EP3601471A1 - Concentrés d'antigel avec protection anticorrosion - Google Patents

Concentrés d'antigel avec protection anticorrosion

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Publication number
EP3601471A1
EP3601471A1 EP18707930.6A EP18707930A EP3601471A1 EP 3601471 A1 EP3601471 A1 EP 3601471A1 EP 18707930 A EP18707930 A EP 18707930A EP 3601471 A1 EP3601471 A1 EP 3601471A1
Authority
EP
European Patent Office
Prior art keywords
glycol
concentrate
weight
antifreeze
compounds
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.)
Withdrawn
Application number
EP18707930.6A
Other languages
German (de)
English (en)
Inventor
Harald Dietl
Nicolas VAUTRAVERS
Henning Althoefer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3601471A1 publication Critical patent/EP3601471A1/fr
Withdrawn legal-status Critical Current

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • 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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/122—Alcohols; Aldehydes; Ketones
    • 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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • 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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C23F11/126—Aliphatic acids
    • 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
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/143—Salts of amines
    • 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
    • C23F11/10—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
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • 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
    • C23F11/181—Nitrogen containing 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
    • C23F11/18—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
    • C23F11/182—Sulfur, boron or silicon containing 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
    • C23F11/18—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
    • C23F11/188—Mixtures of inorganic inhibitors containing phosphates

Definitions

  • the present invention relates to antifreeze / anticorrosive concentrates, to processes for preparing such concentrates from superconcentrates, to aqueous coolant compositions of these concentrates and to their use.
  • Coolant compositions for the cooling circuits of internal combustion engines of, for example, automobiles mostly contain alkylene glycols, mainly ethylene glycol and / or propylene glycol, as antifreeze component.
  • corrosion inhibitors are included. Especially in modern internal combustion engines temperature loads are achieved, which make high demands on the materials used. Any type and extent of corrosion is a potential risk factor that can shorten the life of the motor and reduce its reliability. Furthermore, modern motors are increasingly using a variety of different materials, such as cast iron, copper, brass, soft solder, steel, as well as magnesium and aluminum alloys. This variety of metallic materials also creates potential corrosion problems, especially at the points where different metals are in contact with each other. It can be comparatively easy, especially at these locations a variety of types of corrosion occur, such as pitting, crevice corrosion, erosion or cavitation.
  • coolant compositions must also be compatible with non-metallic components of the refrigeration cycle, for example elastomers and plastics from hose connections or gaskets, and must not alter these.
  • coolant composition is of crucial importance in heat transfer in modern internal combustion engines.
  • Antifreeze / anticorrosive concentrates thus likewise contain components which on the one hand serve for antifreeze protection, ie serve to lower the freezing point of the mixture, and on the other hand serve as corrosion inhibitors which serve to protect against corrosion.
  • the proportion of the anticorrosive component in the concentrate is usually up to 10 wt .-% based on the total amount of the concentrate.
  • the proportion of the concentrate in the ready-to-fill radiator protection Tel is usually 10 to 60 wt .-%.
  • Concentrates may already contain small amounts of water, preferably they are anhydrous.
  • superconcentrates in particular for reasons of transport, are available which have a reduced amount of antifreeze component, ie mostly and preferably ethylene glycol, but also instead or additionally 1,2-propylene glycol and / or glycerol, in order to provide the most compact container possible.
  • a concentrate is usually withdrawn so much amount of antifreeze component that the other ingredients are just in dissolved form.
  • Antifreeze / anticorrosive concentrates are therefore available from superconcentrates by admixing a certain amount of antifreeze component and optionally some water.
  • the proportion of the super concentrate in the concentrate is usually 3 to 60% by weight.
  • alkylene glycols mainly ethylene glycol and / or propylene glycol, are the main constituents of the antifreeze component.
  • the corrosion inhibitors which serve as anticorrosion component are known in the art.
  • Antifreeze compositions containing carboxylic acids, molybdate or triazoles are known from EP-B 552 988 or US Pat. No. 4,561,990.
