EP0368119B1 - Verwendung von Methylpolysiloxanen mit quartären Ammoniumgruppen als Korrosionsinhibitoren für überwiegend aus Wasser bestehende Zubereitungen - Google Patents

Verwendung von Methylpolysiloxanen mit quartären Ammoniumgruppen als Korrosionsinhibitoren für überwiegend aus Wasser bestehende Zubereitungen Download PDF

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Publication number
EP0368119B1
EP0368119B1 EP89120152A EP89120152A EP0368119B1 EP 0368119 B1 EP0368119 B1 EP 0368119B1 EP 89120152 A EP89120152 A EP 89120152A EP 89120152 A EP89120152 A EP 89120152A EP 0368119 B1 EP0368119 B1 EP 0368119B1
Authority
EP
European Patent Office
Prior art keywords
quaternary ammonium
ammonium groups
radical
value
carbon atoms
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
EP89120152A
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German (de)
English (en)
French (fr)
Other versions
EP0368119A1 (de
Inventor
Dietmar Dr. Schaefer
Werner Höhner
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.)
Evonik Operations GmbH
Original Assignee
TH Goldschmidt AG
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Publication date
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Publication of EP0368119A1 publication Critical patent/EP0368119A1/de
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Publication of EP0368119B1 publication Critical patent/EP0368119B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium 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
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/142—Hydroxy 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
    • C23F11/173—Macromolecular compounds

