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
  • C23F11/173—Macromolecular compounds
• • 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

Definitions

• the invention relates to the use of polyaralkylamines as corrosion inhibitors for metallic materials as well as new polyaralkylamines and processes for their production.
• amines with a short chain length or unsubstituted polyalkylene amines usually show no or insufficient corrosion-inhibiting effect on metallic materials.
• the present invention relates to the use of polyaralkylamines of the formula wherein R1 to R4 are the same or different and are hydrogen, C1-C18 alkyl, C5-C12 cycloalkyl, C7-C18 aralkyl, poly-C7-C18 aralkyl having 2 to 50 aralkylene units or C6-C15 aryl or R1 to R4 are linked so that two of the radicals together with the nitrogen atom connecting them or with the NC-containing chain form a 5- to 6-membered ring, at least one of the radicals R1 to R4 C7-C18-aralkyl or Poly-C7-C18 aralkyl means, and R5 and R6 independently of one another are hydrogen, C1-C6-alkyl, C5-C7-cycloalkyl, C7-C12-aralkyl or C6-C10-aryl, m represents an integer from 2 to 10 and n means 0 to 30, where, if
• Suitable alkyl radicals of the formula (I) are those having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms. Called his: methyl, ethyl, propyl, n-butyl, isobutyl, hexyl, ethylhexyl, decyl and stearyl, preferably methyl, ethyl, n-butyl and ethylhexyl, particularly preferably methyl, ethyl and n-butyl.
• Suitable cycloalkyl radicals are those having 5 to 12 carbon atoms, preferably 5 to 7 carbon atoms. Called his: Cyclohexyl and Methylcyclohexyl.
• Suitable aralkyl radicals are those having 7 to 18 carbon atoms, preferably having 7 to 12 carbon atoms, particularly preferably those having 7 to 9 carbon atoms.
• the following may be mentioned: benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, 4-methylbenzyl, tert-butylbenzyl, methoxybenzyl and 3-chlorobenzyl, preferably benzyl.
• Suitable polyaralkyl radicals are those with 7 to 18 carbon atoms per aralkylene unit, preferably those with 7 to 12 carbon atoms, particularly preferably those with 7 to 9 carbon atoms.
• the polyaralkyl radicals generally have 2 to 50 aralkylene units, preferably 2 to 30 aralkylene units, particularly preferably 2 to 12 aralkylene units.
• Suitable aryl radicals are those with 6 to 15 carbon atoms, preferably those with 6 to 12 carbon atoms, particularly preferably those with 6 to 8 carbon atoms.
• the following may be mentioned: phenyl, tolyl and chlorophenyl, preferably phenyl.
• radicals R1 to R4 which may be linked to one another by a nitrogen atom connecting them, are the piperidinyl radical
• radicals R1 to R4 which can be linked to one another with the NC-containing residual chain are the piperazinylene radical
• polyaralkylamines of the formula (I) in which m is an integer from 2 to 6, particularly preferably 2 and 3 and n is 1 to 20, particularly preferably 2 to 10.
• Corrosion-inhibiting polyaralkylamines include the following, for example: in which R for hydrogen, Is methyl, ethyl, n-butyl, isobutyl, stearyl, cyclohexyl, phenethyl, phenyl, chlorophenyl or tolyl, X represents hydrogen, methyl, chlorine or methoxy, p for 2 to 50 and n stands for 1 to 8.
• polyaralkylamines are mentioned by name: di-, tri-, tetra- and pentabenzyl-diethylenetriamine, -triethylenetetramine, -tetraethylenepentamine, -pentaethylenehexamine, -heptaethyleneoctamine, -N, N'-bis-aminoethyl-propylenediamine and -N, N'- bisaminopropylethylene diamine, perbenzyl triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, aminoethyl piperazine and aminopropyl piperidine, tetrabenzyl stearyl diethylene triamine and pentaethylene hexamine, tribenzyl cyclohexyl triethylene pentamines, monenzenzyl cyclohexyl triethylene pentamine -, bis- and tris- (polybenzyl-di
• the corrosion-inhibiting polyaralkylamines can be used both individually and in any mixtures with one another and in a mixture with other inhibitors to protect against corrosion in metallic materials.
• Additional, known corrosion inhibitors are: fatty amines, quaternary ammonium salts, N-heterocycles, such as imidazolines, imidazoles, thiazoles, triazoles and alkynols, such as propargyl alcohol, and phosphonic acids.
• the polyaralkylamines of the formula (I) and the corrosion inhibitors mentioned can be used in any mixing ratio with one another. Preferred mixing ratios can easily be determined by appropriate preliminary tests.
• the polyaralkylamines of the formula (I) according to the invention can be added to all media which have a corrosive action on these materials in order to protect them against corrosion in metallic materials.
• corrosive media are: heat transfer media (cooling and heating fluids), hydraulic fluids, petroleum (fractions), fuels and fuels, metalworking fluids or emulsions, acids for cleaning, pickling and for acidifying boreholes in oil extraction "acidizing", metal coating medium and plastics, for example as insulation or when processing at higher temperatures, for example during extrusion.
