US20090076198A1 - Functionalized nanoparticles - Google Patents

Functionalized nanoparticles Download PDF

Info

Publication number
US20090076198A1
US20090076198A1 US11/665,627 US66562705A US2009076198A1 US 20090076198 A1 US20090076198 A1 US 20090076198A1 US 66562705 A US66562705 A US 66562705A US 2009076198 A1 US2009076198 A1 US 2009076198A1
Authority
US
United States
Prior art keywords
alkyl
hydrogen
phenyl
oxygen
sulfur
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.)
Abandoned
Application number
US11/665,627
Other languages
English (en)
Inventor
Thomas Giesenberg
Andreas Muhlebach
Tunja Jung
Francois Rime
Laurent Michau
Martin Muller
Didier Bauer
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.)
BASF SE
BASF Corp
Original Assignee
Individual
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 Individual filed Critical Individual
Assigned to CIBA SPECIALTY CHEMICALS CORP. reassignment CIBA SPECIALTY CHEMICALS CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAUER, DUDIER, MUHLEBACH, ANDREAS, JUNG, TUNJA, MICHAU, LAURENT, MULLER, MARTIN, RIME, FRANCOIS, GIESENBERG, THOMAS
Publication of US20090076198A1 publication Critical patent/US20090076198A1/en
Assigned to CIBA CORPORATION reassignment CIBA CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: CIBA SPECIALTY CHEMICALS CORPORATION
Assigned to BASF SE reassignment BASF SE ASSET TRANSFER AGREEMENT Assignors: CIBA CORPORATION
Priority to US13/930,848 priority Critical patent/US8877954B2/en
Abandoned 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • 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
    • 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
    • C09C1/40—Compounds of aluminium
    • 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
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to novel functionalized nanoparticles, to compositions comprising an organic material, preferably a synthetic polymer, and to the novel functionalized nanoparticles, as well as to the use thereof as stabilizers and/or flame-retarders and/or compatibilizers for organic materials which are subject to oxidative, thermal or light-induced degradation, in particular synthetic nanocomposite polymers or coatings; or as photoinitiators for the in-situ polymerization or hardening of pre-polymeric nanocomposites to nanocomposite materials.
  • fillers in polymers has the advantage that it is possible to bring about improvement in, for example, the mechanical properties, especially the density, hardness, rigidity or impact strength of the polymer.
  • nano-scaled fillers Using extremely small filler particles ( ⁇ 400 nm), so-called nano-scaled fillers, mechanical properties, long term stability or flame retardant property of the polymers can be improved at a much lower concentration of 5 to 10% by weight compared to 20 to 50% by weight with the micro-scaled normal filler particles.
  • Polymers containing nano-scaled fillers show improved surface qualities like gloss, lower tool wear at processing and better conditions for recycling.
  • Coatings and films comprising nano-scaled fillers show improved stability, flame resistance, gas barrier properties and scratch resistance.
  • Nano-scaled fillers possess an extremely large surface with high surface energy. The reduction of the surface energy and the compatibilization of the nano-scaled fillers with a polymeric substrate is therefore even more important than with a common micro-scaled filler in order to avoid aggregation and to reach an excellent dispersion of the nano-scaled filler in the polymer.
  • the nano-scaled fillers like the phyllosilicates are made organophilic by ion exchange, for example with alkylammonium salts. Such nano-scaled organophilic phyllosilicates are better swellable and easier to disperse (exfoliate) into a polymer matrix [for example Nanomer® from Nanocor or Closite® from Southern Clay Products].
  • WO-A-03/002652 discloses the preparation of additive functionalized organophilic nano-scaled fillers.
  • novel functionalized nanoparticles are especially useful as stabilizers and/or flame-retarders and/or compatibilizers for organic materials which are subject to oxidative, thermal or light-induced degradation, in particular synthetic nanocomposite polymers or coatings; or as photoinitiators for the in-situ polymerization or hardening of pre-polymeric nanocomposites to nanocomposite materials.
  • This invention therefore relates to a functionalized nanoparticle comprising on the surface a covalently bound radical of the formula I
  • nanoparticle is a SiO 2 , Al 2 O 3 or mixed SiO 2 and Al 2 O 3 nanoparticle
  • X is oxygen, sulfur or
  • R 1 is C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen, sulfur or
  • R 2 and R 3 independently of each other are hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
  • R 4 is hydrogen, C 1 -C 25 alkyl or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
  • R 5 is hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
  • R 6 and R 7 independently of each other are hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
  • Highly preferred nanoparticles comprising a radical of formula (I) are those of formula
  • R 1 , R 2 , R 3 , X and n are as defined under formula (I) and wherein R 5 as nanoparticle surface is —SiO 2 surface.
  • the nanoparticle is a SiO 2 , Al 2 O 3 or mixed SiO 2 and Al 2 O 3 nanoparticle
  • R 11 is C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen, sulfur or
  • amino-, mercapto- or hydroxyl substituted C 2 -C 24 alkyl amino-, mercapto- or hydroxyl substituted C 2 -C 24 alkyl; amino-, mercapto- or hydroxyl substituted C 2 -C 24 alkyl which is interrupted by oxygen, sulfur or
  • R 14 is hydrogen, C 1 -C 25 alkyl or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
  • R 15 is hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
  • R 16 and R 17 independently of each other are hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl, phenyl, C 7 -C 9 phenylalkyl or —OR 15 , R 18 , R 19 and R 20 independently of each other are hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl, phenyl or C 7 -C 9 phenylalkyl.
  • Highly preferred nanoparticles comprising a radical of formula (II) are those of formula
  • R 11 , R 12 and R 13 are as defined under formula (II) and wherein R 15 as nanoparticle surface is —SiO 2 surface.
  • Alkyl having up to 25 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexy
  • Hydroxyl-substituted C 2 -C 24 alkyl is a branched or unbranched radical which contains preferably 1 to 3, in particular 1 or 2, hydroxyl groups, such as, for example, hydroxyethyl, 3-hydro-oxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, 5-hydroxypentyl, 4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl, 6-hydroxyhexyl, 5-hydroxyhexyl, 4-hydroxyhexyl, 3-hydroxyhexyl, 2-hydroxyhexyl, 7-hydroxyheptyl, 6-hydroxyheptyl, 5-hydroxyheptyl, 4-hydroxyheptyl, 3-hydroxyheptyl, 2-hydroxyheptyl, 8-hydroxyoctyl, 7-hydroxyoctyl, 6-hydroxyoctyl, 5-hydroxyoctyl, 4-hydroxyoctyl, 3-hydroxyoctyl, 2-hydroxyocty
  • Amino-, mercapto- or hydroxyl substituted C 2 -C 24 alkyl is, for example, —CH 2 —CH(NH 2 )—CH 2 —O—CH 3 , —CH 2 —CH(SH)—CH 2 —O—CH 2 CH 3 or —CH 2 —CH(OH)—CH 2 —O—CH(CH 3 ) 2 .
  • Alkenyl having 2 to 24 carbon atoms is a branched or unbranched radical such as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference is given to alkenyl having 3 to 18, especially 3 to 12, for example 3 to 6, especially 3 to 4 carbon atoms.
  • C 5 -C 12 cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl. Preference is given to cyclohexyl.
  • C 5 -C 12 cycloalkenyl is, for example, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl or cyclododecenyl. Preference is given to cyclo-hexenyl.
  • a polymer is the polymerization product when a polymerizable group, as for example outlined above, is polymerized.
  • Phenylalkyl is, for example, benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl or 2-phenyl-ethyl. Preference is given to benzyl.
  • photoinitiators from which the residue R 1 may be derived, are the following: camphor quinone; benzophenone, benzophenone derivatives, such as 2,4,6-trimethylbenzophenone, 2-methyl benzophenone, 3-methyl benzophenone, 4-methylbenzophenone, 2-methoxycarbonyl benzophenone 4,4′-bis(chloromethyl)benzo-phenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxy-benzophenone, [4-(4-methylphenylthio)phenyl]-phenylmethanone, methyl-2-benzoylbenzoate, 3-methyl-4′-phenylbenzophenone, 2,4,6-trimethyl-4′-phenylbenzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethyl-amino)benzophenone; ketal compounds, as for example benzil
  • acetophenone, acetophenone derivatives for example ⁇ -hydroxycycloalkyl phenyl ketones or 2-hydroxy-2-methyl-1-phenyl-propanone (DAROCUR® 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE® 184) 1-(4-dodecylbenzoyl)-1-hydroxy-1-methyl-ethane, 1-(4-isopropylbenzoyl)-1-hydroxy-1-methyl-ethane, 1-[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (IRGACURE®82959); 2-Hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl ⁇ -2-methyl-propan-1-one (IRGACURE® 127); 2-Hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-phenoxy
  • phenylglyoxalic esters and derivatives thereof e.g. oxo-phenyl-acetic acid 2-(2-hydroxy-ethoxy)-ethyl ester, dimeric phenylglyoxalic esters, e.g. oxo-phenyl-acetic acid 1-methyl-2-[2-(2-oxo-2-phenyl-acetoxy)-propoxy]-ethyl ester (IRGACURE® 754); oxime esters, e.g.
  • (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (DAROCUR® TPO), bisacylphosphine oxides, e.g. bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IRGACURE® 819), bis(2,4,6-trimethyl benzoyl)-2,4-dipentoxyphenylphosphine oxide, trisacylphosphine oxides, halomethyltriazines, e.g.
  • Nitrogen containing flame-retardants include melamine based flame-retardants, examples of which are:
  • Nitrogen-containing flame-retardants comprise compounds of formulae III to VIIIa
  • R 4 to R 6 are each independently of the others hydrogen, C 1 -C 8 alkyl, C 5 -C 6 cycloalkyl or C 1 -C 4 alkyl-C 5 -C 6 cycloalkyl, each unsubstituted or substituted by hydroxy or C 1 -C 4 -hydroxyalkyl; C 2 -C 8 alkenyl, C 1 -C 8 -alkoxy, -acyl, -acyloxy, C 6 -C 12 aryl, —O—R 2 or —N(R 2 )R 3 , and R 2 and R 3 are hydrogen, C 1 -C 4 alkyl, C 5 -C 6 cycloalkyl, C 2 -C 8 alkenyl, C 1 -C 4 hydroxyalkyl or C 6 -C 12 aryl, with the proviso that R 4 to R 6 are not simultaneously hydrogen and also, in formula II, not simultaneously —NH 2 , and in formula VII at least one group is
  • Examples are benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, urea cyanurate, melamine polyphosphate, melamine borate, ammonium polyphosphate, melamine ammonium polyphosphate or melamine ammonium pyrophosphate, preferably a condensation product of melamine from the series melem, melam, melon and/or a higher condensed compound or a reaction product of melamine with phosphoric acid and/or a reaction product of condensation products of melamine with phosphoric acid or a mixture thereof.
  • Special emphasis should be given to: dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, and/or a mixed polysalt of such a type, more especially melamine polyphosphate.
  • Halogen contained in these compounds usually is chloro and/or bromo; preferred are brominated flame-retardants for such systems.
  • Phosphorus containing flame-retardant may be selected from phosphazene flame-retardants, which are well known in the art. They are disclosed for example in EP1104766, JP07292233, DE19828541, DE1988536, JP11263885, U.S. Pat. Nos. 4,107,108, 4,108,805 and 4,079,035 and 6,265,599.
  • the phosphorus containing flame-retardant may be selected from metal or metalloid salts of a phosphonic acid of formula X
  • R is hydrogen, C 1 -C 18 alkyl, C 5 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 6 -C 10 aryl or C 7 -C 11 aralkyl and R′ is hydrogen, C 1 -C 8 alkyl, C 6 -C 10 aryl or C 7 -C 11 aralkyl, the substituents R and R′ that are other than hydrogen being unsubstituted or substituted by halogen, hydroxyl, amino, C 1 -C 4 alkylamino, di-C 1 -C 4 alkylamino, C 1 -C 4 alkoxy, carboxy or C 2 -C 5 alkoxycarbonyl; and the metal or metalloid is from Group IA, IB, IIA, IIB, IIIA, IVA, VA or VIII of the Periodic Table.
  • the salts may be present as simple ionic compounds comprising anions of phosphonic acid and cations of the metal or metalloid.
  • R′ is hydrogen and the metal or metalloid has a valency of more than one, the salt can have a polymeric structure according to the following formula XI
  • R is as defined hereinbefore, M is a metal or metalloid, n has a value corresponding to the valency of M minus 1, m is a number from 2 to 100 and wherein each group
  • the phosphonic acid salts according to the definition either are known or can be prepared in accordance with methods known per se. Examples of such methods are to be found in, inter alia, EP-A-245 207, pages 4 and 5 to 7 (Examples 1 to 14).
  • PTFE polytetrafluoroethylene
  • Teflon® 6C E. I. Du Pont
  • WO 03/016388 PTFE
  • R 1 is an additive selected from the group consisting of phenolic antioxidants, benzofuran-2-ones, sterically hindered amines, aminic antioxidants, 2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, 2-(2-hydroxyphenyl)-1,3,5-triazines, phosphites, phosphonites, thioethers, benzophenones, ⁇ -activated acetophenones, bisacylphosphinoxides (BAPO), monoacylphosphinoxides (MAPO), alkoxamines, thioxanthones, benzoins, benzil ketals, benzoin ethers, ⁇ -hydroxy-alkylphenones and ⁇ -aminoalkylphenones.
  • phenolic antioxidants benzofuran-2-ones, sterically hindered amines, aminic antioxidants, 2-(2′-hydroxyphenyl)benzotriazoles,
  • R 25 is C 1 -C 25 alkyl or C 2 -C 25 alkenyl
  • R 26 is hydrogen or methyl
  • R 27 is hydrogen or methyl
  • R 28 is hydrogen or
  • R 29 is C 1 -C 4 alkylene
  • R 30 and R 31 are each independently of the other hydrogen, C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, phenyl or C 5 -C 8 cycloalkyl
  • R 32 and R 33 are each independently of the other hydrogen, C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, phenyl or C 5 -C 8 cycloalkyl