Definitions

  • DE-PS 30 15 864 recommends polyoxyalkylenediamides with terminal carboxylic acid groups and their salts as corrosion-preventing additives for metalworking agent emulsions. These products are also said to improve the lubricating properties of the preparation.
  • R is a monovalent hydrocarbon radical with up to 18 carbon atoms
  • R ′ is a divalent hydrocarbon radical having up to 18 carbon atoms or a divalent hydrocarbonoxy radical having up to 18 carbon atoms
  • the oxygen in the hydrocarbonoxy radical being in the form of an ether bond and the hydrocarbon portion of the hydrocarbonoxy radical being in the form of a divalent alkylene radical
  • X is the anion of an acid
  • x has an average value from 1 to about 100
  • y has an average value from 0 to about 1000, where the ratio of y: x is no greater than about 50: 1.
  • the object of the invention is to find further organosilicon compounds which have improved corrosion-inhibiting properties and give the person skilled in the art the possibility of formulating aqueous systems which are particularly suitable for dissipating heat with improved corrosion protection.
  • this object is achieved by using methylpolysiloxanes with quaternary ammonium groups bonded to silicon atoms via carbon atoms, the quotient of the number of dimethylsiloxy groups and the number of quaternary ammonium groups being from 0.5 to 15, as corrosion inhibitors for predominantly water existing preparations, in particular coolants, such as water-mixed cooling lubricants, in quantities of 0.01 to 0.1% by weight, based on the total preparation in a form suitable for the application.
  • coolants such as water-mixed cooling lubricants
  • these dimethylsiloxy groups and quaternary ammonium groups which are in the specified ratio to one another, have excellent corrosion-inhibiting properties.
  • the connections are soluble or well dispersible in water. They have a high chemical resistance in aqueous solution and are effective in a very small amount. Quantities of 0.01 to 0.1% by weight, based on the total preparation, which is diluted in a form suitable for the application, are generally sufficient to achieve good corrosion protection.
  • a preferred embodiment of the subject of the present invention is that compounds of the general formula are used as methylpolysiloxanes with quaternary ammonium groups used in which R1 is the same or different in the molecule and is a methyl radical or the radical means R2 is the same or different in the molecule and denotes an alkyl radical with 1 to 18 carbon atoms or the radical R5-CONH- (CH2) 3-, in which R5 is an alkyl radical with 7 to 17 carbon atoms, R3, R4 are the same or different in the molecule and represent an alkyl radical with 1 to 4 carbon atoms, Z the rest or is X (-) is an inorganic or organic anion, n has a value from 5 to 20, m has a value from 1 to 10, wherein the quotient of the number of dimethylsiloxy groups and the number of quaternary ammonium groups has a value from 0.5 to 15.
  • R2 can have different meanings within the polymeric molecule.
  • R2 denotes an alkyl radical having 1 to 18 carbon atoms, such as e.g. the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, decyl, dodecyl or octadecyl radical.
  • R2 can also mean the radical R5-CONH- (CH2) 3-.
  • R5 is an alkyl radical with 7 to 17 carbon atoms, which is usually derived from a fatty acid R5COOH.
  • R3 and R4 can also be the same or different within the polymeric molecule and mean an alkyl radical with 1 to 4 carbon atoms, such as e.g. the methyl, ethyl, propyl, isopropyl, butyl or isobutyl radical.
  • the quaternary ammonium groups are each bonded to a silicon atom via the radical Z.
  • the remainder Z corresponds to the formula
  • X (-) is the counter ion of the ammonium group, so that the number of anions X (-) corresponds to the number of quaternary nitrogen atoms.
  • X can be an inorganic or organic anion.
  • X is usually an inorganic anion, such as a chlorine ion.
  • An example of an organic anion is the acetate anion.
  • n indicates the number of difunctional units.
  • n has a value of 5 to 20.
  • m denotes the methylsiloxy groups to which quaternary ammonium groups are bound laterally in the polymeric molecule.
  • m has a value from 1 to 10. However, the condition must be fulfilled that the quotient of the number of dimethylsiloxy groups and the number of quaternary ammonium groups has a value of 0.5 to 15.
  • a further preferred embodiment of the subject of the present invention is characterized in that compounds of the general formula are used as methylpolysiloxanes with quaternary ammonium groups used where R2, R3, R4, X (-) and Z have the meaning already given and p has a value from 1 to 29.
  • these are linear methylpolysiloxanes which have quaternary ammonium groups only in the ⁇ , ⁇ position.
  • the radicals R2, R3, R4, X (-) and Z have the meaning already given.
  • the index p has a value from 1 to 29.
  • the methylpolysiloxanes containing quaternary ammonium groups to be used according to the invention are preferably added to commercially available concentrates of the preparations.
  • the compounds to be used according to the invention can e.g. dissolve in ethylene glycol, the user then diluting the stock solution to the appropriate concentration.
  • the siloxanes can be added to the concentrated, commercially available emulsion, the essential components of which are vegetable, synthetic or animal oils, water and emulsifier. This stock emulsion is then diluted with water to the application concentration at the point of use.
  • the siloxanes to be used according to the invention can be prepared, for example, according to DE-PS 37 19 086.
  • This production process uses siloxanes of the general formula as starting compounds.
  • R6 has the meaning of a methyl radical or the radical Q.
  • Q is the rest The remaining radicals and indices have the meaning already given.
  • the corrosion protection properties are determined in accordance with DIN 51 360, Part 2, for the testing of cooling lubricants in accordance with the specification of the determination of the corrosion protection properties of water-mixed cooling lubricants using the swarf / filter paper method. Reference is made to the DIN regulation for the details of the determination.
  • the water-mixed cooling lubricant is provided with the anti-corrosion agent.
  • Gray cast iron test chips which were checked visually for freedom from corrosion prior to the determination, are sieved and the fraction is used to carry out the tests used, where 30 ⁇ 5 chips have a total weight of 2 g.
  • a round filter is placed in a Petri dish measuring 80 x 20 mm. 2 g of the chips are evenly applied to the surface of the round filter. The chips are evenly wetted with 2 ml of the aqueous preparation to be tested. Then the lid of the petri dish is put on. The Petri dishes prepared in this way are then exposed to a temperature of about 8 to 22 ° C. for two hours.
  • the chips are then removed, the round filter rinsed under running water, swirled in acetone for about 5 seconds and dried at room temperature.
  • the degree of corrosion of the corrosion markings on the round filter is then determined by visual inspection. The evaluation is based on the following classification:
  • the compounds to be investigated for their corrosion-inhibiting properties are each dissolved in 0.1% by weight in the water-mixed cooling lubricant.
  • the following connections were examined and evaluated:
EP89120152A 1988-11-08 1989-10-31 Verwendung von Methylpolysiloxanen mit quartären Ammoniumgruppen als Korrosionsinhibitoren für überwiegend aus Wasser bestehende Zubereitungen Expired - Lifetime EP0368119B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3837811A DE3837811C1 (es) 1988-11-08 1988-11-08
DE3837811 1988-11-08

