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WO2010043638A2 - Formulation d'époxyde durcissable contenant de la silice - Google Patents

Formulation d'époxyde durcissable contenant de la silice Download PDF

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Publication number
WO2010043638A2
WO2010043638A2 PCT/EP2009/063381 EP2009063381W WO2010043638A2 WO 2010043638 A2 WO2010043638 A2 WO 2010043638A2 EP 2009063381 W EP2009063381 W EP 2009063381W WO 2010043638 A2 WO2010043638 A2 WO 2010043638A2
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WO
WIPO (PCT)
Prior art keywords
solvent
water
epoxy resins
bis
silica
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Ceased
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PCT/EP2009/063381
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English (en)
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WO2010043638A3 (fr
Inventor
Alexander Traut
Norbert Wagner
Andreas FECHTENKÖTTER
Chih-Cheng Peng
Malik Jamal Jaffar Ali
Lily-Liqi Yang
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BASF SE
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BASF SE
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Publication of WO2010043638A3 publication Critical patent/WO2010043638A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • C01B33/149—Coating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • C01B33/151—After-treatment of sols by progressively adding a sol to a different sol, i.e. "build-up" of particles using a "heel"
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00

Definitions

  • the present invention provides novel curable epoxide coating formulations containing silica, methods for their preparation and their use.
  • inorganic particles In order to incorporate inorganic particles into organic coating materials, these particles are frequently prepared as milled or precipitated solids or a slurry or paste and then suspended in the organic coating material.
  • a disadvantage of this is that the particles cannot be transferred into an organic matrix without agglomerates by known methods, such as dry milling, wet milling, ultrasonic treatment or extrusion.
  • particles dispersed by wet milling tend to agglomerate after removal of the solvent, so that the particles are non uniformly distributed on introduction into a medium, such as, for example, a coating material. As a rule, this results in a loss of transparency of the coating material and, owing to the phase separation of the coating material, leads to abrasion-labile coatings having little hardness.
  • US-A-3699049 describes the removal of water by distillation at from 50 to 100 0 C from acidic or basic, colloidal silica sols with polyfunctional alcohols, such as, for example, glycerol.
  • a disadvantage is that the solvent cannot be removed in this method since the glycerol used in the explicitly disclosed examples has a boiling point of about 290 0 C at atmospheric pressure. This prevents removal of the solvent under gentle conditions.
  • EP 1236765 A1 describes a process in which an alkali metal silicate solution is acidified with an acidic ion exchanger and converted into a silica sol and surface- modified with a silane, an isopropanol is then added thereto and water is distilled off.
  • the silicates thus obtained and having a particle size of from 3 to 50 nm can then be taken up in organic coating materials.
  • the silica sols prepared are rendered alkaline after their preparation by acidic polycondensation for protection from agglomeration. Thereafter, i.e. in the alkaline pH range, the surface of the silica sol is optionally modified by reaction with functional silanes.
  • a disadvantage of this preparation process is that the products thus obtained have a relatively high viscosity.
  • Another disadvantage is that commercially available silica sols which are modified in the alkaline pH range have a substantial tendency to agglomeration and gelling.
  • WO 2006/044376 A1 describes the preparation of inorganic oxides, in particular silicates, in an aqueous medium and subsequent distribution in organic coating materials.
  • the process disclosed there comprises, starting from a silica sol, ion exchange with liberation of the acid, mixing with an organic solubilizer, addition of base and addition of a silane for surface modification.
  • the complete surface modification with the silane takes place in the alkaline pH range. Thereafter, the solvent is removed to dryness and the residue is taken up in an organic solvent.
  • a disadvantage of this process is that the resulting solutions of silica sols with the use of commercial silica sols have a high viscosity and in addition the surface on the particles must be completely reacted with silane in order to give a free-flowing powder.
  • the surface treatment with silanes can take place under acidic or basic conditions, only alkaline reaction conditions are explicitly disclosed.
  • US-A-6210790 describes a method to functionalize SiO 2 nanoparticles with trialkoxysilane in the presence of ion exchange resin, where the ion exchange resin serves as a catalyst for the hydrolysis and condensation of trialkoxysilane.