  • R 34 and R 35 are each independently of the other hydrogen, halogen, C 1 -C 4 alkyl, —CN, trifluoromethyl or C 1 -C 4 alkoxy
  • R 36 is a direct bond or —O—
  • R 37 is hydrogen, —O ⁇ , C 1 -C 25 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkinyl, C 1 -C 20 alkoxy, C 5 -C 12 cycloalkoxy
  • R 45 is hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkoxy or
  • R 46 and R 47 are each independently of the other hydrogen, hydroxyl, C 1 -C 18 alkyl, phenyl, C 1 -C 18 alkoxy or C 7 -C 9 phenylakyl
  • R 48 is a direct bond or oxygen
  • R 49 and R 50 are each independently of the other C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, cyclohexyl, phenyl, or phenyl substituted by 1 to 3 alkyl radicals having in total 1 to 18 carbon atoms
  • R 51 , R 52 and R 53 are each independently of the others hydrogen, halogen C 1 -C 4 alkyl or C 1 -C 4 alkoxy
  • R 54 is C 1 -C 20 alkyl, C 5 -C 8 cycloalkyl, C 7 -C 9 phenylalkyl or phenyl
  • R 55 is C 1 -C 25 alkyl
  • R 56 is methylene or ethylene
  • R 11 is C 1 -C 18 alkyl, C 3 -C 18 alkyl which is interrupted by oxygen or sulfur; or 3-aminopropyl.
  • the nanoparticles have particle size below 1000 nm, especially below 500 nm and more preferably below 400 nm.
  • the nanoparticles have a particle size of 10 to 1000 nm, preferably 10 to 500 nm, and more preferably 40 to 500 nm. Highly preferred is a particle size of 40 to 400 nm.
  • the organic content of the nanoparticles according to the present invention is, for example, 5 to 80 percent by weight, especially 10 to 70 percent by weight, based on the total weight of the nanoparticle.
  • Nanoparticles are typically silicon dioxide, aluminum oxide, a heterogeneous mixture thereof or silicon aluminum oxide as mixed oxides.
  • the silicon aluminum oxide nanoparticles according to the present invention can show silicon contents in between 1 to 99 metal-atom %.
  • the expert would preferably use particles showing an index of refraction close to the matrix material.
  • pure silicon dioxide (n D 1.48 to 1.50) or pure aluminum oxide (n D 1.61) or silicon aluminum oxides with the whole range of silicon to aluminum ratio covers material with an index of refraction from 1.48 to 1.61.
  • the preparation of the functionalized nanoparticles comprising on the surface at least a radical of the formula I is preferably carried out by the reaction of corresponding nanoparticles (like unfunctionalized silica or alumina nanoparticles) with a compound of the formula (Ia)
  • X is oxygen, sulfur or
  • R 0 is C 1 -C 25 alkyl
  • R 1 is hydrogen
  • R 2 and R 3 independently of each other are hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur
  • R 4 is hydrogen, C 1 -C 25 alkyl or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur
  • R 5 is hydrogen or C 1 -C 25 alkyl
  • n is 1, 2, 3, 4, 5, 6, 7 or 8.
  • the reaction of the compound of formula (Ia) with the nanoparticles can be carried out in analogy to known processes.
  • the reaction can, for example, be carried out in an organic medium or preferably a mixture of water with an organic medium.
  • organic medium sovents like alcohols, especially methanol or ethanol can be used. It is preferred to carry out the reaction at temperatures like 20 to 90° C., especially 40 to 60° C.
  • the compounds of formula (Ia) it is preferred to use those, wherein at least one of R 0 , R 2 and R 3 is methoxy or ethoxy, especially wherein R 0 , R 2 and R 3 are methoxy or ethoxy. It is highly preferred that R 0 , R 2 and R 3 are methoxy.
  • the products obtained can be redispersed in a suitable medium, like ethanol, toluene or xylol.
  • reaction product of the nanoparticles with the compound of formula (Ia) can easily be derivatized to obtain nanoparticles comprising radicals of the formula (I) by known processes such as for example esterification, amidation, Michael addition or opening of epoxides.
  • Nanoparticles showing active linkage groups such as —SH or —NH 2 (for example nanoparticles as prepared in Example 1) can easily surface modified with additives bearing for instance ester-, epoxy-, carboxy-, carbonyl-, acrylic-, methacrylic-, alkylhalogenide-, alkylsulfate-, anhydride-, terminal double bond-, nitrile- and for instance ⁇ , ⁇ -unsaturated carbonyl-groups.
  • the chemistry of these substances and the molecular organic syntheses are well known and can easily be adapted to the solid phase organic chemistry.
  • Additives can be functionalized by using reactive alkoxysilanes showing functional groups and mechanisms as mentioned in a), b) or c) and then being grafted onto the particle surface using a state of the art silanisation reaction [e.g. Example 17].
  • nanoparticles comprising radicals of formula (I) corresponding unfunctionalized nanoparticles, like commercially available silica or Al 2 O 3 nanoparticles, can be reacted with a compound of the formula (Ia), wherein Ro, R 2 and R 3 are as defined above under formula (Ia) and n, X and R 1 are as defined above under formula (I).
  • the reaction conditions can be chosen as given above for the reaction of the nanoparticles with the compound of formula (Ia).
  • the reaction can, for example, be carried out in analogy to the preparation process described in WO-A-03/002652.
  • the radical of formula (II) can be introduced in analogy to the above preparation processes. These reactions can be carried out simultaneously with the introduction of the radical of formula (I), or stepwise.
  • the functionalized nanoparticles of the present invention comprising on the surface at least a radical of the formula I and optionally a radical of the formula II are suitable for stabilizing or flame-retarding and/or compatibilizing organic materials, which are subject to oxidative, thermal or light-induced degradation, in particular synthetic polymers or coatings, or for photoinitiating in-situ polymerization or hardening of pre-polymeric nanocomposites or sols to nanocomposite materials.
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • LDPE low density
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.
  • ethylene/norbornene like COC ethylene/1-olefins copolymers, where the 1-olefin is gene-rated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate cop
  • Hydrocarbon resins for example C 5 -C 9
  • hydrogenated modifications thereof e.g. tackifiers
  • mixtures of polyalkylenes and starch
  • Homopolymers and copolymers from 1.)-4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of sty
  • Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6. especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
  • PCHE polycyclohexylethylene
  • PVCH polyvinylcyclohexane
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; st
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
  • Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol
  • Polyureas Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
  • Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
  • Crosslinkable acrylic resins derived from substituted acrylates for example epoxy acrylates, urethane acrylates or polyester acrylates.
  • Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
  • Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
  • Blends of the aforementioned polymers for example PP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
  • polyblends for example PP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/
  • Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • Aqueous emulsions of natural or synthetic rubber e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
  • Sols especially organosols, as stable liquid suspensions of colloidal nano-particles in a diluent, a reactive (e.g. crosslinking) diluent or in a polymerizable or crosslinking monomer, or in a mixture of all.
  • the present invention relates therefore also to a composition
  • a composition comprising
  • Preferred organic materials are polymers, for example a pre-polymer for a nanocomposite material, in particular synthetic polymers, for example thermoplastic polymers.
  • Polyamides, polyurethanes and polyolefins are particularly preferred.
  • Examples of preferred polyolefins are polypropylene or polyethylene.
  • the incorporation of the functionalized nanoparticles of the invention and optional further components into the polymer is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil.
  • the functionalized nanoparticles of the invention and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc.), e.g. as a dry mixture or powder or as solution or dispersion or suspension or melt.
  • the incorporation can be carried out in a heatable container equipped with a stirrer, e.g. in a closed apparatus such as a kneader, mixer or stirred vessel.
  • a stirrer e.g. in a closed apparatus such as a kneader, mixer or stirred vessel.
  • the incorporation is preferably carried out in an extruder or in a kneader. It is immaterial whether processing takes place in an inert atmosphere or in the presence of oxygen.
  • the addition of the functionalized nanoparticles or additive blend to the polymer can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
  • the process is preferably carried out in an extruder by introducing the additive during processing.
  • processing machines are single-screw extruders, contra rotating and co rotating twin-screw extruders, planetary-gear extruders, ring extruders or co kneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied.
  • the screw length is 1-60 screw diameters, preferably 35-48 screw diameters.
  • the rotational speed of the screw is preferably 10-600 rotations per minute (rpm), very particularly preferably 25-300 rpm.
  • the maximum throughput is dependent on the screw diameter, the rotational speed and the driving force.
  • the process can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
  • the functionalized nanoparticles of the invention and optional further additives can also be sprayed onto the polymer material. They are able to dilute other additives (for example the conventional additives indicated below) or their melts so that they can be sprayed also together with these additives onto the material. Addition by spraying during the deactivation of the polymerisation catalysts is particularly advantageous; in this case, the steam evolved may be used for deactivation of the catalyst. In the case of spherically polymerised polyolefins it may, for example, be advantageous to apply the functionalized nanoparticles of the invention, optionally together with other additives, by spraying.
  • the functionalized nanoparticles of the invention and optional further additives can also be added to the polymer in the form of a masterbatch (“concentrate”) which contains the components in a concentration of, for example, about 1.0% to about 40.0% and preferably 2.0% to about 20.0% by weight incorporated in a polymer.
  • concentration a masterbatch
  • the polymer must not be necessarily of identical structure than the polymer where the additives are added finally.
  • the polymer can be used in the form of powder, granules, solutions, and suspensions or in the form of lattices.
  • Incorporation can take place prior to or during the shaping operation.
  • the materials containing the functionalized nanoparticles of the invention described herein preferably are used for the production of molded articles, for example rotomolded articles, injection molded articles, profiles and the like.
  • compositions wherein the composition is a coating composition and component (a) is an organic film-forming binder.
  • the coating composition is preferably a coating material or paint, especially an aqueous coating material or an aqueous paint.
  • coating materials are lacquers, paints or varnishes. These always contain an organic film-forming binder in addition to other, optional components.
  • Preferred organic film-forming binders are epoxy resins, polyurethane resins, amino resins, acrylic resins, acrylic copolymer resins, polyvinyl resins, phenolic resins, styrene/butadiene copolymer resins, vinyl/acrylic copolymer resins, polyester resins, UV-curable resins or alkyd resins, or a mixture of two or more of these resins, or an aqueous basic or acidic dispersion of these resins or mixtures of these resins, or an aqueous emulsion of these resins or mixtures of these resins.
  • organic film-forming binders for aqueous coating compositions such as, for example, alkyd resins; acrylic resins, two-component epoxy resins; polyurethane resins; polyester resins, which are usually saturated; water-dilutable phenolic resins or derived dispersions; water-dilutable urea resins; resins based on vinyl/acrylic copolymers; and hybrid systems based on, for example, epoxy acrylates.
  • the alkyd resins can be water-dilutable alkyd resin systems which can be employed in air-drying form or in the form of stoving systems, optionally in combination with water-dilutable melamine resins; the systems may also be oxidatively drying, air-drying or stoving systems which are optionally employed in combination with aqueous dispersions based on acrylic resins or copolymers thereof, with vinyl acetates, etc.
  • the acrylic resins can be pure acrylic resins, epoxy acrylate hybrid systems, acrylic acid or acrylic ester copolymers, combinations with vinyl resins, or copolymers with vinyl monomers such as vinyl acetate, styrene or butadiene. These systems can be air-drying systems or stoving systems.
  • water-dilutable epoxy resins exhibit excellent mechanical and chemical resistance. If liquid epoxy resins are used, the addition of organic solvents to aqueous systems can be omitted.
  • the use of solid resins or solid-resin dispersions usually necessitates the addition of small amounts of solvent in order to improve film formation.
  • Preferred epoxy resins are those based on aromatic polyols, especially those based on bis-phenols.
  • the epoxy resins are employed in combination with crosslinkers.
  • the latter may in particular be amino- or hydroxy-functional compounds, an acid, an acid anhydride or a Lewis acid.
