WO2007061846A2 - Polymeres silyles durcissant a l'humidite pour compositions de durcissement rapide a l'humidite - Google Patents

Polymeres silyles durcissant a l'humidite pour compositions de durcissement rapide a l'humidite Download PDF

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WO2007061846A2
WO2007061846A2 PCT/US2006/044677 US2006044677W WO2007061846A2 WO 2007061846 A2 WO2007061846 A2 WO 2007061846A2 US 2006044677 W US2006044677 W US 2006044677W WO 2007061846 A2 WO2007061846 A2 WO 2007061846A2
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group
member selected
occurrence
different
hydrocarbon radical
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WO2007061846A3 (fr
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Thomas Fay-Oy Lim
Hsien-Kun Chu
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Henkel Corporation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
    • C08C19/36—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with carboxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/54—Nitrogen-containing linkages
    • 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
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • 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
    • C08L83/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/10—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

Definitions

  • the present invention relates to a method of preparing moisture-curable silylated polymers by reacting amino- or carboxy-terminated polymers with silanes containing methylenehydrocarbyloxysilanes, and to the compositions formed thereby.
  • the inventive compositions possess fast moisture-cure capabilities.
  • Alkoxy-terminated polysiloxanes have been used to prepare moisture-curable silicone adhesives with desirable properties. These reactive polysiloxanes are typically prepared by endcapping silanol-terminated silicones with alkoxysilanes which are capable of functioning as crosslinkers The endcapped silicones may then be cured (i.e. cross-linked) by exposure to ambient conditions in the presence of a catalyst and/or heat.
  • non siloxane polymers such as polyethers, polyamides, polycarbonates, and the like.
  • the present invention provides a method of using a wide range of polymers to prepare compositions capable of rapid moisture cure at relatively low temperatures, and to the compositions resulting from such a method.
  • a composition which includes a moisture-cure functionalized polymer which contains at least one moisture curable group having the structure:
  • composition which includes a polymer of Formula (I):
  • composition which includes at least one polymer selected from:
  • composition which includes the reaction product of:
  • the method including the steps of:
  • R 1 in each occurrence may be the same or different, and is a Ci to Qo hydrocarbon radical
  • R 2 in each occurrence may be the same or different, and is a Ci to Cio hydrocarbon radical
  • R 3 in each occurrence may be the same or different and may be selected from H and a Ci to Cio hydrocarbon radical;
  • R 4 in each occurrence may be the same or different and may be selected from H and Ci to C4 alkyl;
  • R 5 may be selected from H and a Ci to Cio hydrocarbon radical
  • R 6 may be a selected from H, a Ci to Ci 0 hydrocarbon radical, an organic cation and an inorganic cation;
  • Q 1 may be selected from:
  • Q 2 may be selected from:
  • X may be selected from halogen
  • Y may be selected from halogen and O R 5 5 — C 'I — O
  • Z is a divalent polymer; and a is 0 or 1.
  • the present invention provides hydrocarbyloxysilyl-functionalized polymers capable of rapid moisture cure.
  • hydrocarbon radical is intended to refer to radicals primarily composed of carbon and hydrogen atoms.
  • the term encompasses aliphatic groups such as alkyl, alkenyl, and alkynyl groups; aromatic groups such as phenyl; and alicyclic groups such as cycloalkyl and cycloalkenyl.
  • Hydrocarbon radicals of the invention may include heteroatoms to the extent that the heteroatoms do not detract from the hydrocarbon nature of the groups.
  • hydrocarbon groups may include such functional groups as ethers, alkoxides, carbonyls, esters, amino groups, amido groups, cyano groups, sulfides, sulfates, sulfoxides, and sulfones.
  • hydrocarbon, alkyl, and phenyl radicals of the present invention may be optionally substituted.