  • EP-B 229 440 describes a corrosion inhibiting component of an aliphatic monobasic acid, a dibasic hydrocarbon acid and a hydrocarbyl triazole.
  • antifreeze agents and their concentrates which cause only a very low corrosion of aluminum materials, especially those which have been prepared using a soldering process with a Fluoroaluminat-flux.
  • the technically commonly used sebacic acid is used here as a corrosion inhibitor.
  • a disadvantage of the use of sebacic acid in antifreeze is their low solubility in the typical media (in water at 20 ° C only about 1 g / l) and their difficult production. The achieved with the previously known mixtures and concentrates corrosion protection and the achievable freezing points are generally good.
  • Diglycolic acid has long been commercially available (see, eg, WM Bruner et al., Industrial and Engineering Chemistry, Aug. 1, 1949, pages 1653-1656) and is prepared according to AA Roscher et al., The Bulletin Society of Pharmacological and Environmental Pathologists, Vol. III, No. 4, December 1975 used as a cleaning component for cooling systems in automobiles and as a complexing agent for calcium and iron.
  • a disadvantage of diglycolic acid is according to A. A. Roscher et al. its toxicity.
  • the object of the present invention is to provide such antifreeze / anticorrosive concentrates, which do not have the disadvantages of the prior art, or at least in a reduced form. These mixtures should have a balance between the properties of corrosion protection, heat transfer and frost resistance.
  • an antifreeze / anticorrosive concentrate containing 1 to 10 wt .-%, preferably 2 to 8 wt .-% and particularly preferably 3 to 7 wt .-%, based on the total amount of the concentrate, of a mixture of
  • n is a positive integer of 1 to 5 and may be the same or different for each of the compounds (Ia), (Ib) and (Ic), with the proviso that the sum of the amounts of compounds (Ia), (Ib) and (Ic) always gives 100% by weight in the mixture.
  • the amount of the mixture is 2 to 8 wt .-%, particularly preferably 3 to 7 wt .-%, based on the total amount of antifreeze or corrosion protection concentrate.
  • the mixture is a mixture of compound (Ia) optionally in combination with compound (Ib) and / or (Ic), which is generally composed as follows:
  • (Ic) 0-30% by weight, preferably 0-20, more preferably 0-15, most preferably 0.05-10, and in particular 0.1-5% by weight, with the proviso that the sum of the amounts of compounds (la), (Ib) and (Ic) in the mixture always yields 100% by weight.
  • the mixture is substantially free of compound (Ic).
  • the mixture is additionally substantially free of compound (Ib).
  • the run number "n" may be a positive integer from 1 to 5, preferably 1 to 4, more preferably 1 to 3 and most preferably 1 or 2.
  • the compounds (Ia), (Ib) and (Ic) are reaction mixtures having a distribution of the product composition depending on the reaction conditions.
  • the chain length is subject to a distribution around a statistical average, which may be distributed around a statistical average n.
  • n for each individual link (Ia), (Ib) and (Ic) are positive integer numbers, may also assume non-integer values for the reaction mixture on a statistical average.
  • the mixture of the compounds (Ia) optionally in combination with (Ib) and / or (Ic) may preferably be present wholly or partly in the form of their alkali metal salts.
  • the compounds are wholly or partly in the form of their sodium or potassium salts, more preferably in the form of their potassium salts.
  • the degree of neutralization is preferably at least 75%, particularly preferably at least 85%, very particularly preferably at least 95% and in particular at least 99%.
  • the running number "n” may be the same or different for each of the compounds (la), (Ib) and (Ic). Since the compounds (Ia) are preferably prepared from the compounds (Ic) by oxidation (see below) and this oxidation can be associated with a degradation of the polymeric chains, it is a preferred embodiment that the sequence number "n" for compounds gen (Ia) in the arithmetic mean by 1, 5 may be lower than for the compounds (Ic) in the mixture, preferably by up to 1 lower, more preferably by up to 0.8 lower, most preferably by up to 0, 7 and in particular by up to 0.6 lower.