  • examples thereof are polyamines, polyaminoamides, polysulfide-based polymers, polyphenols, boron fluorides and their complex compounds, polycarboxylic acids, 1,2-dicarboxylic anhydrides or pyromellitic dianhydride.
  • Polyurethane resins are derived from polyethers, polyesters and polybutadienes with terminal hydroxyl groups, on the one hand, and from aliphatic or aromatic polyisocyanates on the other hand.
  • the polyurethanes are prepared in situ from polyethers, polyesters and polybutadienes with terminal hydroxyl groups, on the one hand, and from aliphatic or aromatic poly-isocyanates on the other hand.
  • polyvinyl resins examples include polyvinylbutyral, polyvinyl acetate or copolymers thereof.
  • Suitable phenolic resins are synthetic resins in the course of whose construction phenols are the principal component, i.e. in particular phenol-, cresol-, xylenol- and resorcinol-form-aldehyde resins, alkylphenolic resins, and condensation products of phenols with acetaldehyde, furfurol, acrolein or other aldehydes. Modified phenolic resins are also of interest.
  • UV-(ultraviolet) curable resins may contain one or more olefinic double bonds. They may be of low (monomeric) or relatively high (oligomeric) molecular mass. Examples of monomers containing a double bond are alkyl or hydroxyalkyl acrylates or methacrylates, such as methyl, ethyl, butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, isobornyl acrylate, methyl meth-acrylate or ethyl methacrylate.
  • acrylnitrile acrylamide, methacrylamide, N-substituted (meth)acrylamides
  • vinyl esters such as vinyl acetate
  • vinyl ethers such as iso-butyl vinyl ether
  • styrene alkylstyrenes and halostyrenes
  • N-vinylpyrrolidone vinyl chloride or vinylidene chloride.
  • Examples of monomers containing two or more double bonds are ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol and bisphenol A diacrylates, 4,4′-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris(2-acryloylethyl)isocyanurate.
  • Examples of relatively high molecular mass (oligomeric) polyunsaturated compounds are acrylated epoxy resin and acrylated or vinyl ether- or epoxy-functional polyesters, polyurethanes and polyethers.
  • Further examples of unsaturated oligomers are unsaturated polyester resins, generally prepared from maleic acid, phthalic acid and one or more diols and having molecular weights of from about 500 to 3000.
  • vinyl ether monomers and oligomers and also maleate-terminated oligomers with poly-esters, polyurethane, polyether, polyvinyl ether and epoxide main chains.
  • Especially suitable are combinations of polymers and oligomers which carry vinyl ether groups, as described in WO-A-90/01512.
  • Also suitable, however, are copolymers of monomers functionalized with maleic acid and vinyl ether.
  • (Meth)acryloyl and, respectively, (meth)acrylic here and below means acryloyl and/or methacryloyl, and acrylic and/or methacrylic, respectively.
  • at least two polymerizable double bonds are present in the molecule in the form of (meth)acryloyl groups.
  • the compounds in question may comprise, for example, (meth)acryloyl-functional oligomeric and/or polymeric compounds of poly(meth)acrylate.
  • the number-average molecular mass of this compound may be for example from 300 to 10 000, preferably from 800 to 10 000.
  • the compounds preferably containing free-radically polymerizable double bonds in the form of (meth)acryloyl groups may be obtained by customary methods, for example by reacting poly(meth)acrylates with (meth)acrylic acid. These and other preparation methods are described in the literature and are known to the person skilled in the art. Unsaturated oligomers of this kind may also be referred to as prepolymers.
  • Functionalized acrylates are also suitable.
  • suitable monomers which are normally used to form the backbone (the base polymer) of such functionalized acrylate and methacrylate polymers are acrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl meth-acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate etc.
  • appropriate amounts of functional monomers are copolymerized during the polymerization in order to give the functional polymers.
  • Acid-functionalized acrylate or methacrylate polymers are obtained using acid-functional monomers such as acrylic acid and methacrylic acid.
  • Hydroxy-functional acrylate or methacrylate polymers are formed from hydroxy-functional monomers, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 3,4-dihydroxybutyl methacrylate.
  • Epoxy-functionalized acrylate or methacrylate polymers are obtained using epoxy-functional monomers such as glycidyl methacrylate, 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate, 2,3-epoxycyclohexyl methacrylate, 10,11-epoxyundecyl methacrylate etc.
  • isocyanate-functionalized polymers may be prepared from isocyanate-functionalized monomers, such as meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, for example.
  • Particularly suitable compounds are, for example, esters of ethylenically unsaturated mono-functional or polyfunctional carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in side groups, such as unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and co-polymers containing (meth)acrylic groups in side chains, and also mixtures of one or more such polymers.
  • esters of ethylenically unsaturated mono-functional or polyfunctional carboxylic acids and polyols or polyepoxides and polymers containing ethylenically unsaturated groups in the chain or in side groups, such as unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, alkyd resins
  • Suitable monofunctional or polyfunctional unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, maleic acid, fumaric acid, unsaturated fatty acids such as linolenic acid or oleic acid.
  • Acrylic acid and methacrylic acid are preferred.
  • saturated dicarboxylic or polycarboxylic acids in a mixture with unsaturated carboxylic acids.
  • suitable saturated dicarboxylic or polycarboxylic acids include tetrachlorophthalic acid, tetrabromophthalic acid, phthalic acid, trimellitic acid, heptanedicarboxylic acid, sebacic acid, dodecanedicarboxylic acid, hexahydrophthalic acid, etc.
  • Suitable polyols include aromatic and especially aliphatic and cycloaliphatic polyols.
  • aromatic polyols are hydroquinone, 4,4′-dihydroxybiphenyl, 2,2-di(4-hydroxyphenyl)propane, and also novolaks and resols.
  • polyepoxides are those based on the aforementioned polyols, especially the aromatic polyols, and epichlorhydrin.
  • Further suitable polyols include polymers and copolymers containing hydroxyl groups in the polymer chain or in side groups, such as polyvinyl alcohol and copolymers thereof or poly-hydroxyalkyl methacrylates or copolymers thereof, for example. Oligoesters containing hydroxyl end groups are further suitable polyols.
  • aliphatic and cycloaliphatic polyols are alkylenediols having preferably from 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having molecular weights of preferably from 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris( ⁇ -hydroxyethyl)amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.
  • the polyols may have been partly or fully esterified with one or more different unsaturated carboxylic acids, the free hydroxyl groups in partial esters possibly having been modified, e.g. etherified or esterified with other carboxylic acids.
  • esters are for example trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane tri-methacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, tri-ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaery
  • Suitable UV-curable resins include the amides of identical or different unsaturated carboxylic acids with aromatic, cycloaliphatic and aliphatic polyamines having preferably from 2 to 6, particularly from 2 to 4 amino groups.
  • polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di- ⁇ -aminoethyl ether, diethylenetriamine, triethylenetetramine, di( ⁇ -aminoethoxy)- or di( ⁇ -aminopropoxy)ethane.
  • polyamines are polymers and copolymers containing possibly additional amino groups in the side chain, and oligoamides having amino end groups.
  • unsaturated amides are: methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane, ⁇ -methacrylamidoethyl methacrylate, and N-[( ⁇ -hydroxyethoxy)ethyl]acrylamide.
  • Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and diols or diamines.
  • the maleic acid may have been replaced in part by other dicarboxylic acids. They may be used together with ethylenically unsaturated comonomers, e.g. styrene.
  • the polyesters and polyamides may also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from relatively long chain ones having, for example, from 6 to 20 carbon atoms.
  • Examples of polyurethanes are those synthesized from saturated or unsaturated diisocyanates and unsaturated or saturated diols, respectively.
  • Polybutadiene and polyisoprene and copolymers thereof are known.
  • suitable comonomers are olefins such as ethylene, propene, butene, hexene, (meth)acrylates, acrylonitrile, styrene or vinyl chloride.
  • Polymers containing (meth)acrylate groups in the side chain are likewise known.
  • They may comprise, for example, reaction products of novolak-based epoxy resins with (meth)acrylic acid, homopolymers or copolymers of vinyl alcohol or the hydroxyalkyl derivatives thereof that have been esterified with (meth)acrylic acid, or homopolymers and copolymers of (meth)acrylates esterified with hydroxyalkyl(meth)acrylates.
  • the UV-curable resins may be used alone or in any desired mixtures. Preference is given to using mixtures of polyol (meth)acrylates.
  • binders to the compositions of the invention, which is especially appropriate when the photopolymerizable compounds are liquid or viscous substances.
  • the amount of the binder can be for example 5-95, preferably 10-90 and especially 40-90% by weight, based on the overall solids.
  • the choice of binder is made depending on the field of use and the properties required for that field, such as developability in aqueous and organic solvent systems, adhesion to substrates, and oxygen sensitivity, for example.
  • the unsaturated compounds may also be used in a mixture with non-photopolymerizable film-forming components. These may be, for example, physically drying polymers or their solutions in organic solvents, such as nitrocellulose or cellulose acetobutyrate, for example. They may also, however, be chemically and/or thermally curable resins, such as polyiso-cyanates, polyepoxides or melamine resins, for example.
  • melamine resins are meant not only condensates of melamine (1,3,5-triazine-2,4,6-triamine) but also those of melamine derivatives.
  • the components comprise a film-forming binder based on a thermo-plastic or thermosettable resin, predominantly on a thermosettable resin.
  • thermally curable resins examples thereof are alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.
  • thermally curable resins is of importance for use in what are known as hybrid systems, which may be both photopolymerized and also thermally crosslinked.
  • Component (a) may comprise, for example, a coating composition comprising (a1) compounds containing one or more free-radically polymerizable double bonds and further containing at least one other functional group which is reactive in the sense of an addition reaction and/or condensation reaction (examples have been given above), (a2) compounds containing one or more free-radically polymerizable double bonds and further containing at least one other functional group which is reactive in a sense of an addition reaction and/or condensation reaction, the additional reactive functional group being complementary to or reactive toward the additional reactive functional groups of component (a1), (a3) if desired, at least one monomeric, oligomeric and/or polymeric compound containing at least one functional group which is reactive in the sense of an addition reaction and/or condensation reaction toward the functional groups from component (a1) or component (a2) that are present in addition to the free-radically polymerizable double bonds.
  • a coating composition comprising (a1) compounds containing one or more free-radically polymerizable double bonds and further containing at least one other functional group which is reactive in the
  • Component (a2) carries in each case the groups which are reactive toward or complementary to component (a1). In this context it is possible in each case for different kinds of functional groups to be present in one component.
  • component (a3) there is a further component available containing functional groups which are reactive in the sense of addition reactions and/or condensation reactions and which are able to react with the functional groups of (a1) or (a2) that are present in addition to the free-radically polymerizable double bonds.
  • Component (a3) contains no free-radically polymerizable double bonds. Examples of such combinations of (a1), (a2), (a3) can be found in WO-A-99/55785.
  • suitable reactive functional groups are selected, for example, from hydroxyl, isocyanate, epoxide, anhydride, carboxyl or blocked amino groups. Examples have been described above.
  • UV-curable systems based on oligomeric urethane acrylates and/or acylate acrylates, optionally with the addition of other oligomers or monomers; 17. dual-cure systems, which are cured first thermally and then by UV, or vice versa, the constituents of the surface-coating formulation containing double bonds that can be caused to react by UV light and photoinitiators and/or by electron-beam curing.
  • coating systems which are based on siloxanes. Such coating systems are described, for example, in WO-A-98/56852, WO-A-98/56853, DE-A-2914427 and DE-A-4338361.
  • Component (b) can also find use in resists, micro resists or solder masks for printed circuit boards, especially for improving the scratch resistance thereof.