  • optionally substituted is intended to mean that one or more hydrogens on a group may be replaced with a corresponding number of substituents selected from alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, aryloxy, carboxy, benzyloxy, haloalkoxy, haloalkenyloxy, haloalkynyloxy, haloaryloxy, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, azido, amino, alkylamino, alkenylamino, alkynylamino
  • halo and halogen are intended to be synonymous, and both are intended to include chlorine, fluorine, bromine, and iodine.
  • compositions of the invention include a moisture-cure functionalized polymer which contains at least one moisture curable group having the structure:
  • Moisture-cure functionalized polymers suitable for use in the present invention are those obtained from silicones, polyethers, polyesters, polyamides, polyimides, polyacrylates polyalkylenes, polyvinyls, polycarbonates, and mixtures thereof.
  • the polymer may be a copolymer, thus having more than one type of repeating monomelic unit.
  • the copolymer may be a random copolymer, block copolymer, or alternating copolymer.
  • the polymeric unit includes polymers selected from silicones, polyethers, polyesters, polyamide: and polyalkylenes.
  • At least one moisture curable group of Formula (VI) must be attached to the polymer.
  • the groups of Formula (VI) may be attached to the polymer in pendant position, terminal positions, or combinations thereof.
  • R 1 in each occurrence may be the same or different, and is a C 1 to Cio hydrocarbon radical.
  • Substituent R 1 in combination with the oxygen to which it is attached, forms a hydrolyzable group, which provides the compositions of the present invention with then ability to undergo room temperature vulcanization (RTV).
  • RTV cure typically occurs through exposure of the compositions of the present invention to moisture. The presence of hydrolyzabl moisture curing groups such as alkoxy groups, permits the compositions of the present invention to undergo moisture cure.
  • Suitable hydrolyzable groups include alkoxy groups such as methoxy ethoxy, propoxy, and butoxy; acyloxy groups such acetoxy; aryloxy groups such as phenoxy; oximinoxy groups such as methylethylketoximinoxy; enoxy groups such as isopropenoxy; and alkoxyalkyl groups such as CH3OCH2CH2-. Larger groups such as propoxy and butoxy are slower to react than smaller groups such as methoxy and ethoxy. Accordingly, the rate at which the compositions of the invention undergo moisture cure can be influenced by choosing appropriately sized groups for substituent R 1 . Desirably, R 1 is Ci to C 4 alkyl or phenyl. More desirably, R 1 is methyl or ethyl.
  • R 2 in each occurrence may be the same or different, and is a Ci to Cio hydrocarbon radical.
  • R is Cj to C4 alkyl or phenyl. More desirably, R is methyl or ethyl.
  • Q 1 is selected from:
  • Q 2 is selected from:
  • R 3 is selected from H and a Ci to Cio hydrocarbon radical.
  • R 4 is selected from H and Ci to C 4 alkyl.
  • R is H or methyl.
  • the inventive compositions include a polymer of Formula (I), in which the moisture cure-groups are located in a terminal position:
  • Z is a divalent polymer, and forms the polymer of the polymer of Formula (I).
  • suitable divalent polymers are those obtained from silicones, polyethers, polyesters, polyamides, polyimides, polyacrylates, polyalkylenes, polyvinyls, polycarbonates, and mixtures thereof.
  • the polymer may be a copolymer, thus having more than one type of repeating monomelic unit.
  • the copolymer may be a random copolymer, block copolymer, or alternating copolymer.
  • the polymeric unit includes polymers selected from silicones, polyethers, polyesters, polyamides, and polyalkylenes.
  • Variable "a” indicates the number of alkyl groups present on the silane silicone, and in each occurrence may be the same or different, and is 0 or 1.
  • “3-a” indicates the number of alkoxy groups on the silane silicone.
  • compositions which include at least one polymer of the formulas:
  • R 1 ; R 2 ; R 3 ; and a are as described hereinabove, and R 5 may be selected from H and a Ci to C 1O hydrocarbon radical
  • inventive compositions may include one or more moisture-cure catalysts.
  • Suitable moisture-cure catalysts include compounds which contain such metals as titanium, tin, or zirconium.
  • titanium compounds include tetra ⁇ sopropyltitanate and tetiabutyl titanate.
  • tin compounds include d ⁇ butyltin dilaurate, dibutyltin diacetate, dioctyltindicarboxylate, dimethyltindicarboxylate, and dibutyltindioctoate.
