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WO2002064664A2 - Systemes sol-gel hydrolises sans eau - Google Patents

Systemes sol-gel hydrolises sans eau Download PDF

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Publication number
WO2002064664A2
WO2002064664A2 PCT/EP2002/001424 EP0201424W WO02064664A2 WO 2002064664 A2 WO2002064664 A2 WO 2002064664A2 EP 0201424 W EP0201424 W EP 0201424W WO 02064664 A2 WO02064664 A2 WO 02064664A2
Authority
WO
WIPO (PCT)
Prior art keywords
acid
group
starting compounds
reaction
inorganic
Prior art date
Application number
PCT/EP2002/001424
Other languages
German (de)
English (en)
Other versions
WO2002064664A8 (fr
WO2002064664A3 (fr
Inventor
Gerhard Jonschker
Original Assignee
Nanogate Technologies Gmbh
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 Nanogate Technologies Gmbh filed Critical Nanogate Technologies Gmbh
Priority to AU2002253008A priority Critical patent/AU2002253008A1/en
Priority to DE10296264T priority patent/DE10296264D2/de
Publication of WO2002064664A2 publication Critical patent/WO2002064664A2/fr
Publication of WO2002064664A3 publication Critical patent/WO2002064664A3/fr
Publication of WO2002064664A8 publication Critical patent/WO2002064664A8/fr

Links

Classifications

    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • 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
    • C08G77/02—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
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups

Definitions

  • the present invention relates to water-free hydrolyzed sol-gel systems.
  • the invention relates to inorganic-organic composites based on silanes or metal alkoxides.
  • BESTATIGUNGSKOPIE Water leads to an often undesirable increase in the polarity of the solvent in which the reaction takes place.
  • many auxiliaries that would be advantageous to use in the sol-gel process are difficult or impossible to dissolve in the water-alcohol mixture formed and therefore limit the educts that can be used and the reaction routes that can be carried out.
  • the hydrolysis of the most frequently used starting materials, the silanes produces alcohol (ethanol or methanol), which is often undesirable either for toxicological reasons (methanol) or because of the poor dissolving behavior (ethanol).
  • sol-gel process It is therefore very desirable to use a sol-gel process have, which does not use alcohol and water as a solvent or reagent.
  • a sol-gel process can be carried out entirely without addition of water and solvent by mixing the silanes or metal alkoxides with anhydrous carboxylic acids, and the polymerization reaction then taking place using suitable catalysts (traces of mineral acids or other strong acids, Metal ions, fluoride ions) catalyzed.
  • silanes which can be used for the anhydrous hydrolysis can also carry (reactive) organic radicals, such as, for. B. methacrylic, alkyl or fluoroalkyl.
  • organically modified inorganic networks in esters can be represented as solvents.
  • Material hardens This property can e.g. B. used are used to produce scratch-resistant, thermoplastic films that can be back-injected with plastics and can be used in a very wide range of areas in plastic production. It is advantageous, but not absolutely necessary, that the polymer still carry reactive groups which can react with the silane polymer.
  • the resulting ethyl acetate dissolves the polymer formed from fluoroalkylsilane and alkylsilane very well, while a phase separation is observed during hydrolysis in an aqueous-alcoholic medium.
  • the polymer formed from the alkyl and fluoroalkylsilane is amphiphilic, which means that it exhibits surface-active properties.
  • the amphiphilic polymer infiltrates the dirt (eg paint residues) and removes it from the surfaces to be treated. 2.
  • the amphiphilic polymer still has reactive groups with which it can bind to the surface to be treated. The formation of a very thin separating layer prevents further soiling and significantly supports future cleaning.
  • the ester solvent formed can also be used further
  • carboxylic acids are: acrylic acid, methacrylic acid, maleic acid or crotonic acid.
  • methacrylic acid ester is formed in the anhydrous hydrolysis and condensation, which is not only an excellent solvent for many organic auxiliaries, but also a polymerizable raw material which can be used in further radical or UV polymerizations.
  • MEMO a methacrylic functional silane
  • methacrylic acid a methacrylic functional inorganic polymer, dissolved in methyl methacrylic acid
  • the inorganic polymer is completely crosslinked with the solvent to form a solid nanocomposite block without loss of solvent. Due to its inorganic-organic network, this nanocomposite block is thermosetting and is characterized by special mechanical properties (e.g. high scratch resistance, higher refractive index, thermal resistance). Further the high inorganic content reduces shrinkage compared to purely organic polymers.
  • Another advantage of the solvent formed in the water-free sol-gel process is the improved spreading capacity and the better adhesion, in particular on plastics, which is probably caused by a surface dissolving of the plastic.
  • the inorganic polymers in the ester solvent can also be used excellently as an additive for solvent-based paints. So far, the incompatibility of the alcohol-water mixture in sol-gel systems has prevented it from being used as an additive for conventional, solvent-based paints. This- * new process makes it possible to produce inorganic polymers that are extremely compatible with common paint formulations. In particular, scratch resistance, chemical resistance, adhesion and corrosion protection properties of these coatings can be improved.
  • Preferred silanes are the ethoxy and methoxysilanes (methoxy has higher reactivity), higher alcohols as leaving groups are also conceivable.
  • Examples of possible acids are e.g. B-. Acetic acid, formic acid, fluorocarboxylic acids, acetoacetic acid, succinic acid or monomethyl succinate and generally all acids which, under the given reaction conditions, can undergo esterification with the alcohol as a leaving group on the silicon.
  • fluorinated esters are formed as solvents. These can have both special solution and special wetting properties, which are advantageous.
  • fluorocarbon resins are lent in various partially fluorinated esters, which opens up the possibility of producing new composite materials with fluorocarbons.
  • Solvent acetoacetic acid ester formed, which is a good complexing agent. As a result, metals, especially heavy metals, can be complexed very effectively, what
  • the anhydrides of the acids can also be used instead of the acids. This can be the case if it is desired that residual acetoxy groups are present in the resulting inorganic polymer, e.g. to produce a polymer that cures under atmospheric humidity or to bind residues of water or alcohol in the mixture.
  • Examples include acetic anhydride, succinic anhydride, methacrylic anhydride or maleic anhydride.
  • anhydrides it is usually desirable to use the anhydrides in a mixture with alcohols.
  • the molar ratio chosen determines the number of residual acetoxy groups on the silicon atom. Up to a ratio of 1: 1 (anhydride: alcohol) residual acetoxy groups remain.
  • a suitable catalyst is generally added when carrying out the reaction.
  • This can e.g. a strong proton supplier, as in the simplest case a mineral acid such as hydrochloric acid or sulfuric acid.
  • This catalyst which is mostly used in traces, accelerates the reaction from a few days to a few hours.
  • catalyzing substances can also be used. These include, in particular, the alkoxides of titanium and tin, as well as fluoride ions, which are known to be able to catalyze the Si-O-Si condensation strongly.
  • fluoride ions which are known to be able to catalyze the Si-O-Si condensation strongly.
  • pre-reacted condensation products of silanes and other alkoxides can also be introduced into the reaction.
  • reactive silicone resins which, for.
  • nanoparticles in a suitable form as nucleating agents for the growth of the inorganic polymers.
  • suitable nanoparticles are: organosilica sols (high-link types from Clariant, preferably in butyl acetate) or dispersions of nanoparticles (boehmite, AIOOH, Si0 2 , Zr0 2 .7) in solvents such as ethyl acetate or the carboxylic acid used for the reaction. If solvents such as water or alcohol are used, it is advisable to use the anhydrides instead of the carboxylic acids in order to eliminate these mostly undesirable components.
  • the nanoparticles result in denser growth of the inorganic polymers in the specified form, while without these nucleating agents, rather open, porous structures are created. Since dense particulate structures are advantageous for increasing the scratch and abrasion resistance of coatings, the use of nanoparticles as nucleating agents or as fillers is preferred.
  • a greasy steel surface is first roughly pre-cleaned with pure gasoline and then thoroughly cleaned of dirt with the modified gasoline and a lint-free cloth. After cleaning, the surface is rubbed with a dry, lint-free cloth. The result is a water and dirt repellent surface.
  • Example 1 The mixture is prepared as in Example 1 and 2% Aerosil R972 is added. Due to the grinding effect of the added powder, the cleaning effect of this mixture is better than that in example 1.
  • hydrophobically silanized Neuburg Siliceous Earth can also be dispersed as an abrasive.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne un procédé pour produire des composés inorganiques-organiques par polymérisation de composés de départ adéquats. Selon l'invention, ces composés de départ adéquats sont mélangés avec un acide carbonique anhydre et un catalyseur adapté est ajouté au mélange réactionnel.
PCT/EP2002/001424 2001-02-12 2002-02-12 Systemes sol-gel hydrolises sans eau WO2002064664A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2002253008A AU2002253008A1 (en) 2001-02-12 2002-02-12 Anhydrously hydrolysed sol-gel systems
DE10296264T DE10296264D2 (de) 2001-02-12 2002-02-12 Wasserfrei hydrolisierte Sol-Gel-Systeme

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10106787A DE10106787A1 (de) 2001-02-12 2001-02-12 Wasserfrei hydrolisierte Sol-Gel-Systeme
DE10106787.9 2001-02-12

Publications (3)

Publication Number Publication Date
WO2002064664A2 true WO2002064664A2 (fr) 2002-08-22
WO2002064664A3 WO2002064664A3 (fr) 2002-10-24
WO2002064664A8 WO2002064664A8 (fr) 2003-10-30

Family

ID=7673980

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/001424 WO2002064664A2 (fr) 2001-02-12 2002-02-12 Systemes sol-gel hydrolises sans eau

Country Status (3)

Country Link
AU (1) AU2002253008A1 (fr)
DE (2) DE10106787A1 (fr)
WO (1) WO2002064664A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8012578B2 (en) 2005-09-05 2011-09-06 Deutsches Wollforschungsinstitut An Der Rwth Aachen E.V. Method for producing composite materials
CN111978860A (zh) * 2020-08-17 2020-11-24 上海金力泰化工股份有限公司 一种耐刮哑光陶瓷树脂及其制备方法

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* Cited by examiner, † Cited by third party
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US6982251B2 (en) 2000-12-20 2006-01-03 Schering Corporation Substituted 2-azetidinones useful as hypocholesterolemic agents
CA2563051A1 (fr) 2001-01-26 2002-08-01 Schering Corporation Combinaisons d'au moins un activateur de recepteurs actives de la proliferation des peroxysomes et d'au moins un inhibiteur de l'absorption des sterols, et traitements de troublesvasculaires
US7071181B2 (en) 2001-01-26 2006-07-04 Schering Corporation Methods and therapeutic combinations for the treatment of diabetes using sterol absorption inhibitors
IL156422A0 (en) 2001-01-26 2004-01-04 Schering Corp The use of substituted azetidinone compounds for the treatment of sitosterolemia
US7056906B2 (en) 2001-09-21 2006-06-06 Schering Corporation Combinations of hormone replacement therapy composition(s) and sterol absorption inhibitor(s) and treatments for vascular conditions in post-menopausal women
US7053080B2 (en) 2001-09-21 2006-05-30 Schering Corporation Methods and therapeutic combinations for the treatment of obesity using sterol absorption inhibitors
ATE345793T1 (de) 2001-09-21 2006-12-15 Schering Corp Behandlung von xanthom mittels azetidinon- derivate als hemmer der sterol absorption
WO2004043456A1 (fr) 2002-11-06 2004-05-27 Schering Corporation Inhibiteurs d'absorption du cholesterol pour le traitement de la demyelination
ATE406364T1 (de) 2003-03-07 2008-09-15 Schering Corp Substituierte azetidinon-derivate, deren pharmazeutische formulierungen und deren verwendung zur behandlung von hypercholesterolemia
JP2006519869A (ja) 2003-03-07 2006-08-31 シェーリング　コーポレイション 置換アゼチジノン化合物、置換アゼチジノン化合物を調製するためのプロセス、それらの処方物および使用
US7459442B2 (en) 2003-03-07 2008-12-02 Schering Corporation Substituted azetidinone compounds, processes for preparing the same, formulations and uses thereof
ES2318274T3 (es) 2003-03-07 2009-05-01 Schering Corporation Compuestos de azetidinona sustituida, formulaciones y uso de los mismos para el tratamiento de hipercolesterolemia.
DE10339912B4 (de) 2003-08-29 2016-07-21 Ivoclar Vivadent Ag Dentale Beschichtungsmaterialien, deren Verwendung sowie Verfahren zur Beschichtung einer Substratoberfläche
EP2938761A1 (fr) 2012-12-28 2015-11-04 Merck Patent GmbH Substances de dopage destinées au dopage local de tranches de silicium
EP2938763A1 (fr) * 2012-12-28 2015-11-04 Merck Patent GmbH Barrières de diffusion imprimables pour tranche de silicium

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL65093C (fr) * 1945-07-25
GB945311A (en) * 1959-10-12 1963-12-23 Nubold Dev Ltd Composition of matter
US3714119A (en) * 1968-12-12 1973-01-30 Lockheed Aircraft Corp Zinc-siloxane polymer and coating and method for making the same
JPS4944951B1 (fr) * 1969-11-24 1974-11-30
DE19706515A1 (de) * 1997-02-19 1998-08-20 Inst Neue Mat Gemein Gmbh Hydroxylgruppen-arme organisch/anorganische Komposite, Verfahren zu deren Herstellung und deren Verwendung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8012578B2 (en) 2005-09-05 2011-09-06 Deutsches Wollforschungsinstitut An Der Rwth Aachen E.V. Method for producing composite materials
CN111978860A (zh) * 2020-08-17 2020-11-24 上海金力泰化工股份有限公司 一种耐刮哑光陶瓷树脂及其制备方法

Also Published As

Publication number Publication date
AU2002253008A1 (en) 2002-08-28
WO2002064664A8 (fr) 2003-10-30
WO2002064664A3 (fr) 2002-10-24
DE10296264D2 (de) 2004-09-09
DE10106787A1 (de) 2002-08-22

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