EP2059572A1 - Revêtement destiné à assurer la décomposition induite par la chaleur de dépôts organiques - Google Patents

Revêtement destiné à assurer la décomposition induite par la chaleur de dépôts organiques

Info

Publication number
EP2059572A1
EP2059572A1 EP07802819A EP07802819A EP2059572A1 EP 2059572 A1 EP2059572 A1 EP 2059572A1 EP 07802819 A EP07802819 A EP 07802819A EP 07802819 A EP07802819 A EP 07802819A EP 2059572 A1 EP2059572 A1 EP 2059572A1
Authority
EP
European Patent Office
Prior art keywords
sol
functional silanes
silanes
composition according
composition
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Withdrawn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
EP07802819A
Other languages
German (de)
English (en)
Inventor
Rudolf Gensler
Heinrich Kapitza
Heinrich Zeininger
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.)
Siemens AG
Original Assignee
Siemens AG
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 Siemens AG filed Critical Siemens AG
Publication of EP2059572A1 publication Critical patent/EP2059572A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58—Metal-containing linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates

Definitions

  • the present invention relates to a coating for the thermally induced decomposition of organic deposits according to the preamble of the main claim.
  • coke-like deposits can, for. B. be reduced by lowering the combustion chamber temperature via a suitable cooling system or optimized heat dissipation.
  • fuel additives can reduce the formation of these deposits ⁇ ments.
  • none of the above measures to a satisfactory reduction or elimination of these deposits leads, although each powered expenses (structural measures, cost of additives) is uplifting ⁇ Lich.
  • ⁇ which in turn leads to high servicing costs.
  • methods for the formation of surface coatings are known in which the coating materials are deposited from a gas plasma (Plasma Enhanced Chemical Vapor Deposition, PECVD).
  • PECVD Enhanced Chemical Vapor Deposition
  • Object of the present invention is to provide a method and a means for reducing the formation of coke-like deposits in internal combustion engines, which allows a satisfactory reduction and / or avoidance of said deposits and at the same time to realize at a reasonable cost.
  • composition for forming a sol-gel coating comprising
  • silicic acid esters and / or organosilanes b) water c) one or more organic metal derivatives based on titanium, cerium and vanadium, d) a solvent, and e) a mineral acid or organic acid as catalyst
  • the metal derivatives mentioned are preferably organic metal derivatives, in particular metal alkoxides or metal acetylacetonates of the metals titanium, cerium and vanadium.
  • the exact properties of the metal derivatives will be discussed below.
  • the solvent may, in particular, be alcohols (for example ethanol, isopropanol, methoxypropanol, butanol).
  • the silicic acid esters and the organosilanes react to ⁇ next in the presence of water and the catalyst by hydrolytic reaction to silanols. Kondensie ⁇ ren then silane oligomers that act silanols in the freshlybilde- th coating as a network-forming inorganic nanoparticle kel. The resulting liquid is called a sol, which can be considered a nanocomposite. Finally, the metal derivative is added to the sol.
  • a sol-gel coating formed by this composition is capable of reducing the formation of coke-like deposits on surfaces. Reference is made to the examples.
  • the metal particles of the sol-gel coating catalyze the thermal decomposition of the deposits that form, in particular the coke deposits.
  • the uniform distribution of the metal particles formed is ensured in particular by the formation of an inorganic-organic network of the silanes used. Consequently, the forming particles can not agglomerate or sediment and remain evenly distributed throughout the layer.
  • sol-gel coating processes The special feature of sol-gel coating processes is that the preparation or deposition of the materials proceeds from a liquid sol state, which is converted into a solid gel state by a sol-gel transformation.
  • Solids are dispersions of solid particles in the size range between 1 nm and 100 nm in water or organic solvents.
  • the transition from the liquid sol to the sol-gel layer is in each case via a gel state.
  • the sol-gel transformation there is a three-dimensional cross-linking of the particles in the solvent, as a result of which the gel acquires solid-state properties.
  • the transfer of the gel in a solid coating is made by a variety of cross-linking hydrolysis and condensation reactions.
  • Both reactions preferably proceed under acidic conditions.
  • Fully functional substituted silanes such as tetraethoxyorthosilane (TEOS) cross-link via polycondensation across all 4 functional groups.
  • silanes which are not completely functionally substituted such as, for example, methyltriethoxysilane (MTES)
  • MTES methyltriethoxysilane
  • MTES methyltriethoxysilane
  • the use of such silanes thus reduces the degree of crosslinking of the sol-gel. Therefore, the properties of the sol-gel may be exactly enced affect by precise metering of such Si ⁇ lane.
  • These silanes are therefore also called network modifiers.
  • silanes that provide functional groups that are capable of undergoing crosslinking reactions.
  • functional groups that are capable of undergoing crosslinking reactions.
  • silanes that provide functional groups that are capable of undergoing crosslinking reactions.
  • silanes are particularly suitable for use in the composition according to the invention because rapid crosslinking prevents sedimentation or agglomeration of the particles.
