5-trihydroxybenzene.
  • Examples 40 to 41 illustrate the preparation of macro-cyclic Mannich bases.
  • Examples 42 to 43 illustrate chemical techniques for attaching of the corrosion inhibitors to inorganic and organic substrates.
  • Example 1 To DMP-30 (2.45g, 0.01 mol) dissolved in distilled water (20 g) in a beaker was added cone. HCI (0.73g, ca. 2.0cm 3 , 0.02mol, 31.5%HCI w/w). After stirring at room temperature, Na 2 Mo ⁇ 4 .2H 2 O (2.41 g, 0.01 mol) was added to the solution and stirred at room temperature for 15 minutes. On the addition of myristic acid (2.3g, 0.01 mol) in ethanol to the above solution, a white precipitate formed, that was removed from the reaction mixture by filtration through a Buchner funnel and washed several times with distilled water to remove the NaCI by-product. After drying in air the product was yellow in colour.
  • the scheme shows the interaction of phosphoric acid with a Mannich Base to give a quaternary salt which is then further reacted with sodium molybdate and finally with a carboxylic acid to give a complex salt.
  • the complex with the molybdate anion is incorporated into polymers and transported to the surface where it inhibits corrosion in presence of water.
  • Example 5 n-Octyltriethoxysilane (27.65g 0.01 mol) and DMP-30 (49.Og, 0.2mol) were heated at (150- 18O 0 C) for ca. 2 hours in a conical flask (500 cm 3 ) under reflux in the presence of dibutyl tin dilaurate with the exclusion of moisture. The colour of the mixture changed from yellow to a dark red-brown during this time.
  • the reaction product (1.Og) was added to water (10Og) in a glass jar. The product initially floated as an oily layer then slowly dispersed on hydrolysis to give a yellow solution.
  • a nail suspended in the humid atmosphere above the solution as well as a nail immersed in the aqueous layer with the hydrolysed product remained visibly rust free after standing for 7 days at room temperature (20-30 0 C).
  • the product was suitable for incorporation in polymeric and other substrates.
  • Oxoaluminium octoate (18.6g, 0.1 mol) and DMP-30 (24.5g 0.1 mol) were allowed to react by heating briefly for 1 -2 minutes at 100 0 C and then cooled.
  • the reaction product (1.Og) was added to water (10Og) in a glass jar.
  • the product initially floated as an oily layer then slowly dispersed on hydrolysis to give a yellow solution and a white precipitate.
  • a nail suspended in the humid atmosphere above the solution as well as a nail immersed in the aqueous layer with the hydrolysed product remained visibly rust free after standing for two months at room temperature (20-30 0 C).
  • the product was suitable for incorporation in polymeric and other substrates.
  • Titanium tetraisopropoxide (28.43g, 0.1 mol) and DMP-30 (49.Og, 0.2mol) were mixed together and an exothermic reaction occurred whilst the reaction mixture became dark red.
  • the reaction product (1.Og) was dispersed in water (100g) in a glass jar with a lid.
  • the product hydrolysed readily in water as evidenced by the fine white precipitate and yellow-coloured aqueous solution.
  • a nail suspended in the humid atmosphere above the solution as well as a nail immersed in the aqueous layer with the hydrolysed product remained visibly rust free after standing for two months at room temperature (20-3O 0 C).
  • the product was suitable for incorporation in polymeric and other substrates.
  • Tetraethylorthosilicate (20.8g, 0.1 mol) and DMP-30 (49.Og, 0.2mol) were mixed in a conical flask (250cm 3 ) and heated on a hot plate under reflux in the presence of dibutyl tin dilaurate (0.5g) with the exclusion of moisture for about 30-40 minutes.
  • the reaction product (1.Og) was dispersed in water (10Og) in a glass jar with a lid. The product hydrolysed readily in water as evidenced by the fine white precipitate and yellow coloured aqueous solution. .
