WO2012003160A1 - Curable composition comprising dual reactive silane functionality - Google Patents

Curable composition comprising dual reactive silane functionality Download PDF

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Publication number
WO2012003160A1
WO2012003160A1 PCT/US2011/042074 US2011042074W WO2012003160A1 WO 2012003160 A1 WO2012003160 A1 WO 2012003160A1 US 2011042074 W US2011042074 W US 2011042074W WO 2012003160 A1 WO2012003160 A1 WO 2012003160A1
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Prior art keywords
combinations
composition
fluorinated
component
compounds
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PCT/US2011/042074
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French (fr)
Inventor
Yu Yang
Michael A. Semonick
George G.I. Moore
Larry D. Boardman
John L. Battiste
Maria A. Appeaning
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3M Innovative Properties Company
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Priority to CN2011800329992A priority Critical patent/CN102985503A/en
Priority to JP2013518543A priority patent/JP5818890B2/en
Priority to US13/807,319 priority patent/US8841399B2/en
Priority to EP11733943.2A priority patent/EP2665788A1/en
Publication of WO2012003160A1 publication Critical patent/WO2012003160A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C267/00—Carbodiimides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
    • C07C279/04—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/062—Organo-phosphoranes without P-C bonds
    • C07F9/065—Phosphoranes containing the structure P=N-
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • C07F9/65842—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring
    • C07F9/65846—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring the phosphorus atom being part of a six-membered ring which may be condensed with another ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen

Definitions

  • This invention relates to curable compositions comprising reactive silane functionality and, in other aspects, to articles comprising the compositions and to processes for curing the compositions.
  • Moisture-curable compositions cure in the presence of moisture to form
  • the moisture for curing is typically obtained from the atmosphere or from a substrate to which the composition has been applied, although it can also be added to the composition (for example, to enable curing in depth or in confinement).
  • Moisture-curable compositions usually comprise polymers having groups (for example, alkoxysilyl or acyloxysilyl moieties) that can react in the presence of moisture to form cured (that is, crosslinked) materials.
  • groups for example, alkoxysilyl or acyloxysilyl moieties
  • a wide variety of polymers can be rendered moisture curable, including polyolefms, polyesters, polyethers, polyacrylates, polyvinyl chloride, polyphosphazenes, polysiloxanes, polysulfides, block copolymers, and fluorinated derivatives thereof, the particular polymer being selected based on the intended use.
  • a polysiloxane or fluorinated polyether is often selected to provide release coatings suitable for use with pressure-sensitive adhesives.
  • Moisture-curable compositions comprising alkoxysilyl or acyloxysilyl
  • the alkoxysilyl or acyloxysilyl groups hydrolyze in the presence of moisture and a catalyst to form silanol compounds having hydroxysilyl groups.
  • the hydroxysilyl groups condense with other hydroxysilyl, alkoxysilyl, or acyloxysilyl groups in the presence of a catalyst to form— Si— O— Si— linkages.
  • the two reactions occur essentially simultaneously upon generation of the silanol compound.
  • Commonly used catalysts for the two reactions include Bronsted and Lewis acids. A single material can catalyze both reactions.
  • the hydrolysis and condensation reactions proceed quickly after the moisture-curable composition has been applied, for example, to a substrate. At the same time, however, the reactions must not occur prematurely, for example, during processing or storage.
  • compositions that have acceptable cure rates without processing and storage difficulties.
  • two-part systems have been developed (one part comprising a functional polymer and the other part comprising a catalyst), with the two parts being mixed immediately prior to use. While this approach has been useful in small-scale applications, it has been less efficient for large-scale manufacturing, where delays caused by having to mix the two parts have been undesirable.
  • coating operations must be completed expeditiously before the composition cures in the pot, and this has been difficult when working with large surface area substrates or a large volume of
  • Ammonium salt catalysts have been developed that are inactive until heated sufficiently to liberate an acid compound that initiates the moisture curing reaction.
  • onium salts such as sulfonium and iodonium salts
  • irradiation with ultraviolet light Such materials have not required heat activation and therefore have enabled the use of heat-sensitive substrates without damage (and without the production of undesirable species requiring removal), but the materials have been relatively expensive, have exhibited cure inhibition on some substrates, and have required moisture control and the use of coating equipment with irradiation capability.
  • tin catalysts such as dibutyl tin dilaurate can provide stable curable compositions that can be processed and coated without premature gelation.
  • curable compositions comprising dual reactive silane functionality in the form of hydrosilyl and hydroxysilyl groups (dehydrogenatively-curable systems) can be cured by using tin catalysts.
  • compositions have been widely used for pressure-sensitive adhesive and mold release applications but have sometimes suffered from relatively short pot lives.
  • use of tin catalysts is becoming particularly problematic because the organotin compounds generally employed as catalysts are now considered to be toxicologically objectionable.
  • compositions that can provide acceptable cure rates without significant processing and storage difficulties (for example, due to premature gelation).
  • these compositions will be efficiently processable (for example, without the need for mixing of a two-part system prior to cure), will employ catalysts that do not generate species requiring removal, and/or will not require heat activation (so as to enable curing at relatively low temperatures and/or the use of heat-sensitive substrates).
  • the compositions will employ catalysts that are relatively non-toxic, provide compositions that are relatively stable in solution but relatively fast-curing upon drying, effective in relatively low concentrations, and/or effective under relatively low (or no) moisture conditions.
  • this invention provides a curable composition comprising dual reactive silane functionality.
  • the curable composition comprises
  • At least one inorganic or organic compound comprising reactive silane functionality comprising at least one hydroxysilyl moiety that is, a monovalent moiety comprising a hydroxyl group bonded directly to a silicon atom, the hydroxysilyl moiety optionally being generated in situ by hydrolysis of at least one hydrosilyl moiety;
  • the base comprises at least one amidine (most preferably, 1,8- diazabicyclo[5.4.0]-7-undecene (DBU)).
  • the composition preferably further comprises at least one solvent (for example, an aprotic organic solvent such as heptane).
  • the above-described bases can effectively catalyze the curing (apparently, by condensation) of compositions comprising reactive silane functionality in the form of hydrosilyl and hydroxysilyl moieties.
  • the bases can provide relatively rapid cure (for example, upon removal of solvent curing can occur within periods of time as short as about 1 minute) even at temperatures as low as ambient (for example, about 23°C), without the need for heat activation, and can be effective in relatively small amounts (for example, at concentrations as low as about 0.5 weight percent or less, based upon the total weight of components (a), (b), and (c)).
  • compositions comprising the bases can exhibit relatively good storage stability (for example, for a period of weeks in a closed container) and/or relatively long pot life (for example, on the order of 8 hours or more) in a variety of solvents (for example, heptane, methyl ethyl ketone, or a combination thereof), without the need for mixing of a two-part system immediately prior to use.
  • solvents for example, heptane, methyl ethyl ketone, or a combination thereof
  • the bases can be effective in the curable composition of the invention in the substantial absence of other condensation catalysts and/or in the substantial absence of moisture.
  • the bases can be used as substitutes for conventional tin catalysts to provide organometallic catalyst-free, curable compositions.
  • at least some of the bases are relatively non-toxic and therefore suitable for use in preparing relatively environmentally friendly or "green" compositions.
  • the curable composition of the invention can be cured to provide crosslinked networks having properties that can be tailored to the requirements of various different applications (for example, by varying the natures, relative amounts, and degrees of reactive silane functionality of starting components (a) and (b)).
  • the curable composition can be used to provide materials having a variety of bulk and/or surface properties for use in numerous applications (for example, for use as sealants, adhesives, release coatings, rubbers, hardcoats, softcoats, molded parts, and the like).
  • the curable composition of the invention can be particularly useful in applications requiring control of surface properties (for example, hydrophilic or hydrophobic surface treatments and release coating applications), as the base catalysts do not appear to produce species requiring removal and, in some embodiments, the base catalysts are sufficiently volatile to be evaporated from the composition during processing, thereby leaving essentially no catalyst contamination in the cured material (in contrast with the metal contamination of conventional tin catalysts, which can be particularly problematic in the area of
  • At least some embodiments of the curable composition of the invention meet the above-described, ongoing need for curable compositions that can provide acceptable cure rates without significant processing and storage difficulties (for example, being relatively stable in solution but relatively fast-curing upon drying), while also being efficiently processable (for example, without the need for mixing of a two-part system prior to cure, for contaminant removal, and/or for heat activation).
  • At least some embodiments of the curable composition also employ catalysts that are relatively nontoxic, while being effective in relatively low concentrations and/or under relatively low (or no) moisture conditions.
  • this invention also provides a curing process comprising
  • this invention provides an article comprising the above- described curable composition of the invention (for example, an article comprising at least one substrate having at least one major surface, the substrate bearing, on at least a portion of at least one major surface, the above-described curable composition of the invention).
  • catenated heteroatom means an atom other than carbon (for example, oxygen, nitrogen, or sulfur) that replaces one or more carbon atoms in a carbon chain (for example, so as to form a carbon-heteroatom-carbon chain or a carbon-heteroatom-heteroatom- carbon chain);
  • cure means conversion to a crosslinked polymer network (for example, through catalysis);
  • fluoro- (for example, in reference to a group or moiety, such as in the case of "fluoroalkylene” or “fluoroalkyl” or “fluorocarbon") or “fluorinated” means only partially fluorinated such that there is at least one carbon-bonded hydrogen atom;
  • fluorochemical means fluorinated or perfluorinated
  • heteroorganic means an organic group or moiety (for example, an alkyl or alkylene group) containing at least one heteroatom (preferably, at least one catenated heteroatom);
  • hydrosilyl refers to a monovalent moiety or group comprising a silicon atom directly bonded to a hydrogen atom (for example, the hydrosilyl moiety can be of formula -Si(R)3-p(H) p , where p is an integer of 1, 2, or 3 and R is a hydrolyzable or non- hydrolyzable group (preferably, non-hydrolyzable) such as alkyl or aryl);
  • hydroxysilyl refers to a monovalent moiety or group comprising a silicon atom directly bonded to a hydroxyl group (for example, the hydroxysilyl moiety can be of formula -Si(R)3_ p (OH) p where p is an integer of 1, 2, or 3 and R is a hydrolyzable or non- hydrolyzable group (preferably, non-hydrolyzable) such as alkyl or aryl);
  • isocyanato means a monovalent group or moiety of formula -NCO
  • mercapto means a monovalent group or moiety of formula -SH
  • oligomer means a molecule that comprises at least two repeat units and that has a molecular weight less than its entanglement molecular weight; such a molecule, unlike a polymer, exhibits a significant change in properties upon the removal or addition of a single repeat unit;
  • oxy means a divalent group or moiety of formula -0-;
  • perfluoro- (for example, in reference to a group or moiety, such as in the case of "perfluoroalkylene” or “perfluoroalkyl” or “perfluorocarbon") or “perfluorinated” means completely fluorinated such that, except as may be otherwise indicated, there are no carbon-bonded hydrogen atoms replaceable with fluorine;
  • polysilazane refers to compounds having at least one of a linear, branched, or cyclic main chain or backbone comprising a plurality of Si— N linkages
  • polysiloxazane refers to compounds having at least one of a linear, branched, or cyclic main chain or backbone comprising both Si— N and Si— O linkages; for simplicity, in this patent application, “polysilazane” also includes “polysiloxazane” and
  • polyureasilazane refers to compounds having at least one of a linear, branched, or cyclic main chain or backbone comprising a plurality of Si— N linkages and having at least one carbonyl group bonded to each of two nitrogen atoms.
  • Compounds suitable for use as component (a) of the curable composition of the invention include inorganic compounds and organic compounds (preferably, inorganic compounds) comprising reactive silane functionality comprising at least one hydrosilyl moiety (that is, a monovalent moiety comprising a hydrogen atom bonded directly to a silicon atom).
  • the compounds can be small molecules, oligomers, polymers, or a combination thereof.
  • the compounds are polymers, which can be linear, branched, or cyclic.
  • Useful polymers include those that have random, alternating, block, or graft structures, or a combination thereof.
  • component (a) can vary widely, depending upon, for example, the molecular weight and the reactive silane functionality of component (b) and the properties desired for the curable and/or cured composition.
  • component (a) or component (b) has an average reactive silane functionality of at least three, and the other of the two components (a) and (b) has an average reactive silane functionality of at least two, so as to enable the formation of a crosslinked network.
  • a class of useful compounds includes those that can be represented by the following general formula:
  • each G is independently a divalent linking group
  • each R is independently selected from alkyl (preferably, having 1 to about 4 carbon atoms), acyl (preferably, having 1 to about 3 carbon atoms), cycloalkyl, aryl (preferably, phenyl), heteroalkyl, heterocycloalkyl, heteroaryl, hydroxyl, triorganosiloxy (- OSi(R')
  • Heteroatoms in A, G. and/or R can include oxygen, sulfur, nitrogen, phosphorus, and combinations thereof (preferably, oxygen, sulfur, and combinations thereof; more preferably, oxygen).
  • R and/or G can contain fluorine, provided that it is separated from silicon by at least two carbon atoms.
  • A is a polymeric radical (more preferably, selected from polysiloxane, polyacrylate, polyolefm, polyether, polyester, fluorinated polysiloxane, fluorinated or perfluorinated polyacrylate, fluorinated or perfluorinated polyolefm, fluorinated or perfluorinated polyether, fluorinated or perfluorinated polyester, and combinations thereof; even more preferably, selected from polysiloxane, polyether, polyacrylate, fluorinated polysiloxane, fluorinated or perfluorinated polyether, fluorinated or perfluorinated polyacrylate, and combinations thereof; most preferably selected from polysiloxane, fluorinated polysiloxane, and combinations thereof).
  • R is preferably alkyl (more preferably, methyl), and p is preferably equal to one.
  • the compounds useful as component (a) can be used in the curable composition of the invention singly or in the form of mixtures of different compounds.
  • the compounds can be prepared by known synthetic methods, and some (for example, silicone hydrides) are commercially available.
  • reactive silane functionality can be introduced to inorganic or organic compounds (for example, polymers) by reaction (for example, by free radical addition) of a compound having at least one unsaturated (for example, vinyl) group with a compound having both a mercapto group and reactive silane functionality.
  • An inorganic or organic compound having at least one isocyanato group can also be reacted with a compound having both an active hydrogen-containing group and reactive silane functionality.
  • the reactive silane functionality can be introduced by such methods at a terminus of a polymer's main chain, at the terminus of a side chain, and/or at one or more non-terminal positions along the main or side chain(s), depending upon the nature of component (b) and the properties desired for the curable and/or cured composition.
  • hydrosilyl-functional compounds include the following (wherein Me is methyl):
  • Me 3 SiO(Me2SiO) m (MeHSiO) adjoinSiMe3 (for example, having a percentage of -MeHSiO- units of 0.5 to 55 and a MW of 900 to 65,000),
  • Me 3 SiO(MeHSiO) n SiMe 3 (for example, having a MW of 1400 to 2400),
  • HMe 2 SiC 3 H 6 OCH 2 R f H 2 OC 3 H6SiMe 2 H (for example, wherein R f is C n F 2n wherein n is an integer of 1 to 12 or R f is (C n F 2n O)C n F 2n wherein n is an integer of 1+2, 2, or 3; such materials can be made, for example, by platinum-catalyzed condensation of excess SiMe 2 H 2 with an olefin or by condensation of SiMe 2 HCl with olefins, followed by reduction of the chloride with tributyltin hydride),
  • HMe 2 SiOSiMe 2 C 3 H 6 OCH 2 R f CH 2 0C 3 H 6 SiMe 2 OSiMe 2 H (for example, wherein R f is C n F2n wherein n is an integer of 1 to 12 or Rf is (C n F2 n O)C n F2 n wherein n is an integer of 1+2, 2, or 3; such materials can be made from olefins by first condensing excess SiMe 2 HCl and hydrolyzing with water to form a diol of component (b) structure (as described below), then condensing with SiMe 2 Cl 2 and reducing),
  • n is an integer of 2 to about
  • Preferred hydrosilyl-functional compounds include the following (wherein Me is methyl):
  • Me 3 SiO(Me 2 SiO) m (MeHSiO) gripSiMe 3 (for example, having a percentage of -MeHSiO- units of 0.5 to 55 and a MW of 900 to 65,000),
  • Me 3 SiO(MeHSiO) n SiMe 3 (for example, having a MW of 1400 to 2400),
  • Compounds suitable for use as component (b) of the curable composition of the invention include inorganic compounds and organic compounds (preferably, inorganic compounds) comprising reactive silane functionality comprising at least one hydroxysilyl moiety (that is, a monovalent moiety comprising a hydroxyl group bonded directly to a silicon atom).
  • the compounds can be small molecules, oligomers, polymers, or a combination thereof.
  • the compounds are polymers, which can be linear, branched, or cyclic.
  • Useful polymers include those that have random, alternating, block, or graft structures, or a combination thereof.
  • the molecular weight and the reactive silane functionality can vary widely, depending upon, for example, the molecular weight and the reactive silane functionality of component (a) and the properties desired for the curable and/or cured composition.
  • component (a) (the compound comprising at least one hydrosilyl moiety) is an organic polymer
  • component (b) (the compound comprising at least one hydroxysilyl moiety) is different from component (a) and is not generated in situ (that is, in the presence of components (a) and (c)) by hydrolysis of component (a).
  • component (a) is a compound other than an organic polymer
  • a single compound comprising both hydrosilyl and hydroxysilyl moieties and, optionally, being generated in situ
  • a class of useful compounds includes those that can be represented by the following general formula:
  • A-[G-Si(R) 3 - p -(OH) p ] m (II) wherein A, G, p, and m are as defined above for Formula (I) and each R (which can optionally contain at least one heteroatom, as defined above for Formula (I)) is independently selected from alkyl (preferably, having 1 to about 4 carbon atoms), acyl (preferably, having 1 to about 3 carbon atoms), cycloalkyl, aryl, heteroalkyl,
  • heterocycloalkyl heteroaryl, hydrogen, triorganosiloxy (-OSi(R') 3 , wherein R' is an organic or heteroorganic group; preferably, a group having 1 to about 20 carbon atoms), and combinations thereof.
  • R is preferably alkyl (more preferably, methyl).
  • the compounds useful as component (b) can be used in the curable composition of the invention singly or in the form of mixtures of different compounds.
  • the compounds can be prepared by known synthetic methods, and some (for example, silicone diols) are commercially available. Synthetic methods analogous to those described above for component (a) can be utilized.
  • Reactive silane functional polymers for example, reactive silane functional poly(meth)acrylates
  • hydroxysilyl-functional compounds include the following (wherein Me is methyl):
  • Bases suitable for use as component (c) of the curable composition of the invention include amidines, guanidines (including substituted guanidines such as biguanides), phosphazenes, proazaphosphatranes (also known as Verkade's bases), and combinations thereof.
  • bases can be prepared by known synthetic methods, and some are commercially available.
  • Self-protonatable forms of the bases for example, aminoacids such as arginine
  • Preferred bases include amidines, guanidines, and combinations thereof (more preferably, amidines and combinations thereof; most preferably, cyclic amidines and combinations thereof).
  • the bases of the listed structural classes can effectively catalyze reaction between components (a) and (b), as described above.
  • the bases can be used in the curable composition singly (individually) or in the form of mixtures of one or more different bases (including bases from different structural classes).
  • the base(s) can be present in photolatent form (for example, in the form of an activatable composition that, upon exposure to radiation or heat, generates the base(s) in situ).