  • component (b) is added to the material to be stabilized, compatibilized, flame-retarded and/or polymerization regulated in an amount from 0.01 to 80%, in particular 1 to 50%, for example 2 to 20%, relative to the weight of the organic material to be stabilized, compatibilized, flame-retarded and/or polymerization regulated.
  • compositions according to the invention can contain, in addition to components (a) and (b), additional additives, for example, from the group consisting of pigments, dyes, fillers, flow control agents, dispersants, thixotropic agents, adhesion promoters, antioxidants, light stabilizers and curing catalysts such as, for example, the following:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutyl phenol, 2,6-dicyclopentyl-4-methyl phenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl-phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth-oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-y
  • Alkylthiomethyl phenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethyl phenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.
  • 2,6-di-tert-butyl-4-methoxy-phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hydroxylated thiodiphenyl ethers for example 2, 2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methyl phenol), 4,4′-thiobis(3,6-di-sec-amyl phenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.
  • Hydroxylated thiodiphenyl ethers for example 2, 2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methyl phenol), 4,4′-thiobis(3,6
  • Alkylidenebisphenols for example 2, 2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)-phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methyl phenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butyl-phenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)-4-
  • O-, N- and S-benzyl compounds for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecyl mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • Aromatic hydroxybenzyl compounds for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethyl benzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri-azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)isocyanurate, 2,4,6--
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol-propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly-hydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo
  • esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
  • esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
  • Aminic antioxidants for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-
  • 2-(2′-Hydroxyphenyl)benzotriazoles for example 2-(2′-hydroxy-5′-methylphenyl)-benzo-triazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyl
  • 2-Hydroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl-oxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.
  • Esters of substituted and unsubstituted benzoic acids for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butyl phenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl- ⁇ -methoxycinnamate, butyl ⁇ -cyano- ⁇ -methyl- ⁇ -methoxy-cinnamate, methyl ⁇ -carbomethoxy- ⁇ -methoxycinnamate, N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methyl indoline, neopentyl tetra( ⁇ -cyano- ⁇ , ⁇ -di-phenylacrylate.
  • Nickel compounds for example nickel complexes of 2,2′-thio-bis[4-(1,1,3,3-tetramethyl-butyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarba
  • Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,
  • Oxamides for example 4, 4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and ⁇ -methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example N,N′-diphenyloxamide, N-salicylal-N′-salicyloyl hydrazine, N, N′-bis(salicyloyl)hydrazine, N, N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N′-diacetyladipoyl dihydrazide, N N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.
  • N,N′-diphenyloxamide N-
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphit
  • Hydroxylamines for example N,N-dibenzyl hydroxylamine, N,N-diethyl hydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecyl hydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecyl hydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptyinitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecyl nitrone, N-hexadecyl-alpha-heptadecyl nitrone, N-ocatadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-hepta-decylnitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrone derived
  • Thiosynergists for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.
  • Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ -dodecyl mercapto)propionate.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide pentaerythritol tetrakis( ⁇ -dodecy
  • Polyamide stabilizers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ric
  • Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car-bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • the additional additives are added, for example, in concentrations of 0.01 to 10%, relative to the total weight of the material to be stabilized, flame protected and/or compatibilized.
  • component (b) and, if desired, further additives into the polymeric, organic material is carried out by known methods, for example before or during moulding or else by applying the dissolved or dispersed compounds to the polymeric, organic material, if appropriate with subsequent slow evaporation of the solvent.
  • Component (b) can also be added to the materials to be stabilized in the form of a masterbatch or a colloidal sol or organosol containing for example 5 to 50% by weight of component (b).
  • Component (b) can also be added before or during polymerisation or before crosslinking.
  • Component (b) can be incorporated into the material to be stabilized and/or compatibilized in pure form or encapsulated in waxes, oils or polymers.
  • Component (b) can also be sprayed onto the material to be stabilized, compatibilized, flame-retarded and/or polymerized.
  • the materials thus treated as mentioned above can be used in various forms, for example as films, fibres, ribbons, moulded materials, profiles, coatings or as binders for paints, adhesives or cement.
  • the present invention further provides a process for stabilizing, flame-retarding and/or compatibilizing an organic material which is subject to oxidative, thermal or light-induced degradation, which comprises incorporating therein, or applying thereto, at least a functionalized nanoparticle of the present invention comprising on the surface at least a radical of the formula I and optionally a radical of the formula II.
  • the present invention also provides a process for photoinitiating in-situ polymerization or hardening of a pre-polymeric nanocomposite or sol to a nanocomposite material, which comprises incorporating therein, or applying thereto, at least a functionalized nanoparticle of the present invention comprising on the surface at least a radical of the formula I and optionally a radical of the formula II.
  • a further embodiment of the present invention is the use of a functionalized nanoparticle of the present invention comprising on the surface at least a radical of the formula I and optionally a radical of the formula II as stabilizer and/or flame-retarder and/or compatibilizer for organic materials which are subject to oxidative, thermal or light-induced degradation.
  • the present invention also provides the use of a functionalized nanoparticle of the present invention comprising on the surface at least a radical of the formula I and optionally a radical of the formula II as photoinitiator for the in-situ polymerization or hardening of pre-polymeric nanocomposites or sols to nanocomposite materials.
  • a preferred embodiment of the present invention is also the use of component (b) as reinforcer of coatings and improver of scratch resistance in coating compositions for surfaces.
  • the present invention also relates to a process for protecting a substrate, which comprises applying thereto a coating composition comprising components (a) and (b) and then drying and/or curing it.
  • the present invention likewise relates to a process for preparing a reinforced coating with improved scratch resistance on a surface, which comprises treating this surface with a coating composition comprising components (a) and (b), and then drying and/or curing it.
  • the preferred functionalized nanoparticles and organic materials for the process and use are the same as those for the compositions according to the invention.
  • Ludox TMA Ludox TMA [available from Helm AG; 34% nanosilica dispersion in water]
  • RTM Ludox TMA
  • 345 g 3-aminopropyl-trimethoxysilane Fluka purum
  • the mixture is heated at 50° C. for 18 hours.
  • the volume of this mixture is then reduced to ca. 1 liter by evaporating ethanol/water in the rotary evaporator.
  • a total of 4 liter of hexane is added, the mixture is shaken vigorously and the two phases separated in a separation funnel to remove unreacted aminosilane.
  • the acqueous/ethanolic lower phase is concentrated to a wet paste in the rotary evaporator in vacuo and then resuspended in 1 liter of ethanol. A total of 1199 g solution is obtained with a solid content of 27.3 wt. %.
  • Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C. to 600° C.): Weight loss: 25.2% corresponding to the organic material. Elemental analysis: found: C, 17.68%, H, 4.65%, N, 6.73%: corresponding to an organic content of 28.1% in relatively good agreement to the TGA value.
  • Dynamic light scattering (DLS): Average diameter d 90-110 nm.
  • Ludox TMA [available from Helm AG, 34% nanosilica dispersion in water] is mixed with 250 ml of ethanol. Then is added a mixture of 2.29 g (12.8 mmol) 3-aminopropyl-trimethoxysilane (Fluka purum) and 8.42 g (51.3 mmol) of propyltrimethoxysilane (Fluka purum) dropwise during 15 minutes with stirring. After the addition, the mixture is heated at 50° C. for 16 hours. The reaction mixture is centrifuged (1 hour, 2000 rpm) and the sedimented product redispersed in 200 ml of ethanol followed by a second centrifugation (1 hour, 2000 rpm).
  • RTM Ludox TMA
  • the sedimented product is re-dispersed in 70 ml toluene to give a dispersion with a solid content of 13.5 wt. %.
  • Thermographimetric analysis TGA; heating rate: 10° C./min from 50° C. to 600° C.
  • Weight loss 5.9% corresponding to the organic material.
  • Elemental analysis found: C, 4.70%, H, 1.22%, N, 0.37%: corresponding to an aminopropyl content of 2.36 wt. % and a n-propyl content of 3.53 wt. %.
  • Dynamic light scattering (DLS): Average diameter d 69 nm.
  • Ludox TMA (RTM) [available from Helm AG, 34% nanosilica dispersion in water] is mixed with 1.4 liter of ethanol. Then is added a mixture of 47.2 g (263.3 mmol) of 3-aminopropyltrimethoxysilane (Fluka purum) and 47.2 g (136.2 mmol) of hexadecyltrimethoxysilane (Fluka purum) and heated at 50° C. for 16 hours. The reaction mixture is centrifuged (1 hour, 3000 rpm) and the sedimented product is redispersed in 200 ml of ethanol. This is repeated two more times.
  • RTM Ludox TMA
  • the sedimented product is re-dispersed in 250 ml of xylene to give a dispersion with a solid content of 23.9 wt. %.
  • Thermographimetric analysis TGA; heating rate: 10° C./min from 50° C. to 600° C.
  • Weight loss 26.2% corresponding to the organic material.
  • Elemental analysis found: C, 17.43%, H, 3.69%, N, 1.81%: corresponding to an aminopropyl content of 7.5 wt. % and a n-propyl content of 18.7 wt. %.
  • Dynamic light scattering (DLS): Average diameter d 97 nm.
  • Ludox TMA [available from Helm AG, 34% nanosilica dispersion in water] is mixed with 250 ml of ethanol. Then is added a mixture of 2.29 g (12.8 mmol) of 3-aminopropyltrimethoxysilane (Fluka purum) and 7.0 g (51.3 mmol) of methyltrimethoxysilane (Fluka purum) dropwise during 15 min with stirring. After the addition, the mixture is heated at 50° C. for 16 hours. The reaction mixture is centrifuged (1 h, 2000 rpm) and the sedimented product is re-dispersed in 200 ml of ethanol followed by a second centrifugation (1 hour, 2000 rpm).
  • RTM Ludox TMA
  • the sedimented product is re-dispersed in 80 ml toluene to give 177.4 g of a dispersion with a solid content of 10.0 wt. %.
  • Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C. to 600° C.): Weight loss: 5.9% corresponding to the organic material. Elemental analysis: found: C, 3.96%, H, 1.20%, N, 0.67%: corresponding to an aminopropyl content of 2.77 wt. % and a methyl content of 3.08 wt. %.
  • the reaction mixture is concentrated in the rotary evaporator to about half the volume and 800 ml of ethanol is added which leads to the precipitation of the modified particles.
  • the product is isolated by centrifugation (20 minutes at 2000 rpm) and the sedimented product redispersed in 60 ml toluene. Yield: 100 g dispersion with 12.3 wt. % solid content.
  • Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C. to 800° C.): Weight loss: 73.0% corresponding to the organic material. Elemental analysis: found: C, 52.53%, H, 5.61%, N, 6.27%: corresponding to an organic content of 73.9% in relatively good agreement to the TGA value.
  • Dynamic light scattering (DLS): Average diameter d 100 nm.
  • the reaction mixture is concentrated in the rotary evaporator to about half the volume and 400 ml of ethanol is added which leads to the precipitation of the modified particles.
  • the product is isolated by centrifugation (1 hour, 2000 rpm) and the sedimented product redispersed in 70 ml of toluene. Yield: 74.1 g dispersion with 15.7 wt. % solid content.
  • Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C. to 800° C.): Weight loss: 71.4% corresponding to the organic material. Elemental analysis: found: C, 49.20%, H, 5.83%, N, 6.60%: corresponding to an organic content of 71.0% in good agreement to the TGA value.
  • Dynamic light scattering (DLS): Average diameter d 99 nm.
  • Example 1 100 g of the dispersion according to Example 1 is mixed with 13.9 g (120.5 mmol) of glycidyl-isopropylether (Fluka, purum) and stirred at 50° C. for 18 h. The mixture is concentrated in the rotary evaporator to give 38.05 g of a paste. The product is re-dispersed in all kind of organic solvents (e.g. toluene). Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C. to 600° C.): Weight loss: 50.2% corresponding to the organic material. Elemental analysis: found: C, 34.23%, H, 6.55%, N, 4.22%: corresponding to an organic content of 54.7%.