  • Titanium tetraisopropoxide 28.43g, 0.1 mol
  • reaction product (0.6g) was added to water (100g) in a glass jar at room temperature.
  • the product initially floated then slowly dissolved to give a yellow solution.
  • a nail suspended in the humid atmosphere above the solution became rusty after ca. 12h, whereas a nail immersed in the aqueous layer with the dissolved product remained visibly rust free after standing for two months at room temperature (20-30 0 C).
  • the results show that the reaction product is not hydrolysed under the present conditions as evidenced by the rusting of the suspended nail.
  • the product was suitable for incorporation in polymeric and other substrates.
  • Oxoaluminium stearate (6Og, 184mmol in 100g hydrocarbon solution of white spirits) was allowed to react with DMP-30 (9Og, 368mmol) at room temperature ⁇ ca. 25° C) and then gradually heated to 110-120° C and kept at this temperature for about 10-20 minutes. The reaction product remained fluid and stable after heating without any thickening. . The product was suitable for incorporation in polymeric and other substrates.
  • Example 14 To an excess of zinc oxide (8.1g, o.i mol) was added DMP-30 (24.5g, 0.1 mol) and acetic acid (0.14g) as catalyst. The mixture was heated and stirred in a beaker to about 170-180° C after which the colour changed from white to a pale yellow. If heated beyond 200° C a brown toffee-like substance results. A nail immersed in the aqueous layer with the hydrolysed product remained visibly rust free after standing for 7 days at room temperature (20-30°C).
  • reaction product (49.Og, 0.2mol) were heated to ca ⁇ 00-11O 0 C in an open beaker. A white soft material formed that was water soluble. A small sample of the reaction product (0.5g) was added to water (10Og) in a glass jar at room temperature. The product dissolved to give a colourless solution into which an abraded nail was immersed. The nail remained visibly rust free after standing for two months at room temperature 20-3O 0 C.
  • Aluminium isopropoxide (20.43g, 0.1 mol) was dissolved in dry hexane (5Og).
  • Methacrylic acid (8.61 g, 0.1 mol) was dissolved in dry hexane (5Og) and added to the alkoxide solution over a period of about 15 minutes. After the addition, the mixture was stirred for an additional 10 minutes at room temperature ⁇ ca. 25 0 C). DMP-30 (24.5Og, 0.1 mol) was added to the above mixture and heated under reflux for about 30 minutes. The resultant VPCI precursor was added tolOOOg of dry hexane in a 2-1 beaker to which was added 50Og of hydrotalcite previously dried at 50-60 0 C and vigorously stirred.
  • the dispersion was dried by rotary evaporation under vacuum to remove all volatile substances affording a modified hydrotalcite that was further dried in an oven at 50-60° C.
  • the treated hydrotalcite can be added directly to melted polyolefinic substrates or grafted to such polymers as polyethylene vinyl alcohol (EVOH) in the presence of radical initiators.
  • Example 20 Triisopropyl borate (18.81 , 0.1 mol) was dissolved in dry hexane (5Og). Methacrylic acid (8.61 g, 0.1 mol) was dissolved in dry hexane (5Og) and added to the alkoxide solution over a period of about 15 minutes. After the addition, the mixture was stirred for an additional 10 minutes at room temperature (ca. 25°C). DMP-30 (49.0Og, 0.2 mol) was added to the above mixture and heated under reflux for about 30 minutes. The volatile substances were removed ' by vacuum distillation to afford the VPCI precursor that can be grafted to other polymeric substrates.
  • Triisopropyl borate (18.81 , 0.1 mol) was dissolved in dry hexane (5Og).
  • Methacrylic acid (8.61 g, 0.1 mol) was dissolved in dry hexane (5Og) and added to the alkoxide solution over a period of about 15 minutes.
  • Methacrylic acid (8.61 g, 0.1 mol) was dissolved in dry hexane (5Og) and added to the alkoxide solution over a period of about 15 minutes. After the addition, the mixture was stirred for an additional 10 minutes at room temperature (ca. 25°C).