  • the running number "n" for compounds (Ib) in the arithmetic mean can be up to 1 lower than for the compounds (Ic) in the mixture, preferably up to 0.8 lower, more preferably up to 0.7 lower, more preferably up to 0.6 and especially lower by up to 0.5.
  • the compound (Ia) is preferably prepared in an oxidation process from compound (Ic) in which the run number "n" is reduced as little as possible, more preferably not more than 1, very preferably not more than 0.7 and in particular by not more than 0.5.
  • the antifreeze / anticorrosive concentrate additionally contains, as a rule, at least one alcohol as antifreeze component.
  • alcohols selected from monohydric, dihydric, trihydric alcohols, polyhydroxy alcohols, their ethers or mixtures thereof may be contained as antifreeze component.
  • Additional alcohols may be selected from the group consisting of ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentafluoroethylene glycol, hexaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, 1,3-propylene glycol, glycerol, Monoethers of glycols such as the methyl, ethyl, propyl and butyl ethers of ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
  • the additional alcohols are preferably selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and glycerol. They are particularly preferably selected from the group consisting of ethylene glycol, propylene glycol and glycerol, ethylene glycol is very particularly preferred.
  • the alcohol used is other than an alcohol of the formula (Ic).
  • propylene glycol is understood in the context of the present invention, unless expressly stated otherwise, 1, 2-propanediol.
  • the amount of at least one further corrosion inhibitor as corrosion protection component in addition to the amount of antifreeze component and the mixture of components (Ia) and optionally (Ib) and / or (Ic) is preferably 0.01 to 5 wt .-% based on the total amount of the concentrate , More preferably, the amount is 0.1 to 4 wt .-%, particularly preferably 0.5 to 3 wt .-%.
  • a preferred embodiment of the present invention is a antifreeze / anticorrosive concentrate containing 1 to 10% by weight, preferably 2 to 8% by weight and more preferably 3 to 7% by weight, based on the total amount of the concentrate, of a mixture
  • n is a positive integer of 1 to 5 and may be the same or different for each of the compounds (Ia), (Ib) and (Ic), with the proviso that the sum of the amounts of compounds (Ia), (Ib ) and (Ic) in the mixture always gives 100% by weight and additionally 0.01 to 5 wt .-% based on the total amount of the concentrate, preferably 0.1 to 4 wt .-% and particularly preferably 0.5 to 3 wt. % of at least one other corrosion inhibitor than the compounds (Ia), (Ib) and (Ic).
  • a further preferred embodiment of the present invention is an antifreeze / anticorrosive concentrate consisting of 1 to 10% by weight, preferably 2 to 8% by weight and more preferably 3 to 7% by weight, based on the total amount of the concentrate , a mixture of
  • n is a positive integer of 1 to 5 and may be the same or different for each of the compounds (Ia), (Ib) and (Ic), with the proviso that the sum of the amounts of compounds (Ia), (Ib ) and (Ic) in the mixture always yields 100% by weight and additionally from 0.01 to 5% by weight, based on the total amount of the concentrate, preferably from 0.1 to 4% by weight and more preferably from 0.5 to 3% by weight of at least one other corrosion inhibitor than the compounds (Ia) , (Ib) and (Ic), optionally one or more further typical ingredients of antifreeze / anticorrosive concentrates and additionally the difference amount to 100 wt .-% based on the total amount of the concentrate of at least one alcohol as antifreeze component, preferably selected from the group consisting of Ethylene glycol, 1, 2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hex
  • an antifreeze / anticorrosive concentrate according to the present invention may optionally additionally contain at least one of the following components as typical antifreeze / anticorrosive concentrate ingredients in a given amount based on the total amount of the concentrate:
  • alkali metal borates up to 1% by weight of one or more alkali metal borates, alkali metal phosphates, alkali metal silicates, alkali metal nitrites, alkali metal or alkaline earth metal nitrates, alkali metal molybdate or alkali metal or alkaline earth metal fluorides;
  • Suitable linear or branched-chain aliphatic or cycloaliphatic monocarboxylic acids (a) are, for example, propionic acid, pentanoic acid, hexanoic acid, cyclohexylacetic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, isononanoic acid, decanoic acid, 2-propylheptanoic acid, undecanoic acid or dodecanoic acid.
