EP0306831B1 - Verwendung von Polyaralkylaminen als Korrosionsinhibitoren - Google Patents

Verwendung von Polyaralkylaminen als Korrosionsinhibitoren Download PDF

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Publication number
EP0306831B1
EP0306831B1 EP88114264A EP88114264A EP0306831B1 EP 0306831 B1 EP0306831 B1 EP 0306831B1 EP 88114264 A EP88114264 A EP 88114264A EP 88114264 A EP88114264 A EP 88114264A EP 0306831 B1 EP0306831 B1 EP 0306831B1
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EP
European Patent Office
Prior art keywords
aralkyl
mol
bis
radicals
polyaralkylamines
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88114264A
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German (de)
English (en)
French (fr)
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EP0306831A1 (de
Inventor
Artur Dr. Botta
Christian Dr. Wegner
Heinz-Joachim Dr. Rother
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Bayer AG
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Bayer AG
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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.
  • amines with a short chain length or unsubstituted polyalkylene amines usually show no or insufficient corrosion-inhibiting effect on metallic materials.
  • 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. Mention may be made of: 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
  • n 1 to 8
  • polyaralkylamines are mentioned by name: di-, tri-, tetra- and pentabenzyl-di-ethylene-triamine, -triethylene-tetramine, -tetraethylene-pentamine, -pentaethylene-hexamine, -heptaethylene-octamine, -N, N'-bis-aminoethyl-propylene diamine and -N, N '-Bisaminopropylethylenediamine, perbenzyl-triethylene tetramine, -tetraethylenepentamine, -pentaethylenehexamine, -hexaethyleneheptamine, -aminoethylpiperazine and -aminopropylpiperidine, tetrabenzyl-stearyl-diethylenetriamine and -pentaethylenehexamine, tribenzyl-cyclohexyl-trietethylenediamine (triethylethylened
  • 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) to be used according to the invention can be added to all media which have a corrosive effect 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 agents as well as 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.
  • solvents and dispersants are: 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.
  • 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). However, it may also be advantageous to use an excess of amines of the formula (III) (2 to 10 mol of amine per mol of aralkyl halide) and to remove excess amine again after the reaction has ended. This is preferably done by distillation in vacuo.
  • 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 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 to R17 and X have the meaning given above and
  • condensing agents that can be used are: iron, zinc, iron III chloride, iron II and III oxide, zinc chloride, zinc acetate, zinc stearate, aluminum chloride, aluminum oxide, silicon dioxide, clays, such as montmoril ionite 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 is controlled, for example, by determining the amount of hydrogen halide split off. This can be done, for example, using a rotameter or 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 is usually 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 about 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.
  • Example 35 using 82.6 g (0.8 mol) of diethylenetriamine gives 249 g (94.8% of theory) of a light brown, viscous oil.
  • 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)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Springs (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP88114264A 1987-09-11 1988-09-01 Verwendung von Polyaralkylaminen als Korrosionsinhibitoren Expired - Lifetime EP0306831B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88114264T ATE64961T1 (de) 1987-09-11 1988-09-01 Verwendung von polyaralkylaminen als korrosionsinhibitoren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3730475 1987-09-11
DE19873730475 DE3730475A1 (de) 1987-09-11 1987-09-11 Polyaralkylamine als korrosionsinhibitoren

Publications (2)

Publication Number Publication Date
EP0306831A1 EP0306831A1 (de) 1989-03-15
EP0306831B1 true EP0306831B1 (de) 1991-07-03

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EP88114264A Expired - Lifetime EP0306831B1 (de) 1987-09-11 1988-09-01 Verwendung von Polyaralkylaminen als Korrosionsinhibitoren

Country Status (6)

Country Link
US (1) US5059391A (da)
EP (1) EP0306831B1 (da)
AT (1) ATE64961T1 (da)
DE (2) DE3730475A1 (da)
DK (1) DK501988A (da)
NO (1) NO883846L (da)

Families Citing this family (12)

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Publication number Priority date Publication date Assignee Title
US5070196A (en) * 1986-02-01 1991-12-03 Nippon Chemiphar Co., Ltd. Alkylenediamine derivatives
IL88757A (en) * 1988-12-21 1997-04-15 Bromine Compounds Ltd Halogen-containing amine compounds, process for their preparation and their use as flame retardants
US5204314A (en) * 1990-07-06 1993-04-20 Advanced Technology Materials, Inc. Method for delivering an involatile reagent in vapor form to a CVD reactor
US5354782A (en) * 1991-01-17 1994-10-11 Merrell Dow Pharmaceuticals Inc. Polyamine phenols as radioprotective agents
US6080865A (en) * 1995-04-26 2000-06-27 Lonza Ag Piperidinopentanamines, process for producing them and their use as a catalyst for producing urethanes
US20060131248A1 (en) * 2004-12-17 2006-06-22 Charkhutian Kostan B Process for removing dissolved oxygen from an aqueous system
US20060180794A1 (en) * 2005-02-15 2006-08-17 Goddard Richard J Polyamine-based corrosion inhibitors
US8198395B2 (en) * 2007-02-07 2012-06-12 Air Products And Chemicals, Inc. Alkylated aminopropylated ethylenediamines and uses thereof
US7993751B2 (en) * 2007-02-07 2011-08-09 Air Products And Chemicals, Inc. Alkylated aminopropylated methylene-di-(cyclohexylamine) and uses thereof
US8318309B2 (en) * 2007-02-07 2012-11-27 Air Products And Chemicals, Inc. Benzylated aminopropylated alkylenediamines and uses thereof
US20100140098A1 (en) * 2008-05-15 2010-06-10 Solopower, Inc. Selenium containing electrodeposition solution and methods
CN113667467B (zh) * 2021-08-25 2022-09-02 卫辉市化工有限公司 油田用粘土缩膨剂及其制备方法

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US2318729A (en) * 1941-05-24 1943-05-11 Carbide & Carbon Chem Corp Process for making amino-alkyl compounds
US2886604A (en) * 1953-10-07 1959-05-12 Universal Oil Prod Co Preparation of compounds having a benzylbenzyl halide structure
US3303219A (en) * 1961-11-20 1967-02-07 Sinclair Research Inc Amines
US3280097A (en) * 1964-05-04 1966-10-18 Atlas Chem Ind Corrosion inhibitors
US3539633A (en) * 1965-10-22 1970-11-10 Standard Oil Co Di-hydroxybenzyl polyamines
US3687859A (en) * 1971-02-09 1972-08-29 Drew Chem Corp Corrosion inhibiting processes and compositions of aliphatic amines and diquaternary diamines
DE2530002A1 (de) * 1975-07-04 1977-01-27 Dow Corning Gmbh Verfahren zur verbesserung der schmiereigenschaften von festschmierstoffen
EP0006155A1 (de) * 1978-06-08 1980-01-09 Ciba-Geigy Ag 3-Phenoxybenzylamine sowie 3-Benzylbenzylamine und Verfahren zu ihrer Herstellung
SU842111A1 (ru) * 1979-01-10 1981-06-30 Днепродзержинский Индустриальныйинститут Им. M.И. Арсеничева Раствор дл химического полировани МЕди и EE СплАВОВ
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Title
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Also Published As

Publication number Publication date
DE3863517D1 (de) 1991-08-08
NO883846D0 (no) 1988-08-29
NO883846L (no) 1989-03-13
DE3730475A1 (de) 1989-03-23
DK501988A (da) 1989-03-12
DK501988D0 (da) 1988-09-09
EP0306831A1 (de) 1989-03-15
US5059391A (en) 1991-10-22
ATE64961T1 (de) 1991-07-15

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