  • Useful amidines include those that can be represented by the following general formula: wherein Rl, R2, R3, and R4 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups (for example, comprising nitrogen, oxygen, phosphorus, or sulfur in the form of groups or moieties that do not contain acid functionality such as carboxylic or sulfonic), and combinations thereof; and wherein any two or more of Rl, R2, R3, and R4 optionally can be bonded together to form a ring structure (preferably, a five-, six-, or seven-membered ring; more preferably, a six- or seven-membered ring).
  • the organic and heteroorganic groups preferably have from 1 to about 20 carbon atoms (more preferably, from 1 to about 10 carbon atoms; most preferably, from 1 to about 6 carbon atoms).
  • R4 is not hydrogen.
  • Amidines comprising at least one ring structure that is, cyclic amidines
  • Cyclic amidines comprising two ring structures that is, bicyclic amidines
  • useful amidine compounds include 1 ,2-dimethyl- 1 ,4,5 ,6-tetrahydropyrimidine, 1 -ethyl-2-methyl- 1 ,4,5 ,6-tetrahydropyrimidine, 1 ,2-diethyl- 1 ,4,5 ,6-tetrahydropyrimidine, 1 -n-propyl-2-methyl- 1 ,4,5 ,6-tetrahydropyrimidine, 1 - isopropyl-2-methyl- 1 ,4,5 ,6-tetrahydropyrimidine, 1 -ethyl-2-n-propyl- 1 ,4,5 ,6- tetrahydropyrimidine, l-ethyl-2-isopropyl-l,4,5,6-tetrahydropyrimidine, DBU (that is, 1,8- diazabicyclo[5.4.0]-7-undecene), DBN (that is, l,5-diazabicyclo[4.3.0
  • Preferred amidines include l,2-dimethyl-l,4,5,6-tetrahydropyrimidine, DBU (that is, 1,8- diazabicyclo[5.4.0]-7-undecene), DBN (that is, l,5-diazabicyclo[4.3.0]-5-nonene), 2,3,6,7- tetrahydro-5H-thiazolo[3,2-a]pyrimidine, 3,4,7,8-tetrahydro-2H,6H-pyrimido[2,l-b]-[l,3]- thiazine, 2,3,6,7-tetrahydroimidazo[2,l-b]thiazine, and combinations thereof, with DBU, DBN, and combinations thereof being more preferred and DBU most preferred.
  • Useful guanidines include those that can be represented by the following general formula:
  • Rl, R2, R3, R4, and R5 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups (for example, comprising nitrogen, oxygen, phosphorus, or sulfur in the form of groups or moieties that do not contain acid functionality such as carboxylic or sulfonic), and combinations thereof; and wherein any two or more of Rl, R2, R3, R4, and R5 optionally can be bonded together to form a ring structure (preferably, a five-, six-, or seven-membered ring; more preferably, a five- or six-membered ring; most preferably, a six-membered ring).
  • the organic and heteroorganic groups preferably have from 1 to about 20 carbon atoms (more preferably, from 1 to about 10 carbon atoms; most preferably, from 1 to about 6 carbon atoms).
  • R5 is not hydrogen.
  • Guanidines comprising at least one ring structure (that is, cyclic guanidines) are generally preferred. Cyclic guanidines comprising two ring structures (that is, bicyclic guanidines) are more preferred.
  • guanidine compounds include 1- methylguanidine, 1-n-butylguanidine, 1,1-dimethylguanidine, 1,1-diethylguanidine, 1,1,2- trimethylguanidine, 1,2,3-trimethylguanidine, 1,3-diphenylguanidine, 1,1,2,3,3- pentamethylguanidine, 2-ethyl- 1 , 1 ,3 ,3-tetramethylguanidine, 1 , 1 ,3 ,3-tetramethyl-2-n- propylguanidine, 1 , 1 ,3 ,3-tetramethyl-2-isopropylguanidine, 2-n-butyl- 1 , 1 ,3 ,3- tetramethylguanidine, 2-tert-butyl-l , 1 ,3,3-tetramethylguanidine, 1 ,2,3- tricyclohexylguanidine, TBD (that is, l,5,7-triazabicyclo
  • Preferred guanidines include TBD (that is, l,5,7-triazabicyclo[4.4.0]dec-5-ene), MTBD (that is, 7- methyl-1 ,5,7-triazabicyclo[4.4.0]dec-5-ene), 2-tert-butyl-l , 1 ,3,3-tetramethylguanidine, and combinations thereof. More preferred are TBD, MTBD, and combinations thereof.
  • the amidines and guanidines can be selected from those exhibiting a pH value lower than 13.4 when measured according to JIS Z 8802 (for example, 1,3- diphenylguanidine, DBU, DBN, or a combination thereof; preferably, DBU, DBN, or a combination thereof).
  • component (a) is an organic polymer
  • such lower pH amidines and guanidines can be selected and can function effectively.
  • the referenced method for determining the pH of aqueous solutions, JIS Z 8802 is carried out by first preparing an aqueous solution of base by adding 5 millimoles of base to 100 g of a mixed solvent composed of isopropyl alcohol and water in a weight ratio of 10:3. The pH of the resulting solution is then measured at 23°C using a pH meter (for example, a Horiba Seisakusho Model F-22 pH meter).
  • Useful phosphazenes include those that can be represented by the following general formula:
  • Rl, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups (for example, comprising nitrogen, oxygen, phosphorus, or sulfur in the form of groups or moieties that do not contain acid functionality such as carboxylic or sulfonic), and combinations thereof; and wherein any two or more of Rl, R2, R3, R4, R5, R6, and R7 optionally can be bonded together to form a ring structure (preferably, a five-, six-, or seven-membered ring; more preferably, a five- or six-membered ring; most preferably, a six-membered ring).
  • the organic and heteroorganic groups preferably have from 1 to about 20 carbon atoms (more preferably, from 1 to about 10 carbon atoms; most preferably, from 1 to about 6 carbon atoms).
  • R7 is not hydrogen.
  • Preferred phosphazenes include 2-tert-butylimino- 2-diethylamino-l ,3-dimethylperhydro-l ,3,2-diazaphosphorine, phosphazene base Pi-t-Bu- tris(tetramethylene), phosphazene base P 4 -t-Bu, and combinations thereof.
  • Useful proazaphosphatrane bases include those that represented by the following general formula: wherein Rl, R2, and R3 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups (for example, comprising nitrogen, oxygen, phosphorus, or sulfur in the form of groups or moieties that do not contain acid functionality such as carboxylic or sulfonic), and combinations thereof (less preferably hydrogen).
  • the organic and heteroorganic groups preferably have from 1 to about 20 carbon atoms (more preferably, from 1 to about 10 carbon atoms; most preferably, from 1 to about 6 carbon atoms).
  • useful proazaphosphatrane compounds include
  • the curable composition of the invention can be prepared by combining components (a), (b), and (c) in essentially any order (preferably, with agitation or stirring). Preferably, components (a) and (b) are combined initially, followed by addition of component (c).
  • the composition can be maintained as a relatively shelf-stable, 2-part system (for example, by keeping component (c) separate from the other two components), if desired, but a 1-part system (comprising all three components) can also be stable for periods of up to, for example, about two weeks in dry solvent (a relatively long pot life), prior to coating or other application of the composition.
  • the relative amounts of components (a) and (b) can vary widely, depending upon their nature and the desired properties of the curable and/or cured composition. Although stoichiometry prescribes a 1 : 1 molar ratio of reactive silane functionality (for example, one mole of hydrosilyl moieties for every mole of hydroxysilyl moieties), in practice it can be useful to have a deficiency or an excess of hydrosilyl functionality (for example, this can be useful when cure inhibitors are present). Molar ratios (of hydrosilyl moieties to hydroxysilyl moieties) up to, for example, about 8: 1 or about 13: 1 or even as high as about 35: 1 can be useful.
  • Component (c) (the base catalyst(s)) can be present in the curable composition in amounts ranging, for example, from about 0.1 to about 10 weight percent (preferably, from about 0.1 to about 5 weight percent; more preferably, from about 0.5 to about 2 weight percent), based upon the total weight of components (a), (b), and (c).
  • the curable composition comprises at least one solvent or diluent to aid in storage stability, mixing, and/or coating, particularly when components (a) and (b) are oligomeric or polymeric.
  • Suitable solvents for use in the curable composition of the invention include aprotic solvents such as aromatic solvents (for example, xylene, toluene, 1 ,2-dichlorobenzene, 1,3-dichlorobenzene, 1 ,4-dichlorobenzene, and the like, and mixtures thereof), ketones (for example, methyl ethyl ketone (MEK), cyclohexanone, and the like, and mixtures thereof), alkyl esters (for example, ethyl acetate, butyl acetate, and the like, and mixtures thereof), alkanes (for example, heptane, isoparaffinic hydrocarbons, and the like, and mixtures thereof), ethers (for example, t-butyl methyl
  • solvents include aromatic solvents, alkanes, ketones, and mixtures thereof; with xylene, heptane, methyl ethyl ketone, and mixtures thereof being more preferred and heptane, methyl ethyl ketone, and mixtures thereof most preferred.
  • compositions can comprise conventional additives such as, for example, catalysts
  • condensation catalysts such as tin catalysts, which can be added as co-catalysts if desired
  • initiators including conventional condensation catalysts such as tin catalysts, which can be added as co-catalysts if desired
  • surfactants including conventional condensation catalysts such as tin catalysts, which can be added as co-catalysts if desired
  • stabilizers including conventional condensation catalysts such as tin catalysts, which can be added as co-catalysts if desired
  • anti-oxidants such as tin catalysts, which can be added as co-catalysts if desired
  • adhesion promoters such as tackifiers
  • plasticizers including conventional condensation catalysts such as tin catalysts, which can be added as co-catalysts if desired
  • release modifiers including conventional condensation catalysts such as tin catalysts, which can be added as co-catalysts if desired
  • dyes including conventional condensation catalysts such as t
  • the curable composition of the invention can be used in various different applications.
  • the composition can be used in molding applications
  • composition(s) also can be used as sealants, adhesives, release coatings, surface treatments, rubbers, hardcoats, softcoats, and the like.
  • fluorinated surface treatments a degree of hydrophobicity and/or oleophobicity can be imparted to a variety of substrates (for example, for surface protection or to enhance ease of cleaning).
  • both components (a) and (b) of the curable composition are difunctional
  • application of the base catalyst can result in a chain extension reaction (for example, for silicones: H(Me 2 SiO) friendshipSiMe 2 H + HO(SiMe 2 0) ceremoniH ⁇ -[0(SiMe 2 0) 2n ] x -).
  • a relatively small amount of a multifunctional component for example, Me 3 SiO(MeHSiO) n SiMe 3
  • the resulting lightly-branched polymer can be an elastomer and can be compounded with MQ resin(s) to make pressure-sensitive adhesives.
  • Use of a larger amount of multifunctional component can provide a crosslinked coating.
  • Polyperfluoroethers can be chain-extended with minimally polar connecting groups, optionally crosslinking as above (for example,
  • the curable composition of the invention (or, alternatively, its components) can be applied to at least a portion of at least one major surface of a substrate (for example, a sheet, fiber, or shaped object) by essentially any known or hereafter-developed application method, so as to form a variety of different coated articles.
  • a substrate for example, a sheet, fiber, or shaped object
  • the composition can be applied in essentially any manner (and with essentially any thickness) that can form a useful coating.
  • Useful application methods include coating methods such as dip coating, spin coating, spray coating, wiping, roll coating, and the like, and combinations thereof.
  • the composition can be applied in neat form or in the form of solvent solutions (for example, in solvents such as alkyl esters, ketones, alkanes, aromatics, and the like, and mixtures thereof).
  • solvent such as alkyl esters, ketones, alkanes, aromatics, and the like, and mixtures thereof.
  • useful concentrations of the composition can vary over a wide range (for example, from about 1 to about 90 weight percent), depending upon the viscosity of the composition, the application method utilized, the nature of the substrate, and the desired properties.
  • Substrates suitable for use in preparing the coated articles include those having at least one surface comprising a material that is solid and preferably substantially inert to any coating or application solvent that is used.
  • the curable composition can adhere to the substrate surface through chemical interactions, physical interactions, or a combination thereof (more preferably, a combination thereof).
  • Suitable substrates can comprise a single material or a combination of different materials and can be homogeneous or heterogeneous in nature.
  • Useful heterogeneous substrates include coated substrates comprising a coating of a material (for example, a metal or a primer) borne on a physical support (for example, a polymeric film).
  • Useful substrates include those that comprise wood, glass, minerals (for example, both man-made ceramics such as concrete and naturally-occurring stones such as marble and the like), polymers (for example, polycarbonate, polyester, polyacrylate, and the like), metals (for example, copper, silver, gold, aluminum, iron, stainless steel, nickel, zinc, and the like), metal alloys, metal compounds (for example, metal oxides and the like), leather, parchment, paper, Kraft paper, polyolefm-coated paper, textiles, painted surfaces, and combinations thereof.
  • Preferred substrates include glass, minerals, wood, metals, metal alloys, metal compounds, polymers, and combinations thereof (more preferably, metals, metal alloys, metal compounds, polymers, and combinations thereof).
  • the substrate is a polar substrate (for example, having a surface energy of greater than or equal to about 30 dynes per centimeter).
  • the curable composition can be cured by concentration (for example, by allowing solvent evaporation).
  • concentration for example, by allowing solvent evaporation).
  • the preferred curing conditions will vary, depending upon the particular application and its accompanying requirements and conditions. Moisture can be present but generally is not necessary.
  • Cure generally can be effected at temperatures ranging from room temperature (for example, about 20-23°C) up to about 150°C or more (preferably, temperatures of about 20°C to about 125°C; more preferably, about 20°C to about 100°C; most preferably, about 20°C to about 80°C). Curing times can range from a few minutes (for example, at room temperature) to hours (for example, under low catalyst conditions).
  • the starting materials were 3,4,5,6-tetrahydro-2-pyrimidinethiol and 1 ,3-dibromopropane (both obtained from Aldrich Chemical Company, Milwaukee, WI), and the remainder of the preparation process was essentially the same as described above.
  • the resulting crude product was 93 percent (%) pure and was used directly for catalysis.
  • the starting materials were 2- imidazolidinethione and 1,3-dibromopropane (both obtained from Aldrich Chemical Company, Milwaukee, WI), and the remainder of the preparation process was
  • hydroxysilyl-functional siloxane polymer(s) (said to comprise hydroxyl-terminated polydimethylsiloxane) and hydrosilyl-functional polysiloxane crosslinker (said to comprise poly(methyl)(hydrogen)siloxane) in xylene (a premium release coating composition obtained from Dow Corning Corporation, Midland, MI, under the trade designation Syl-OffTM 292) was diluted to 10 weight percent solids with heptane.
  • the resulting coated 3 SAB PET samples were set aside at room temperature (about 23°C) and their curing status (level of tackiness) was monitored. A coated sample was deemed cured if the coating solidified within 5 minutes. A coated sample was deemed not cured if the coating did not solidify and remained tacky for at least 24 hours at room temperature. The results are shown in Table 1 below. Table 1.
  • the coated film was taped to a cardboard and then left under ambient conditions (about 23 °C) for at least 3 minutes. After 2 minutes, the coating was not greasy but could be scuffed with a light finger rub. After 2 minutes and 40 seconds, the coating was firm and could not be scuffed with a finger rub. The coated film was then placed in a Despatch oven (Model RFD2-19-2E, commercially available from Despatch Industries,
  • the coated film was taped to a cardboard and then left under ambient conditions (about 23°C) for at least 3 minutes. After 1 minute and 30 seconds, the coating was dry and felt cured to the touch. The coated film was then placed in a Despatch oven with the heat turned off and the fans turned on for 3 minutes in order to remove the solvents.
  • the coated film was taped to a cardboard and then left under ambient conditions (about 23°C) for at least 3 minutes. After 1 minute and 15 seconds, the coating was dry and felt cured to the touch. The coated film was then placed in a Despatch oven with the heat turned off and the fans turned on for 3 minutes in order to remove the solvents.
  • TTP 2,8,9-Triisopropyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane
  • 56.45 g heptane 14.1 g MEK
  • 29.4 g of Syl-OffTM 292 release coating composition were weighed into a 240 mL glass jar. The glass jar was shaken until the contents were homogeneous. The homogeneous mixture was coated on the primed side of a 50 micrometers thick 3 SAB PET film and left in the hood to air dry (at about 23°C). The coated film was dry to the touch and anchored well within minutes.
  • methyl(perfluorobutylethyl), methylhydrogen siloxane obtained from Dow Corning Corporation, Midland, MI, under the trade designation Syl-OffTM Q2-7560
  • sil-OffTM Q2-7560 0.8 g of hydroxyl-terminated polydimethylsiloxane
  • PDMS hydroxyl-terminated polydimethylsiloxane
  • MW molecular weight
  • GELEST DMS-S12 hydroxyl-terminated polydimethylsiloxane
  • 8.86 g of heptane 8.86 g of heptane were mixed to prepare a 10 weight percent solids solution.
  • 0.04 g of DBU catalyst was added to the solution. After mixing, the resulting fresh solution was coated on the primed side of a 50 micrometers thick 3 SAB PET film. The coating was dried and cured at room temperature (about 23°C; cured after about 6 minutes).
  • Example 11 (comprising 3.3 weight percent DBU) was used for a bath life study.
  • the viscosity of the coating solution was measured periodically using a viscometer (Model DV-II+ made by Brookfield Engineering Laboratories, Inc., Middleboro, MA) to determine if and/or when the solution would congeal.
  • the solution was adversely affected 15 hours after solution preparation.
  • the coating solutions of Examples 11, 12, and 13 were allowed to age at room temperature (about 23°C), and, periodically (at 0, 1, 2, 4, and 6 hours of aging), each solution was coated on the primed side of a 50 micrometers thick 3 SAB PET film.
  • the cure time defined as the elapsed time needed so that the coating could not be rubbed off by finger, was determined for each coating (for each coating solution and for each aging time). The resulting cure times are shown in Table 2 below.
  • a bicyclic isothiourea catalyst (2,3,6,7-tetrahydro-5H-thiazolo[3,2- ajpyrimidine, prepared essentially as described above) was added to 3 g of a 30 weight percent solids dispersion of a blend of reactive hydroxysilyl-functional siloxane polymer(s) (said to comprise hydroxyl-terminated polydimethylsiloxane) and
  • hydrosilyl-functional polysiloxane crosslinker (said to comprise
  • Example 19 the resulting mixture was diluted to 10 weight percent solids by adding 6.81 g of toluene and then thoroughly mixing.
  • Example 20 the resulting mixture was diluted to 5 weight percent solids by adding 6.4 g of toluene and then thoroughly mixing.
  • 3 SAB PET film obtained from Mitsubishi Polyester Film, Greer, SC, under the trade designation HostaphanTM 3 SAB, referred to hereinafter as 3 SAB PET film, which has one side chemically treated or primed to improve the adhesion of silicone coatings
  • the resulting coated 3 SAB PET films were set aside at room temperature (about 23°C) and their curing status (level of tackiness) was monitored. The films were deemed cured if the coatings solidified within 5 minutes. Results are shown in Table 3 below.
  • Examples 21-22 were carried out in essentially the same manner as Examples 19-20 above, except that different bicyclic isothiourea catalysts were utilized.
  • the bicyclic isothiourea catalyst was 3,4,7,8-tetrahydro-2H,6H- pyrimido[2,l-b]-[l,3]-thiazine
  • the bicyclic isothiourea catalyst was 2,3,6,7-tetrahydroimidazo[2,l-b]thiazine (both catalysts having been prepared essentially as described above).
  • the resulting coated films were deemed cured if the coatings solidified within 5 minutes. Results are shown in Table 3 below.
  • a reaction mixture containing triethyl silanol (TES), hydrosilyl-functional polysiloxane crosslinker (obtained from Dow Corning Corporation, Midland, MI, under the trade designation Syl-OffTM 7048, said to comprise poly(methyl)(hydrogen)siloxane), and DBU was prepared by mixing 600 microliters Syl-OffTM 7048, 260 microliters TES, 6 microliters DBU, and 134 microliters of deuterated toluene.
  • the mole ratio of TES to Syl- OffTM 7048 was about 20:80, providing an excess of Si-H relative to Si-OH.
  • DBU was present in an amount equivalent to about 1 percent by weight of Syl-OffTM 7048
  • Nuclear magnetic resonance (NMR) spectra of the reaction mixture were then acquired on a BRUKERTM AVANCETM 500 MHz NMR spectrometer equipped with a broadband cryoprobe (obtained from Bruker Corporation, Billerica, MA).

