WO2011072056A2 - Régulation de la vitesse de durcissement pour des polymères à terminaison bloquée par un alcoxysilyle - Google Patents

Régulation de la vitesse de durcissement pour des polymères à terminaison bloquée par un alcoxysilyle Download PDF

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Publication number
WO2011072056A2
WO2011072056A2 PCT/US2010/059536 US2010059536W WO2011072056A2 WO 2011072056 A2 WO2011072056 A2 WO 2011072056A2 US 2010059536 W US2010059536 W US 2010059536W WO 2011072056 A2 WO2011072056 A2 WO 2011072056A2
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ingredient
composition
group
alkoxy groups
groups
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WO2011072056A3 (fr
Inventor
Loren Lower
Timothy B. Lueder
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Dow Silicones Corp
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Dow Corning Corp
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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0617—Polyalkenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/065—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0657—Polyethers

Definitions

  • a moisture curable composition contains a polymer having alkoxysilyl end- blocking groups.
  • the composition is useful for making and curing sealants and adhesives.
  • Organic polymers having alkoxysilyl end-blocking groups are useful in the preparation of moisture curable sealants and adhesives.
  • the organic polymer backbones are exemplified by polyacrylates, polybutadienes, polyethers, and polyolefins.
  • Certain polymers having higher alkoxysilyl end-blocking groups suffer from the drawback of having cure time too long to be practical for use in sealant and adhesive compositions.
  • compositions containing polymers having lower alkoxysilyl, e.g., methoxysilyl, end-blocking groups may suffer from the drawback of instability, or insufficient shelf life for some applications.
  • a transesterified polymer may be prepared by mixing ingredients comprising: (A) a polymer selected from organic polymers and silicone-organic block copolymers, wherein said polymer has an average, per molecule, of at least two alkoxy group functionalized silyl end-blocking groups;
  • (C) a transesterification catalyst, with the proviso that the alkoxy groups on ingredient (B) are more reactive than the alkoxy groups on ingredient (A).
  • "More reactive" means that when a polymer is formulated into a condensation reaction curable composition, a polymer with the alkoxy groups of ingredient (B) will cure faster than a polymer with the alkoxy groups of ingredient (A) would cure in the same composition.
  • the transesterified polymer may be prepared by mixing ingredients comprising (A), (B), and (C), described above.
  • Ingredient (A) is a polymer selected from organic polymers and silicone-organic block copolymers.
  • Ingredient (A) has an average, per molecule, of at least two alkoxy group functionalized end-blocking groups. Suitable polymers for ingredient (A), and methods for their preparation, are known in the art.
  • an organic polymer having OH end-groups such as a polyether glycol or poly(propylene glycol) may be reacted with an isocyanate- functional alkoxysilane, such as isocyanatopropyltriethoxysilane in the presence of a tin catalyst, such as dibutyl tin dilaurate.
  • an alkenyl functional organic polymer may be reacted with a dialkoxysilane or trialkoxysilane having a silicon bonded hydrogen atom via a hydro silylation reaction.
  • an allyl functional organic polymer may be reacted with methyldiethoxysilane in the presence of a platinum group metal hydrosilylation catalyst.
  • Such polymers for ingredient (A), and methods for their preparation, are known in the art.
  • the organic polymers modified to include alkoxy groups on their chain terminals disclosed in U.S. Patent 6,168,253 at col. 4, line 1 to col. 5, line 50 are suitable for use herein when the alkoxy groups have two or more carbon atoms.
  • EP 1 746 133 A 1 at paragraphs [0036] to [0040], [0044] to [0045], [0050] to [0052], [0054] to [0066], [0075] to [0076] discloses methods of preparing silicone modified organic polymers; and paragraphs [0025] to [0035], [0043], [0047] to [0049], [0053], [0074], disclose the silicone modified organic polymers.
  • US 4,291,316 discloses alkoxysilane modified alkylene alkylacrylate copolymers.
  • US 4,889,903 discloses alkoxysilane modified polyurethanes.
  • Suitable organic polymers for use in preparing ingredient (A) are known in the art and are commercially available.
  • the organic polymer can be a polyacrylate, polybutadiene, polyether, polyisobutylene, polyolefin, or polyurethane, as disclosed in the patent publications cited above.
  • ingredient (A) may be a silicone-organic block copolymer.
  • exemplary silicone organic block copolymers include polyorganosiloxane-polyether block copolymers, polyorganosiloxane-polyoxyalkylene block copolymers such as those disclosed in WO2008/132236; crosslinked polyorganosiloxane-polyoxyalkylene block copolymers such as those disclosed in WO2008/132237; polyorganosiloxane- polyorganoamine block copolymers such as those disclosed in U.S.
  • Patent 5,489,622 polyorganosiloxane-polyurethane block copolymers such as those disclosed in WO1990/06958 and W01999/65966; and polycarbosiloxanes such as those disclosed in European Patent Application EP09306051.5 filed on 3 November 2009.