  • DMP-30 (24.5Og, 0.1 mol) was added to the above mixture and heated under reflux for about 30 minutes.
  • the resultant VPCI precursor was added to100Og of dry hexane in a 2-I beaker to which was added 50Og of hydrotalcite previously dried at 50-60 0 C and vigorously stirred.
  • the dispersion was dried by rotary evaporation under vacuum to remove all volatile substances affording a modified hydrotalcite that was further dried in an oven at 50- 60° C.
  • the treated hydrotalcite can be added directly to melted polyolefinic substrates or grafted to such polymers as polyethylene vinyl alcohol (EVOH) in the presence of radical initiators
  • Example 22 To titanium tetraisopropoxide (56.8g, 0.2mol) was added sequentially isostearic acid (56.8g, 0.2moi) and DMP-30 (98g, 0.4mol). The mixture was stirred and heated to 100 C in a beaker to allow the displaced isopropanol to volatilise in the fume-hood. The reaction mixture remained stable after heating. The product was incorporated into low-molecular weight polyisobutene whilst hot for ease of mixing. The mixture was easily incorporated into polyethylene during extrusion and the precursor was tested as a vapour-phase corrosion inhibitor and found to be highly effective.
  • Aqueous formaldehyde (16.22g of 37%solution, 6.Og CH 2 O, 0.2 mol) was added drop-wise to a mixture of hydroquinone (11.Og, 0.1 mol) and diethylamine (14.6g, 20.7cm 3 , 0.2mol). The mixture was stirred and maintained at about 30-4O 0 C for about 30 minutes. The reaction mixture was extracted with ether, dried, the ether evaporated to give the reaction product. The resultant reaction product (1.Og) was dispersed in water (100g) in a glass jar with a lid. A nail immersed in the aqueous layer with the reaction product remained visibly rust free after standing for two months at room temperature (20-30 0 C).
  • Aqueous formaldehyde (32.4g of 37%solution, 12.Og CH 2 O, 0.4 mol) was added drop-wise to a mixture of hydroquinone (11.Og, 0.1 mol) and diethylamine (29.2g, 41.4cm 3 , 0.4 mol). The mixture was stirred and maintained at about 30-40 0 C for about 30 minutes. The reaction mixture was extracted with ether, dried, the ether evaporated to give the reaction product. The resultant reaction product (1.Og) was dispersed in water (100g) in a glass jar with a lid. A nail immersed in the aqueous layer with the reaction product remained visibly rust free after standing for two months at room temperature (20-30 0 C).
  • Aqueous formaldehyde (32.4g of 37%solution, 12.Og CH 2 O, 0.4 mol) was added drop-wise to a mixture of hydroquinone (11.0g, 0.1 mol) and dimethylamine (45g; 50.7cm 3 , 40% aqueous solution, 0.4mol). The mixture was stirred and maintained at about 30-40 0 C for about 30 minutes. The reaction mixture was extracted with ether, dried, the ether evaporated to give the reaction product. The resultant reaction product (1.Og) was dispersed in water (100g) in a glass jar with a lid. A nail immersed in the aqueous layer with the reaction product remained visibly rust free after standing for two months at room temperature (20-30 0 C).
  • Example 30 To paraformaldehyde (9.Og, 0.3mol) dissolved in isopropanol (20cm 3 ) was added diethylamine (21.9g, 31.0cm 3 , 0.3mol) and the mixture was heated under reflux for about 20 minutes until homogeneous. Resorcinol (11.Og, 0.1 mol) in 30 cm 3 isopropanol was added to the mixture and the resultant solution heated under reflux for 1-2 hour. The volatile material was removed by distillation under vacuum to leave a liquid residue. The reaction product (1.Og) was dispersed in water (100g) in a glass jar with a lid. A nail suspended in the humid atmosphere above the solution remained visibly rust free for 7 days. A nail immersed in the aqueous layer with the reaction product remained visibly rust free after standing for two months at room temperature (20-30 0 C).