Abstract

A curable composition comprises (a) at least one inorganic or organic compound comprising reactive silane functionality comprising at least one hydrosilyl moiety; (b) at least one inorganic or organic compound comprising reactive silane functionality comprising at least one hydroxysilyl moiety, the hydroxysilyl moiety optionally being generated in situ by hydrolysis of at least one hydrosilyl moiety; and (c) at least one base selected from amidines, guanidines, phosphazenes, proazaphosphatranes, and combinations thereof; with the proviso that, when component (a) is an organic polymer, then component (b) is different from component (a) and is not generated in situ by hydrolysis of component (a).

Description

CURABLE COMPOSITION COMPRISING DUAL REACTIVE
SILANE FUNCTIONALITY
STATEMENT OF PRIORITY
This application claims the priorities of U.S. Provisional Applications Nos.
61/359,985, filed June 30, 2010; 61/360,019, filed June 30, 2010; and 61/423,119, filed December 15, 2010; the contents of which are hereby incorporated by reference.
FIELD
This invention relates to curable compositions comprising reactive silane functionality and, in other aspects, to articles comprising the compositions and to processes for curing the compositions.
BACKGROUND
Moisture-curable compositions cure in the presence of moisture to form
crosslinked materials such as adhesives, sealants, and coatings that are useful in many industries. The moisture for curing is typically obtained from the atmosphere or from a substrate to which the composition has been applied, although it can also be added to the composition (for example, to enable curing in depth or in confinement).
Moisture-curable compositions usually comprise polymers having groups (for example, alkoxysilyl or acyloxysilyl moieties) that can react in the presence of moisture to form cured (that is, crosslinked) materials. A wide variety of polymers can be rendered moisture curable, including polyolefms, polyesters, polyethers, polyacrylates, polyvinyl chloride, polyphosphazenes, polysiloxanes, polysulfides, block copolymers, and fluorinated derivatives thereof, the particular polymer being selected based on the intended use. For example, a polysiloxane or fluorinated polyether is often selected to provide release coatings suitable for use with pressure-sensitive adhesives.
Moisture-curable compositions comprising alkoxysilyl or acyloxysilyl
functionality typically cure in two reactions. In the first reaction, the alkoxysilyl or acyloxysilyl groups hydrolyze in the presence of moisture and a catalyst to form silanol compounds having hydroxysilyl groups. In the second reaction, the hydroxysilyl groups condense with other hydroxysilyl, alkoxysilyl, or acyloxysilyl groups in the presence of a catalyst to form— Si— O— Si— linkages. The two reactions occur essentially simultaneously upon generation of the silanol compound. Commonly used catalysts for the two reactions include Bronsted and Lewis acids. A single material can catalyze both reactions.
Preferably, the hydrolysis and condensation reactions proceed quickly after the moisture-curable composition has been applied, for example, to a substrate. At the same time, however, the reactions must not occur prematurely, for example, during processing or storage.
A good balance between these properties is often difficult to obtain, as rapid reactivity and storage stability are opposite properties to each other. For example, highly active catalysts such as tetraalkyl titanate esters rapidly accelerate the moisture-curing reaction but, at the same time, can make it difficult to process the materials without risking premature gelation in feed tanks, coating equipment, and other manufacturing and handling apparatus. Control of the amount of moisture can be critical, with too little moisture potentially resulting in slow or incomplete cure and too much moisture resulting in premature cure.
A variety of approaches have been used for providing moisture-curable
compositions that have acceptable cure rates without processing and storage difficulties. For example, two-part systems have been developed (one part comprising a functional polymer and the other part comprising a catalyst), with the two parts being mixed immediately prior to use. While this approach has been useful in small-scale applications, it has been less efficient for large-scale manufacturing, where delays caused by having to mix the two parts have been undesirable. Furthermore, coating operations must be completed expeditiously before the composition cures in the pot, and this has been difficult when working with large surface area substrates or a large volume of
composition.
Ammonium salt catalysts have been developed that are inactive until heated sufficiently to liberate an acid compound that initiates the moisture curing reaction.
Liberation of the acid also generates an amine, however, that must be removed by evaporation. In addition, the heat used to activate the catalyst can damage heat-sensitive substrates onto which the composition has been applied.
Other materials (for example, onium salts such as sulfonium and iodonium salts) have been used to generate acid species in situ upon irradiation (for example, irradiation with ultraviolet light). Such materials have not required heat activation and therefore have enabled the use of heat-sensitive substrates without damage (and without the production of undesirable species requiring removal), but the materials have been relatively expensive, have exhibited cure inhibition on some substrates, and have required moisture control and the use of coating equipment with irradiation capability.
Conventional tin catalysts such as dibutyl tin dilaurate can provide stable curable compositions that can be processed and coated without premature gelation. In addition to typical moisture-curable systems, it has been found that curable compositions comprising dual reactive silane functionality in the form of hydrosilyl and hydroxysilyl groups (dehydrogenatively-curable systems) can be cured by using tin catalysts. The
compositions have been widely used for pressure-sensitive adhesive and mold release applications but have sometimes suffered from relatively short pot lives. In addition, the use of tin catalysts is becoming particularly problematic because the organotin compounds generally employed as catalysts are now considered to be toxicologically objectionable.
Acceleration of cure has been achieved by the use of compounds such as substituted guanidines, diorganosulfoxides, imidazoles, amidines, and amines in combination with tin catalysts in room temperature vulcanizing silicone compositions. Amine compounds including amidines have also been proposed for use in the absence of tin catalysts for curing moisture-curable, silyl-functional organic polymers, but practical curability of alkoxysilyl-functional polymers and acceptable adhesion to substrates were achieved only with strongly basic amines (those exhibiting a pH of at least 13.4 in aqueous solution).
SUMMARY
Thus, we recognize that there exists an ongoing need for curable compositions that can provide acceptable cure rates without significant processing and storage difficulties (for example, due to premature gelation). Preferably, these compositions will be efficiently processable (for example, without the need for mixing of a two-part system prior to cure), will employ catalysts that do not generate species requiring removal, and/or will not require heat activation (so as to enable curing at relatively low temperatures and/or the use of heat-sensitive substrates). Ideally, the compositions will employ catalysts that are relatively non-toxic, provide compositions that are relatively stable in solution but relatively fast-curing upon drying, effective in relatively low concentrations, and/or effective under relatively low (or no) moisture conditions.
Briefly, in one aspect, this invention provides a curable composition comprising dual reactive silane functionality. The curable composition comprises
(a) at least one inorganic or organic compound comprising reactive silane functionality comprising at least one hydrosilyl moiety (that is, a monovalent moiety comprising a hydrogen atom bonded directly to a silicon atom);
(b) at least one inorganic or organic compound comprising reactive silane functionality comprising at least one hydroxysilyl moiety (that is, a monovalent moiety comprising a hydroxyl group bonded directly to a silicon atom), the hydroxysilyl moiety optionally being generated in situ by hydrolysis of at least one hydrosilyl moiety; and
(c) at least one base selected from amidines, guanidines, phosphazenes,
proazaphosphatranes, and combinations thereof;
with the proviso that, when component (a) (the compound comprising at least one hydrosilyl moiety) is an organic polymer, then component (b) (the compound comprising at least one hydroxysilyl moiety) is different from component (a) and is not generated in situ (that is, in the presence of components (a) and (c)) by hydrolysis of component (a). Preferably, the base comprises at least one amidine (most preferably, 1,8- diazabicyclo[5.4.0]-7-undecene (DBU)). The composition preferably further comprises at least one solvent (for example, an aprotic organic solvent such as heptane).
It has been discovered that, unlike standard amine bases such as 4,4'- trimethylenebis(l-methylpiperidine) (which are ineffective), the above-described bases can effectively catalyze the curing (apparently, by condensation) of compositions comprising reactive silane functionality in the form of hydrosilyl and hydroxysilyl moieties. The bases can provide relatively rapid cure (for example, upon removal of solvent curing can occur within periods of time as short as about 1 minute) even at temperatures as low as ambient (for example, about 23°C), without the need for heat activation, and can be effective in relatively small amounts (for example, at concentrations as low as about 0.5 weight percent or less, based upon the total weight of components (a), (b), and (c)). In spite of such effective curability, compositions comprising the bases can exhibit relatively good storage stability (for example, for a period of weeks in a closed container) and/or relatively long pot life (for example, on the order of 8 hours or more) in a variety of solvents (for example, heptane, methyl ethyl ketone, or a combination thereof), without the need for mixing of a two-part system immediately prior to use.
In surprising contrast with prior art compositions, the bases can be effective in the curable composition of the invention in the substantial absence of other condensation catalysts and/or in the substantial absence of moisture. The bases can be used as substitutes for conventional tin catalysts to provide organometallic catalyst-free, curable compositions. Unlike the conventional tin catalysts, at least some of the bases (for example, DBU) are relatively non-toxic and therefore suitable for use in preparing relatively environmentally friendly or "green" compositions.
The curable composition of the invention can be cured to provide crosslinked networks having properties that can be tailored to the requirements of various different applications (for example, by varying the natures, relative amounts, and degrees of reactive silane functionality of starting components (a) and (b)). Thus, the curable composition can be used to provide materials having a variety of bulk and/or surface properties for use in numerous applications (for example, for use as sealants, adhesives, release coatings, rubbers, hardcoats, softcoats, molded parts, and the like). The curable composition of the invention can be particularly useful in applications requiring control of surface properties (for example, hydrophilic or hydrophobic surface treatments and release coating applications), as the base catalysts do not appear to produce species requiring removal and, in some embodiments, the base catalysts are sufficiently volatile to be evaporated from the composition during processing, thereby leaving essentially no catalyst contamination in the cured material (in contrast with the metal contamination of conventional tin catalysts, which can be particularly problematic in the area of
electronics).
In view of the foregoing, at least some embodiments of the curable composition of the invention meet the above-described, ongoing need for curable compositions that can provide acceptable cure rates without significant processing and storage difficulties (for example, being relatively stable in solution but relatively fast-curing upon drying), while also being efficiently processable (for example, without the need for mixing of a two-part system prior to cure, for contaminant removal, and/or for heat activation). At least some embodiments of the curable composition also employ catalysts that are relatively nontoxic, while being effective in relatively low concentrations and/or under relatively low (or no) moisture conditions.
In another aspect, this invention also provides a curing process comprising
(a) providing the above-described curable composition of the invention; and
(b) allowing or inducing the curable composition to cure.
In yet another aspect, this invention provides an article comprising the above- described curable composition of the invention (for example, an article comprising at least one substrate having at least one major surface, the substrate bearing, on at least a portion of at least one major surface, the above-described curable composition of the invention).
DETAILED DESCRIPTION
In the following detailed description, various sets of numerical ranges (for example, of the number of carbon atoms in a particular moiety, of the amount of a particular component, or the like) are described, and, within each set, any lower limit of a range can be paired with any upper limit of a range. Such numerical ranges also are meant to include all numbers subsumed within the range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, and so forth).
As used herein, the term "and/or" means one or all of the listed elements or a combination of any two or more of the listed elements.
The words "preferred" and "preferably" refer to embodiments of the invention that may afford certain benefits under certain circumstances. Other embodiments may also be preferred, however, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
The term "comprises" and variations thereof do not have a limiting meaning where these terms appear in the description and claims.
As used herein, "a," "an," "the," "at least one," and "one or more" are used interchangeably.
The above "Summary of the Invention" section is not intended to describe every embodiment or every implementation of the invention. The detailed description that follows more particularly describes illustrative embodiments. Throughout the detailed description, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, a recited list serves only as a representative group and should not be interpreted as being an exclusive list.
Definitions
As used in this patent application:
"catenated heteroatom" means an atom other than carbon (for example, oxygen, nitrogen, or sulfur) that replaces one or more carbon atoms in a carbon chain (for example, so as to form a carbon-heteroatom-carbon chain or a carbon-heteroatom-heteroatom- carbon chain);
"cure" means conversion to a crosslinked polymer network (for example, through catalysis);
"fluoro-" (for example, in reference to a group or moiety, such as in the case of "fluoroalkylene" or "fluoroalkyl" or "fluorocarbon") or "fluorinated" means only partially fluorinated such that there is at least one carbon-bonded hydrogen atom;
"fluorochemical" means fluorinated or perfluorinated;
"heteroorganic" means an organic group or moiety (for example, an alkyl or alkylene group) containing at least one heteroatom (preferably, at least one catenated heteroatom);
"hydrosilyl" refers to a monovalent moiety or group comprising a silicon atom directly bonded to a hydrogen atom (for example, the hydrosilyl moiety can be of formula -Si(R)3-p(H)p , where p is an integer of 1, 2, or 3 and R is a hydrolyzable or non- hydrolyzable group (preferably, non-hydrolyzable) such as alkyl or aryl);
"hydroxysilyl" refers to a monovalent moiety or group comprising a silicon atom directly bonded to a hydroxyl group (for example, the hydroxysilyl moiety can be of formula -Si(R)3_p(OH)p where p is an integer of 1, 2, or 3 and R is a hydrolyzable or non- hydrolyzable group (preferably, non-hydrolyzable) such as alkyl or aryl);
"isocyanato" means a monovalent group or moiety of formula -NCO;
"mercapto" means a monovalent group or moiety of formula -SH;
"oligomer" means a molecule that comprises at least two repeat units and that has a molecular weight less than its entanglement molecular weight; such a molecule, unlike a polymer, exhibits a significant change in properties upon the removal or addition of a single repeat unit;
"oxy" means a divalent group or moiety of formula -0-;
"perfluoro-" (for example, in reference to a group or moiety, such as in the case of "perfluoroalkylene" or "perfluoroalkyl" or "perfluorocarbon") or "perfluorinated" means completely fluorinated such that, except as may be otherwise indicated, there are no carbon-bonded hydrogen atoms replaceable with fluorine;
"polysilazane" refers to compounds having at least one of a linear, branched, or cyclic main chain or backbone comprising a plurality of Si— N linkages;
"polysiloxazane" refers to compounds having at least one of a linear, branched, or cyclic main chain or backbone comprising both Si— N and Si— O linkages; for simplicity, in this patent application, "polysilazane" also includes "polysiloxazane" and
"polyureasilazane"; and
"polyureasilazane" refers to compounds having at least one of a linear, branched, or cyclic main chain or backbone comprising a plurality of Si— N linkages and having at least one carbonyl group bonded to each of two nitrogen atoms.
Component (a)
Compounds suitable for use as component (a) of the curable composition of the invention include inorganic compounds and organic compounds (preferably, inorganic compounds) comprising reactive silane functionality comprising at least one hydrosilyl moiety (that is, a monovalent moiety comprising a hydrogen atom bonded directly to a silicon atom). The compounds can be small molecules, oligomers, polymers, or a combination thereof. Preferably, the compounds are polymers, which can be linear, branched, or cyclic. Useful polymers include those that have random, alternating, block, or graft structures, or a combination thereof.
The molecular weight and the reactive silane functionality (including the number and nature of the hydrosilyl moieties) of component (a) can vary widely, depending upon, for example, the molecular weight and the reactive silane functionality of component (b) and the properties desired for the curable and/or cured composition. Preferably, either component (a) or component (b) has an average reactive silane functionality of at least three, and the other of the two components (a) and (b) has an average reactive silane functionality of at least two, so as to enable the formation of a crosslinked network.
A class of useful compounds includes those that can be represented by the following general formula:
A-[G-Si(R)3-p-(H)p]m (I) wherein A is an m-valent non-polymeric radical (optionally containing at least one heteroatom) selected from alkyl (preferably, having 1 to about 30 carbon atoms; more preferably, having about 12 to about 20 carbon atoms), fluoroalkyl (preferably, having 1 to about 12 carbon atoms; more preferably, having about 6 to about 10 carbon atoms), perfluoroalkyl (preferably, having 1 to about 12 carbon atoms; more preferably, having about 6 to about 10 carbon atoms), aryl, fluoroaryl, perfluoroaryl, cycloalkyl,