  • the organically modified silanes are alkylsilanes, arylsilanes, amino functional silanes, chlorosilanes, epoxy-functional silanes, glycol-functional silanes, mercapto-functional silanes, acrylate-functional silanes or vinyl-functional silanes.
  • the alkyl- and arylsilanes are preferably methyltrimethoxysilane, methyltriethoxysilane, tetraethoxorethosilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane or phenyltriethoxysilane.
  • the aminofunctional silanes are preferably 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 2-aminoethyl-3-aminopropyltrimethoxysilane, triaminofunctional propyltrimethoxysilane, bis (triethoxysilylproyl) amine, N- (n-butyl) -3-aminopropyltrimethoxysilane, polyglycol ether-modified aminosilane , 2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3
  • the chlorosilanes are, for example, silicon tetrachloride, dichlorosilane or triethylchlorosilane.
  • the epoxy- and glycol-functional silanes are preferably 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane or polyetherpropyltrimethoxysilane.
  • the mercapto-functional silanes are preferably 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane or bis (3-triethoxysilylpropyl) polysulfan.
  • the acylated silanes are, for example, 3-methacryloxypropyltrimethoxysilane.
  • the vinyl-functional silanes are, for example, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane or their oligomers.
  • the silicic acid esters are, for example, tetramethyl orthosilicate, tetraethyl orthosilicate, ethyl polysilicate, tetra-n-propyl orthosilicate or tetrabutyl glycol orthosilicate.
  • silanes are triethylsilane, chloromethyltrimethylsilane, trimethylsilylnitrile, 1-bromo-4-trimethylsiloxybenzene, 1-trimethylsilyl-1,2,2-triazole and 1,2-divinyl-1,1,2,2-tetramethyldisiloxane
  • silanes mentioned are partly, according to the above definition, completely functionally substituted silanes, partly not completely functionally substituted silanes (network modifiers) and partly network formers.
  • metal derivatives is to be understood hereinafter as meaning those compounds which are capable of providing the metal oxides in question under the conditions according to the invention.
  • the metal derivatives are precursor derivatives of TiO 2 , CeO 2 or V 2 O 5 .
  • the metal derivatives may be titanium tetraalkoxides, such as, for example, tetraethyl titanate and tetraisopropyl titanate, or titanium tetra-trimethylsiloxide.
  • R denotes, for example, ethyl groups (tetraethyltitanate), isopropyl groups (tetraisopropyl titanate) or trimethylsiloxide groups (titanium tetra-trimethylsiloxide).
  • a method for forming ei ⁇ ner sol-gel coating on a surface using a composition according to the invention comprises the following steps:
  • the organic metal derivatives form uniformly distributed particles of a size between 10 and 30 nm.
  • the surface is cured at 150 ° C.-300 ° C. inclusive.
  • the uniform distribution of the ge ⁇ formed particles is in particular ensured by the Ausbil ⁇ dung of an inorganic-organic network of the silanes used. Consequently, the forming particles can not agglomerate or sediment and remain evenly distributed throughout the layer.
  • the invention provides for the use of a composition according to the invention for forming a sol-gel coating on a surface of objects.
  • the latter may in particular be the Oberflä ⁇ chen of
  • Combustion chambers Combustion chambers, spark plugs, fuel injectors and / or valves of internal combustion engines, but also to exhaust sensors, air mass sensors, catalytic converters, or lines and actuators of exhaust gas recirculation act.
  • a steel plate and a glass pane with ⁇ means of dip coating with the sol-gel coated.
  • the layers are cured for 3 hours at 150 0 C and then for 2 hours at 250 0 C.
  • the nanoparticles are formed uniformly from the tetraisopropyl titanate in the coating ver ⁇ handed out.
  • the coatings become opaque to white.
  • methyltriethoxysilane (trade name Dynasylan MTES, available from Degussa) is initially charged together with 1 g of H 2 O and stirred with the addition of 2 drops of HCl. After a few minutes, the hydrolysis of the silane begins, the temperature increases to about 50 0 C. Then it is stirred for one hour. To the mixture are then successively added Ig tetraisopropyl titanate, 2.5 g methoxypropanol and 10 g ethanol pa with stirring.
  • the transparent sol-gel is used to coat steel sheets.
  • the layers are cured for 2 hours at 150 0 C and remain clear.
  • a steel sheet coated with the sol-gel coating of Example 1 is partially coated with a thin layer of multipurpose grease (trade name Alvania RL3, available from Shell). As a blind sample is unpretreated
  • Sheet steel also partially coated with the multipurpose grease.
  • the samples are placed in an oven and heated to 300 0 C for about 2h. Due to the heat effect, the multipurpose grease is degraded. The surface of the coated sample regenerated as the ⁇ while adheres to the blanks a black crust of comparable kokten products.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition destinée à former un revêtement sol-gel, contenant un ester d'acide silicique et/ou un organosilane, de l'eau, un ou plusieurs dérivés de métaux organiques à base de titane, de cérium et de vanadium, un solvant, et un acide minéral ou un acide organique en tant que catalyseur.
EP07802819A 2006-09-05 2007-08-23 Revêtement destiné à assurer la décomposition induite par la chaleur de dépôts organiques Withdrawn EP2059572A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610041555 DE102006041555A1 (de) 2006-09-05 2006-09-05 Beschichtung zur thermisch induzierten Zersetzung von organischen Ablagerungen
PCT/EP2007/058757 WO2008028815A1 (fr) 2006-09-05 2007-08-23 Revêtement destiné à assurer la décomposition induite par la chaleur de dépôts organiques