  • TGA heating rate: 10° C./min from 50° C. to 600° C.
  • the product is isolated by centrifugation (1 hour, 2000 rpm) and the sedimented product redispersed in 30 g toluene. Yield: 57.3 g dispersion with 14.7 wt. % solid content.
  • Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C. to 800° C.): Weight loss: 54.4% corresponding to the organic material. Elemental analysis: found: C, 44.35%, H, 5.30%, N, 6.12%: corresponding to an organic content of 64.9%.
  • Dynamic light scattering (DLS): Average diameter d 107 nm.
  • MPEG(8)acrylate poly(ethyleneglycol)methyl ether acrylate
  • Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C. to 600° C.): Weight loss: 74.9%, corresponding to the organic material. Elemental analysis: found: C, 42.79%, H, 7.46%, N, 2.09%: corresponding to an organic content of 74.2%.
  • Ludox TMA (RTM) [available from Helm AG; 34% nanosilica dispersion in water] is mixed with 100 ml of ethanol. To this mixture is added 11.7 g (25.6 mmol) of a photoinitiator [see reaction scheme] and 12.7 g (51 mmol) of 3-(trimethoxysilyl)propyl methacrylate at room temperature. The mixture is stirred at 50° C. for 20 houry. The amount of solvent is halved by evaporation in the rotary evaporator. By adding 150 ml of cyclohexane the product precipitates and is separated by centrifugation.
  • RTM Ludox TMA
  • Ludox TMA (RTM) dispersion (Aldrich) is mixed with 100 ml of ethanol.
  • Ludox TMA (RTM) dispersion (Aldrich) is mixed with 100 ml of ethanol. To this mixture is added 4.4 g (9.6 mmol) of the photoinitiator trimethoxysilane [see Example 11 and scheme above] and 16.6 g (67.3 mmol) of octyl trimethoxysilane [CAS 2943-75-1, purum >97% GC, Fluka] at room temperature. The mixture is stirred at 50° C. for 20 hours. By adding 150 ml of hexane the product precipitates and is separated by centrifugation. After re-dispersing the product in xylene a dispersion with 28 wt. % solid content is obtained.
  • RTM Ludox TMA
  • Thermographimetric analysis (TGA; heating rate: 10° C./min from 25° C. to 600° C.): Weight loss: 19.7%, corresponding to the organic material. Elemental analysis: found: C, 12.79%, H, 2.18%, O: 2.85%, S: 0.69%: corresponding to an organic content of 18.51%.
  • the product is than dispersed in 35 ml of xylene to give 72 g of a dispersion with 47.2 wt. % solid content.
  • Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C. to 800° C.): Weight loss: 73%, corresponding to the organic material. Elemental analysis: found: C, 44.2%, H, 6.2%, N, 4.7%, O: 14.6%: corresponding to an organic content of 70%.
  • the product is then dispersed in 50 ml butyl acetate (BuOAc) to give 80 g of a dispersion with 41.3 wt. % solid content.
  • Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C. to 800° C.): Weight loss: 76.2%, corresponding to the organic material. Elemental analysis: found: C: 48. ⁇ %, H, 6.1%, N, 2.2%, O: 16.2%: corresponding to an organic content of 72.6%.
  • the acqueous/ethanolic lower phase is concentrated to a wet paste in the rotary evaporator in vacuo and then re-suspended in 350 ml EtOH to give 506 g of a solution with a solid content of 25.7 wt. %.
  • Thermographimetric analysis TGA; heating rate: 10° C./min from 50° C. to 800° C.
  • Weight loss 21.5% corresponding to the organic material.
  • Elemental analysis found: C, 11.47%, H, 2.43%, N, 2.70%: corresponding to an organic content of 18%.
  • Dynamic light scattering (DLS): Average diameter d 64.5 nm.
  • Ludox TMA (RTM) dispersion (Aldrich) is mixed with 100 ml of ethanol. To this mixture is added 16.7 g (67.3 mmol) of 3-methacryloyloxypropyl)-trimethoxysilane [Silan A 174, CAS 2530-85-0, purum 99% GC, Fluka] and the mixture is stirred at 50° C. for 22 hours. By adding 150 ml of hexane the product precipitates and is separated by centrifugation.
  • RTM Ludox TMA
  • alumina nanoparticles (Nyacol Corp., Nyacol A120 DW, 22% nanoalumina dispersion in water) is mixed with 250 mL ethanol (EtOH).
  • EtOH ethanol
  • 27 g 3-Aminopropyltrimethoxysilane (Fluka purum) are added dropwise to this homogeneous mixture. After the addition, the mixture is heated to 50° C. for 15 hours. The volume of this mixture is then reduced to ca. 1 L by evaporating EtOH/H 2 O in the rotary evaporator. The obtained solid is redispersed in EtOH to a 11.4 weight-% opaque dispersion.
  • Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C. to 800° C.): Weight loss: 27.9 wt. % corresponding to the organic material.
  • Elemental analysis found: N, 4.16 wt. %: corresponding to an organic content of 17.3 wt. %.
  • the difference between TGA and EA results is due to the loss of water out of the inorganic matrix and water generated from condensation processes on the surface during thermal treatment.
  • TEM Transmission Electron Microscopy
  • Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C. to 800° C.): Weight loss: 72.6 wt. % corresponding to the organic material.
  • Elemental analysis found: N, 1.7 wt. %, C, 36.4 wt %, H, 6.7 wt %.
  • Solution A consisting of 10 g of cinnamic acid chloride (cinnamoyl chloride, Fluka) dissolved at a temperature of 0° C. in 50 g of toluene, is run under stirring into Solution B, consisting of 12.2 g of 3-amino-propyl-trimethoxysilane (APS, purum Fluka) in a mixture of 50 g of dry toluene and 60 g of dry pyridine at a temperature of 0° C. A pale yellow product precipitates and the stirring is continued for additional 2 hours at a temperature of 0° C., then 12 hours at room temperature.
  • APS 3-amino-propyl-trimethoxysilane
  • reaction mixture is poured into 300 ml of deionized water, the yellow organic phase is washed and separated.
  • the solvent toluene
  • a rotary evaporator at a temperature of 40° C. (60 hPa)
  • the residual solvent is removed from the orange oil in vacuum (100 hPa) at a temperature of 70° C. during 16 hours.
  • the suspension is centrifuged (4500 rpm) and the obtained residual is re-dispersed in 160 g of xylene, washed, centrifuged and re-dispersed thrice until no educt is found in the washing liquid (controlled by TLC).
  • the white gel is separated and dispersed in xylene.
  • Solution A consisting of 2.4 g of succinic acid methylester chloride (Fluka) dissolved at a temperature of 0° C. in 10 g of tetrahydrofuran (THF), is run under nitrogen and stirring subsequent into Solution B, consisting of 3 g of 4-amino-2,2,6,6-tetramethyl-1-methyl piperidine into a mixture of 10 g of dry tetrahydrofuran (THF) and 1 g of triethyl amine at a temperature of 0° C. A white product precipitates and stirring is continued for additional 2 hours at a temperature of 0° C., then 12 hours at room temperature.
  • Fluka succinic acid methylester chloride
  • THF tetrahydrofuran
  • the product containing solvent is filtered off and the white solid is washed with 20 g of THF.
  • the pale yellow THF-solution is evaporated from the solvent in a rotary evaporator at a temperature of 50° C. (65 hPa), the residual solvent is removed from the bright orange oil in vacuum (100 hPa) at a temperature of 70° C. during 16 hours.
  • Thermogravimetric analysis (TGA; heating rate: 10° C./min from 25° C. to 800° C.): Weight loss: 24.7%, corresponding to the organic material.
  • the IR shows a weak band at 1571 and ⁇ 1650 cm ⁇ 1 corresponding to the amide-bond.
  • the suspension is centrifugated (4500 rpm), the isolated product re-dispersed in ethanol, washed and centrifugated twice.
  • the solvent is evaporated in the rotary evaporator to obtain a transparent oil. It is verified by 1 H-NMR that there are no residual acrylic double bonds left.
  • Solution A consisting of 2.4 g of succinic acid methyl ester chloride (Fluka) dissolved at a temperature of 0° C. in 10 g of tetrahydrofuran (THF), is run under nitrogen and stirring subsequent into Solution B, consisting of 6.37 g of the UV-absorber (indicated in the above reaction scheme) in a mixture of 10 g of dry tetrahydrofuran (THF) and 1 g of triethylamine at a temperature of 0° C. An additional amount of 1 g triethylamine is added and stirring is continued for additional 2 hours at a temperature of 0° C., then 16 hours at room temperature.
  • Fluka succinic acid methyl ester chloride
  • the product mixture is poured into 200 ml of deionized water and the pH is adapted from 10.2 to 3.2 by addition of 3.26 g of 4% aqueous hydrochloric acid. The mixture is stirred for 40 minutes and then the pale precipitated product is filtered off and washed thrice with 200 ml of water.
  • the residual water is removed during 16 hours from the pale brownish product in vacuum at a temperature of 70° C. (100 hPa).
  • the structure is confirmed by 1 H-NMR, UV-VIS and IR spectroscopy.
  • This solution is added within 5 seconds under stirring to a mixture consisting of 0.75 g of the UV-absorber obtained as given above under a) and 0.05 g of dibutyltinoxide dissolved in 30 g of dimethylacetamide (DMA).
  • DMA dimethylacetamide
  • the milky yellowish reaction mixture is stirred and heated to a temperature of 130° C. for 6 hours whereby methanol is distilled off. Thereafter, the mixture is cooled to room temperature and stirred for 1 hour, combined with 140 g of tetrahydrofuran (THF) and stirred for 30 minutes, then 140 g of n-hexane are added and the mixture is stirred for additional 16 hours.
  • the suspension is centrifugated (4500 rpm), the isolated product redispersed in 80 g of xylene, washed and centrifugated. The obtained white gel is separated and dispersed up to ten times in xylene.
  • Thermogravimetric analysis (TGA; heating rate: 10° C./min from 25° C. to 800° C.): Weight loss: 18.5%, corresponding to the organic material.
  • the IR shows a band at 1562 and -1644 cm ⁇ 1 corresponding to the amide-bond.
  • the suspension is centrifugated (4500 rpm), the isolated product re-dispersed in ethanol, washed and centrifugated twice.
  • the solvent is evaporated in the rotary evaporator to obtain a transparent oil. It is verified by 1 H-NMR that there are no residual acrylic double bonds left.
  • MPEG(8)acrylate poly(ethyleneglycol)methyl ether acrylate
  • Thermogravimetric analysis (TGA; heating rate: 10° C./min from 25° C. to 800° C.): Weight loss: 33.9%, corresponding to the organic material.
  • the IR shows a band at 1555 and 1642 cm ⁇ 1 corresponding to the amide-bond.
  • the suspension is centrifugated (4500 rpm), the isolated product re-dispersed in ethanol, washed and centrifugated twice.
  • the solvent is evaporated in the rotary evaporator to obtain a transparent oil. It is verified by 1 H-NMR that there are no residual acrylic double bonds left.
  • This solution is added within 5 seconds under stirring to a mixture consisting of 1 g of the hindered amine light stabilizer (succinic acid methylester 4-amido-(2,2,6,6)-tetramethyl-1-methyl-piperidine; see the formula given in the above reaction scheme), 1 g of the benztriazole UV-absorber (see the formula given in the above reaction scheme) and 120 mg of dibutyltinoxide dissolved in 20 g of dimethylacetamide (DMA).
  • DMA dimethylacetamide
  • the mixture is cooled to 50° C., combined with 200 g of tetrahydrofuran (THF) and 200 g of n-hexane and stirred for additional 16 hours.
  • the suspension is centrifugated (4500 rpm), the isolated product re-dispersed in 160 g of xylene, washed and centrifugated twice.
  • the obtained gel is separated and dispersed in xylene.
  • the suspension is centrifugated (4500 rpm), the isolated product re-dispersed in ethanol, washed and centrifugated twice.
  • the solvent is evaporated in the rotary evaporator to obtain a transparent oil. It is verified by 1 H-NMR that there are no residual acrylic double bonds left.
  • Macrynal SM 510n (60% supply form from Solution), 11.5 g of butylglycol acetate, 4.70 g of Solvesso 100 (obtained from Exxon), 5.68 g of Methyl isobutyl ketone, 0.07 g of zinc octoate and 0.15 g of BYK 300 (Byk-Chemie, Germany, anti-foaming agent) are mixed to give 76.9 of the polyol component.
  • the amount of each silica nanoparticle dispersion is calculated to be 5 wt.-% SiO 2 of the final clear coat formulation.
  • These formulations are treated with 2.8 g of Desmo-dur N 75 (RTM) (Isocyanate from Bayer).
  • RTM Desmo-dur N 75
  • the resulting clear coat formulation solids content 50% is subsequently applied as transparent topcoat at a dry film thickness of 40 ⁇ m onto steel panels (10 cm ⁇ 30 cm) precoated with a black basecoat. After application, the clear coat is cured at 120° C. for 45 minutes.
  • the scratch resistance of the coated panels is measured using the following method: The 20° gloss of the panels is measured 48 hours after curing (DIN 67 530). The panels are sub-sequently exposed to scratching by an Amtec Kistler apparatus according to DIN concept 55668 for the number of cycles as indicated in Table 1. The 20° gloss is measured again on the scratched area of each test panel. The results are summarized in Table 1.
  • Ebecryl 604 (75% Epoxyacrylate in HDDA; Cytec) 89 Sartomer SR 344 (Polyethylenglykol 400 Diacrylat; Cray Valley) 10 Ebecryl 350 (Silikondiacrylat; Cytec) 1
  • Example 14 20 g of the above formulation is mixed with 18 g of the dispersion obtained according to Example 14 (comprising the corresponding surface functionalized silica nanoparticle).
  • the resulting homogenized formulation is applied to a white-based chipboard by a 150 ⁇ m slit coater.
  • the panel with the applied coating is placed in an oven at 40° C. for 10 minutes to evaporate the solvent, which has been incorporated through the nano particle dispersion.
  • the coatings are cured with two 80 W/cm mercury medium pressure lamps at a belt speed of 5 m/min using a PPG equipment from AETEC. A hard and scratch resistant coating is obtained.
US11/665,627 2004-10-25 2005-10-17 Functionalized nanoparticles Abandoned US20090076198A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/930,848 US8877954B2 (en) 2004-10-25 2013-06-28 Functionalized nanoparticles