  • aromatic monocarboxylic acid (a) is particularly suitable benzoic acid, in addition, for example, are also C to C alkylbenzoic, such as o-, m-, p-methylbenzoic, and hydroxyl-containing aromatic monocarboxylic acids such as o-, m-, or p-hydroxybenzoic acid, o -, m- or p- (hydroxymethyl) benzoic acid or halobenzoic acids such as o-, m- or p-fluorobenzoic acid into consideration.
  • C to C alkylbenzoic such as o-, m-, p-methylbenzoic
  • hydroxyl-containing aromatic monocarboxylic acids such as o-, m-, or p-hydroxybenzoic acid, o -, m- or p- (hydroxymethyl) benzoic acid or halobenzoic acids such as o-, m- or p-fluorobenzoic acid into consideration.
  • di- or tricarboxylic acids are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dicyclopentadienedicarboxylic acid, phthalic acid, terephthalic acid and triazinetriiminocarboxylic acids such as 6,6 ', 6 " - (1,3,5-triazine-2,4,6-triyltriimino) trihexanoic acid.
  • carboxylic acids of groups (a) and (b) are present as alkali metal salts, especially as sodium or potassium salts, or as ammonium salts or substituted ammonium salts (ammonium salts), eg. B. with ammonia, trialkylamines or trialkanolamines.
  • Typical examples of corrosion inhibitors mentioned under (c) are sodium tetraborate (borax), disodium hydrogenphosphate, trisodium phosphate, sodium metasilicate, sodium nitrite, sodium nitrate, magnesium nitrate, sodium fluoride, potassium fluoride, magnesium fluoride and sodium molybdate.
  • alkali metal silicates When using alkali metal silicates, these are expediently stabilized by customary organosilicon phosphonates or organosilicon sulfonates in conventional amounts.
  • aliphatic, cycloaliphatic or aromatic amines (d) having 2 to 15, preferably 4 to 8 carbon atoms, which in addition ether oxygen atoms, in particular 1 to 3 Ethersauerstoff-, or hydroxyl groups, in particular 1 to 3 hydroxyl groups may contain, for example, come ethylamine , Propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, isononylamine, di-n-propylamine, diisopropylamine, di-n-butylamine.
  • n-butylamine mono-, di- and triethanolamine, piperidine, morpholine, aniline or benzylamine in question.
  • Aliphatic and cycloaliphatic amines (d) are usually saturated.
  • ethoxylated alkylamines are conceivable, preferably those which carry at least one straight-chain or branched C 3 -C 20 -alkyl chain, preferably C 6 -C 13 -alkyl chain, particularly preferably C 7 -C 12 -alkyl chain and particularly preferably C 5 -C 6 -alkyl chain.
  • the degree of ethoxylation may be from 1 to 35 ethylene oxide groups per alkylamine, preferably from 1.5 to 15, particularly preferably from 1.8 to 9 and in particular from 2 to 6.
  • Preferred amines are n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, tert-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine , n-nonylamine, n-decylamine, 2-propylheptylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, isotridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine , n
  • the heterocycles (e) are, for example, mononuclear five- or six-membered systems having 1, 2 or 3 nitrogen atoms or having one nitrogen atom and one sulfur atom, which may be benzanellated. It is also possible to use binuclear systems of five-membered and / or six-membered partial rings with typically 2, 3 or 4 nitrogen atoms.
  • the heterocycles (e) may additionally carry functional groups, preferably C 1 -C 4 -alkoxy, amino and / or mercapto.
  • the heterocyclic skeleton may of course also carry alkyl groups, in particular C 1 -C 4 -alkyl groups.