  • Suitable polycarbosiloxanes may be prepared by a process comprising: a) ring opening polymerization of a cyclic monomer of the structure
  • each R is the same or different and is selected from H, OH, a monovalent organic group having from 1 to 18 member atoms, and subscript n is an integer having a value ranging from 1 to 6 in the presence of an acidic or basic ring opening polymerisation catalyst; b) removing linear oligomer prepared in step (a) optionally using a suitable solvent; and
  • each R may be a hydrocarbon group having from 1 to 18 carbon atoms or a hydrocarbonoxy group having 1 to 18 carbon atoms.
  • the alkoxy end-blocking groups of ingredient (A) may have formula 0R1, alkoxy groups bonded to ingredient (B) and other ingredients of the composition may have formula OR ⁇ , and at least 60 mol % of the R ⁇ groups differ from the R1 groups.
  • Each of the alkoxy groups on ingredient (A) may have at least two carbon atoms, and at least a portion of the alkoxy groups on ingredient (B) have fewer carbon atoms than the alkoxy groups on ingredient (A).
  • each alkoxy group of ingredient (A) may be an ethoxy group.
  • the alkoxy end-blocking groups on ingredient (A) may be terminal or pendant.
  • the alkoxy groups of ingredient (B) may be methoxy.
  • each alkoxy group of ingredient (A) may have at least two carbon atoms, and the composition may further comprise at least one other ingredient having alkoxy groups (i.e. , in addition to ingredients (A) and (B)), and at least 60 mol % of all the alkoxy groups on the ingredients in the composition are methoxy groups. At least 60 % of the alkoxy groups in the composition which are not bonded to ingredient (A) may be methoxy.
  • Ingredient (B) is a reactant having alkoxy groups bonded to silicon, where at least a portion of the alkoxy groups of ingredient (B) differ from the alkoxy groups of ingredient (A).
  • Ingredient (B) may be a silane.
  • the alkoxy groups of ingredient (A) differ from at least a portion of the alkoxy groups of ingredient (B) and any other alkoxy groups in the composition (e.g. , in the transesterification catalyst and any additional ingredients of the composition, if present).
  • ingredient (B) depends on various factors including the alkoxy groups on each of ingredients (A) and (B) and the structures of ingredients (A) and (B), however, the amount of ingredient (B) may range from 0.5 to 15 parts based on 100 parts by weight of ingredient (A).
  • the relative amounts of ingredients (A) and (B) may be varied to change the modulus and/or cure rate of a sealant prepared containing ingredients (A) and (B).
  • Ingredient (B) may comprise a silane crosslinker having alkoxy groups or partial or full hydrolysis products thereof.
  • Suitable silane crosslinkers may have the general formula (III) R ⁇ c Si(R ⁇ )(4-c)' where each R4 is independently a monovalent hydrocarbon group such as an alkyl group; each is an alkoxy group having at least one carbon atom fewer than the alkoxy groups on ingredient (A); and subscript c is 0, 1, 2, or 3.
  • Ingredient (B) may comprise an alkoxysilane exemplified by a dialkoxysilane, such as a dialkyldialkoxysilane; a trialkoxysilane, such as an alkyltrialkoxysilane; a tetraalkoxysilane; or partial or full hydrolysis products thereof, or another combination thereof.
  • Suitable trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, and a combination thereof, and alternatively methyltrimethoxysilane or isobutyltrimethoxysilane.
  • suitable tetraalkoxysilanes include trimethoxyethoxysilane, tetramethoxysilane and tetraethoxysilane.
  • the amount of the alkoxysilane used to prepare the transesterified polymer may range from 0.5 to 15 parts by weight per 100 parts by weight of ingredient (A).
  • Examples of alkoxysilane crosslinkers are disclosed in U.S. Patents 4,962,076; 5,051,455; and 5,053,442.
  • Ingredient (C) is a transesterification catalyst.
  • Ingredient (C) may be selected from alumina compounds, titanate compounds, and zirconate compounds.
  • ingredient (C) may be a titanate compound.
  • Suitable compounds for ingredient (C) include a compound of formula (V): M(0R3) , where M is Al, Ti, or Zr and each is an organic group.
  • M is Al, Ti, or Zr and each is an organic group.
  • OR ⁇ may represent an alkoxy group of 1 to 20 carbon atoms or an acyloxy group. Each OR ⁇ may be the same or different.
  • M may be Ti.
  • titanates represented by general formula (V) include titanium tetraethoxide, titanium tetraallyloxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium tetra-sec- butoxide, titanium tetra-t-butoxide, titanium tetra-t-amyloxide, titanium tetra-n- pentyloxide, titanium tetracyclopentyloxide, titanium tetrahexyloxide, titanium tetracyclohexyloxide, titanium tetrabenzyloxide, titanium tetraoctyloxide, titanium tetrakis(2-ethylhexyloxide), titanium tetradecyloxide, titanium tetradodecyloxide, titanium tetrastearyloxide, titanium tetradecy
  • examples of titanates of formula (V) include tetrabutyl titanate (TTBT), titanium chelates such as dialkoxytitanium-bis-(acetylacetonates), dialkoxytitanium-bis-(alkylacetonates), and dialkoxytitanium-bis-(alkylacetoacetonate).