  • the zirconium compounds include zirconium octanoate.
  • the moisture- cure catalysts are employed in an amount sufficient to effectuate moisture-cure, which generally is from about 0.05% to about 5.00% by weight, and advantageously from about 0.5% to about 2.5% by weight.
  • hydrocarbyloxy groups on the silicon atom permit the compositions of the present invention cure in the presence of moisture.
  • the hydrocarbyloxysilyl groups present in the polymer of Formula (I) are methylenehydrocarbyloxysilyl groups, in which the ⁇ carbon provides the hydrocarbyloxy groups with enhanced capacity as leaving groups. Because the compositions of the present invention ewe rapidly, they do not require moisture-cure catalysts to the extent that such catalysts are used with traditional RTV materials. Reducing the amount of moisture-cure catalyst may be desirable to prevent shelf-life problems. As the presence of any moisture in the packaging may lead to premature crosslinking and curing, the ability to use less moisture-cure catalyst in the inventive compositions provides additionally stability without compromise of the cure speed.
  • a variety of additional useful components may be added to the present inventive compositions.
  • vinyl trimethoxysilane may be added as a moisture scavenger.
  • Other useful additives include plasticizers, fillers, viscosity modifiers, flow modifiers, pigments, stabilizers, inhibitors, adjuvants, catalysts, accelerators, thixotropic agents and combinations thereof. These additives should be present in amounts suitable to effectuate their intended purpose.
  • the present invention also provides methods for preparing compositions which include a moisture-cure functionalized polymer.
  • hydrocarbyloxysilyl-containing polymers are prepared by reacting amine- or carboxy-containing polymers with silanes which contain hydrocarbyloxysilylmethylene groups, thereby producing the moisture-cure functionalized polymer.
  • Pathway A Amino-Containing Polymer Starting Material
  • One approach to preparing the moisture-cure functionalized polymer includes mixing: a) a compound of Formula (II):
  • X may be selected from halogen
  • R 4 may be selected from H and Ci to C 4 alkyl.
  • R 4 is hydrogen.
  • R 5 may be selected from H and a Ci to Cio hydrocarbon radical
  • Organic bases useful in the present invention include amines such as trialklyamines such as triethylamine, and Hunig's base.
  • Inorganic bases useful in the present invention include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide; metal carbonates such as sodium carbonate; and metal alkoxides such as sodium ethoxide and potassium ethoxide.
  • the method relates to the preparation of compositions which include polymers of Formula (I).
  • the method includes mixing a compound of Formula (II) with an amino end-capped polymer of Formula (III):
  • R 1 , R 2 , R 3 , X 5 Z, and a are as discussed above.
  • the method may take the form of an amine- containing polymer reacting with a halomethylhydrocarbyloxysilane (such as the chloromethylalkoxysilane shown in Scheme 1):
  • the moisture-cure functionalized polymer may be formed via a
  • the method may take the form of an amine-containing polymer reacting with an acetoxymethylsilane.
  • a reaction different coupling products are possible.
  • Scheme 3 shown below shows an amine end-capped polymer reacting with an hydrocarbyloxyacetoxymethylsilane.
  • One possible pathway resulting in each of the nitrogens displacing the acetoxy group, resulting in polymer (A).
  • Another possible pathway results in the nitrogens each replacing one or more hydrocarbyloxy groups on a silicon atom, as is exemplified by polymer (B).
  • one of the nitrogens replaces an acetoxy group, and the other nitrogen replaces a hydrocarbyloxy group, resulting in polymer (C).
  • Pathway B Carboxy Containing Polymer Starting Material
  • the moisture-cure functionalized polymer may also be obtained by mixing:
  • R 1 , R 2 , R 6 , and a are as discussed hereinabove.
  • Y may be selected from halogen and
  • R 5 may be selected from H and a Ci to Cio hydrocarbon radical.
  • R 6 may be selected from H, a Ci to Qo hydrocarbon radical, an organic cation and an inorganic cation.
  • Organic cations suitable for use in the present invention include quaternary nitrogens, such as those which contain a nitrogen atom bearing four alkyl or hydrogen substituents.