• ferrous metals cast or steel
• copper brass, zinc, lead and aluminum
• ferrous metals and copper very particularly preferably ferrous metals.
• the amount of polyaralkylamines of the formula (I) to be used can be varied within a wide range and depends in particular on the type of the corrosive medium. As a rule, the polyaralkylamines are used in an amount of about 0.001 to 3% by weight, preferably 0.05 to 1% by weight, based on the corrosive medium.
• the polyaralkylamines of the formula (I) are preferably used in combination with customary formulation agents, such as solvents and dispersants.
• customary formulation agents such as solvents and dispersants.
• solvents and dispersants aliphatic or araliphatic alcohols, such as isooctanol and benzyl alcohol, amides, such as dimethylformamide, ethoxylated derivatives of alcohols or amines, such as 2-ethylhexanol, lauryl alcohol, cetyl alcohol, dodecylamine, tallow fatty amine and nonylphenol.
• the most favorable amount of solvent and / or dispersant can easily be determined by preliminary tests.
• R7 to R10 are the same or different and are hydrogen, C1-C18-alkyl, C5-C12-cycloalkyl, C7-C18-aralkyl, poly-C7-C18-aralkyl with 2 to 50 aralkylene units or C6-C15-aryl or R7 to R10 are linked to one another in such a way that two of the radicals together with the nitrogen atom connecting them or with the NC-containing residual chain form a 5- to 7-membered ring, at least one of the radicals R7 to R18 poly-C7-C18- aralkyl means 2 to 50 aralkylene units, R5 and R6 independently of one another are hydrogen, C1-C6-alkyl, C5-C7-cycloalkyl, C7-C12-aralkyl or C6-C10-aryl, m represents an integer from 2 to 10 and n means 0 to
• R for hydrogen Is methyl, ethyl, n-butyl, isobutyl, stearyl, cyclohexyl, phenethyl, phenyl, chlorophenyl or tolyl
• X represents hydrogen, methyl, chlorine or methoxy
• at least one of the radicals R means.
• polyaralkylamines may be mentioned by name: mono-, bis- and tris- (polybenzyl) -diethylene triamine, -triethylene tetramine, -tetraethylenepentamine, -pentaethylenehexamine, -heptaethyleneoctamine, -1,2- and 1,3-dipropylenetriamine, -tripropylenetetramine, -stearyl- hexamethylenediamine, -N, N'-bis-aminoethyl-propylenediamine, -N, N'-bis-aminopropyl-ethylenediamine, -aminoethylpiperazine and -aminopropylpiperidine, (polybenzyl) -tetrabenzyldiethylenetriamine, -triethylenetetramine, -tetraethylenepentamine and -N, N' bis-aminoethyl-propylene diamine, (pol
• the invention also relates to a process for the preparation of new polyaralkylamines of the formula (II) wherein R7 to R10 are the same or different and are hydrogen, C1-C18-alkyl, C5-C12-cycloalkyl, C7-C18-aralkyl, poly-C7-C18-aralkyl with 2 to 50 aralkylene units or C6-C15-aryl or R7 to R10 are linked to one another in such a way that two of the radicals together with the nitrogen atom connecting them or with the NC-containing residual chain form a 5- to 7-membered ring, at least one of the radicals R7 to R18 poly-C7-C18- aralkyl means 2 to 50 aralkylene units, R5 and R6 independently of one another are hydrogen, C1-C6-alkyl, C5-C7-cycloalkyl, C7-C12-aralkyl or C6-C10-aryl, m represents an integer
• aralkyl halides with 2 to 50 aralkylene units of the formula IV are those which are derived from benzyl chloride, benzyl bromide, the o-, m- and p-isomers of methyl, ethyl and butyl - Derive, chlorine, methoxy-benzyl chloride and ⁇ -methyl and ⁇ , ⁇ -dimethylbenzyl chloride, preferably benzyl chloride.
• the amines of the formula (III) are generally reacted in a stoichiometric ratio with the aralkyl halides of the formula (IV).
• reaction of the amines with the aralkyl halides can be carried out without the use of special hydrogen halide acceptors.
• the hydrohalides of the process products according to formula (II) are obtained.
• condensation is carried out in the presence of customary hydrogen halide acceptors, for example in the presence of tertiary amines, preferably in the presence of alkali metal hydroxides and / or carbonates.
• the amines can be reacted in bulk without the presence of special solvents.
• solvents or mixtures thereof can also be used.
• hydrocarbons such as petroleum ether, cyclohexane, ligroin, benzene, toluene, xylene, chlorinated hydrocarbons such as methylene chloride, chloroform, tri- and tetrachloroethane, chlorobenzene, dichlorobenzene, esters such as ethyl or butyl acetate.
• Alcohols such as methanol, ethanol, isopropanol and methyl glycol.