  • diethylamine 21.9g, 31.0cm 3 , 0.3mol
  • Resorcinol 11.Og, 0.1 mol
  • Hydroquinone (5.5g, 0.25mol) was dissolved in about 20 cm 3 of an alcohol /water
  • Oxoaluminium stearate (6.Og, 18.4mmol in 100g hydrocarbon solution of white spirits) was allowed to react with the reaction product from Example 27 (8.2g, 36.8mmol) at room temperature ⁇ ca. 25° C) and then gradually heated to 110-120° C and kept at this temperature for about 10-20 minutes.
  • the reaction product remained fluid and stable after heating without any thickening.
  • the product was suitable for incorporation in polymeric and other substrates.
  • 2,4,6-Tris(diethylaminomethyl)-1 ,3,5-trihydroxybenzene (11.4g, 0.03mol) from example 8 was added to boric acid (0.62g, 0.01 mol) and the mixture was heated to 100-110 0 C allowing the boric acid to react completely with the evolution of water.
  • the addition of further amounts of boric acid (3.72g, O.O ⁇ mol) was carried out over a period of ca. 20 minutes whilst the reaction temperature was maintained at 100- 11O 0 C. On completion of the reaction the 2 nd generation dendrimer was formed.
  • the dendrimer of this example comprises a core 1 , and three generations or shells numbered from 2 to 4.
  • the core of this example is derived from B(OH) 3 , but may also be derived from B(OR) 3 .
  • OM is an organometallic compound with unreacted alkoxy groups OR 1 where R is alkyl an moiety such as isopropyl, CA is a carboxylic acid, MB is a Mannich base.
  • a corrosion inhibiting material derived from the organometallic compound, the carboxylic acid and the Mannich base reacts with a polymeric substrate (polyvinyl alcohol) containing hydroxyl groups, to afford a composite in which the Mannich base and carboxylic acid are attached to the polymer through metal-oxygen-carbon bonds.
  • a polymeric substrate polyvinyl alcohol
  • Example 43 In this example, as illustrated in Fig. 7 a corrosion inhibiting material is attached to a particulate carrier (shaded area).
  • the corrosion inhibiting material has two corrosion inhibitors, one of which is a Mannich Base attached to the carrier through an organometallic compound OM1 whereas the other is an amino alcohol attached to the carrier through the same organometallic compound OM1.
  • a carboxylic acid (CA) with unsaturated carbon bonds is attached to the carrier through another organometallic compound OM2.
  • the unsaturated bonds are available for further bonding with a polymeric substrate EVOH by radical graft initiators.
  • the resulting composite is, therefore, (i) attached to the polymer through covalent carbon-carbon bond and (ii) is ready to liberate corrosion inhibitors in presence of humidity upon hydrolysis.

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Abstract

D'une façon générale, cette invention concerne de nouveaux matériaux inhibiteurs de corrosion obtenus par une réaction chimique entre une base de Mannich et d'autres réactifs adaptés. Les bases de Mannich de cette invention seront dérivées de composés hydroxyaromatiques, d'amines secondaires ou d'amines secondaires cycliques et d'aldéhydes. Les autres réactifs comprennent des composés organo-métalliques, des oxydes métalliques, des acides carboxyliques, des acides inorganiques, des dérivés d'acides inorganiques, des halogénures alkyle, des organosilanes et des dérivés d'ammonium quaternaire et des dérivés métalliques. Les inhibiteurs de corrosion de cette invention sont libérés lors de l'hydrolyse en présence d'humidité et conviennent particulièrement pour une incorporation dans des polymères, des ciments, des peintures, des papiers, des cartons et des textiles.