  • Illustrative of the inorganic cations suitable for use in the present invention are alkali metal cations, such as those of lithium, sodium, and potassium.
  • the invention provides a method for producing compositions which include a polymer of Formula (I).
  • the method includes the step of mixing:
  • the polymer of Formula (I) may be obtained by reacting a halomethylhydrocarbyloxysilane (such as the chloromethylalkoxysilane shown in Scheme 4 with a carboxy containing polymer:
  • R 6 is advantageously a member selecte from the group consisting of an organic cation and an inorganic cation.
  • a starting material may be obtained, for example, by reacting a carboxylic acid containing polymer with a basic component, such as alkali metal hydrides, hydroxides, and alkoxides.
  • the moisture-cure functionalized polymer may also be obtained by reacting a carboxymethylenesilane with a carboxy-containing polymer, as shown in Scheme 4, using an appropriate catalyst such as the tin or titanium catalyst, such as those discussed hereinabove as moisture-cure catalysts.
  • inventive compositions can be used in a variety of applications, including those where the ability to quickly moisture-cure is necessary.
  • Illustrative examples of such uses include use as a sealant, use as an adhesive, gasketing, and potting applications.
  • a method of using a composition of the invention includes the steps of:
  • composition is as described hereinabove.
  • the compositions may be used, for example, to seal or bond substrates, such as, but not limited to, gaskets.
  • substrates such as, but not limited to, gaskets.
  • the moisture curable composition may be applied to one of the substrates which will form part of the gasket, cured or at least partially cured, and then joined to a second substrate to form a gasket assembly.
  • gasketing applications include, for example, form-in-place gaskets.
  • the compositions may be applied to a substrate and subjected to curing conditions.
  • compositions may be used to seal together substrates by applying the composition to at least one of two substrate surfaces, mating the substrate surfaces in an abutting relationship to form an assembly, and exposing the ccoommppoossiittiioonn ttoo mmooiissttuurree ttoo eeffffeecctt ccuurree.
  • TThhee ssuutbstrates should be maintained in the abutting relationship for a time sufficient to effect cure.
  • compositions of the invention are shown below.
  • the mixture in the reaction kettle was further stirred at room temperature for 5 days followed by vacuum filtration to remove the solid. An aliquot of the clear filtrate was withdrawn and placed in an aluminum dish. The liquid formed a non-tacky skin in 30 seconds and cured to a dry solid in a few hours. In comparison, the ethylaminoisobutyldimethoxysilyl terminated polydimethylsiloxane exhibited no skin formation even after several hours when exposed in ambient conditions.
  • Triethylamine 40.74 g and chloromethyltrimethoxysilane 68.20 g were then sequentially added with stirring.
  • the mixture was further heated to 90 0 C under nitrogen blanketing with stirring for 4.5 hours, during which time an insoluble salt formation of triethylammonium chloride was observed.
  • An aliquot of the mixture was placed in an aluminum dish and exposed to ambient conditions. It showed a skin formation of ⁇ 10 seconds and several millimeter depth of cure overnight.
  • 2000X162 (a carboxylic acid terminated polybutadiene from Noveon).
  • a 21% solution of sodium ethoxide in ethanol (29.81 g) was added with vigorous mixing under nitrogen blanketing. The mixture turned very thick and became opaque in appearance.
  • Chloromethyltrimethoxysilane (15.69 g) was further added with vigorous mixing. The mixture was heated at 7O 0 C with mixing for 5 hours. An aliquot of the mixture was placed in an aluminum dish and exposed to ambient conditions. It showed a skin formation of 10 seconds and several millimeter depth of cure overnight.
  • a 20% toluene solution of Nucrel 599 (an ethylene-methacrylic acid copolymer from DuPont) was prepared by dissolving 45 g of Nucrel 599 in 180 g of anhydrous toluene at 80 0 C in a 500 mL reaction vessel. The solution was heated to 90-100 0 C under nitrogen with stirring. A 21% sodium ethoxide solution in ethanol (9.43 g) was then added with vigorous stirring for 10 minutes. Chloromethyltriethoxysilane (6.18 g) was further added at 90 0 C. The mixture was further reacted for 3 hours at 90-100 0 C. Dibutyltindilaurate (0.1 g) was added with stirring.