Publications (1)

Publication Number Publication Date
EP2059572A1 true EP2059572A1 (fr) 2009-05-20

Family

ID=38895696

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07802819A Withdrawn EP2059572A1 (fr) 2006-09-05 2007-08-23 Revêtement destiné à assurer la décomposition induite par la chaleur de dépôts organiques

Country Status (3)

Country Link
EP (1) EP2059572A1 (fr)
DE (1) DE102006041555A1 (fr)
WO (1) WO2008028815A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008059861A1 (de) * 2008-12-01 2010-06-02 Daimler Ag Kühlaggregat zum Kühlen von Abgasen einer Verbrennungskraftmaschine eines Kraftfahrzeugs
WO2017072259A1 (fr) * 2015-10-30 2017-05-04 Agc Glass Europe Feuille de verre revêtue
US10300460B1 (en) * 2017-11-17 2019-05-28 Chevron Phillips Chemical Company L.P. Aqueous methods for titanating a chromium/silica catalyst
US10259893B1 (en) 2018-02-20 2019-04-16 Chevron Phillips Chemical Company Lp Reinforcement of a chromium/silica catalyst with silicate oligomers
US11186656B2 (en) 2019-05-24 2021-11-30 Chevron Phillips Chemical Company Lp Preparation of large pore silicas and uses thereof in chromium catalysts for olefin polymerization

Family Cites Families (8)

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US3442824A (en) * 1967-05-12 1969-05-06 Hempel S Marine Paints Inc Polymeric compositions and protective coatings
US4339559A (en) * 1980-05-21 1982-07-13 Phillips Petroleum Company Polymerization using silica from single phase controlled hydrolysis of silicate ester
DE3407087C2 (de) * 1984-02-27 1994-07-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 8000 München Verfahren und Lack zur Herstellung von kratzfesten Beschichtungen
US4547557A (en) * 1984-07-09 1985-10-15 Phillips Petroleum Company Silica-titania cogel from two-step hydrolysis
FR2720404B1 (fr) * 1994-05-30 1996-10-25 Lorraine Laminage Procédé de protection d'un substrat en acier au moyen d'un film mince de polymère hybride organique-inorganique.
DE19737475A1 (de) * 1997-08-28 1999-03-04 Bayer Ag Beschichtungszusammensetzungen auf der Basis von Epoxidgruppen enthaltenden Silanen
DE19915377A1 (de) * 1999-04-06 2000-10-12 Inst Neue Mat Gemein Gmbh Katalytische Zusammensetzung, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102004046406A1 (de) * 2004-09-24 2006-04-06 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Transparente Beschichtungszusammensetzung und Verfahren zu deren Herstellung sowie entsprechend transparent beschichtete Substrate

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Also Published As

Publication number Publication date
WO2008028815A1 (fr) 2008-03-13
DE102006041555A1 (de) 2008-03-20

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