  • a disadvantage of this method is that without a proper removal of metal ion from the SiO 2 dispersion, instead of reacting with silanol groups on SiO 2 surface the hydrolyzed trialkoxysilane tends to condense with each other. It usually leads to a lower degree of surface modification.
  • WO 2007/146521 A1 describes a method to formulate surface modified SiO 2 into epoxy resin for adhesive applications.
  • the native alkaline SiO 2 nanoparticle dispersion is acidified with ion exchange resin.
  • a water miscible solvent must be added to the system prior to the removal of water.
  • a disadvantage of this method is that the choice of epoxy resin is therefore limited to its compatibility to water miscible solvent only.
  • the present invention refers to a method for the preparation of curable epoxide coating formulations containing silica comprising the steps of
  • Silica in the context of the present invention is silicon dioxide including its sol and silicic acid.
  • a typical curable epoxide coating formulation according to the present invention con- tains preferably 1 to 60 weight-% (based on the total weight of the formulation) of silica nanoparticles wherein the silica nanoparticles are modified by an organosilane and an epoxy resin or precursor thereof, e.g. an aliphatic, cycloaliphatic or aromatic epoxide and optionally at least one of the following ingredients: an UV photo initiator, a monothiol or polythiol, a solvent and optionally other additives.
  • an organosilane and an epoxy resin or precursor thereof e.g. an aliphatic, cycloaliphatic or aromatic epoxide and optionally at least one of the following ingredients: an UV photo initiator, a monothiol or polythiol, a solvent and optionally other additives.
  • Preferred curable epoxides are:
  • Aliphatic epoxy resins including long-chain diol modified epoxides, such as the d i g l y c i d y l e t h e r of p o l y p ro p y l e n e g l y c o l [ ⁇ , ⁇ -bis(2,3-epoxy- propoxy)poly(oxypropylene)] or diglycidyl ether of polyethylene glycol [ ⁇ , ⁇ - bis(2,3-epoxyethoxy)poly(oxyethylene)].
  • Polyglycidyl ethers or esters of sorbitol, glycerol, and pentaerythiol can be used as aliphatic epoxy resins.
  • Cycloaliphatic epoxy resins are well known to the art and, as described herein, are compounds that contain at least about one cycloaliphatic group and at least one oxirane group. More preferred cycloaliphatic epoxides are compounds that contain about one cycloaliphatic group and at least two oxirane rings per mole- c u l e .
  • Aromatic epoxy resins may also be used with the present invention.
  • aromatic epoxy resins useful in the present invention include bisphenol-A epoxy resins, bisphenol-F epoxy resins, phenol novolac epoxy resins, cresol- novolac epoxy resins, biphenol epoxy resins, biphenyl epoxy resins, 4,4'- biphenyl epoxy resins, polyfunctional epoxy resins, divinylbenzene dioxide, and 2-glycidylphenylglycidyl ether.
  • resins, including aromatic, aliphatic and cycloaliphatic resins are described throughout the specification and claims, either the specifically-named resin or molecules having a moiety of the named resin are envisioned.
  • epoxy resins Numerous commercially available epoxy resins can be utilized.
  • epoxides that are readily available include octadecylene oxide, epichlorohydrin, styrene oxide, vinyl cyclohexene oxide, glycidol, glycidyl methacrylate, diglycidyl ethers of Bisphenol A (for example, EPON 828, EPON 825, EPON 1004, and EPON 1001 from Resolution Performance Products, Houston, TX as well as DER 221 , DER 332, and DER 334 from Dow Chemical Co., Midland, Ml), vi- nylcyclohexene dioxide (for example, ERL 4206 from Dow Chemical, Midland, Ml), 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexene carboxylate (for exam- pie, ERL 4221 , CYRACURE UVR 61 10, and CYRACURE UVR 6105 from Dow
  • the nanoparticles are prepared and functionalized according to the following steps 1 ) - 3):
  • the SiO 2 nanoparticle dispersion (sol) used comprises particles having a mean particle diameter of from 1 to 150 nm, preferably from 2 to 120 nm, particularly preferably from 3 to 100 nm, very particularly preferably from 4 to 80 nm, in particular from 5 to 50 nm and especially from 8 to 40 nm.
  • the content of silicic acid, calculated as SiO 2 is from 10 to 60 wt% by weight, preferably from 20 to 55 % by weight, particularly preferably from 25 to 40 wt%. It is also possible to use silica sols having a lower content, but the additional content of water must then be separated off by distillation in a subsequent step.
  • the SiO 2 nanoparticle dispersion (sol) which, if appropriate, can be stabilized to a slight extent with alkali metal, alkaline earth metal, ammonium, aluminum, iron(ll), iron (III) and/or zirconium ions, preferably alkali metal, alkaline earth metal, ammonium and/or iron(lll) ions, particularly preferably alkali metal, alkaline earth metal and/or ammonium ions, very particularly preferably alkali metal and/or alkaline earth metal ions and in particular alkali metal ions.
  • alkali metal ions sodium and/or potassium ions are preferred and sodium ions are particularly preferred.
  • alkaline silica sols have as a rule a pH of from 7 to 10, preferably from 8 to 9. These alkaline silica sols are commercially available and are therefore a readily available and preferred starting material for the process according to the invention.