  • heterocycles are benzotriazole, tolutriazole (tolyltriazole), hydrogenated tolutriazole, 1H-1, 2,4-triazole, benzimidazole, benzthiazole, adenine, purine, 6-methoxypurine, indole, isoindole, isoindoline, pyridine, pyrimidine , 3,4-diaminopyridine, 2-aminopyrimidine and 2-mercaptopyrimidine.
  • Suitable tetra- (C 1 -C 8 -alkoxy) -silanes (f) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane or tetra-n-butoxysilane.
  • the amides (g) may optionally be alkyl-substituted on the nitrogen atom of the amide group, for example by a Ci-C4-alkyl group.
  • aromatic or heteroaromatic backbones of the molecule can also carry such alkyl groups.
  • One or more, preferably one or two, amide groups may be present in the molecule.
  • the amides may carry additional functional groups, preferably C 1 -C 4 -alkoxy, amino, chlorine, fluorine, hydroxyl and / or acetyl; in particular, such functional groups are found as substituents on existing aromatic or heteroaromatic rings.
  • Nicotinic acid amide (pyridine-3-carboxamide), picolinic acid amide (pyridine-2-carboxamide); aliphatic carboxylic acid amides:
  • Succinic diamide, adipamide, propionamide, hexanoic acid amide ; Cycloaliphatic carboxylic acid amides having the amide moiety as a constituent of the ring: 2-pyrrolidone, N-methyl-2-pyrrolidone, 2-piperidone, ⁇ -caprolactam; aliphatic sulfonic acid amides: Methanesulfonic acid amide, hexane-1-sulfonic acid amide; aromatic sulfonic acid amides:
  • the antifreeze / anticorrosion concentrate according to the invention additionally contains in each case up to 5% by weight, in particular 0.5 to 3% by weight, of two different carboxylic acids from groups (a) and / or (b) and 0.05 to 5 wt .-%, in particular 0.1 to 0.5 wt .-%, of one or more heterocycles from group (e).
  • carboxylic acids for example, mixtures of an aliphatic monocarboxylic acid and an aliphatic dicarboxylic acid, of an aromatic monocarboxylic acid and an aliphatic dicarboxylic acid, of an aliphatic monocarboxylic acid and an aromatic monocarboxylic acid, of two aliphatic monocarboxylic acids or of two aliphatic dicarboxylic acids can be used.
  • Benzotriazole and toluotriazole are in particular suitable here as heterocycles to be used.
  • the pH of the antifreeze concentrates according to the invention is usually in the range of 4 to 11, preferably 5 to 10, particularly preferably 7 to 9.5 and in particular 8.5 to 9.5. If desired, the desired pH can also be adjusted by adding alkali metal hydroxide, ammonia or amines to the formulation; solid sodium or potassium hydroxide and aqueous sodium or potassium hydroxide are particularly suitable for this purpose.
  • carboxylic acids to be used are conveniently added as appropriate alkali metal salts to automatically be in the desired pH range.
  • carboxylic acids may also be added as free acids and then neutralized with alkali metal hydroxide, ammonia or amines and adjusted to the desired pH range.
  • antifreeze / anticorrosive concentrate according to the invention can also be defoamers (usually in amounts of 0.003 to 0.008% by weight) in customary small amounts and, for reasons of hygiene and safety, in the event of swallowing bitter substances (eg. Denatonium benzoate type) and dyes.
  • Another object of the present invention is an antifreeze / anticorrosive concentrate containing
  • n is a positive integer of 1 to 5 and may be the same or different for each of the compounds (Ia), (Ib) and (Ic), with the proviso that the sum of the amounts of compounds (Ia), (Ib ) and (Ic) in the mixture of (Ia), (Ib) and (Ic) always gives 100% by weight,
  • At least one alcohol preferably selected from the group consisting of ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, 1, 3 Propylene glycol, glycerol, mono-methyl, ethyl, Propyl and butyl ethers of ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, more preferably selected from the group consisting of ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol,
  • the antifreeze / anticorrosion concentrates according to the invention can be prepared by simple mixing of the individual components, preferably with stirring until a homogeneous mixture is achieved.