• the reaction temperatures can be varied within wide limits. They are generally from -20 to 200 ° C., preferably from 20 to 120 ° C.
• the isolation of the new polyaralkylamines of the formula (II) depends on whether the hydrohalides or the free bases of the amines of the formula (II) are desired. If the hydrohalides are desired, any excess amine is separated off by vacuum distillation. The remaining residues are generally resinous; in many cases they can be made into aqueous and / or alcoholic, i.e. Process colloidal solutions.
• the free amine bases are desired, they are generally obtained in solution in an organic solvent when using alkali metal hydroxides as hydrogen halide acceptors. They can be processed as such or isolated by distilling off the solvent.
• R15 represents hydrogen, halogen, C1-C4-alkoxy or C1-C6-alkyl
• R16 and R17 are identical or different and are hydrogen or C
• condensing agents that can be used are: iron, zinc, ferric chloride, ferric oxide and ferric oxide, zinc chloride, zinc acetate, zinc stearate, aluminum chloride, aluminum oxide, silicon dioxide, clays, such as Montmoril lonite and / or zeolite. Zinc chloride and / or zinc stearate are preferably used.
• the condensing agents are usually used in catalytic amounts, for example in amounts of 0.01 to 1, preferably 0.1 to 0.5 wt .-%, based on the C7-C18 monoaralkyl halide (V) used.
• the aralkyl halides are preferably condensed up to a conversion of 10 to 50 mol%, particularly preferably up to a conversion of 15 to 40 mol%, of the amount of hydrogen halide to be split off.
• the conversion of the condensation reaction according to the invention is controlled, for example, by determining the amount of hydrogen halide split off. This can e.g. by means of rotameters or by titration.
• inhibitors or deactivators are usually added to the condensation reaction. Examples include the following as inhibitors or deactivators: quaternary ammonium salts, amines and / or amides, such as caprolactam and / or phosphines, such as triphenylphosphine.
• the condensation reaction according to the invention is generally carried out in bulk; can also be carried out with the participation of suitable solvents, for example chlorinated hydrocarbons, such as methylene chloride and / or chloroform. It can be carried out continuously or batchwise.
• suitable solvents for example chlorinated hydrocarbons, such as methylene chloride and / or chloroform. It can be carried out continuously or batchwise.
• the reaction temperature can be varied within wide limits depending on the type and / or the amount of the condensing agent and in view of the desired degree of condensation. It is generally about -50 to 200 ° C, preferably 0 to 180 ° C, particularly preferably 50 to 150 ° C.
• the unreacted monoaralkyl halide of the formula (V) can be separated off from the condensation mixture, for example by vacuum distillation.
• the hydrochloride is taken up in approx. 300 ml of toluene and shaken out with dilute sodium hydroxide solution ( ⁇ 0.2 mol). After drying and concentrating the toluene phase in vacuo, 37 g of a slightly cloudy brownish viscous oil are obtained.
• the degree of benzyl resin condensation is varied in the following examples using the procedure according to Example 22: E.g. % Separation HCl Benzyl resin polyamine HCl 23 30th 112 g (98.2%) C41H49ClN4 (633.3) Ber. C. 77.76% H 7.80% Cl 5.60% N 8.85% Gef. 77.89 7.69 5.48 8.77 24th 40 122 g (98.4%) C55H61ClN4 (813.6) Ber. C. 81.20 H 7.56 Cl 4.36 N 6.89 Gef. 81.33 7.49 4.23 6.75 25th 50 140 g (93.3%) C62H67ClN4 (903.7) Ber. C.
• the corrosion inhibitor is dissolved or dispersed in hydrochloric acid, if appropriate in combination with an acetylene alcohol. It is advisable to prepare a formulation beforehand from a solvent that is miscible with water or hydrochloric acid and a surfactant. Preferred solvents are lower alcohols, ketones or glycols, and also dimethylformamide, formamide, acetonitrile, N-methylpyrrolidone.
• a degreased steel coupon is placed in the hydrochloric acid. After 6 hours, the weight loss of the coupon is determined and converted into a surface removal rate.
• a 2 l two-necked flask is equipped with a 400 ml Soxhlet extractor and a reflux condenser. Another glass tube is placed between the extractor and the reflux condenser, into which dropping taps for the inhibitor solution are introduced.
• Two metal coupons made of ST 37 steel are hung in such a way that two are in the Soxhlet extractor, i.e. in the liquid phase, and two in the gas space below the dropping points for the inhibitor solution. The latter pair of coupons is placed so that the inhibitor solution drips directly onto the coupons.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Springs (AREA)
• Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1987
  • 1987-09-11 DE DE19873730475 patent/DE3730475A1/de not_active Withdrawn
• 1988
  • 1988-08-29 NO NO88883846A patent/NO883846L/no unknown
  • 1988-09-01 EP EP88114264A patent/EP0306831B1/fr not_active Expired - Lifetime
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  • 1988-09-01 AT AT88114264T patent/ATE64961T1/de not_active IP Right Cessation
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