fluorocycloalkyl, perfluorocycloalkyl, and combinations thereof, or is an m-valent polymeric radical comprising an oligomer or polymer selected from polysiloxane, polyacrylate, polyolefm, polyether, polyester, polyurethane, polyphosphazene, fluorinated polysiloxane, fluorinated or perfluorinated polyacrylate, fluorinated or perfluorinated polyether, fluorinated or perfluorinated polyester, polysilazane, fluorinated polysilazane, and derivatives and combinations thereof; each G is independently a divalent linking group; each R is independently selected from alkyl (preferably, having 1 to about 4 carbon atoms), acyl (preferably, having 1 to about 3 carbon atoms), cycloalkyl, aryl (preferably, phenyl), heteroalkyl, heterocycloalkyl, heteroaryl, hydroxyl, triorganosiloxy (- OSi(R')3, wherein R' is an organic or heteroorganic group; preferably, a group having 1 to about 20 carbon atoms) and combinations thereof; each p is independently an integer of 1 , 2, or 3; and m is an integer that is greater than or equal to 1 (preferably, 1 to about 50; more preferably, 1 to about 5). Each divalent linking group, G, is preferably
independently selected from a covalent bond, oxy, diorganosiloxy, diheteroorganosiloxy, alkylene, arylene, heteroalkylene, heteroarylene, cycloalkylene, heterocycloalkylene, and combinations thereof (more preferably, selected from a covalent bond, oxy, alkylene, arylene, and combinations thereof). Heteroatoms (in A, G. and/or R) can include oxygen, sulfur, nitrogen, phosphorus, and combinations thereof (preferably, oxygen, sulfur, and combinations thereof; more preferably, oxygen). R and/or G can contain fluorine, provided that it is separated from silicon by at least two carbon atoms.
Preferably, A is a polymeric radical (more preferably, selected from polysiloxane, polyacrylate, polyolefm, polyether, polyester, fluorinated polysiloxane, fluorinated or perfluorinated polyacrylate, fluorinated or perfluorinated polyolefm, fluorinated or perfluorinated polyether, fluorinated or perfluorinated polyester, and combinations thereof; even more preferably, selected from polysiloxane, polyether, polyacrylate, fluorinated polysiloxane, fluorinated or perfluorinated polyether, fluorinated or perfluorinated polyacrylate, and combinations thereof; most preferably selected from polysiloxane, fluorinated polysiloxane, and combinations thereof). R is preferably alkyl (more preferably, methyl), and p is preferably equal to one.
The compounds useful as component (a) can be used in the curable composition of the invention singly or in the form of mixtures of different compounds. The compounds can be prepared by known synthetic methods, and some (for example, silicone hydrides) are commercially available.
In exemplary synthetic methods, reactive silane functionality can be introduced to inorganic or organic compounds (for example, polymers) by reaction (for example, by free radical addition) of a compound having at least one unsaturated (for example, vinyl) group with a compound having both a mercapto group and reactive silane functionality. An inorganic or organic compound having at least one isocyanato group can also be reacted with a compound having both an active hydrogen-containing group and reactive silane functionality. In polymeric materials, the reactive silane functionality can be introduced by such methods at a terminus of a polymer's main chain, at the terminus of a side chain, and/or at one or more non-terminal positions along the main or side chain(s), depending upon the nature of component (b) and the properties desired for the curable and/or cured composition.
Representative examples of useful hydrosilyl-functional compounds include the following (wherein Me is methyl):
HMe2SiOSiMe2H ,
HMe2SiC2H4SiMe2H ,
HMe2SiC6H4SiMe2H ,
H(Me2SiO)nSiMe2H (for example, having a weight average molecular weight (MW) of 400-500, 1000, 6000, 28,000, or 62,700),
Me3SiO(Me2SiO)m(MeHSiO)„SiMe3 (for example, having a percentage of -MeHSiO- units of 0.5 to 55 and a MW of 900 to 65,000),
Me3SiO(MeHSiO)nSiMe3 (for example, having a MW of 1400 to 2400),
HMe2SiC3H6OCH2Rf H2OC3H6SiMe2H (for example, wherein Rf is CnF2n wherein n is an integer of 1 to 12 or Rf is (CnF2nO)CnF2n wherein n is an integer of 1+2, 2, or 3; such materials can be made, for example, by platinum-catalyzed condensation of excess SiMe2H2 with an olefin or by condensation of SiMe2HCl with olefins, followed by reduction of the chloride with tributyltin hydride),
HMe2SiOSiMe2C3H6OCH2RfCH20C3H6SiMe2OSiMe2H (for example, wherein Rf is CnF2n wherein n is an integer of 1 to 12 or Rf is (CnF2nO)CnF2n wherein n is an integer of 1+2, 2, or 3; such materials can be made from olefins by first condensing excess SiMe2HCl and hydrolyzing with water to form a diol of component (b) structure (as described below), then condensing with SiMe2Cl2 and reducing),
HMe2SiOSiMe2C2H40(C2H40)nC2H4SiMe20SiMe2H (for example, wherein n is an
integer of 1 to about 50),
C2H5C[(C2H40)nC3H6SiMe2H]3 (for example, wherein n is an integer of 1 to about 10)
HMe2SiOSiMe2CnH2nSiMe20SiMe2H (for example, wherein n is an integer of 2 to about
40),
and the like, and combinations thereof.
Preferred hydrosilyl-functional compounds include the following (wherein Me is methyl):
Me3SiO(Me2SiO)m(MeHSiO)„SiMe3 (for example, having a percentage of -MeHSiO- units of 0.5 to 55 and a MW of 900 to 65,000),
Me3SiO(MeHSiO)nSiMe3 (for example, having a MW of 1400 to 2400),
and combinations thereof, including the especially preferred compound
Me3SiOSiHMeOSiHMeOSiMe3.
Component (b)
Compounds suitable for use as component (b) of the curable composition of the invention include inorganic compounds and organic compounds (preferably, inorganic compounds) comprising reactive silane functionality comprising at least one hydroxysilyl moiety (that is, a monovalent moiety comprising a hydroxyl group bonded directly to a silicon atom). The compounds can be small molecules, oligomers, polymers, or a combination thereof. Preferably, the compounds are polymers, which can be linear, branched, or cyclic. Useful polymers include those that have random, alternating, block, or graft structures, or a combination thereof. The molecular weight and the reactive silane functionality (including the number and nature of the hydroxysilyl moieties) can vary widely, depending upon, for example, the molecular weight and the reactive silane functionality of component (a) and the properties desired for the curable and/or cured composition.
When component (a) (the compound comprising at least one hydrosilyl moiety) is an organic polymer, then component (b) (the compound comprising at least one hydroxysilyl moiety) is different from component (a) and is not generated in situ (that is, in the presence of components (a) and (c)) by hydrolysis of component (a). When component (a) is a compound other than an organic polymer, then a single compound (comprising both hydrosilyl and hydroxysilyl moieties and, optionally, being generated in situ) can serve as both component (a) and component (b), if desired.
A class of useful compounds includes those that can be represented by the following general formula:
A-[G-Si(R)3-p-(OH)p]m (II) wherein A, G, p, and m are as defined above for Formula (I) and each R (which can optionally contain at least one heteroatom, as defined above for Formula (I)) is independently selected from alkyl (preferably, having 1 to about 4 carbon atoms), acyl (preferably, having 1 to about 3 carbon atoms), cycloalkyl, aryl, heteroalkyl,
heterocycloalkyl, heteroaryl, hydrogen, triorganosiloxy (-OSi(R')3, wherein R' is an organic or heteroorganic group; preferably, a group having 1 to about 20 carbon atoms), and combinations thereof. R is preferably alkyl (more preferably, methyl).
The compounds useful as component (b) can be used in the curable composition of the invention singly or in the form of mixtures of different compounds. The compounds can be prepared by known synthetic methods, and some (for example, silicone diols) are commercially available. Synthetic methods analogous to those described above for component (a) can be utilized. Reactive silane functional polymers (for example, reactive silane functional poly(meth)acrylates) can also be prepared by copolymerization of reactive silane functional monomer with reactive comonomer.
Representative examples of useful hydroxysilyl-functional compounds include the following (wherein Me is methyl):
HO(SiMe20)nH (for example, having a weight average molecular weight (MW) of 400 to 139,000),
HOSiMe20(SiMe(C2H4CF3)0)mSiMe20H (for example, having a MW of 550 to 1200), Polysesquioxane resins RSiOi.s ,
HOSiMe2C3H6OCH2RfCH2OC3H6SiMe2OH (for example, wherein Rf is
CnF2n wherein n is an integer of 1 to 12 or Rf is (CnF2nO)CnF2n wherein n is an integer of 1+2, 2, or 3),
HOSiMe2C2H40(C2H40)nC2H4SiMe2OH ,
HOMe2SiC2H4SiMe2OH ,
HOMe2SiC6H4SiMe2OH ,
and the like, and combinations thereof.
Component (c)
Bases suitable for use as component (c) of the curable composition of the invention include amidines, guanidines (including substituted guanidines such as biguanides), phosphazenes, proazaphosphatranes (also known as Verkade's bases), and combinations thereof. Such bases can be prepared by known synthetic methods, and some are commercially available. Self-protonatable forms of the bases (for example, aminoacids such as arginine) generally are less suitable and therefore excluded, as such forms are self- neutralized. Preferred bases include amidines, guanidines, and combinations thereof (more preferably, amidines and combinations thereof; most preferably, cyclic amidines and combinations thereof).
It has been discovered that the bases of the listed structural classes can effectively catalyze reaction between components (a) and (b), as described above. The bases can be used in the curable composition singly (individually) or in the form of mixtures of one or more different bases (including bases from different structural classes). If desired, the base(s) can be present in photolatent form (for example, in the form of an activatable composition that, upon exposure to radiation or heat, generates the base(s) in situ).
Useful amidines include those that can be represented by the following general formula:
Figure imgf000015_0001
wherein Rl, R2, R3, and R4 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups (for example, comprising nitrogen, oxygen, phosphorus, or sulfur in the form of groups or moieties that do not contain acid functionality such as carboxylic or sulfonic), and combinations thereof; and wherein any two or more of Rl, R2, R3, and R4 optionally can be bonded together to form a ring structure (preferably, a five-, six-, or seven-membered ring; more preferably, a six- or seven-membered ring). The organic and heteroorganic groups preferably have from 1 to about 20 carbon atoms (more preferably, from 1 to about 10 carbon atoms; most preferably, from 1 to about 6 carbon atoms). Preferably, R4 is not hydrogen.
Amidines comprising at least one ring structure (that is, cyclic amidines) are generally preferred. Cyclic amidines comprising two ring structures (that is, bicyclic amidines) are more preferred.
Representative examples of useful amidine compounds include 1 ,2-dimethyl- 1 ,4,5 ,6-tetrahydropyrimidine, 1 -ethyl-2-methyl- 1 ,4,5 ,6-tetrahydropyrimidine, 1 ,2-diethyl- 1 ,4,5 ,6-tetrahydropyrimidine, 1 -n-propyl-2-methyl- 1 ,4,5 ,6-tetrahydropyrimidine, 1 - isopropyl-2-methyl- 1 ,4,5 ,6-tetrahydropyrimidine, 1 -ethyl-2-n-propyl- 1 ,4,5 ,6- tetrahydropyrimidine, l-ethyl-2-isopropyl-l,4,5,6-tetrahydropyrimidine, DBU (that is, 1,8- diazabicyclo[5.4.0]-7-undecene), DBN (that is, l,5-diazabicyclo[4.3.0]-5-nonene), 2,3,6,7- tetrahydro-5H-thiazolo[3,2-a]pyrimidine, 3,4,7,8-tetrahydro-2H,6H-pyrimido[2,l-b]-[l,3]- thiazine, 2,3 ,6,7-tetrahydroimidazo[2, 1 -b]thiazine, 9, 10-dihydro-thiazolo[3 ,2- ajpyrimidine, 2,3-dihydro-5H-thiazolo[2,3-b]quinazoline, 7,8-dihydro-10H-l,3- dioxolo[4,5-g]thiazolo[2,3-b]quinazoline, and the like, and combinations thereof.
Preferred amidines include l,2-dimethyl-l,4,5,6-tetrahydropyrimidine, DBU (that is, 1,8- diazabicyclo[5.4.0]-7-undecene), DBN (that is, l,5-diazabicyclo[4.3.0]-5-nonene), 2,3,6,7- tetrahydro-5H-thiazolo[3,2-a]pyrimidine, 3,4,7,8-tetrahydro-2H,6H-pyrimido[2,l-b]-[l,3]- thiazine, 2,3,6,7-tetrahydroimidazo[2,l-b]thiazine, and combinations thereof, with DBU, DBN, and combinations thereof being more preferred and DBU most preferred.
Useful guanidines include those that can be represented by the following general formula:
Figure imgf000016_0001
wherein Rl, R2, R3, R4, and R5 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups (for example, comprising nitrogen, oxygen, phosphorus, or sulfur in the form of groups or moieties that do not contain acid functionality such as carboxylic or sulfonic), and combinations thereof; and wherein any two or more of Rl, R2, R3, R4, and R5 optionally can be bonded together to form a ring structure (preferably, a five-, six-, or seven-membered ring; more preferably, a five- or six-membered ring; most preferably, a six-membered ring). The organic and heteroorganic groups preferably have from 1 to about 20 carbon atoms (more preferably, from 1 to about 10 carbon atoms; most preferably, from 1 to about 6 carbon atoms).
Preferably, R5 is not hydrogen.
Guanidines comprising at least one ring structure (that is, cyclic guanidines) are generally preferred. Cyclic guanidines comprising two ring structures (that is, bicyclic guanidines) are more preferred.
Representative examples of useful guanidine compounds include 1- methylguanidine, 1-n-butylguanidine, 1,1-dimethylguanidine, 1,1-diethylguanidine, 1,1,2- trimethylguanidine, 1,2,3-trimethylguanidine, 1,3-diphenylguanidine, 1,1,2,3,3- pentamethylguanidine, 2-ethyl- 1 , 1 ,3 ,3-tetramethylguanidine, 1 , 1 ,3 ,3-tetramethyl-2-n- propylguanidine, 1 , 1 ,3 ,3-tetramethyl-2-isopropylguanidine, 2-n-butyl- 1 , 1 ,3 ,3- tetramethylguanidine, 2-tert-butyl-l , 1 ,3,3-tetramethylguanidine, 1 ,2,3- tricyclohexylguanidine, TBD (that is, l,5,7-triazabicyclo[4.4.0]dec-5-ene), MTBD (that is, 7-methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene), 7-ethyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-propyl- 1 ,5 ,7-triazabicyclo [4.4.0]dec-5 -ene, 7-isopropyl- 1 ,5 ,7-triazabicyclo [4.4.0] dec- 5-ene, 7-n-butyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-isobutyl- 1 ,5,7- triazabicyclo[4.4.0]dec-5-ene, 7-tert-butyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 7- cyclohexyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-octyl-l,5,7-triazabicyclo[4.4.0]dec-5- ene, 7-2-ethylhexyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-decyl-l,5,7- triazabicyclo[4.4.0]dec-5-ene, biguanide, 1-methylbiguanide, 1-n-butylbiguanide, l-(2- ethylhexyl)biguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1- diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, l-n-butyl-N2-ethylbiguanide, 1 , 1 '-ethylenebisguanide, 1 -[3-(diethylamino)propyl]biguanide, 1 -[3- (dibutylamino)propyl]biguanide, N',N"-dihexyl-3 , 12-diimino-2,4, 11,13- tetraazatetradecanediamidine, and the like, and combinations thereof. Preferred guanidines include TBD (that is, l,5,7-triazabicyclo[4.4.0]dec-5-ene), MTBD (that is, 7- methyl-1 ,5,7-triazabicyclo[4.4.0]dec-5-ene), 2-tert-butyl-l , 1 ,3,3-tetramethylguanidine, and combinations thereof. More preferred are TBD, MTBD, and combinations thereof.
If desired, the amidines and guanidines can be selected from those exhibiting a pH value lower than 13.4 when measured according to JIS Z 8802 (for example, 1,3- diphenylguanidine, DBU, DBN, or a combination thereof; preferably, DBU, DBN, or a combination thereof). When component (a) is an organic polymer, for example, such lower pH amidines and guanidines can be selected and can function effectively. The referenced method for determining the pH of aqueous solutions, JIS Z 8802, is carried out by first preparing an aqueous solution of base by adding 5 millimoles of base to 100 g of a mixed solvent composed of isopropyl alcohol and water in a weight ratio of 10:3. The pH of the resulting solution is then measured at 23°C using a pH meter (for example, a Horiba Seisakusho Model F-22 pH meter).
Useful phosphazenes include those that can be represented by the following general formula:
R2X R1
N
^N-P=N-R7 (v)
/ I
R4 /N^
R5 R6
wherein Rl, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups (for example, comprising nitrogen, oxygen, phosphorus, or sulfur in the form of groups or moieties that do not contain acid functionality such as carboxylic or sulfonic), and combinations thereof; and wherein any two or more of Rl, R2, R3, R4, R5, R6, and R7 optionally can be bonded together to form a ring structure (preferably, a five-, six-, or seven-membered ring; more preferably, a five- or six-membered ring; most preferably, a six-membered ring). The organic and heteroorganic groups preferably have from 1 to about 20 carbon atoms (more preferably, from 1 to about 10 carbon atoms; most preferably, from 1 to about 6 carbon atoms). Preferably, R7 is not hydrogen.
Representative examples of useful phosphazene compounds include
Figure imgf000018_0001
Figure imgf000019_0001
phosphazene base P2-t-Bu
\ N— V P-N /
phosphazene base P2-t-Bu N /
\ I I 1 /
N-P-N=P-N
/ 1 1 \
A /N-
phosphazene base P4-t-Bu
Figure imgf000020_0001
phosphazene base P4-t-Bu tetrafluoroborate salt
Figure imgf000021_0001
phosphazene base P4-t-Oct
Figure imgf000021_0002
tetrakis[tris(dimethylamino)phosphoranylidena mino] phosphonium fluoride
Figure imgf000021_0003
tert-butylimino- tris(dimethylamino)phosphorane
\ N /
\ I I /
N-P-N
/ A \
and the like, and combinations thereof. Preferred phosphazenes include 2-tert-butylimino- 2-diethylamino-l ,3-dimethylperhydro-l ,3,2-diazaphosphorine, phosphazene base Pi-t-Bu- tris(tetramethylene), phosphazene base P4-t-Bu, and combinations thereof. Useful proazaphosphatrane bases (Verkade's bases) include those that represented by the following general formula:
Figure imgf000022_0001
wherein Rl, R2, and R3 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups (for example, comprising nitrogen, oxygen, phosphorus, or sulfur in the form of groups or moieties that do not contain acid functionality such as carboxylic or sulfonic), and combinations thereof (less preferably hydrogen). The organic and heteroorganic groups preferably have from 1 to about 20 carbon atoms (more preferably, from 1 to about 10 carbon atoms; most preferably, from 1 to about 6 carbon atoms).
Representative examples of useful proazaphosphatrane compounds include
Figure imgf000022_0002
and the like, and combinations thereof. 2,8,9-triisopropyl-2,5,8,9-tetraaza-l- phosphabicyclo[3.3.3]undecane is a preferred proazaphosphatrane compound. Preparation of Curable Composition
The curable composition of the invention can be prepared by combining components (a), (b), and (c) in essentially any order (preferably, with agitation or stirring). Preferably, components (a) and (b) are combined initially, followed by addition of component (c). The composition can be maintained as a relatively shelf-stable, 2-part system (for example, by keeping component (c) separate from the other two components), if desired, but a 1-part system (comprising all three components) can also be stable for periods of up to, for example, about two weeks in dry solvent (a relatively long pot life), prior to coating or other application of the composition.
The relative amounts of components (a) and (b) can vary widely, depending upon their nature and the desired properties of the curable and/or cured composition. Although stoichiometry prescribes a 1 : 1 molar ratio of reactive silane functionality (for example, one mole of hydrosilyl moieties for every mole of hydroxysilyl moieties), in practice it can be useful to have a deficiency or an excess of hydrosilyl functionality (for example, this can be useful when cure inhibitors are present). Molar ratios (of hydrosilyl moieties to hydroxysilyl moieties) up to, for example, about 8: 1 or about 13: 1 or even as high as about 35: 1 can be useful. Component (c) (the base catalyst(s)) can be present in the curable composition in amounts ranging, for example, from about 0.1 to about 10 weight percent (preferably, from about 0.1 to about 5 weight percent; more preferably, from about 0.5 to about 2 weight percent), based upon the total weight of components (a), (b), and (c).