  • the antifreeze is prepared by mixing the antifreeze / anticorrosive concentrates according to the invention with water in the desired ratio.
  • Another object of the present invention is a super concentrate for a antifreeze / anticorrosive concentrate consisting of 5 to 40 wt .-%, based on the total amount of the super concentrate, a mixture of
  • n is a positive integer of 1 to 5 and may be the same or different for each of the compounds (Ia), (Ib) and (Ic), with the proviso that the sum of the amounts of compounds (Ia), (Ib ) and (Ic) in the mixture of (Ia), (Ib) and (Ic) always gives 100% by weight,
  • Another object of the present invention is a process for preparing an antifreeze / anticorrosive concentrate comprising the step
  • an antifreeze superconcentrate containing a mixture of the compound (Ia) optionally in combination with compound (Ib) and / or (Ic) with an alcohol as antifreeze component the proportion of the antifreeze component in the resulting mixture being 80 to 99% by weight. % based on the total amount of the mixture.
  • the weight ratio of supercontent to antifreeze component is preferably in the range from 5: 1 to 1:50. More preferably, it is in the range of 1: 1 to 1:20.
  • the amount of antifreeze component in the super concentrate is preferably at least 15 wt .-%, more preferably at least 20 wt .-%, based on the total amount.
  • water may be present.
  • the present invention also relates to aqueous coolant compositions having a reduced freezing point, in particular for the radiator protection of internal combustion engines in the automotive sector, comprising water and 10 to 90% by weight, in particular 20 to 60% by weight, of the antifreeze / anticorrosion concentrates according to the invention.
  • the water used for dilution should preferably be ion-free, which may be pure distilled or double-distilled water or ion-deionized water, for example.
  • Another object of the present invention is the use of coolant compositions according to the invention in installations where the antifreeze of water (usually for the range from 0 ° C to -40 ° C, especially -20 ° C to -35 ° C) and at the same time the corrosion protection of metal housings of water-containing containers to be ensured.
  • the cooling circuits of internal combustion engines especially in automobiles such as passenger cars and trucks, are of interest.
  • the coolant compositions according to the invention can also be used in stationary engines, in hot water circuits of central heating systems, in radiators heated by resistors, in solar circuits, but also in refrigerated refrigeration plants. Examples
  • Sample preparation The catalyst was filtered off and the water was removed. 50mg of the anhydrous mixture was then mixed with 1mL of MSTFA (N-methyl-N- (trimethylsilyl) -trifluoroacetamide), heated to 80 ° C for 1 hour, and the sample injected into the gas chromatograph.
  • MSTFA N-methyl-N- (trimethylsilyl) -trifluoroacetamide
  • Example 1 2.5 mol% Pt based on (Ic) 200 g of powdered catalyst with 5 wt .-% platinum on activated carbon, corresponding to 10 g or 0.0513 mol Pt (source Sigma-Aldrich) were in a 4-liter glass reactor filled and stirred with 957 g of water at 1000 rev / min. Subsequently, 410 g of oxydiol (I) with the distribution shown in the table below and an average molecular weight of 200 g / mol were added, thermostated at 60 ° C and 50 l / h of oxygen passed through the reaction mixture with further stirring.
  • the molar ratio of Pt to oxydiol (I) was thus 0.025, and the concentration of water in the liquid phase was 70% by weight. Since no base was added, the initial pH was 6.9. After 27 hours, full turnover was achieved. The supply of oxygen was stopped, the reaction cooled and drained from the glass reactor. The reaction mixture had a pH of 1.5. It was filtered on a D4 glass filter and the filter cake was washed three times with 200 ml of warm water. The filtrate was then concentrated on a rotary evaporator at 45 ° C at a pressure of up to 10 mbar. There were obtained 280 g of product mixture having the composition shown in the table below. The analyzes of the organic components were carried out by gas chromatography. The water content was determined by titration according to Karl Fischer. Educt distribution (gas chromatographic):
  • the product (Ia) also contains 4.5 area% hydroxyacetic acid.