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04105278 2004-10-25
EP04105278.8 2004-10-25
PCT/EP2005/055287 WO2006045713A1 (en) 2004-10-25 2005-10-17 Functionalized nanoparticles

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/055287 A-371-Of-International WO2006045713A1 (en) 2004-10-25 2005-10-17 Functionalized nanoparticles

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/930,848 Continuation US8877954B2 (en) 2004-10-25 2013-06-28 Functionalized nanoparticles

Publications (1)

Publication Number Publication Date
US20090076198A1 true US20090076198A1 (en) 2009-03-19

Family

ID=34929759

Family Applications (2)

Application Number Title Priority Date Filing Date
US11/665,627 Abandoned US20090076198A1 (en) 2004-10-25 2005-10-17 Functionalized nanoparticles
US13/930,848 Active US8877954B2 (en) 2004-10-25 2013-06-28 Functionalized nanoparticles

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/930,848 Active US8877954B2 (en) 2004-10-25 2013-06-28 Functionalized nanoparticles

Country Status (6)

Country Link
US (2) US20090076198A1 (zh)
EP (2) EP2028228B1 (zh)
JP (1) JP5524449B2 (zh)
ES (1) ES2712912T3 (zh)
TW (1) TW200619298A (zh)
WO (1) WO2006045713A1 (zh)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090018229A1 (en) * 2004-11-17 2009-01-15 Sogah Dotsevi Y Nanocomposites prepared using nanoadditive containing dispersed silicate layers or inorganic nanoparticles
US20100162494A1 (en) * 2007-05-11 2010-07-01 Ciba Corporation Functionalized nanoparticles
US20100178512A1 (en) * 2006-12-06 2010-07-15 Ciba Corporation Changing surface properties by functionalized nanoparticles
US20100192312A1 (en) * 2007-05-11 2010-08-05 Ciba Corporation Polymeric dyes
US20100317819A1 (en) * 2007-03-05 2010-12-16 Ciba Corporation Surface-modified nanoparticles comprising a cationic colorant for use in color filters
US20110111659A1 (en) * 2009-11-09 2011-05-12 E. I. Du Pont De Nemours And Company Method using fluoropolymer emulsions
WO2012018451A2 (en) * 2010-08-06 2012-02-09 Baker Hughes Incorporated Method to disperse nanoparticles into elastomer and articles produced therefrom
EP2626329A1 (en) * 2010-10-07 2013-08-14 Consejo Superior De Investigaciones Científicas (CSIC) Method for coating and functionalizing nanoparticles by means of a michael reaction
WO2013058843A3 (en) * 2011-07-05 2013-08-22 Luna Innovations Incorporated Fluid-resistant textile fabrics and methods
US20130261209A1 (en) * 2011-02-14 2013-10-03 Lg Chem Ltd Uv-curable coating compositions with self-healing capabilities, coating films, and methods of producing coating films
US20130331484A1 (en) * 2010-10-27 2013-12-12 Kronotec Ag Hybrid Adhesive and the Use Thereof in Engineered Wood Boards
US20140000152A1 (en) * 2011-03-14 2014-01-02 Akzo Nobel Chemicals International B.V. Modified silica particles
US20150279507A1 (en) * 2012-11-23 2015-10-01 Schwering & Hasse Elektrodraht Gmbh Enamelled wire
WO2015187705A1 (en) * 2014-06-03 2015-12-10 International Business Machines Corporation Sulfur scavenging materials
WO2016073365A1 (en) * 2014-11-03 2016-05-12 Baker Hughes Incorporated Initiator nanoconstituents for elastomer crosslinking and related methods and articles
US9592470B2 (en) 2014-05-27 2017-03-14 International Business Machines Corporation Sulfur scavenging materials for filters and coatings
US9666321B2 (en) 2015-04-09 2017-05-30 International Business Machines Corporation Optical capture and isolation of circulating tumor cells in a micro-fluidic device utilizing size selective trapping with optical cogwheel tweezers
US9770702B2 (en) 2014-06-16 2017-09-26 International Business Machines Corporation Methods and apparatus for controlling metals in liquids
US9827590B2 (en) 2015-06-17 2017-11-28 International Business Machines Corporation Method of glass fabric production including resin adhesion for printed circuit board formation
US10053572B2 (en) 2012-07-25 2018-08-21 Industrial Technology Research Institute Masterbatch, method for fabricating the same, and a film fabricated from the masterbatch
US11008458B2 (en) * 2016-03-17 2021-05-18 Qed Labs Inc. Articles with improved flame retardancy and/or melt dripping properties
US11072710B2 (en) 2016-12-28 2021-07-27 Namics Corporation Surface-treated silica filler, and resin composition containing surface-treated silica filler
CN113292973A (zh) * 2021-06-22 2021-08-24 西南石油大学 一种抗高温二氧化硅接枝叔胺纳米封堵剂及水基钻井液
CN114736590A (zh) * 2022-03-25 2022-07-12 天津市新丽华色材有限责任公司 一种uv固化镜背保护涂料及其制备工艺