Preferably, the curable composition comprises at least one solvent or diluent to aid in storage stability, mixing, and/or coating, particularly when components (a) and (b) are oligomeric or polymeric. Suitable solvents for use in the curable composition of the invention include aprotic solvents such as aromatic solvents (for example, xylene, toluene, 1 ,2-dichlorobenzene, 1,3-dichlorobenzene, 1 ,4-dichlorobenzene, and the like, and mixtures thereof), ketones (for example, methyl ethyl ketone (MEK), cyclohexanone, and the like, and mixtures thereof), alkyl esters (for example, ethyl acetate, butyl acetate, and the like, and mixtures thereof), alkanes (for example, heptane, isoparaffinic hydrocarbons, and the like, and mixtures thereof), ethers (for example, t-butyl methyl ether,
tetrahydrofuran (THF), and the like, and mixtures thereof), and the like, and mixtures thereof. Preferred solvents include aromatic solvents, alkanes, ketones, and mixtures thereof; with xylene, heptane, methyl ethyl ketone, and mixtures thereof being more preferred and heptane, methyl ethyl ketone, and mixtures thereof most preferred.
Minor amounts of optional components can be added to the curable composition to impart particular desired properties for particular curing methods or uses. Useful compositions can comprise conventional additives such as, for example, catalysts
(including conventional condensation catalysts such as tin catalysts, which can be added as co-catalysts if desired), initiators, surfactants, stabilizers, anti-oxidants, flame retardants, adhesion promoters, tackifiers, plasticizers, release modifiers, dyes, pigments, fillers, and the like, and mixtures thereof.
Use and Curing of Curable Composition
The curable composition of the invention can be used in various different applications. For example, the composition can be used in molding applications
(optionally in combination with at least one filler) to form various shaped articles. The composition(s) also can be used as sealants, adhesives, release coatings, surface treatments, rubbers, hardcoats, softcoats, and the like. When used as fluorinated surface treatments, a degree of hydrophobicity and/or oleophobicity can be imparted to a variety of substrates (for example, for surface protection or to enhance ease of cleaning).
If both components (a) and (b) of the curable composition are difunctional, application of the base catalyst can result in a chain extension reaction (for example, for silicones: H(Me2SiO)„SiMe2H + HO(SiMe20)„H^ -[0(SiMe20)2n]x-). If a relatively small amount of a multifunctional component (for example, Me3SiO(MeHSiO)nSiMe3) is included in the curable composition, the resulting lightly-branched polymer can be an elastomer and can be compounded with MQ resin(s) to make pressure-sensitive adhesives. Use of a larger amount of multifunctional component can provide a crosslinked coating. Polyperfluoroethers can be chain-extended with minimally polar connecting groups, optionally crosslinking as above (for example,
HMe2SiOSiMe2C3H6OCH2C2F4(C3F60)ioC2F4CH2OC3H6SiMe2OSiMe2H +
H(SiMe20)ioH -> -[Si Me2C3H6OCH2RfCH2OC3H6(SiMe20)i3]-x).
The curable composition of the invention (or, alternatively, its components) can be applied to at least a portion of at least one major surface of a substrate (for example, a sheet, fiber, or shaped object) by essentially any known or hereafter-developed application method, so as to form a variety of different coated articles. The composition can be applied in essentially any manner (and with essentially any thickness) that can form a useful coating.
Useful application methods include coating methods such as dip coating, spin coating, spray coating, wiping, roll coating, and the like, and combinations thereof. The composition can be applied in neat form or in the form of solvent solutions (for example, in solvents such as alkyl esters, ketones, alkanes, aromatics, and the like, and mixtures thereof). When solvent is used, useful concentrations of the composition can vary over a wide range (for example, from about 1 to about 90 weight percent), depending upon the viscosity of the composition, the application method utilized, the nature of the substrate, and the desired properties.
Substrates suitable for use in preparing the coated articles include those having at least one surface comprising a material that is solid and preferably substantially inert to any coating or application solvent that is used. Preferably, the curable composition can adhere to the substrate surface through chemical interactions, physical interactions, or a combination thereof (more preferably, a combination thereof).
Suitable substrates can comprise a single material or a combination of different materials and can be homogeneous or heterogeneous in nature. Useful heterogeneous substrates include coated substrates comprising a coating of a material (for example, a metal or a primer) borne on a physical support (for example, a polymeric film).
Useful substrates include those that comprise wood, glass, minerals (for example, both man-made ceramics such as concrete and naturally-occurring stones such as marble and the like), polymers (for example, polycarbonate, polyester, polyacrylate, and the like), metals (for example, copper, silver, gold, aluminum, iron, stainless steel, nickel, zinc, and the like), metal alloys, metal compounds (for example, metal oxides and the like), leather, parchment, paper, Kraft paper, polyolefm-coated paper, textiles, painted surfaces, and combinations thereof. Preferred substrates include glass, minerals, wood, metals, metal alloys, metal compounds, polymers, and combinations thereof (more preferably, metals, metal alloys, metal compounds, polymers, and combinations thereof). Preferably, the substrate is a polar substrate (for example, having a surface energy of greater than or equal to about 30 dynes per centimeter). The curable composition can be cured by concentration (for example, by allowing solvent evaporation). The preferred curing conditions will vary, depending upon the particular application and its accompanying requirements and conditions. Moisture can be present but generally is not necessary. Cure generally can be effected at temperatures ranging from room temperature (for example, about 20-23°C) up to about 150°C or more (preferably, temperatures of about 20°C to about 125°C; more preferably, about 20°C to about 100°C; most preferably, about 20°C to about 80°C). Curing times can range from a few minutes (for example, at room temperature) to hours (for example, under low catalyst conditions).
EXAMPLES
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. These examples are merely for illustrative purposes only and are not meant to be limiting on the scope of the appended claims.
Materials
Unless otherwise noted, all parts, percentages, ratios, etc., in the examples and in the remainder of the specification are by weight. Unless otherwise noted, all chemicals were obtained from, or are available from, chemical suppliers such as Aldrich Chemical Company, Milwaukee, WI.
Preparation of 2 3,6,7-Tetrahvdro-5H-thiazolo[3,2-alpyrimidine
2,3,6,7-Tetrahydro-5H-thiazolo[3,2-a]pyrimidine was prepared by cycloalkylation of a cyclic thiourea essentially according to the reaction scheme described in Org. Lett., Vol. 9, No. 1, 2007, and shown below (wherein n=2 and m=l):
Figure imgf000026_0001
reflux To a mixture of 10.2 g of 3,4,5,6-tetrahydro-2-pyrimidinethiol (obtained from Aldrich Chemical Company, Milwaukee, WI) and 10.53 g of Na2C03 was added absolute ethanol (100 mL) and 16.81 g of 1 ,2-dibromoethane (obtained from Aldrich Chemical Company, Milwaukee, WI). The resulting mixture was refluxed overnight and was then cooled and filtered through CELITE™ 521 filter medium (a diatomaceous earth material, obtained from Sigma Aldrich, St. Louis, MO) and finally concentrated using a rotary evaporator. The resulting residue was basified to pH=14 using a 20 weight percent aqueous solution of NaOH. The resulting mixture was extracted 3 times with dichloromethane. The resulting organic layer was dried over Na2S04 and concentrated via a rotary evaporator. The reaction had a yield of 50 percent (%), as determined by flash chromatography.
Preparation of 3,4,7,8-Tetr ahvdro-2H,6H-pyrimido [2, 1-bl - [ 1 ,31 -thiazine
3,4,7, 8-Tetrahydro-2H,6H-pyrimido[2,l-b]-[l,3]-thiazine was prepared by the above-described reaction scheme wherein n=2 and m=2. The starting materials were 3,4,5,6-tetrahydro-2-pyrimidinethiol and 1 ,3-dibromopropane (both obtained from Aldrich Chemical Company, Milwaukee, WI), and the remainder of the preparation process was essentially the same as described above. The resulting crude product was 93 percent (%) pure and was used directly for catalysis.
Preparation of 2,3i6,7-Tetrahvdroimidazo[2,l-blthiazine
2,3,6,7-Tetrahydroimidazo[2,l-b]thiazine was prepared by the above-described reaction scheme wherein n=l and m=2. The starting materials were 2- imidazolidinethione and 1,3-dibromopropane (both obtained from Aldrich Chemical Company, Milwaukee, WI), and the remainder of the preparation process was
essentially the same as described above. The resulting crude product was 98 percent (%) pure and was used directly for catalysis.
Examples 1 - 10 and Comparative Examples C-l - C-12
A sample of a 30 weight percent solids dispersion of a blend of reactive
hydroxysilyl-functional siloxane polymer(s) (said to comprise hydroxyl-terminated polydimethylsiloxane) and hydrosilyl-functional polysiloxane crosslinker (said to comprise poly(methyl)(hydrogen)siloxane) in xylene (a premium release coating composition obtained from Dow Corning Corporation, Midland, MI, under the trade designation Syl-Off™ 292) was diluted to 10 weight percent solids with heptane. For each of Examples 1-10 and Comparative Examples C-l- C-12, 0.02 g of catalyst (listed in Table 1 below; all catalysts were obtained from Aldrich Chemical Company, Milwaukee, WI) was added to 5 g of Syl-Off™ 292 solution (10 weight percent in heptane) and then mixed. The resulting mixtures were coated on the primed side of a 50 micrometer thick polyester terephthalate (PET) film (obtained from Mitsubishi Polyester Film, Greer, SC, under the trade designation Hostaphan™ 3 SAB, referred to hereinafter as 3 SAB PET film, which has one side chemically treated or primed to improve the adhesion of silicone coatings) using a number 4 rod. The resulting coated 3 SAB PET samples were set aside at room temperature (about 23°C) and their curing status (level of tackiness) was monitored. A coated sample was deemed cured if the coating solidified within 5 minutes. A coated sample was deemed not cured if the coating did not solidify and remained tacky for at least 24 hours at room temperature. The results are shown in Table 1 below. Table 1.
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Example 11
9 g of Syl-Off™ 292 release coating composition, 0.1 g l,8-diazabicyclo[5.4.0]-7- undecene (DBU, obtained from Aldrich Chemical Company, Milwaukee, WI), 16.7 g heptane, and 4.2 g methyl ethyl ketone (MEK) were weighed into a 120 mL glass jar. The glass jar was shaken until the contents were homogeneous. The homogeneous mixture was coated on the primed side of a 50 micrometers thick 3 SAB PET film.
The coated film was taped to a cardboard and then left under ambient conditions (about 23 °C) for at least 3 minutes. After 2 minutes, the coating was not greasy but could be scuffed with a light finger rub. After 2 minutes and 40 seconds, the coating was firm and could not be scuffed with a finger rub. The coated film was then placed in a Despatch oven (Model RFD2-19-2E, commercially available from Despatch Industries,
Minneapolis, MN) with the heat turned off and the fans turned on for 3 minutes in order to remove the solvents.
Example 12
29.4 g of Syl-Off™ 292 release coating composition, 0.1 g DBU, 56.4 g heptane, and 14.1 g MEK were weighed into a 120 mL glass jar. The glass jar was shaken until the contents were homogeneous. The homogeneous mixture was coated on the primed side of a 50 micrometers thick 3 SAB PET film.
The coated film was taped to a cardboard and then left under ambient conditions (about 23°C) for at least 3 minutes. After 1 minute and 30 seconds, the coating was dry and felt cured to the touch. The coated film was then placed in a Despatch oven with the heat turned off and the fans turned on for 3 minutes in order to remove the solvents.
Example 13
29.4 g of Syl-Off™ 292 release coating composition, 0.05 g DBU, 56.4 g heptane, and 14.1 g MEK were weighed into a 120 mL glass jar. The glass jar was shaken until the contents were homogeneous. The homogeneous mixture was coated on the primed side of a 50 micrometers thick 3 SAB PET film.
The coated film was taped to a cardboard and then left under ambient conditions (about 23°C) for at least 3 minutes. After 1 minute and 15 seconds, the coating was dry and felt cured to the touch. The coated film was then placed in a Despatch oven with the heat turned off and the fans turned on for 3 minutes in order to remove the solvents.
Example 14
0.1 g 2-tert-Butylimino-2-diethylamino- 1 ,3 -dimethylperhydro- 1,3,2- diazaphosphorine (BEMP, obtained from Aldrich Chemical Company, Milwaukee, WI), 56.4 g heptane, 14.1 g MEK, and 29.4 g of Syl-Off™ 292 release coating composition were weighed into a 120 mL glass jar in the indicated order. The glass jar was shaken until the contents were homogeneous. The homogeneous mixture was coated on the primed side of a 50 micrometers thick 3 SAB PET film. The coated film was taped to a cardboard and then left under ambient conditions (about 23°C) for at least 3 minutes. After 1 minute and 30 seconds, the coating was dry and felt cured to the touch. The coated film was then placed in a Despatch oven with the heat turned off and the fans turned on for 3 minutes in order to remove the solvents.
Example 15
0.05 g 2,8,9-Triisopropyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane (TTP, obtained from Aldrich Chemical Company, Milwaukee, WI), 56.45 g heptane, 14.1 g MEK, and 29.4 g of Syl-Off™ 292 release coating composition were weighed into a 240 mL glass jar. The glass jar was shaken until the contents were homogeneous. The homogeneous mixture was coated on the primed side of a 50 micrometers thick 3 SAB PET film and left in the hood to air dry (at about 23°C). The coated film was dry to the touch and anchored well within minutes.
Example 16
0.34 g of 100 percent active solids fluorofunctional silicone crosslinker (said to comprise greater than 60 weight percent trimethylsiloxy-terminated
methyl(perfluorobutylethyl), methylhydrogen siloxane; obtained from Dow Corning Corporation, Midland, MI, under the trade designation Syl-Off™ Q2-7560) and 0.8 g of hydroxyl-terminated polydimethylsiloxane (silanol-terminated PDMS, molecular weight (MW) of 400-700, obtained from Gelest, Inc., Morrisville, PA, under the trade designation GELEST DMS-S12) and 8.86 g of heptane were mixed to prepare a 10 weight percent solids solution. 0.04 g of DBU catalyst was added to the solution. After mixing, the resulting fresh solution was coated on the primed side of a 50 micrometers thick 3 SAB PET film. The coating was dried and cured at room temperature (about 23°C; cured after about 6 minutes).
Example 17
The coating solution of Example 11 (comprising 3.3 weight percent DBU) was used for a bath life study. For this study, the viscosity of the coating solution was measured periodically using a viscometer (Model DV-II+ made by Brookfield Engineering Laboratories, Inc., Middleboro, MA) to determine if and/or when the solution would congeal. The solution was adversely affected 15 hours after solution preparation.
Example 18
The coating solutions of Examples 11, 12, and 13 were allowed to age at room temperature (about 23°C), and, periodically (at 0, 1, 2, 4, and 6 hours of aging), each solution was coated on the primed side of a 50 micrometers thick 3 SAB PET film. The cure time, defined as the elapsed time needed so that the coating could not be rubbed off by finger, was determined for each coating (for each coating solution and for each aging time). The resulting cure times are shown in Table 2 below.
Table 2.
Figure imgf000035_0001
Examples 19-20
0.09 g of a bicyclic isothiourea catalyst (2,3,6,7-tetrahydro-5H-thiazolo[3,2- ajpyrimidine, prepared essentially as described above) was added to 3 g of a 30 weight percent solids dispersion of a blend of reactive hydroxysilyl-functional siloxane polymer(s) (said to comprise hydroxyl-terminated polydimethylsiloxane) and
hydrosilyl-functional polysiloxane crosslinker (said to comprise
poly(methyl)(hydrogen)siloxane) in xylene (a premium release coating composition obtained from Dow Corning Corporation, Midland, MI, under the trade designation SYL-OFF™ 292). For Example 19, the resulting mixture was diluted to 10 weight percent solids by adding 6.81 g of toluene and then thoroughly mixing. For Example 20, the resulting mixture was diluted to 5 weight percent solids by adding 6.4 g of toluene and then thoroughly mixing. Each of the resulting diluted mixtures were immediately coated on the primed sides of 50 micrometer thick polyester terephthalate (PET) films (obtained from Mitsubishi Polyester Film, Greer, SC, under the trade designation Hostaphan™ 3 SAB, referred to hereinafter as 3 SAB PET film, which has one side chemically treated or primed to improve the adhesion of silicone coatings) using a number 4 rod. The resulting coated 3 SAB PET films were set aside at room temperature (about 23°C) and their curing status (level of tackiness) was monitored. The films were deemed cured if the coatings solidified within 5 minutes. Results are shown in Table 3 below.
Examples 21-22
Examples 21-22 were carried out in essentially the same manner as Examples 19-20 above, except that different bicyclic isothiourea catalysts were utilized. For Example 21, the bicyclic isothiourea catalyst was 3,4,7,8-tetrahydro-2H,6H- pyrimido[2,l-b]-[l,3]-thiazine, and, for Example 22, the bicyclic isothiourea catalyst was 2,3,6,7-tetrahydroimidazo[2,l-b]thiazine (both catalysts having been prepared essentially as described above). The resulting coated films were deemed cured if the coatings solidified within 5 minutes. Results are shown in Table 3 below.
Table 3.
Figure imgf000036_0001
Example
No. Catalyst Curing
2,3 ,6,7-Tetrahydroimidazo[2, 1 -b]thiazine
22 Yes
Example 23
A reaction mixture containing triethyl silanol (TES), hydrosilyl-functional polysiloxane crosslinker (obtained from Dow Corning Corporation, Midland, MI, under the trade designation Syl-Off™ 7048, said to comprise poly(methyl)(hydrogen)siloxane), and DBU was prepared by mixing 600 microliters Syl-Off™ 7048, 260 microliters TES, 6 microliters DBU, and 134 microliters of deuterated toluene. The mole ratio of TES to Syl- Off™ 7048 was about 20:80, providing an excess of Si-H relative to Si-OH. DBU was present in an amount equivalent to about 1 percent by weight of Syl-Off™ 7048
(equivalent to about 0.7 percent by weight of the total solids in the mixture). Nuclear magnetic resonance (NMR) spectra of the reaction mixture were then acquired on a BRUKER™ AVANCE™ 500 MHz NMR spectrometer equipped with a broadband cryoprobe (obtained from Bruker Corporation, Billerica, MA).
The reaction mixture bubbled extensively upon mixing, and an analysis of the NMR spectra indicated that the TES was fully reacted within 5-10 minutes. 2D 1H-29Si NMR spectra of the mixture obtained after 10 minutes of reaction showed the presence of T-groups at -65 ppm, conversion of the triethyl silyl 29Si from 17 ppm to 12 ppm
(formation of M group), and reduction of the Si-H integral relative to S1-CH3, in accordance with the reaction depicted below.
Figure imgf000037_0001
The NMR data was believed to show that DBU had catalyzed the reaction of an organic silanol (TES) with Si-H functionality in a DH polymer such as Syl-Off™ 7048, to form T- group structures.
The referenced descriptions contained in the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. Various unforeseeable modifications and alterations to this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. It should be understood that this invention is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only, with the scope of the invention intended to be limited only by the claims set forth herein as follows.