  • Example 2 1 mol% Pt based on (Ic)
  • the molar ratio of Pt to oxydiol (I) was thus 0.0098, and the concentration of water in the liquid phase was 70% by weight. Since no base was added, the initial pH was 6.9. After 67 hours, full turnover was achieved. The supply of oxygen was stopped, the reaction cooled and drained from the glass reactor. The reaction mixture also had a pH of 1.5. It was filtered through a D4 glass filter and the filter cake washed three times with 200 ml of warm water. The filtrate was then concentrated on a rotary evaporator at 45 ° C at a pressure of up to 10 mbar. There were obtained 436 g of product mixture having the composition shown in the table below. The analyzes of the organic components were carried out by gas chromatography. The water content was determined by titration according to Karl Fischer.
  • the catalyst (16 g) (Pt / C from Sigma-Aldrich, 10% by weight platinum on activated charcoal) was introduced into a 250 mL glass reactor and stirred with 1 14 g of water at 1000 U / min.
  • thermostated at 60 ° C. and 80 l / h of pure oxygen were passed through the reaction mixture.
  • the batch was cooled, drained and filtered through a D4 glass filter.
  • the filter cake was washed with 300 ml of warm water.
  • the subsequent corrosion tests were carried out in accordance with ASTM D 4340.
  • This standard test serves to determine the susceptibility to corrosion of aluminum or aluminum alloys in cooling devices for internal combustion engines.
  • the standard apparatus used for this simulates the aluminum-containing hot inner surface of a cooling circuit of an internal combustion engine.
  • An aluminum test plate is heated from below while it is in contact with the coolant to be tested on its upper side.
  • the test temperature is 135 ° C.
  • the panel is visually assessed for corrosion and the weight change is determined by weighing.
  • the corrosion erosion is determined according to ASTM D1384 in dilution with water to 33%.
  • compositions of the test fluids are provided.

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Abstract

La présente invention concerne des concentrés d'antigel/protection anti-corrosion, un procédé de fabrication de tels concentrés à partir de superconcentrés, de compositions de liquides de refroidissement aqueuses élaborés à partir de ces concentrés ainsi que leur utilisation.
EP18707930.6A 2017-03-21 2018-03-06 Concentrés d'antigel avec protection anticorrosion Withdrawn EP3601471A1 (fr)

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US10968524B2 (en) * 2018-09-21 2021-04-06 Baker Hughes Holdings Llc Organic blend additive useful for inhibiting localized corrosion of equipment used in oil and gas production
KR20210079596A (ko) * 2019-12-20 2021-06-30 현대자동차주식회사 글리콜을 포함하지 않는 부동냉각액 조성물
JP7017612B1 (ja) * 2020-08-13 2022-02-08 トヨタ自動車株式会社 冷却液組成物
MX2023014951A (es) 2021-06-18 2024-02-20 Basf Se Polimeros de injerto biodegradables.
EP4105259A1 (fr) 2021-06-18 2022-12-21 Basf Se Polymère d'ester d'oxyde de polyalkylène, sa préparation et son utilisation
EP4386020A1 (fr) 2022-12-12 2024-06-19 Basf Se Polymères greffés biodégradables pour l'inhibition du transfert de colorant
WO2024126268A1 (fr) 2022-12-12 2024-06-20 Basf Se Polymères greffés biodégradables pour inhibition de transfert de colorant
KR20240098666A (ko) * 2022-12-21 2024-06-28 주식회사 케이디중앙연구소 글리콜계 화합물 및 실란계 화합물을 포함하는 제빙 또는 방빙용 조성물 및 이를 이용한 제빙 또는 방빙 방법

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JP2020514514A (ja) 2020-05-21

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