Families Citing this family (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5275021B2 (ja) * 2005-03-23 2013-08-28 ディーエスエム アイピー アセッツ ビー．ブイ． 発色団で被覆された金属酸化物粒子
DE102006012467A1 (de) 2006-03-17 2007-09-20 Merck Patent Gmbh Redispergierbare Nanopartikel
US8084522B2 (en) * 2006-10-24 2011-12-27 Basf Se Thermally stable cationic photocurable compositions
KR100762298B1 (ko) * 2006-12-29 2007-10-04 제일모직주식회사 내스크래치성이 향상된 열가소성 나노복합체 수지 조성물
DE102007008663A1 (de) 2007-02-20 2008-08-21 Merck Patent Gmbh Bindemittel
FR2914631B1 (fr) 2007-04-06 2009-07-03 Eads Europ Aeronautic Defence Materiau nanostructure particulier, comme revetement protecteur de surfaces metalliques.
JP2009120700A (ja) * 2007-11-14 2009-06-04 Niigata Univ 機能性微粒子及びその製造方法、並びにこれを配合してなる被覆性組成物
US20090148653A1 (en) 2007-12-07 2009-06-11 E.I. Du Pont De Nemours And Company Fluoropolymer emulsions
KR20100119873A (ko) 2008-02-21 2010-11-11 바스프 에스이 양이온성 나노입자의 제조 및 상기 나노입자를 포함하는 개인 케어 조성물
NO328788B1 (no) 2008-03-14 2010-05-18 Jotun As Bindemiddel til lufttørkende maling
BRPI0911453A2 (pt) 2008-04-18 2018-03-20 Saint Gobain Abrasifs Sa modificação da superfície de silanos hidrófilos e hidrfóbicos de orgãos abrasivos
WO2010030023A1 (ja) * 2008-09-10 2010-03-18 住友化学株式会社 水酸化アルミニウム複合材
KR101462657B1 (ko) 2008-12-19 2014-11-17 삼성전자 주식회사 반도체 나노 결정 복합체
WO2011023266A1 (en) * 2009-08-28 2011-03-03 Basf Se Modified nanoparticles
US8329822B2 (en) 2009-11-09 2012-12-11 E.I. Du Pont De Nemours And Company Fluoropolymer emulsions
CN102206432B (zh) * 2010-03-31 2013-03-20 中国科学院化学研究所 表面接枝抗氧剂分子的纳米二氧化硅及其制备方法和用途
JP5615620B2 (ja) * 2010-08-09 2014-10-29 日東電工株式会社 金属酸化物粒子の製造方法
WO2012059936A1 (en) 2010-11-03 2012-05-10 Padma Venkitachalam Devarajan Pharmaceutical compositions for colloidal drug delivery
KR101385833B1 (ko) * 2012-03-22 2014-04-16 한국세라믹기술원 배향성을 가지는 무기 나노 입자 복합체
US8829694B1 (en) * 2013-03-15 2014-09-09 Henkel IP & Holding GmbH Thermosetting resin compositions with low coefficient of thermal expansion
CN105593255A (zh) * 2013-10-04 2016-05-18 日本曹达株式会社 具有耐光性、且机械强度优异的丙烯酸改性pb固化性组合物
CN105612241B (zh) * 2013-11-26 2018-09-25 株式会社艾迪科 光稳定剂组合物以及其树脂组合物
CN104843724B (zh) * 2015-04-09 2016-09-07 河北工业大学 一种无机分级孔结构材料的制备方法
CA2992266A1 (en) 2015-07-13 2017-01-19 Saudi Arabian Oil Company Polysaccharide coated nanoparticle compositions comprising ions
US10344202B2 (en) 2015-07-13 2019-07-09 Saudi Arabian Oil Company Stabilized nanoparticle compositions comprising ions
CN109312110B (zh) 2016-02-28 2022-04-19 本古里安大学B.G.内盖夫科技应用有限公司 用于保护聚合物对抗紫外光的添加剂
EP3491077B1 (en) * 2016-07-26 2020-02-26 Unilever N.V. Surface treatment composition capable of imparting underwater superoleophobicity
US10710883B2 (en) * 2017-12-07 2020-07-14 The King Abdulaziz City For Science And Technology Graphite-titanium-nanocomposite complex and method of preparation thereof
JP7266858B2 (ja) * 2019-04-08 2023-05-01 ナトコ株式会社 フィラー粒子、膜形成用組成物、膜を備えた物品、成形用樹脂材料および成形品
WO2020243234A1 (en) 2019-05-29 2020-12-03 Saudi Arabian Oil Company Flow synthesis of polymer nanoparticles
US11566165B2 (en) 2019-05-30 2023-01-31 Saudi Arabian Oil Company Polymers and nanoparticles for flooding
NO346733B1 (en) 2019-06-28 2022-12-05 Klingelberg Products As Flame retardant, method for its preparation and article comprising same
WO2021026432A1 (en) 2019-08-07 2021-02-11 Saudi Arabian Oil Company Determination of geologic permeability correlative with magnetic permeability measured in-situ
KR102424847B1 (ko) * 2019-09-27 2022-07-27 주식회사 케미랜드 자외선 차단용 분산체 조성물
US11795107B2 (en) 2020-08-12 2023-10-24 Saudi Arabian Oil Company Encapsulation of silica nanoparticle for release
WO2022051628A1 (en) 2020-09-03 2022-03-10 Saudi Arabian Oil Company Injecting multiple tracer tag fluids into a wellbore
US20230323142A1 (en) * 2020-09-18 2023-10-12 Ryan ROEDER Methacrylated nanoparticles and related method
WO2022097418A1 (ja) * 2020-11-09 2022-05-12 関西ペイント株式会社 塗料組成物及び複層塗膜形成方法
NO346598B1 (en) 2020-12-23 2022-10-24 Klingelberg Products As Method for the preparation of amidines and amide manufactured by the method
CN112657815B (zh) * 2020-12-23 2023-08-08 合肥工业大学 一种316L不锈钢管内壁Al2O3/SiO2复合阻氚涂层的制备方法
US11660595B2 (en) 2021-01-04 2023-05-30 Saudi Arabian Oil Company Microfluidic chip with multiple porosity regions for reservoir modeling
US11534759B2 (en) 2021-01-22 2022-12-27 Saudi Arabian Oil Company Microfluidic chip with mixed porosities for reservoir modeling
US11879328B2 (en) 2021-08-05 2024-01-23 Saudi Arabian Oil Company Semi-permanent downhole sensor tool
US11796517B2 (en) 2021-11-09 2023-10-24 Saudi Arabian Oil Company Multifunctional magnetic tags for mud logging
US11725139B2 (en) 2021-12-13 2023-08-15 Saudi Arabian Oil Company Manipulating hydrophilicity of conventional dye molecules for water tracer applications
US11860077B2 (en) 2021-12-14 2024-01-02 Saudi Arabian Oil Company Fluid flow sensor using driver and reference electromechanical resonators
US11867049B1 (en) 2022-07-19 2024-01-09 Saudi Arabian Oil Company Downhole logging tool
US11913329B1 (en) 2022-09-21 2024-02-27 Saudi Arabian Oil Company Untethered logging devices and related methods of logging a wellbore

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5258024A (en) * 1989-05-12 1993-11-02 Essilor International (Compaigne Generale D'optique) Method of manufacture of a lens of transparent polymer having a modulated refractive index
US6015843A (en) * 1998-01-14 2000-01-18 Dendreon Corporation Process for making silanized colloidal silica
US6160067A (en) * 1995-10-03 2000-12-12 Dsm N.V. Reactive silica particles, process for manufacturing the same, use of the same
US20020094439A1 (en) * 2000-10-05 2002-07-18 Roland Edelmann Organosilicon nanocapsules
US20030194715A1 (en) * 2002-04-08 2003-10-16 Affymetrix, Inc. Photoactivatable silane compounds and methods for their synthesis and use
US20040020451A1 (en) * 2000-11-15 2004-02-05 Johannes Denteler Internal combustion engine comprising an electromagnetic actuator which is situated on a cylinder head
US20050059766A1 (en) * 2003-09-12 2005-03-17 Jones Clinton L. Durable optical element

Family Cites Families (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2244325A (en) 1940-04-15 1941-06-03 Paul G Bird Colloidal solutions of inorganic oxides
DE1988536U (de) 1966-06-06 1968-06-27 Palitex Project Co Gmbh Vorrichtung zum einsetzen von spulen in spindeln.
US4079035A (en) 1974-11-21 1978-03-14 Ethyl Corporation Halophenoxyphosphazene fire retardants and polyesters containing same
US4122233A (en) * 1975-05-08 1978-10-24 E. I. Du Pont De Nemours And Company Ultraviolet screening agents and coating materials containing organosilane ester groups
US4107108A (en) 1977-02-08 1978-08-15 Armstrong Cork Company Polyphosphazene plasticized resins
US4108805A (en) 1977-09-06 1978-08-22 Armstrong Cork Company Structurally regulated polyphosphazene copolymers
GB2042562B (en) 1979-02-05 1983-05-11 Sandoz Ltd Stabilising polymers
DE2914427A1 (de) 1979-04-10 1980-10-23 Bayer Ag Beschichtung fuer thermoplasten
JPS59197401A (ja) 1983-04-26 1984-11-09 Nippon Oil & Fats Co Ltd 光重合開始剤
JPS6042437A (ja) * 1983-08-17 1985-03-06 Kao Corp 表面被覆された無機填料
DE3403975A1 (de) 1984-02-04 1985-08-14 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von abs-formmassen mit verbessertem brandverhalten
JPS60240769A (ja) * 1984-05-16 1985-11-29 Nippon Steel Chem Co Ltd 表面疎水性無機材料の製造法
JPS61261365A (ja) * 1985-05-14 1986-11-19 Nippon Oil Co Ltd 光硬化性被覆組成物
GB8611357D0 (en) 1986-05-09 1986-06-18 Ciba Geigy Ag Flame retardent polymer compositions
DE3634949A1 (de) 1986-05-30 1988-03-24 Gerard Brozio Kombinierter-kalk-kohlensaeure-gleichgewicht-stabilisator
IT1231221B (it) * 1987-09-11 1991-11-26 Enichem Sintesi Cariche e pigmenti dotati anche di proprieta' stabilizzanti nei riguardi dei polimeri organici e procedimento per la loro preparazione
WO1990001512A1 (en) 1988-08-12 1990-02-22 Desoto, Inc. Photo-curable vinyl ether compositions
DE3834949A1 (de) * 1988-10-13 1990-04-19 Greber Gerd Verfahren zur herstellung von neuen kunststoff-additiven auf basis vn modifizierten aerosilen
JPH0351274A (ja) 1989-07-17 1991-03-05 Hitachi Elevator Eng & Service Co Ltd エレベータの呼び登録装置
US5175312A (en) 1989-08-31 1992-12-29 Ciba-Geigy Corporation 3-phenylbenzofuran-2-ones
US5252643A (en) 1991-07-01 1993-10-12 Ciba-Geigy Corporation Thiomethylated benzofuran-2-ones
TW206220B (zh) 1991-07-01 1993-05-21 Ciba Geigy Ag
JPH05194932A (ja) * 1991-07-10 1993-08-03 Noevir Co Ltd 紫外線吸収性顔料、及びこれを配合した化粧料
TW260686B (zh) 1992-05-22 1995-10-21 Ciba Geigy
GB2267490B (en) 1992-05-22 1995-08-09 Ciba Geigy Ag 3-(Carboxymethoxyphenyl)benzofuran-2-one stabilisers
NL9300801A (nl) 1992-05-22 1993-12-16 Ciba Geigy 3-(acyloxyfenyl)benzofuran-2-on als stabilisatoren.
JP2671727B2 (ja) * 1992-09-17 1997-10-29 信越化学工業株式会社 表面処理シリカ並びにその製造方法及び半導体封止用樹脂組成物用充填剤
TW255902B (zh) 1992-09-23 1995-09-01 Ciba Geigy
MX9305489A (es) 1992-09-23 1994-03-31 Ciba Geigy Ag 3-(dihidrobenzofuran-5-il)benzofuran-2-onas, estabilizadores.
US5374138A (en) * 1993-05-18 1994-12-20 Byles; Joe D. Subsurface irrigation apparatus and method
US5393812A (en) 1993-08-31 1995-02-28 Hercules Incorporated Flame retardant, light stable composition
DE4338361A1 (de) 1993-11-10 1995-05-11 Inst Neue Mat Gemein Gmbh Verfahren zur Herstellung von Zusammensetzungen auf der Basis von Epoxidgruppen-haltigen Silanen
JPH07292233A (ja) 1994-04-27 1995-11-07 Denki Kagaku Kogyo Kk 難燃性樹脂組成物
JP3223752B2 (ja) * 1994-04-28 2001-10-29 東洋インキ製造株式会社 水性被覆剤組成物、およびその製造方法、ならびに水性印刷インキ
JPH08319400A (ja) * 1995-05-26 1996-12-03 Matsushita Electric Works Ltd 封止用エポキシ樹脂組成物
JP3474330B2 (ja) * 1995-10-03 2003-12-08 Ｊｓｒ株式会社 反応性シリカ粒子、その製法および用途
JPH09151274A (ja) * 1995-11-29 1997-06-10 Sumitomo Bakelite Co Ltd 熱可塑性樹脂複合材料の製造方法及び熱可塑性樹脂複合材料
US5851507A (en) 1996-09-03 1998-12-22 Nanomaterials Research Corporation Integrated thermal process for the continuous synthesis of nanoscale powders
US6652967B2 (en) 2001-08-08 2003-11-25 Nanoproducts Corporation Nano-dispersed powders and methods for their manufacture
DE19724397A1 (de) 1997-06-10 1999-01-14 Bayer Ag UV-Stabilisatoren für Siloxan-Systeme
DE19724396A1 (de) 1997-06-10 1998-12-24 Bayer Ag UV-Stabilisatoren für Siloxan-Systeme
JPH11263885A (ja) 1998-03-17 1999-09-28 Chemiprokasei Kaisha Ltd 難燃性ポリオレフィン系樹脂組成物およびそれよりなる成形品
DE19818735A1 (de) 1998-04-27 1999-10-28 Herberts Gmbh Strahlungshärtbare Beschichtungsmittel und deren Verwendung
DE19828541A1 (de) 1998-06-26 1999-12-30 Bayer Ag Flammwidrige Polycarbonat-ABS-Formmassen
TW445276B (en) 1998-08-13 2001-07-11 Otsuka Chemical Co Ltd Crosslinked phenoxyphosphazene compounds, process for the preparation thereof, flame retardants, flame-retardant resin compositions, and moldings of flame-retardant resins
DE19919635A1 (de) 1999-04-30 2000-11-23 Degussa Silicium-Aluminium-Mischoxid
US6265599B1 (en) 2000-07-12 2001-07-24 Chung-Shan Institute Of Science & Technology Process for preparing a mixture of amino-containing phosphazenes
US6586483B2 (en) * 2001-01-08 2003-07-01 3M Innovative Properties Company Foam including surface-modified nanoparticles
US6719821B2 (en) 2001-02-12 2004-04-13 Nanoproducts Corporation Precursors of engineered powders
EP1236765A1 (de) 2001-02-28 2002-09-04 hanse chemie GmbH Siliciumdioxiddispersion
JP2002363438A (ja) * 2001-06-04 2002-12-18 Wakayama Prefecture 無機補強充填剤及びこれを含有した熱可塑性樹脂組成物
FR2825293B1 (fr) 2001-06-05 2004-05-07 Coletica Particules solides insolubles dans l'eau traitees, preparation et utilisation
CN100506898C (zh) * 2001-06-29 2009-07-01 西巴特殊化学品控股有限公司 添加剂官能化的亲有机物纳米级填料
WO2003016388A1 (en) 2001-08-15 2003-02-27 Ciba Specialty Chemicals Holding Inc. Flame retardant compositions
TW593303B (en) 2001-09-11 2004-06-21 Ciba Sc Holding Ag Stabilization of synthetic polymers
US6833186B2 (en) * 2002-04-10 2004-12-21 Ppg Industries Ohio, Inc. Mineral-filled coatings having enhanced abrasion resistance and wear clarity and methods for using the same
JP4041968B2 (ja) * 2002-10-09 2008-02-06 信越化学工業株式会社 下塗り剤組成物、該組成物を用いたコーティング方法、及びコーティング物品
DE10342828A1 (de) 2003-09-17 2005-04-14 Degussa Ag Hochreines, pyrogen hergestelltes Siliciumdioxid