Claims

We Claim:
1. A curable composition comprising
(a) at least one inorganic or organic compound comprising reactive silane
functionality comprising at least one hydrosilyl moiety;
(b) at least one inorganic or organic compound comprising reactive silane
functionality comprising at least one hydroxysilyl moiety, said hydroxysilyl moiety optionally being generated in situ by hydrolysis of at least one said hydrosilyl moiety; and
(c) at least one base selected from amidines, guanidines, phosphazenes,
proazaphosphatranes, and combinations thereof;
with the proviso that, when said component (a) is an organic polymer, then said component (b) is different from said component (a) and is not generated in situ by hydrolysis of said component (a).
2. The composition of Claim 1, wherein said component (a) is selected from compounds that are represented by the following general formula:
A-[G-Si(R)3-p-(H)p]m (I) wherein A is an m-valent non-polymeric radical (optionally containing at least one heteroatom) selected from alkyl, fluoroalkyl, perfluoroalkyl, aryl, fluoroaryl,
perfluoroaryl, cycloalkyl, fluorocycloalkyl, perfluorocycloalkyl, and combinations thereof, or is an m-valent polymeric radical comprising an oligomer or polymer selected from polysiloxane, polyacrylate, polyolefin, polyether, polyester, polyurethane,
polyphosphazene, fluorinated polysiloxane, fluorinated or perfluorinated polyacrylate, fluorinated or perfluorinated polyether, fluorinated or perfluorinated polyester,
polysilazane, fluorinated polysilazane, and derivatives and combinations thereof; each G is independently a divalent linking group; each R is independently selected from alkyl, acyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, hydroxyl, triorganosiloxy (- OSi(R')3, wherein R' is an organic or heteroorganic group), and combinations thereof; each p is independently an integer of 1, 2, or 3; and m is an integer that is greater than or equal to 1.
3. The composition of Claim 1 or Claim 2, wherein said component (b) is selected from compounds that are represented by the following general formula:
A-[G-Si(R)3-p-(OH)p]m (II) wherein A is an m-valent non-polymeric radical (optionally containing at least one heteroatom) selected from alkyl, fluoroalkyl, perfluoroalkyl, aryl, fluoroaryl,
perfluoroaryl, cycloalkyl, fluorocycloalkyl, perfluorocycloalkyl, and combinations thereof, or is an m-valent polymeric radical comprising an oligomer or polymer selected from polysiloxane, polyacrylate, polyolefm, polyether, polyester, polyurethane,
polyphosphazene, fluorinated polysiloxane, fluorinated or perfluorinated polyacrylate, fluorinated or perfluorinated polyether, fluorinated or perfluorinated polyester,
polysilazane, fluorinated polysilazane, and derivatives and combinations thereof; each G is independently a divalent linking group; each R is independently selected from alkyl, acyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, hydrogen, triorganosiloxy (- OSi(R')3, wherein R' is an organic or heteroorganic group), and combinations thereof; each p is independently an integer of 1, 2, or 3; and m is an integer that is greater than or equal to 1.
4. The composition of Claim 2 or Claim 3, wherein said A is a polymeric radical; each said G is independently selected from a covalent bond, oxy, diorganosiloxy, diheteroorganosiloxy, alkylene, arylene, heteroalkylene, heteroarylene, cycloalkylene, heterocycloalkylene, and combinations thereof; each said R is independently alkyl; each said p is an integer of 1; and/or said m is an integer of 1 to 50.
5. The composition of Claim 4, wherein said A is a polymeric radical selected from polysiloxane, polyacrylate, polyolefm, polyether, polyester, fluorinated polysiloxane, fluorinated or perfluorinated polyacrylate, fluorinated or perfluorinated polyolefm, fluorinated or perfluormated polyether, fluorinated or perfluormated polyester, and combinations thereof.
6. The composition of Claim 5, wherein said A is a polymeric radical selected from polysiloxane, polyether, polyacrylate, fluorinated polysiloxane, fluorinated or perfluormated polyether, fluorinated or perfluormated polyacrylate, and combinations thereof.
7. The composition of Claim 1 or any other of the preceding claims, wherein at least one of said components (a) and (b) is inorganic.
8. The composition of Claim 1 or any other of the preceding claims, wherein said component (c) is selected from
(1) amidine compounds that are represented by the following general formula:
Figure imgf000041_0001
(2) guanidine compounds that are represented by the following general formula:
Figure imgf000041_0002
(3) phosphazene compounds that are represented by the following general formula: R2V ^R1
N
N— P=N-R7
/ I (V)
R4
R5 R6 (4) proazaphosphatrane compounds that are represented by the following general formula:
Figure imgf000042_0001
(VI), and combinations thereof; wherein Rl, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups, and combinations thereof; and wherein any two or more of Rl, R2, R3, R4, R5, R6, and R7 of said amidine, guanidine, and/or phosphazene compounds optionally can be bonded together to form a ring structure.
9. The composition of Claim 8, wherein said component (c) is selected from amidine compounds, guanidine compounds, phosphazene compounds, and combinations thereof that each comprise at least one said ring structure.
10. The composition of Claim 1 or Claim 8, wherein said component (c) is selected from l,2-dimethyl-l,4,5,6-tetrahydropyrimidine, l,8-diazabicyclo[5.4.0]-7- undecene (DBU), l,5-diazabicyclo[4.3.0]-5-nonene (DBN), 2,3,6,7-tetrahydro-5H- thiazolo[3,2-a]pyrimidine, 3,4,7, 8-tetrahydro-2H,6H-pyrimido[2,l-b]-[l,3]-thiazine, 2,3,6,7-tetrahydroimidazo[2,l-b]thiazine, l,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7- methyl-1 ,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 2-ierf-butyl-l , 1 ,3,3- tetramethylguanidine, 2-tert-butylimino-2-diethylamino-l,3-dimethylperhydro- 1,3,2- diazaphosphorine, phosphazene base Pi-t-Bu-tris(tetramethylene), phosphazene base P4-t- Bu, 2, 8 ,9-triisopropyl-2,5 , 8 ,9-tetraaza- 1 -phosphabicyclo [3.3.3 ]undecane, and
combinations thereof.
11. The composition of Claim 1 or any other of the preceding claims, wherein said base is selected from amidines, guanidines, and combinations thereof.
12. The composition of Claim 11, wherein said base is selected from amidines and combinations thereof.
13. The composition of Claim 12, wherein said amidine is selected from 1,8- diazabicyclo[5.4.0]-7-undecene (DBU), l,5-diazabicyclo[4.3.0]-5-nonene (DBN), and combinations thereof.
14. The composition of Claim 1 or any other of the preceding claims, wherein when said component (a) is an organic polymer, said amidines and guanidines are selected from those exhibiting a pH value lower than 13.4, when measured according to JIS Z 8802, and combinations thereof.
15. The composition of Claim 1 or any other of the preceding claims, wherein said composition is an organometallic catalyst-free composition.
16. The composition of Claim 1 or any other of the preceding claims, wherein said composition has been cured.
17. A curable composition comprising
(a) at least one inorganic or organic compound comprising reactive silane
functionality comprising at least one hydrosilyl moiety;
(b) at least one inorganic or organic compound comprising reactive silane
functionality comprising at least one hydroxysilyl moiety, said hydroxysilyl moiety optionally being generated in situ by hydrolysis of at least one said hydrosilyl moiety; and
(c) at least one base selected from amidines and guanidines exhibiting a pH value lower than 13.4, when measured according to JIS Z 8802, and combinations thereof.
18. The curable composition of Claim 17, wherein said base is selected from l,8-diazabicyclo[5.4.0]-7-undecene (DBU), l,5-diazabicyclo[4.3.0]-5-nonene (DBN), and combinations thereof.
19. A curing process comprising
(a) providing the curable composition of Claim 1 or any other of the preceding claims; and
(b) allowing or inducing said curable composition to cure.
20. An article comprising at least one substrate having at least one major surface, said substrate bearing, on at least a portion of at least one said major surface, the curable composition of Claim 1 or any other of the preceding claims.
21. The article of Claim 20, wherein said curable composition has been cured.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014025456A3 (en) * 2012-06-27 2014-05-08 3M Innovative Properties Company Moisture-curable polysiloxane coating composition
EP2813528A1 (en) 2013-06-11 2014-12-17 Sika Technology AG Curable composition on the basis of polyethers containing alkoxysilane groups and a phosphazene base
KR20160021793A (en) 2013-06-20 2016-02-26 모멘티브 퍼포먼스 머티리얼즈 인크. Moisture curable compound with thiourea
JP2016524637A (en) * 2013-05-17 2016-08-18 モーメンティブ・パフォーマンス・マテリアルズ・インク Catalyst for siloxane synthesis
US9914809B2 (en) 2013-08-30 2018-03-13 Momentive Performance Materials Inc. Moisture curable composition with amino acids
US10287454B2 (en) 2013-08-23 2019-05-14 Evonik Degussa Gmbh Coating compositions
US10364382B2 (en) 2011-12-29 2019-07-30 3M Innovative Properties Company Curable polysiloxane compositions and pressure sensitive adhesives made therefrom