  • the acidification of native SiO 2 nanoparticle dispersion can be performed, for example, by three different methods:
  • low molecular weight silicic acids preferably waterglass, i.e. salt-like particles having a diameter of less than 1 nm, or by condensation of esters of low molecular weight silicic acids.
  • the preparation of the silica sols to be used according to the invention from these alkaline silica sols is effected by establishing the desired pH in these silica sols, for example by addition of mineral acids or by addition of an ion exchanger to the alkaline silica sols.
  • the preparation of the silica sols from waterglass by acidification, for example with an ion exchanger, or by addition of a mineral acid is also conceivable.
  • a waterglass preferably used for this purpose is potassium and/or sodium silicate, which particularly preferably has a ratio of 1 - 10 mol of SiO 2 to 1 mol of alkali metal oxide, very particularly preferably 1 .5 - 6 and in particular 2 - 4 mol of SiO 2 to 1 mol of alkali metal oxide.
  • the surface of the SiO 2 nanoparticles from 0 to 10 times, preferably from 0.2 to 5 times, particularly preferably from 0.4 to 3 times and very particularly preferably from 0.5 to 2 times the amount of water (based on the amount of the silica sol used) and from 0.1 to 20 times, preferably from 0.3 to 10 times, particularly preferably from 0.5 to 5 times and very particularly preferably from 1 to 2 times the amount (based on the amount of the silica sol used) of at least one organic solvent (L) are added to the acidified solution obtained.
  • the solvent (L) can be added to the reaction mixture before or during the reaction with the organosilane (S), preferably before or during and particularly preferably before the reaction with the organosilane.
  • Functionalizing in the context of the present invention means that the surface of the silica nanoparticles is modified by adsorbing and/ or reacting with functionalizing organosilanes S which have an affinity to said surface. Without limiting the present invention this might be an adsorption, a coordinative or chemical bond.
  • Preferred organosilanes S correspond to the following formula:
  • substituents have the following meaning: R reactive group or alkyl, aryl or alkoxy which may be substituted by at least one reactive group
  • each R 1 is independently selected from the group consisting of H or alkoxy, especially CrC 4 -alkoxy, especially methoxy or ethoxy; acyloxy, especially acetoxy; amino; halogene, especially Cl; wherein at least one of the groups R 1 is hydrolysable and is especially methoxy or ethoxy.
  • a hydrolysable group in the context of the present invention is a group which reacts with water or a hydroxyl group.
  • alkyl examples include methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n- hexadecyl, n-octadecyl and n-eicosyl.
  • Preferred examples of d- to C 4 -alkyl are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
  • Preferred radicals are methyl, ethyl, n-butyl and tert-butyl, particularly preferably methyl and ethyl.
  • Reactive groups are preferably those which have a group identical or complimentary to the binder/cross-linking agent combination of organic coating material to be used according to the present invention.
  • Preferred reactive groups are primary amino, secondary amino, amide, hydrazide, imidazoles, thiol, carboxylic acid, anhydride, hydroxyl.
  • the reactive group means hydroxyl, epoxy, amino or acid groups in the case of epoxy resins or melamine/formaldehyde resins, hydroxyl, amino or isocyanate groups in the case of polyurethane resins or groups capable of free radical polymerization in the case of radiation-curable resins.
  • Groups capable of free radical polymerization are, for example, allyl ether, vinyl ether, acrylate or methacrylate groups, preferably vinyl ether, acrylate or methacrylate groups and particularly preferably acrylate or methacrylate groups, which are referred to for short as (meth)acrylate groups in this document.
  • These reactive groups are as a rule linked to the silyl groups by spacer groups.
  • spacer groups are divalent organic radicals having 1 to 20 carbon atoms, for example alkylene or arylene groups, preferably alkylene groups.
  • Examples of these are methylene, 1 ,2-ethylene (-CH 2 -CH 2 -), 1 ,2- propylene (-CH(CHs)-CH 2 -) and/or 1 ,3-propylene (-CH 2 -CH 2 -CH 2 -), 1 ,2-, 1 ,3- and/or 1 ,4-butylene, 1 ,1-dimethyl-1 ,2-ethylene, 1 ,2-dimethyl-1 ,2-ethylene, 1 ,6-hexylene, 1 ,8- octylene or 1 ,10-decylene, preferably methylene, 1 ,2-ethylene, 1 ,2- or 1 ,3-propylene, 1 ,2-, 1 ,3- or 1 ,4-butylene, particularly preferably methylene, 1 ,2-ethylene, 1 ,2- and/or 1 ,3-propylene and/or 1 ,4-butylene and very particularly preferably methylene, 1 ,2- ethylene, 1
  • Preferred compounds (S) are 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4- epoxycyclohexy ⁇ ethyltrimethoxysilane, isooctyltrimethoxysilane, N-(3-triethoxysilyl- propyl)methoxyethoxyethoxyethyl carbamate (PEG3TES), N-(3-triethoxysilylpropyl)- methoxyethoxyethoxyethyl carbamate (PEG2TES), 3-(methacryloyloxy)propyl- trimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyl- triethoxysilane, 3-(methacryloyloxy)methyltriethoxysilane, 3-(methacryloyloxy)ethyl- triethoxysilane,