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5258024A (en) * 1989-05-12 1993-11-02 Essilor International (Compaigne Generale D'optique) Method of manufacture of a lens of transparent polymer having a modulated refractive index
US6160067A (en) * 1995-10-03 2000-12-12 Dsm N.V. Reactive silica particles, process for manufacturing the same, use of the same
US6015843A (en) * 1998-01-14 2000-01-18 Dendreon Corporation Process for making silanized colloidal silica
US20020094439A1 (en) * 2000-10-05 2002-07-18 Roland Edelmann Organosilicon nanocapsules
US20040020451A1 (en) * 2000-11-15 2004-02-05 Johannes Denteler Internal combustion engine comprising an electromagnetic actuator which is situated on a cylinder head
US20030194715A1 (en) * 2002-04-08 2003-10-16 Affymetrix, Inc. Photoactivatable silane compounds and methods for their synthesis and use
US20050059766A1 (en) * 2003-09-12 2005-03-17 Jones Clinton L. Durable optical element

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090018229A1 (en) * 2004-11-17 2009-01-15 Sogah Dotsevi Y Nanocomposites prepared using nanoadditive containing dispersed silicate layers or inorganic nanoparticles
US20100178512A1 (en) * 2006-12-06 2010-07-15 Ciba Corporation Changing surface properties by functionalized nanoparticles
US20100317819A1 (en) * 2007-03-05 2010-12-16 Ciba Corporation Surface-modified nanoparticles comprising a cationic colorant for use in color filters
US20100162494A1 (en) * 2007-05-11 2010-07-01 Ciba Corporation Functionalized nanoparticles
US20100192312A1 (en) * 2007-05-11 2010-08-05 Ciba Corporation Polymeric dyes
US7976585B2 (en) 2007-05-11 2011-07-12 BASF SE Ludwigshafen Polymeric dyes
US8962140B2 (en) 2007-05-11 2015-02-24 Basf Se Functionalized core-shell nanoparticles
US20110111659A1 (en) * 2009-11-09 2011-05-12 E. I. Du Pont De Nemours And Company Method using fluoropolymer emulsions
US8507601B2 (en) * 2009-11-09 2013-08-13 E. I. Du Pont De Nemours And Company Method using fluoropolymer emulsions
WO2012018451A2 (en) * 2010-08-06 2012-02-09 Baker Hughes Incorporated Method to disperse nanoparticles into elastomer and articles produced therefrom
WO2012018451A3 (en) * 2010-08-06 2012-07-05 Baker Hughes Incorporated Method to disperse nanoparticles into elastomer and articles produced therefrom
EP2626329A1 (en) * 2010-10-07 2013-08-14 Consejo Superior De Investigaciones Científicas (CSIC) Method for coating and functionalizing nanoparticles by means of a michael reaction
EP2626329A4 (en) * 2010-10-07 2015-03-25 Consejo Superior Investigacion PROCESS FOR COATING AND FUNCTIONALIZING NANOPARTICLES BY MEANS OF A MICHAEL REACTION
US20130331484A1 (en) * 2010-10-27 2013-12-12 Kronotec Ag Hybrid Adhesive and the Use Thereof in Engineered Wood Boards
US9238767B2 (en) * 2010-10-27 2016-01-19 Kronotec Ag Hybrid adhesive and the use thereof in engineered wood boards
US20130261209A1 (en) * 2011-02-14 2013-10-03 Lg Chem Ltd Uv-curable coating compositions with self-healing capabilities, coating films, and methods of producing coating films
CN103370384A (zh) * 2011-02-14 2013-10-23 Lg化学株式会社 具有自修复能力的紫外光可固化涂料组合物、涂膜以及制备涂膜的方法
TWI507491B (zh) * 2011-02-14 2015-11-11 Lg Chemical Ltd 具自行復原特性之ｕｖ固化塗佈組成物、塗膜、以及塗膜之製備方法
US8975308B2 (en) * 2011-02-14 2015-03-10 Lg Chem, Ltd. UV-curable coating compositions with self-healing capabilities, coating films, and methods of producing coating films
US20140000152A1 (en) * 2011-03-14 2014-01-02 Akzo Nobel Chemicals International B.V. Modified silica particles
WO2013058843A3 (en) * 2011-07-05 2013-08-22 Luna Innovations Incorporated Fluid-resistant textile fabrics and methods
US9708755B2 (en) 2011-07-05 2017-07-18 Luna Innovations Incorporated Fluid-resistant textile fabrics and methods
US10053572B2 (en) 2012-07-25 2018-08-21 Industrial Technology Research Institute Masterbatch, method for fabricating the same, and a film fabricated from the masterbatch
US20150279507A1 (en) * 2012-11-23 2015-10-01 Schwering & Hasse Elektrodraht Gmbh Enamelled wire
US9592470B2 (en) 2014-05-27 2017-03-14 International Business Machines Corporation Sulfur scavenging materials for filters and coatings
US9610535B2 (en) 2014-05-27 2017-04-04 International Business Machines Corporation Sulfur scavenging materials for filters and coatings
US11447507B2 (en) 2014-06-03 2022-09-20 International Business Machines Corporation Sulfur scavenging materials
US9469660B2 (en) 2014-06-03 2016-10-18 International Business Machines Corporation Sulfur scavenging materials comprising hexahydrotriazine-modified particle
US10604539B2 (en) 2014-06-03 2020-03-31 International Business Machines Corporation Sulfur scavenging materials
WO2015187705A1 (en) * 2014-06-03 2015-12-10 International Business Machines Corporation Sulfur scavenging materials
US10525442B2 (en) 2014-06-16 2020-01-07 International Business Machines Corporation Methods and apparatus for controlling metals in liquids
US9770702B2 (en) 2014-06-16 2017-09-26 International Business Machines Corporation Methods and apparatus for controlling metals in liquids
US10328415B2 (en) 2014-06-16 2019-06-25 International Business Machines Corporation Methods and apparatus for controlling metals in liquids
WO2016073365A1 (en) * 2014-11-03 2016-05-12 Baker Hughes Incorporated Initiator nanoconstituents for elastomer crosslinking and related methods and articles
US9938771B2 (en) 2014-11-03 2018-04-10 Baker Hughes, A Ge Company, Llc Initiator nanoconstituents for elastomer crosslinking and related methods
RU2676057C2 (ru) * 2014-11-03 2018-12-25 Бейкер Хьюз Инкорпорейтед Нанокомпоненты инициатора для поперечного сшивания эластомеров и родственные способы и изделия
US9666321B2 (en) 2015-04-09 2017-05-30 International Business Machines Corporation Optical capture and isolation of circulating tumor cells in a micro-fluidic device utilizing size selective trapping with optical cogwheel tweezers
US9734927B2 (en) 2015-04-09 2017-08-15 International Business Machines Corporation Optical capture and isolation of circulating tumor cells in a micro-fluidic device utilizing size selective trapping with optical cogwheel tweezers
US9827590B2 (en) 2015-06-17 2017-11-28 International Business Machines Corporation Method of glass fabric production including resin adhesion for printed circuit board formation
US11008458B2 (en) * 2016-03-17 2021-05-18 Qed Labs Inc. Articles with improved flame retardancy and/or melt dripping properties
US11072710B2 (en) 2016-12-28 2021-07-27 Namics Corporation Surface-treated silica filler, and resin composition containing surface-treated silica filler
CN113292973A (zh) * 2021-06-22 2021-08-24 西南石油大学 一种抗高温二氧化硅接枝叔胺纳米封堵剂及水基钻井液
US11692121B2 (en) 2021-06-22 2023-07-04 Southwest Petroleum University Tertiary amine-grafted silica nano-plugging agent and water-based drilling fluids
CN114736590A (zh) * 2022-03-25 2022-07-12 天津市新丽华色材有限责任公司 一种uv固化镜背保护涂料及其制备工艺

Also Published As

Publication number Publication date
JP2008518067A (ja) 2008-05-29
US8877954B2 (en) 2014-11-04
TW200619298A (en) 2006-06-16
JP5524449B2 (ja) 2014-06-18
EP2028228B1 (en) 2018-12-12
US20130296453A1 (en) 2013-11-07
EP2028228A2 (en) 2009-02-25
EP2028228A3 (en) 2011-11-09
WO2006045713A1 (en) 2006-05-04
EP1805255A1 (en) 2007-07-11
ES2712912T3 (es) 2019-05-16

Similar Documents

Publication Publication Date Title
US8877954B2 (en) Functionalized nanoparticles
US20090099282A1 (en) Functionalized nanoparticles
JP4271566B2 (ja) 添加剤で官能化された有機親和性ナノスケール充填剤
US10047231B2 (en) Tris(hydroxyphenyl) triazines
US7829643B2 (en) Coating compositions containing levelling agents prepared by nitroxyl mediated polymerisation
ZA200602175B (en) Reinforced coatings with improved scratch resistance
US7002010B2 (en) Process for the preparation of morpholinones as light stabilizers
US7368525B2 (en) Polymeric alkoyamines prepared by atom transfer radical addition (ATRA)

Legal Events

Date Code Title Description
AS Assignment

Owner name: CIBA SPECIALTY CHEMICALS CORP., NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GIESENBERG, THOMAS;MUHLEBACH, ANDREAS;JUNG, TUNJA;AND OTHERS;REEL/FRAME:021917/0369;SIGNING DATES FROM 20070119 TO 20070129

AS Assignment

Owner name: BASF SE, GERMANY

Free format text: ASSET TRANSFER AGREEMENT;ASSIGNOR:CIBA CORPORATION;REEL/FRAME:030509/0334

Effective date: 20090702

Owner name: CIBA CORPORATION, NEW YORK

Free format text: CHANGE OF NAME;ASSIGNOR:CIBA SPECIALTY CHEMICALS CORPORATION;REEL/FRAME:030509/0319

Effective date: 19960816

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION