EP1299456A1 - Procede pour produire des compositions de type sol-gel presentant une teneur reduite en solvant et une stabilite au stockage amelioree, et utilisation desdites compositions - Google Patents

Procede pour produire des compositions de type sol-gel presentant une teneur reduite en solvant et une stabilite au stockage amelioree, et utilisation desdites compositions

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Publication number
EP1299456A1
EP1299456A1 EP01951602A EP01951602A EP1299456A1 EP 1299456 A1 EP1299456 A1 EP 1299456A1 EP 01951602 A EP01951602 A EP 01951602A EP 01951602 A EP01951602 A EP 01951602A EP 1299456 A1 EP1299456 A1 EP 1299456A1
Authority
EP
European Patent Office
Prior art keywords
sol
solvent
organo
gel
gel compositions
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Withdrawn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
EP01951602A
Other languages
German (de)
English (en)
Inventor
Michael Mager
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.)
Bayer AG
Original Assignee
Bayer 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 Bayer AG filed Critical Bayer AG
Publication of EP1299456A1 publication Critical patent/EP1299456A1/fr
Withdrawn legal-status Critical Current

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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
    • C08G77/48—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
    • C08G77/50—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 by carbon linkages

Definitions

  • the present invention relates to a process for the preparation of inorganic or organic-inorganic (hybrid) materials by hydrolysis and condensation of mono- or low-molecular alkoxides and their use for coating surfaces and modifying organic polymers.
  • alkoxides usually (organo) silicon alkoxides
  • sol-gel reactions are usually used in sol-gel reactions and are reacted in a solvent with water in the presence of a catalyst. After a certain reaction time, the reaction solution is then applied to the desired surface and, after the volatile constituents have evaporated, is finally subjected to thermal or radiation-induced curing.
  • the mostly highly cross-linked sol-gel coatings obtained in this way are generally transparent, outstandingly solvent- and chemical-resistant and wear-resistant.
  • a fundamental problem of the sol-gel reactive solutions is that the amount of solvent is reduced only to a very limited extent and the solids content can thus be increased without the pot life becoming too short.
  • the solvent content increases further, since in the condensation of e.g. Theoretically, 72% by weight of tetraethyl orthosilicate can be released.
  • Alkoxides and silanols based on cyclic carbosiloxanes are particularly suitable for the production of organic-inorganic hybrid materials, for example in WO 94/06807, EP-A-0 787 734 and EP-A-0 947 520.
  • a major disadvantage of the sol-gel solutions described there, however, is their high solvent content and the limited pot life. Solvent contents of more than 70% by weight are no longer accepted from an ecological point of view in the paint industry, especially in areas where the disposal of the solvent cannot be handled properly.
  • WO 98/52992 describes oligomers of the cyclic carbosiloxanes mentioned, which can be co-condensed in a solvent in the presence of a catalyst and water with alkoxides and / or nanoparticles.
  • the production of such condensates corresponds to e.g. described in DE-A-196 03 242 and in WO 94/06897, whereby only low solids contents can be achieved.
  • the object of the present invention was therefore to provide sol-gel compositions based on cyclic carbosiloxanes with a solvent content of less than 60% by weight and a pot life of at least 7 days.
  • the present invention relates to a process for the production of sol-gel compositions from cyclic carbosiloxanes and (organo) metal alkoxides with a solvent content of less than 60% by weight and a storage stability of at least 7 days, characterized in that the process steps
  • the sol-gel compositions are produced by the successive process steps,
  • the sol-gel compositions produced according to the invention preferably contain less than 50% by weight, particularly preferably less than 40% by weight, of solvent. They are stable for at least 7 days (i.e. the sol-gel compositions are not gelled), but they are condensed to the extent that they can be cured after application to a surface, for example, without the addition of components (e.g. water, catalysts).
  • Cyclic carbosiloxanes for the purposes of the invention are those of the formula (I) in which
  • R 1 for C to C alkyl
  • R 2 for hydrogen and / or CV ⁇ to C 4 alkyl a for the number 0.1 or 2, n for the number 2 to 10 and m for the number 3 to 5
  • Oligomeric cyclic carbosiloxanes of the formula (I) and their preparation are described in WO 98/52992 and can also be used in the process according to the invention.
  • (organo) metal alkoxides are (organo) silicon alkoxides of the formula (II),
  • R, 4 for a Ci to C 4 alkyl radical
  • Tetraethoxysilane is particularly preferably used as the silicon alkoxide of the formula (II).
  • water is used in a molar ratio of 1: 2 to 3: 1, preferably 3: 1 to 1.5: 1.
  • 1 to 90 preferably 25 to 60% by weight of the cyclic carbosiloxane and 99 to 20, preferably 75 to 40% by weight of the (organo) metal alkoxide are used to prepare the sol-gel compositions according to the invention.
  • catalysts are e.g. called: aqueous inorganic or organic acids or bases, such as formic acid, p-toluenesulfonic acid, hydrochloric acid or sodium and potassium hydroxide or organic metal compounds.
  • the catalyst is preferably an acid, particularly preferably para-toluenesulfonic acid.
  • Suitable solvents are those with a boiling point greater than 80 ° C, for example
  • the alcohols liberated during the hydrolysis and condensation and any solvent added are removed by distillation, preferably under normal pressure.
  • the process according to the invention for the production of sol-gel compositions also allows the exchange of protic solvents such as alcohols with non-protic solvents such as ketones, esters or ethers. Since non-protic solvents, for example, are not reactive towards isocyanates, mixtures of sol-gel compositions with isocyanate group-containing and OH groups can be prepared in this way. Pen-containing polymers are obtained without the blocked isocyanants described in WO 98/38251 having to be used for the production of such organic-inorganic hybrid materials. Inorganically modified polyurethanes can be obtained from these mixtures, which can be used as coatings with improved wear resistance.
  • protic solvents such as alcohols
  • non-protic solvents such as ketones, esters or ethers. Since non-protic solvents, for example, are not reactive towards isocyanates, mixtures of sol-gel compositions with isocyanate group-containing and OH groups can be prepared in this way. Pen-containing polymers are obtained without the blocked isocyanants
  • Additives such as leveling or wetting aids can be added to the sol-gel compositions produced according to the invention before, during or after production, in order, for example, to improve the film appearance.
  • organic or inorganic dyes (soluble) or pigments (insoluble) By adding organic or inorganic dyes (soluble) or pigments (insoluble), the
  • Sol-gel coatings can be colored.
  • the addition of UV protection agents primarily serves to protect the coated substrate, e.g. Plastic.
  • the mechanical properties of the coatings that can be produced from them can also be improved, for example, by adding nanoparticles to the sol-gel compositions produced according to the invention.
  • suitable preparations of nanoparticles are dispersions of SiO 2 , Al 2 O 3 or TiO 2 -containing particles in water or solvents.
  • the particle size of the nanoparticles is preferably less than 100 nm, particularly preferably less than 50 nm (determined by means of ultracentrifugation).
  • the invention furthermore relates to the use of the sol-gel compositions produced according to the invention for producing coatings, for example on glass, ceramics, metals and plastics.
  • the application can be carried out according to all common painting techniques such as spraying, dipping, spinning, pouring, flooding or painting.
  • Another object of the invention is the use of the sol-gel compositions according to the invention for the inorganic modification of organic polymers.
  • organic polymers are polyethers, polyesters, polyvinyl alcohols, polycarbonates or copolymers and mixtures (blends) of these.
  • Organic polymers containing hydroxyl groups can be modified particularly well with the sol-gel compositions, since the compatibility with them is generally very good.
  • the modification of epoxides or polyurethanes by the sol-gel compositions produced according to the invention leads, for example, to coatings with significantly improved wear resistance.
  • D4-diethoxide oligomer an oligomer mixture of partially condensed cyclo- ⁇ SiO [(CH 2 ) 2 SiCH 3 (OEt) 2 ] ⁇ 4 , was produced as described in WO 98/52992. Tetraethyl orthosilicate (TEOS) and the solvents used were used without further purification. A 0.1 N aqueous solution of p-toluenesulfonic acid (p-TSS solution) was used as the catalyst for the condensation and hydrolysis.
  • p-TSS solution 0.1 N aqueous solution of p-toluenesulfonic acid
  • the calculated calculated solids contents relate to the theoretically remaining solid after complete hydrolysis and condensation of the alkoxides contained in the sol-gel reactive solution and complete removal of the volatile constituents.
  • the experimental determination of the solids content was carried out by weighing 1 g of the sol-gel reactive solution into a crystallizing dish (diameter: 7.5 cm) and evaporating the volatile constituents for one hour at 130 ° C. in a circulating air cabinet.
  • the storage stability of the sol-gel compositions produced according to the invention was checked by standing at room temperature and at 50 ° C in a well-sealed sample glass for at least 14 days (gelation).
  • Example 1 Sol-gel composition (52%) in l-methoxy-2-propanol
  • Example 2 Sol-gel composition (73%) in l-methoxy-2-propanol
  • Example 3 Sol-gel composition (57%) in 1-butanol
  • Example 4 Sol-gel composition (61%) in 1-pentanol
  • Example 5 Sol-gel composition (40%) in methoxypropylacetate
  • Example 6 Sol-gel composition (41%) in n-butyl acetate
  • Example 7 Sol-gel composition (53%) in l-methoxy-2-propanol
  • Example 8 Sol-gel composition (44%) in methoxypropylacetate
  • Example 9 Sol-gel composition (50%) in l-methoxy-2-propanol
  • Boiling point of ⁇ 90 ° C (mainly the ethanol formed) distilled off. To on cooling, 83.9 g of the sol-gel composition were obtained as a low-viscosity, clear liquid.
  • Example 10 Sol-gel composition (55%) in l-methoxy-2-propanol with