  • the compounds (S) are preferably 3-(methacryloyloxy) propyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane or 3-(methacryloyloxy)propylmethyldimethoxysilane and isobutyltriethoxysilane.
  • the amount of organosilane used can be adjusted according to its compatibility to specific epoxy resin, which is typically in the range of 1 to 50 wt% (based on the amount of the silica sol used).
  • solvent L is used as an addition solvent to improve the miscibility of water and solvent (K).
  • the organic solvent (L) is selected according to the following criteria: under the mixing conditions, it should have both sufficient miscibility with water and miscibility with the organic coating material.
  • the miscibility with water under the reaction conditions should be at least 20 wt% (based on the prepared water/solvent mixture), preferably at least 50 wt% and particularly preferably at least 80 wt%. If the miscibility is too low, one can select another organic solvent (polar or non-polar) to improve the compatibility between the organic solvent (L) and epoxy resin.
  • a certain amount of isopropanol (here refer to L) can be a good solvent both for the surface modification for SiO 2 and improving the compatibility between water and butyl acetate.
  • the solvent (L) forms an azeotrope or heteroazeotrope with water under the distillation conditions, so that the distillate forms an aqueous and an organic phase after the distillation.
  • suitable solvents (L) are ethanol, 1- propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-chloro-2-propanol, cyclopentanol, cyclohexanol, 1 ,4-dioxane, tetrahydrofuran, 1-methoxy-2-propanol, 1- ethoxy-2-propanol, 2-ethoxyethanol, 2-methyl-2-propanol, 2-methoxyethanol, dimethylformamide, acetonitrile and acetone.
  • water and solvent (L) are added simultaneously to the solution of the silicate, and it may also be expedient to add water and solvent (L) in a form premixed with one another.
  • the addition of water and solvent (L) or of the mixture thereof can be effected in one portion, in portions or continuously.
  • Solvent K are soluble in water at 20 0 C.
  • the solvents K which can be used include aromatic hydrocarbons, halogenated aromatic hydrocarbons, and ketones, acetates, ethers, esters and and the like.
  • the type and amount of solvent used can be selected according to its compatibility to specific epoxy resin and the final system viscosity.
  • a preferred solvent K is butyl acetate especially for water-immiscible epoxy resins.
  • Acidifying the silica nanoparticles by ion exchange is preferably performed with anionic ion exchange resins which are able to remove the cationic counter ions in the native silica dispersions.
  • any suitable additives known for coating formulations may be used additionally, pref- erably initiators, photoinitiators, polythiols, flame retardants and stabilizers.
  • Any suitable photoinitiator can be used in the present formulations.
  • the photoinitiator is a single-component system such as an ultraviolet cationic photoinitiator.
  • Suitable ultraviolet cationic photoinitiators often include a sulfonium salt or an iodonium salt.
  • Exemplary triarylsulfonium salts include triarylsulfonium hexafluorophosphate and triarylsulfonium hexafluoroantimonate such as those commercially available from Dow Chemical Co., Midland, Ml under the trade designation CYRACURE (UVI-6976, UVI-6992, UVI-6974, or UVI-6990) and from Sartomer, Exton, PA under the trade designation SARCAT (Kl 85 or SRIOIO).
  • Exemplary iodonium salts typically are diaryliodonium salts such as those further described in U.S. Patent Nos.
  • the iodonium salts can be a simple salt containing an anion such as Cl “ , Br “ , I “ , or C 4 H 5 SO 3 " or a metal complex salt containing an anion such as SbF 6 " , PF 6 “ , BF 4 " , tetrakis(perfluorophenyl)borate, SbF 5 OH “ , or AsF 6 " .
  • the cation of the iodonium salt is often diphenyliodonium. Mixtures of iodonium salts can be used, if de- sired.
  • Examples of a polythiol compound which may be combined include aliphatic polythiol compounds such as methanedithiol, ethanedithiol, 1 ,1-propanedithiol, 1 ,2- propanedithiol, 1 ,3-propanedithiol, 1 ,6-hexanedithiol, 1 ,2,3-propanetrithiol, 1 ,1- cyclohexanedithiol, 1 ,2-cyclohexanedithiol, 2,2-dimethylpropane-1 ,3-dithiol, 3,4- dimethoxybutane-1 ,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1 ,1-bis(mercapto- methyl)cyclohexane, bis(2-mercaptoethyl) thiomalate, 2, 3-dimercapto-1-propanol (2- mercaptoa
  • An epoxy-SiO 2 hybrid coating containing the composition given in example 4 was prepared using a doctor blade of a thickness of 24.0 ⁇ m. The coating was then tested using a 5135 Abraser (TABER Industries) following the ASTM 4060 standard method. As a benchmark comparison, similar tests were done with three commercial epoxy-SiO 2 hybrid resins C 450, C 460 and C 620 (NanoResins ® ). The the test results are shown as the following table.
  • composition of example 4 according to the present invention uses a low concentration of 10 % of SiO 2 provides for much better or similar resistance to mass abrasion as compared with the state of the art comprising 4 times as much SiO 2 .

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Abstract

La présente invention porte sur de nouvelles formulations de revêtement d'époxyde durcissables contenant de la silice, sur des procédés pour leur préparation et sur leur utilisation.
PCT/EP2009/063381 2008-10-15 2009-10-14 Formulation d'époxyde durcissable contenant de la silice Ceased WO2010043638A2 (fr)

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EP08166626 2008-10-15
EP08166626.5 2008-10-15

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2012082224A1 (fr) * 2010-12-17 2012-06-21 Dow Global Technologies Llc Compositions durcissables
US9080259B2 (en) 2009-06-30 2015-07-14 Basf Se Polyamide fibers with dyeable particles and production thereof
CN110526636A (zh) * 2019-09-19 2019-12-03 重庆兴渝新材料研究院有限公司 一种疏水硅溶胶及其制备方法

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AU2003234394A1 (en) * 2002-05-23 2003-12-12 3M Innovative Properties Company Nanoparticle filled underfill
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US20040102529A1 (en) * 2002-11-22 2004-05-27 Campbell John Robert Functionalized colloidal silica, dispersions and methods made thereby
US20050008865A1 (en) * 2003-07-07 2005-01-13 General Electric Company Curable epoxy compositions and articles made therefrom
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US9080259B2 (en) 2009-06-30 2015-07-14 Basf Se Polyamide fibers with dyeable particles and production thereof
WO2012082224A1 (fr) * 2010-12-17 2012-06-21 Dow Global Technologies Llc Compositions durcissables
CN103347925A (zh) * 2010-12-17 2013-10-09 陶氏环球技术有限责任公司 可固化组合物
CN110526636A (zh) * 2019-09-19 2019-12-03 重庆兴渝新材料研究院有限公司 一种疏水硅溶胶及其制备方法
CN110526636B (zh) * 2019-09-19 2022-02-15 重庆兴渝新材料研究院有限公司 一种疏水硅溶胶及其制备方法

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