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2665788A1 (en) 2010-06-30 2013-11-27 3M Innovative Properties Company Curable composition comprising dual reactive silane functionality
WO2012003152A1 (en) 2010-06-30 2012-01-05 3M Innovative Properties Company Curable-on-demand composition comprising dual reactive silane functionality
EP2588550A1 (en) 2010-06-30 2013-05-08 3M Innovative Properties Company Curable polysiloxane coating composition
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CN104080838B (en) 2011-12-29 2016-08-17 3M创新有限公司 Can the polysiloxane coating composition of on-demand solidification
US10428291B2 (en) 2014-03-28 2019-10-01 Cummins Filtration Ip, Inc. Ashless oil additives and their use as TBN boosters
US9897914B2 (en) * 2015-12-28 2018-02-20 Shin-Etsu Chemical Co., Ltd. Resist composition and patterning process
JP6668288B2 (en) * 2017-04-04 2020-03-18 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ Film-forming composition
CN109467707B (en) * 2017-09-07 2022-02-01 青岛科技大学 Linear polyphosphazene compound and preparation method and application thereof
US11084897B2 (en) * 2017-12-12 2021-08-10 International Business Machines Corporation Chemical compounds with perfluoroaryl groups that can facilitate post-synthesis functionalization
US11118008B2 (en) 2018-07-06 2021-09-14 International Business Machines Corporation Ring-opening polymerizations using a flow reactor
US10738153B2 (en) 2018-07-06 2020-08-11 International Business Machines Corporation Ring-opening polymerizations using a flow reactor
US10815335B2 (en) 2018-07-06 2020-10-27 International Business Machines Corporation Ring-opening polymerizations using a flow reactor
US20210324229A1 (en) 2018-08-21 2021-10-21 Evonik Operations Gmbh Heat-curable coating compositions containing silane-functional polyurethane resins catalyzed by amidine salts
WO2020073892A1 (en) * 2018-10-08 2020-04-16 广东美的厨房电器制造有限公司 Coating compound and preparation therefor, coated component and preparation method therefor, and household appliance
WO2020109920A1 (en) * 2018-11-26 2020-06-04 3M Innovative Properties Company Curable coating compositions, methods, and articles
US20220185965A1 (en) * 2019-06-04 2022-06-16 Dow Silicones Corporation Thermally initiated acid catalyzed reaction between silyl hydride and silyl ether and/or silanol

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0444633A2 (en) * 1990-02-28 1991-09-04 Dow Corning Toray Silicone Company, Limited Polyorganosiloxane-based elastomer powder and method for its preparation
US6235832B1 (en) * 1998-12-21 2001-05-22 Dow Corning Corporation RTV silicone compositions with rapid development of green strength
US20060014844A1 (en) * 2002-04-05 2006-01-19 Lim Thomas F Curable foam elasomeric compositions
US7482391B1 (en) * 2005-05-09 2009-01-27 Henkel Corporation Foaming RTV silicone compositions
WO2010146254A1 (en) * 2009-06-19 2010-12-23 Bluestar Silicones France Silicone composition which is cross-linkable by dehydrogenative condensation in the presence of a non-metal catalyst

Family Cites Families (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2708289A (en) 1951-10-03 1955-05-17 Dow Corning Method of preparing pressure sensitive organosiloxane sheet material
NL126303C (en) 1965-01-08 1900-01-01
NL129544C (en) 1965-08-04
US3628996A (en) 1969-06-27 1971-12-21 Dow Corning Polydimethylsiloxane release agent
GB1451623A (en) 1973-10-01 1976-10-06 Mullard Ltd Method of prov8ding a patterned layer of silicon-containing oxide on a substrate
US4181752A (en) 1974-09-03 1980-01-01 Minnesota Mining And Manufacturing Company Acrylic-type pressure sensitive adhesives by means of ultraviolet radiation curing
US4269963A (en) 1979-12-03 1981-05-26 Dow Corning Corporation Mercaptoorganopolysiloxanes and curable compositions including same
US4489199A (en) 1983-08-08 1984-12-18 General Electric Company Room temperature vulcanizable organopolysiloxane compositions
JPS6122094A (en) 1984-07-10 1986-01-30 Toray Silicone Co Ltd Preparation of organosilicon compound
US4761443A (en) 1987-06-04 1988-08-02 Dow Corning Corporaton Multiple release mold coating for high water, high resiliency polyurethane foam
EP0448154A1 (en) 1990-03-20 1991-09-25 Akzo Nobel N.V. Coating composition including a blocked basic catalyst
US5286815A (en) 1992-02-07 1994-02-15 Minnesota Mining And Manufacturing Company Moisture curable polysiloxane release coating compositions
US5371162A (en) 1992-07-09 1994-12-06 Minnesota Mining And Manufacturing Company Storage-stable silicone composition
US5403909A (en) 1993-07-15 1995-04-04 General Electric Company Catalysts for polycondensation and redistribution of organosiloxane polymers
JP3499032B2 (en) 1995-02-02 2004-02-23 ダウ コーニング アジア株式会社 Radiation curable composition, curing method and pattern forming method
US6136996A (en) 1995-12-13 2000-10-24 General Electric Company Catalysts for polycondensation and redistribution of organosiloxane polymers
US6124371A (en) 1996-02-22 2000-09-26 Dsm N.V. Anionic photocatalyst
JP3628098B2 (en) 1996-03-29 2005-03-09 ダウ コーニング アジア株式会社 Radiation curable composition and method for producing cured product pattern using the same
JPH09268228A (en) 1996-04-01 1997-10-14 Dow Corning Asia Ltd Ultraviolet-curing composition and formation of cured material pattern using the same
US5688888A (en) 1996-04-08 1997-11-18 General Electric Company Peralkylated phosphazene base-catalyzed silanol condensation method
US6441118B2 (en) 1996-04-25 2002-08-27 3M Innovative Properties Company Polydiorganosiloxane oligourea segmented copolymers and a process for making same
JP4246268B2 (en) 1997-01-22 2009-04-02 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド Photoactivatable nitrogen-containing bases based on α-amino ketones
US6551761B1 (en) 1997-02-26 2003-04-22 Ciba Specialty Chemical Corporation Photoactivatable nitrogen-containing bases based on α-ammonium ketones, iminium ketones or amidinium ketones and aryl borates
WO1998040439A1 (en) 1997-03-14 1998-09-17 Minnesota Mining And Manufacturing Company Cure-on-demand, moisture-curable compositions having reactive silane functionality
US5866222A (en) 1997-07-18 1999-02-02 Minnesota Mining And Manufacturing Co. Silicone copolymer modified release tapes
DE19752935A1 (en) 1997-11-28 1999-06-02 Basf Ag Process for the preparation of bicyclic amidines, diazacycloalkenes and a process for their preparation
GB9818539D0 (en) * 1998-08-26 1998-10-21 Dow Corning Process for producing a silicone polymer
US6780484B2 (en) 2001-02-02 2004-08-24 3M Innovative Properties Company Adhesive article and method of preparing
US6805933B2 (en) 2001-07-31 2004-10-19 3M Innovative Properties Company Articles comprising a release liner having a high coefficient of friction and good roll stability
RU2332419C2 (en) 2001-10-17 2008-08-27 Циба Спешиалти Кемикэлз Холдинг Инк. Photoactivatable nitrogen base, photopolymer composition and application
DE10237271A1 (en) 2002-08-14 2004-03-04 Consortium für elektrochemische Industrie GmbH Polymer masses based on alkoxysilane-terminated polymers with adjustable curing speed
US7064173B2 (en) 2002-12-30 2006-06-20 General Electric Company Silicone condensation reaction
US6777512B1 (en) 2003-02-28 2004-08-17 Dow Global Technologies Inc. Amine organoborane complex initiated polymerizable compositions containing siloxane polymerizable components
EP1564255B1 (en) 2004-02-16 2007-09-26 Mitsubishi Gas Chemical Company, Inc. Photobase generator and curable composition
US7148370B1 (en) 2005-07-20 2006-12-12 General Electric Company Process for synthesis of diorganosilanes by disproportionation of hydridosiloxanes
EP1939257B1 (en) 2005-09-30 2017-06-21 Kaneka Corporation Curable composition
WO2007037484A1 (en) 2005-09-30 2007-04-05 Kaneka Corporation Curable composition
WO2007149422A2 (en) 2006-06-20 2007-12-27 Dow Corning Corporation Curable organosilicon composition
JP5258575B2 (en) 2006-11-22 2013-08-07 株式会社カネカ Curable composition and catalyst composition
FR2929286A1 (en) 2008-03-28 2009-10-02 Bluestar Silicones France Soc GUANIDINE-STRUCTURED COMPOUNDS AND THEIR USE AS ORGANOPOLYSILOXANE POLYCONDENSATION CATALYSTS
KR101588912B1 (en) 2008-03-31 2016-01-26 산아프로 가부시키가이샤 Photobase generator
EP2443178B1 (en) 2009-06-19 2013-07-24 Bluestar Silicones France Silicone composition suitable for cross-linking by dehydrocondensation in the presence of a non-metal catalyst
EP2588550A1 (en) 2010-06-30 2013-05-08 3M Innovative Properties Company Curable polysiloxane coating composition
WO2012003152A1 (en) 2010-06-30 2012-01-05 3M Innovative Properties Company Curable-on-demand composition comprising dual reactive silane functionality
EP2665788A1 (en) 2010-06-30 2013-11-27 3M Innovative Properties Company Curable composition comprising dual reactive silane functionality

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0444633A2 (en) * 1990-02-28 1991-09-04 Dow Corning Toray Silicone Company, Limited Polyorganosiloxane-based elastomer powder and method for its preparation
US6235832B1 (en) * 1998-12-21 2001-05-22 Dow Corning Corporation RTV silicone compositions with rapid development of green strength
US20060014844A1 (en) * 2002-04-05 2006-01-19 Lim Thomas F Curable foam elasomeric compositions
US7482391B1 (en) * 2005-05-09 2009-01-27 Henkel Corporation Foaming RTV silicone compositions
WO2010146254A1 (en) * 2009-06-19 2010-12-23 Bluestar Silicones France Silicone composition which is cross-linkable by dehydrogenative condensation in the presence of a non-metal catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ORG. LETT., vol. 9, no. 1, 2007

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10364382B2 (en) 2011-12-29 2019-07-30 3M Innovative Properties Company Curable polysiloxane compositions and pressure sensitive adhesives made therefrom
WO2014025456A3 (en) * 2012-06-27 2014-05-08 3M Innovative Properties Company Moisture-curable polysiloxane coating composition
CN104540909A (en) * 2012-06-27 2015-04-22 3M创新有限公司 Moisture-curable polysiloxane coating composition
JP2015527436A (en) * 2012-06-27 2015-09-17 スリーエム イノベイティブ プロパティズ カンパニー Moisture curable polysiloxane coating composition
US9175188B2 (en) 2012-06-27 2015-11-03 3M Innovative Properties Company Moisture-curable polysiloxane coating composition
JP2016524637A (en) * 2013-05-17 2016-08-18 モーメンティブ・パフォーマンス・マテリアルズ・インク Catalyst for siloxane synthesis
EP2813528A1 (en) 2013-06-11 2014-12-17 Sika Technology AG Curable composition on the basis of polyethers containing alkoxysilane groups and a phosphazene base
KR20160021793A (en) 2013-06-20 2016-02-26 모멘티브 퍼포먼스 머티리얼즈 인크. Moisture curable compound with thiourea
US9944770B2 (en) 2013-06-20 2018-04-17 Momentive Performance Materials Inc. Moisture curable compound with thiourea
US10287454B2 (en) 2013-08-23 2019-05-14 Evonik Degussa Gmbh Coating compositions
US9914809B2 (en) 2013-08-30 2018-03-13 Momentive Performance Materials Inc. Moisture curable composition with amino acids

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