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé pour produire des matériaux (hybrides) inorganiques ou organiques-inorganiques par hydrolyse et condensation d'alcoxydes monomoléculaires ou à faible poids moléculaire, ainsi que l'utilisation de ces matériaux pour revêtir des surfaces et modifier des polymères organiques.
EP01951602A 2000-06-29 2001-06-18 Procede pour produire des compositions de type sol-gel presentant une teneur reduite en solvant et une stabilite au stockage amelioree, et utilisation desdites compositions Withdrawn EP1299456A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10031764A DE10031764A1 (de) 2000-06-29 2000-06-29 Verfahren zur Herstellung von Sol- Gel-Kompositionen mit verringertem Lösungsmittelgehalt und verbesserter Lagerstabilität und deren Verwendung
DE10031764 2000-06-29
PCT/EP2001/006835 WO2002000767A1 (fr) 2000-06-29 2001-06-18 Procede pour produire des compositions de type sol-gel presentant une teneur reduite en solvant et une stabilite au stockage amelioree, et utilisation desdites compositions

Publications (1)

Publication Number Publication Date
EP1299456A1 true EP1299456A1 (fr) 2003-04-09

Family

ID=7647261

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01951602A Withdrawn EP1299456A1 (fr) 2000-06-29 2001-06-18 Procede pour produire des compositions de type sol-gel presentant une teneur reduite en solvant et une stabilite au stockage amelioree, et utilisation desdites compositions

Country Status (7)

Country Link
US (1) US20030114540A1 (fr)
EP (1) EP1299456A1 (fr)
JP (1) JP2004502007A (fr)
AU (1) AU2001272486A1 (fr)
CA (1) CA2412537A1 (fr)
DE (1) DE10031764A1 (fr)
WO (1) WO2002000767A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10102739A1 (de) 2001-01-23 2002-07-25 Bayer Ag Verfahren zur Herstellung von Sol-Gel-Kondensaten auf Basis polyfunktioneller Organosilane sowie deren Verwendung
KR20050024721A (ko) * 2003-09-01 2005-03-11 삼성전자주식회사 신규 실록산계 수지 및 이를 이용한 반도체 층간 절연막
US7811374B2 (en) * 2005-08-30 2010-10-12 The Boeing Company Colored coating and formulation
CN102079947B (zh) * 2010-12-01 2012-11-21 北京航空航天大学 一种钛合金表面溶胶-凝胶转化膜的制备方法
WO2012162642A2 (fr) 2011-05-26 2012-11-29 Advenira Enterprises, Inc. Système et procédé pour revêtir un objet
US8710169B2 (en) 2012-01-18 2014-04-29 United Technologies Corporation Method of treating a preceramic material
JP7389538B2 (ja) * 2020-04-02 2023-11-30 関西ペイント株式会社 有機ケイ素化合物の加水分解縮合物分散液の製造方法
WO2023235488A1 (fr) * 2022-06-01 2023-12-07 Genesee Polymers Corporation Intermédiaire d'aérogel et son procédé de production

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19603241C1 (de) * 1996-01-30 1997-07-10 Bayer Ag Multifunktionelle, cyclische Organosiloxane, Verfahren zu deren Herstellung und deren Verwendung
DE19807634A1 (de) * 1997-05-23 1998-11-26 Agfa Gevaert Ag Beschichtete Partikel
DE19814060A1 (de) * 1998-03-30 1999-10-07 Bayer Ag Borhaltige Mischungen, Hybridmaterialien und Beschichtungen
DE19935326A1 (de) * 1999-07-28 2001-02-01 Bayer Ag Verwendung selbstorganisierender Beschichtungen auf Basis fluorfreier polyfunktioneller Organosilane zur Herstellung ultrahydrophober Beschichtungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0200767A1 *

Also Published As

Publication number Publication date
JP2004502007A (ja) 2004-01-22
AU2001272486A1 (en) 2002-01-08
DE10031764A1 (de) 2002-01-10
US20030114540A1 (en) 2003-06-19
CA2412537A1 (fr) 2002-12-19
WO2002000767A1 (fr) 2002-01-03

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