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Abstract

L'invention concerne un procédé de préparation de polymères silylés durcissant à l'humidité, qui consiste à faire réagir des polymères amino ou carboxy avec des méthylènehydrocarbyloxysilanes ; elle concerne en outre les compositions ainsi formées. Plus particulièrement, les compostions de l'invention possèdent des capacités de durcissement rapide à l'humidité. Des exemples de compositions de l'invention contiennent un polymère de formule (I).
PCT/US2006/044677 2005-11-22 2006-11-16 Polymeres silyles durcissant a l'humidite pour compositions de durcissement rapide a l'humidite WO2007061846A2 (fr)

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JP2012031411A (ja) * 2010-08-02 2012-02-16 Evonik Goldschmidt Gmbh 変性アルコキシル化生成物を使用して製造されるポリマーの貯蔵寿命が延び、かつ、延伸性が増加される、少なくとも１つの非末端アルコキシシリル基を有する変性アルコキシル化生成物
EP2456824A2 (fr) * 2009-07-21 2012-05-30 Henkel Corporation Compositions de silicone durcissables contenant des résines réactives ne contenant pas de siloxane
US20120277370A1 (en) * 2011-04-28 2012-11-01 Shin-Etsu Chemical Co., Ltd. Room temperature curable organopolysiloxane composition
WO2017191455A1 (fr) * 2016-05-05 2017-11-09 Itaconix (U.K.) Limited Promoteurs d'adhésion
CN109563265A (zh) * 2016-07-28 2019-04-02 3M创新有限公司 链段型有机硅聚酰胺嵌段共聚物以及含有其的制品

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WO2004037868A1 (fr) * 2002-10-23 2004-05-06 Henkel Corporation Compositions de sechage double uv-humidite et de sechage rapide de l'humidite
EP1431328A1 (fr) * 2002-12-19 2004-06-23 Sika Technology AG Polymères contenant 3-(N-Silyalkyl)-amino-propenate et leur production
US20040181025A1 (en) * 2001-08-09 2004-09-16 Wolfram Schindler Alcoxy cross-linking, single-component, moisture-hardening materials
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US5223575A (en) * 1988-11-29 1993-06-29 Sunstar Giken Kabushiki Kaisha Moisture-crosslinkable primer for polyolefins
JPH05165217A (ja) * 1991-12-19 1993-07-02 Hitachi Ltd 感光性耐熱重合体組成物
US20040181025A1 (en) * 2001-08-09 2004-09-16 Wolfram Schindler Alcoxy cross-linking, single-component, moisture-hardening materials
US20040204539A1 (en) * 2001-08-28 2004-10-14 Wolfram Schindler Rapid-cure, one-component mixtures, which contain alkoxysilane-terminated polymers
WO2004022618A1 (fr) * 2002-08-14 2004-03-18 Consortium für elektrochemische Industrie GmbH Masses polymeres a base de polymeres a terminaison alkoxysilane presentant une vitesse de durcissement regulable
WO2004037868A1 (fr) * 2002-10-23 2004-05-06 Henkel Corporation Compositions de sechage double uv-humidite et de sechage rapide de l'humidite
EP1431328A1 (fr) * 2002-12-19 2004-06-23 Sika Technology AG Polymères contenant 3-(N-Silyalkyl)-amino-propenate et leur production
US20050131188A1 (en) * 2003-12-15 2005-06-16 Henkel Loctite Corporation Moisture curable high strength, flexible RTV organic copolymer compositions and methods of preparation

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2456824A2 (fr) * 2009-07-21 2012-05-30 Henkel Corporation Compositions de silicone durcissables contenant des résines réactives ne contenant pas de siloxane
EP2456824A4 (fr) * 2009-07-21 2014-08-20 Henkel US IP LLC Compositions de silicone durcissables contenant des résines réactives ne contenant pas de siloxane
JP2012031411A (ja) * 2010-08-02 2012-02-16 Evonik Goldschmidt Gmbh 変性アルコキシル化生成物を使用して製造されるポリマーの貯蔵寿命が延び、かつ、延伸性が増加される、少なくとも１つの非末端アルコキシシリル基を有する変性アルコキシル化生成物
US20120277370A1 (en) * 2011-04-28 2012-11-01 Shin-Etsu Chemical Co., Ltd. Room temperature curable organopolysiloxane composition
JP2012233040A (ja) * 2011-04-28 2012-11-29 Shin-Etsu Chemical Co Ltd 室温硬化性オルガノポリシロキサン組成物
WO2017191455A1 (fr) * 2016-05-05 2017-11-09 Itaconix (U.K.) Limited Promoteurs d'adhésion
CN109563265A (zh) * 2016-07-28 2019-04-02 3M创新有限公司 链段型有机硅聚酰胺嵌段共聚物以及含有其的制品

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