Publications (2)

Publication Number Publication Date
EP0368119A1 EP0368119A1 (de) 1990-05-16
EP0368119B1 true EP0368119B1 (de) 1992-12-30

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP89120152A Expired - Lifetime EP0368119B1 (de) 1988-11-08 1989-10-31 Verwendung von Methylpolysiloxanen mit quartären Ammoniumgruppen als Korrosionsinhibitoren für überwiegend aus Wasser bestehende Zubereitungen

Country Status (3)

Country Link
US (1) US5246607A (es)
EP (1) EP0368119B1 (es)
DE (2) DE3837811C1 (es)

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US5399737A (en) * 1994-04-04 1995-03-21 Alcon Laboratories, Inc. Quaternary ammonium siloxane compounds and methods for their use
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DE19610234C2 (de) * 1996-03-15 1999-08-05 Goldschmidt Ag Th Verwendung von Siloxanen mit betainischen und quaternären Gruppen zur Herstellung von Dämmstoffplatten auf Mineral- und Papierfaserbasis
DE19651287A1 (de) * 1996-12-10 1998-06-18 Wacker Chemie Gmbh Ionische Organosiliciumverbindungen, deren Herstellung und Verwendung
ES2124195B1 (es) * 1997-05-29 1999-09-16 Krafft S A Composicion anticongelante/refrigerante.
US6072735A (en) * 1998-06-22 2000-06-06 Lucent Technologies, Inc. Built-in redundancy architecture for computer memories
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US6482969B1 (en) * 2001-10-24 2002-11-19 Dow Corning Corporation Silicon based quaternary ammonium functional compositions and methods for making them
JP2005528484A (ja) * 2002-05-31 2005-09-22 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 腐蝕抑制剤としてのアルキルアミノシロキサン
US7759408B2 (en) * 2005-12-21 2010-07-20 Bausch & Lomb Incorporated Silicon-containing monomers end-capped with polymerizable cationic hydrophilic groups
US7622512B2 (en) * 2005-12-21 2009-11-24 Bausch & Lomb Incorporated Cationic hydrophilic siloxanyl monomers
US20070161769A1 (en) * 2006-01-06 2007-07-12 Schorzman Derek A Polymerizable silicon-containing monomer bearing pendant cationic hydrophilic groups
US7960447B2 (en) * 2006-04-13 2011-06-14 Bausch & Lomb Incorporated Cationic end-capped siloxane prepolymer for reduced cross-link density
US20080152540A1 (en) * 2006-12-22 2008-06-26 Bausch & Lomb Incorporated Packaging solutions
US7691917B2 (en) 2007-06-14 2010-04-06 Bausch & Lomb Incorporated Silcone-containing prepolymers
ATE509136T1 (de) * 2008-10-21 2011-05-15 Atotech Deutschland Gmbh Nachbehandlungszusammensetzung zur steigerung des rostschutzes von metall oder metalllegierungsflächen
KR101366420B1 (ko) * 2009-01-22 2014-02-24 실테크 코포레이션 알킬 쿼터늄 실리콘 화합물
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Also Published As

Publication number Publication date
DE58903171D1 (de) 1993-02-11
DE3837811C1 (es) 1990-04-26
EP0368119A1 (de) 1990-05-16
US5246607A (en) 1993-09-21

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