PCT/AU2006/000540 2005-04-22 2006-04-24 Nouveaux materiaux inhibiteurs de corrosion WO2006110961A2 (fr)

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AU2005902014A AU2005902014A0 (en) 2005-04-22 Coatings for metals
AU2005902014 2005-04-22
AU2005902926 2005-06-07
AU2005902926A AU2005902926A0 (en) 2005-06-07 Coatings
AU2005906612A AU2005906612A0 (en) 2005-11-28 Polymers, Precursors and Substrates
AU2005906612 2005-11-28
AU2006900708A AU2006900708A0 (en) 2006-02-14 Novel chemical compounds
AU2006900708 2006-02-14
AU2006901985A AU2006901985A0 (en) 2006-04-18 Macro-cyclic mannich base compounds
AU2006901986 2006-04-18
AU2006901985 2006-04-18
AU2006901986A AU2006901986A0 (en) 2006-04-18 Polyisobutenes & polymers

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CN101451242B (zh) * 2007-12-04 2010-09-29 中国石油天然气集团公司 一种用于含Cr油管的高温酸化缓蚀剂
WO2011033526A3 (fr) * 2009-09-17 2011-11-24 Bharat Petroleum Corporation Limited Composition de carburant alcool-essence pour moteurs à combustion interne
WO2013045258A1 (fr) * 2011-09-27 2013-04-04 Basf Se Silicates stratifiés comme protection anticorrosion
CN103484090A (zh) * 2013-09-27 2014-01-01 桂林理工大学 对甲氧基苯甲醛缩对氨基苯甲酸席夫碱基聚乙二醇月桂酸单酯及其应用
ITTO20130416A1 (it) * 2013-05-23 2014-11-24 Fiat Ricerche Composizione di rivestimento per superfici metalliche con migliorate proprieta' anticorrosione
WO2015003066A1 (fr) 2013-07-02 2015-01-08 Surtreat Holding, Llc Revêtements résistant à la corrosion pour surfaces métalliques
CN106380538A (zh) * 2016-08-25 2017-02-08 陕西科技大学 一种双效有机高分子化合物及其制备方法
CN108217663A (zh) * 2018-01-30 2018-06-29 清华大学 一种四氯化硅制备白炭黑的低温气相水解设备
EP3461931A1 (fr) * 2017-09-27 2019-04-03 EXCOR Korrosionsforschung GmbH Compositions des inhibiteurs de corrosion à phase vapeur et leur utilisation ainsi que leur procédé de production
CN110172179A (zh) * 2019-05-30 2019-08-27 苏州拓锐新材料科技有限公司 一种膨胀型阻燃剂及其制备方法
CN113930773A (zh) * 2021-09-09 2022-01-14 华中科技大学 一种双醛淀粉席夫碱缓蚀剂及其制备方法和应用
CN114214052A (zh) * 2021-12-13 2022-03-22 中海石油(中国)有限公司 一种微含硫环境中高密度完井液用复配型缓蚀剂及其制法与应用
CN115058713A (zh) * 2022-05-16 2022-09-16 华南理工大学 一种有机无机杂化纳米复合缓蚀剂的制备方法及应用
CN115160843A (zh) * 2022-07-05 2022-10-11 中国石油大学(北京) 一种防腐涂层及其制备方法
EP4122987A1 (fr) * 2021-07-21 2023-01-25 Daw Se Matière aqueuse de revêtement, revêtement obtenu pourvu de matière de revêtement, substrat revêtu, utilisation de la matière de revêtement et procédé de fabrication de la matière aqueuse de revêtement
CN117512599A (zh) * 2023-11-17 2024-02-06 武汉三友石化有限公司 一种耐温高缓蚀水溶性缓蚀剂的制备方法及其应用

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CN101451242B (zh) * 2007-12-04 2010-09-29 中国石油天然气集团公司 一种用于含Cr油管的高温酸化缓蚀剂
WO2011033526A3 (fr) * 2009-09-17 2011-11-24 Bharat Petroleum Corporation Limited Composition de carburant alcool-essence pour moteurs à combustion interne
US9447343B2 (en) 2009-09-17 2016-09-20 Bharat Petroleum Corporation Limited Gasohol fuel composition for internal combustion engines
WO2013045258A1 (fr) * 2011-09-27 2013-04-04 Basf Se Silicates stratifiés comme protection anticorrosion
ITTO20130416A1 (it) * 2013-05-23 2014-11-24 Fiat Ricerche Composizione di rivestimento per superfici metalliche con migliorate proprieta' anticorrosione
WO2014188390A1 (fr) 2013-05-23 2014-11-27 C.R.F. Societa' Consortile Per Azioni Composition de revêtement pour surfaces métalliques ayant des propriétés améliorées de résistance à la corrosion
WO2015003066A1 (fr) 2013-07-02 2015-01-08 Surtreat Holding, Llc Revêtements résistant à la corrosion pour surfaces métalliques
EP3017007A4 (fr) * 2013-07-02 2017-02-22 Surtreat Holding, LLC Revêtements résistant à la corrosion pour surfaces métalliques
CN103484090A (zh) * 2013-09-27 2014-01-01 桂林理工大学 对甲氧基苯甲醛缩对氨基苯甲酸席夫碱基聚乙二醇月桂酸单酯及其应用
CN106380538A (zh) * 2016-08-25 2017-02-08 陕西科技大学 一种双效有机高分子化合物及其制备方法
EP3461931A1 (fr) * 2017-09-27 2019-04-03 EXCOR Korrosionsforschung GmbH Compositions des inhibiteurs de corrosion à phase vapeur et leur utilisation ainsi que leur procédé de production
CN108217663A (zh) * 2018-01-30 2018-06-29 清华大学 一种四氯化硅制备白炭黑的低温气相水解设备
CN108217663B (zh) * 2018-01-30 2020-06-02 清华大学 一种四氯化硅制备白炭黑的低温气相水解设备
CN110172179A (zh) * 2019-05-30 2019-08-27 苏州拓锐新材料科技有限公司 一种膨胀型阻燃剂及其制备方法
EP4122987A1 (fr) * 2021-07-21 2023-01-25 Daw Se Matière aqueuse de revêtement, revêtement obtenu pourvu de matière de revêtement, substrat revêtu, utilisation de la matière de revêtement et procédé de fabrication de la matière aqueuse de revêtement
EP4122987B1 (fr) 2021-07-21 2023-09-27 Daw Se Matière aqueuse de revêtement, revêtement obtenu pourvu de matière de revêtement, substrat revêtu, utilisation de la matière de revêtement et procédé de fabrication de la matière aqueuse de revêtement
CN113930773A (zh) * 2021-09-09 2022-01-14 华中科技大学 一种双醛淀粉席夫碱缓蚀剂及其制备方法和应用
CN114214052A (zh) * 2021-12-13 2022-03-22 中海石油(中国)有限公司 一种微含硫环境中高密度完井液用复配型缓蚀剂及其制法与应用
CN115058713A (zh) * 2022-05-16 2022-09-16 华南理工大学 一种有机无机杂化纳米复合缓蚀剂的制备方法及应用
CN115058713B (zh) * 2022-05-16 2024-01-23 华南理工大学 一种有机无机杂化纳米复合缓蚀剂的制备方法及应用
CN115160843A (zh) * 2022-07-05 2022-10-11 中国石油大学(北京) 一种防腐涂层及其制备方法
CN117512599A (zh) * 2023-11-17 2024-02-06 武汉三友石化有限公司 一种耐温高缓蚀水溶性缓蚀剂的制备方法及其应用
CN117512599B (zh) * 2023-11-17 2024-04-12 武汉三友石化有限公司 一种耐温高缓蚀水溶性缓蚀剂的制备方法及其应用

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