  • examples of dialkoxytitanium-bis-(acetylacetonates) include diisopropoxytitanium-bis- (acetylacetonate), isopropoxyethoxytitanium-bis-(acetylacetonate).
  • dialkoxytitanium-bis-(alkylacetoacetates) include dialkoxytitanium-bis- (methylacetoacetate) and dialkoxytitanium-bis-(ethylacetoacetate).
  • zirconates of formula (V) include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraallyloxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetraisobutoxide, zirconium tetra-sec-butoxide, zirconium tetra-t-butoxide, zirconium tetra-pentyloxide, zirconium tetracyclopentyloxide, zirconium tetrahexyloxide, zirconium tetracyclohexyloxide, zirconium tetrabenzyloxide, zirconium tetraoctyloxide, zirconium tetrakis(2-ethylhex
  • zirconium acylates of formula (V) include zirconium acrylate triisopropoxide, zirconium methacrylate triisopropoxide, zirconium dimethacrylate diisopropoxide, zirconium isopropoxide trimethacrylate, zirconium hexanoate triisopropoxide, zirconium stearate triisopropoxide and combinations thereof.
  • transesterification catalysts may be selected from acids and bases. Catalyst selection depends on various factors including the alkoxy group being transesterified and the substrate to which the alkoxy group is bonded.
  • an amino containing alkoxy-end-blocked polymer may be transesterified with a basic catalyst such a metal alkoxide, e.g., sodium alkoxide (such as sodium ethoxide or sodium methoxide).
  • a basic catalyst such as a metal alkoxide, e.g., sodium alkoxide (such as sodium ethoxide or sodium methoxide).
  • An alkoxy-end-blocked polymer containing non-functional or base sensitive alkyl or alkoxy group could be transesterified with an acid catalyst, such as para- toluenesulfonic acid.
  • the transesterification catalysts can be heterogeneous, such as in the form of pellets or beads, or homogenous (i.e., soluble).
  • the amount of transesterification catalyst depends on the type of catalyst selected, the groups to be transesterified, and the desired rate of transesterification, however the amount may range from 0.001 % to 1 % based on the combined weights of ingredients (A), (B), and (C).
  • the transesterification method comprises: 1) in a polymer selected from silicon modified organic polymers and silicone-organic block copolymers, wherein said polymer has an average, per molecule, of at least two alkoxy group functionalized end-blocking groups, converting at least 60 % of the alkoxy groups on the polymer to different alkoxy groups. Thereafter, the product of step 1) may be cured in combination with a crosslinker and a condensation reaction catalyst.
  • the method may comprise:
  • ingredient ( ⁇ ') a polymer in which at least a portion of the alkoxy groups from ingredient (A) have been replaced with alkoxy groups from ingredient (B);
  • crosslinker having an average, per molecule, of at least two condensation reaction curable groups
  • condensation reaction catalyst other than ingredient (C) and optionally
  • step (1) alkoxy groups bonded to ingredient (A) are replaced with different alkoxy groups, which are initially bonded to reactant (B).
  • the reactant may be a silane, such as an alkoxysilane or a different polymer from the substrate, such as a polyorganosiloxane, a different organic polymer, or a different silicone-organic block copolymer.
  • the end-blocking groups on ingredient (A) may be alkoxy groups having two or more carbon atoms, and the reactant (B) may have alkoxy groups, at least some of which differ from the alkoxy groups bonded to ingredient (A).
  • Ingredient (A) may have alkoxy groups of two or more carbon atoms and the reactant (B) may have methoxy groups.
  • ingredient (A) may have ethoxy groups and ingredient (B) may have methoxy groups.
  • methoxy groups will cure faster in step (2) than alkoxy groups having two or more carbon atoms, and the process can be used to prepare a composition with a controlled cure rate.
  • step (1) at least 60 mol % of the alkoxy groups on ingredient (A) may be replaced, alternatively at least 70 mol %, alternatively 60 mol % to 100 mol %, alternatively 60 mol % to 90 mol %, alternatively at least 80 mol %, and alternatively, 70 mol % to 80 mol %.
  • the amount of end -blocking groups replaced will depend on various factors including the end-blocking groups on the substrate, the groups that will replace the end-blocking groups on the substrate, the relative amounts of ingredients (A) and (B) (and other alkoxy containing ingredients, if any), and the end use of the product of step (1), ingredient ( ⁇ ').
  • step (1) an optional step may be added to the method.
  • the method may optionally further comprise a step of pre-treating the product of step (1) and/or reacting the product of step (1) with a catalyst deactivating agent thereby deactivating ingredient (C) before step (2).
  • the product of step (1) may optionally be pre-treated (for example, by stripping or distillation to remove remaining reactants and/or transesterification catalyst).
  • the catalyst deactivating agent may be selected from a glycol, an alcohol such as methanol, a catechol, and a combination thereof.
  • Ingredient ( ⁇ ') prepared in step (1) is reacted (e.g. , cured) in step (2).
  • Ingredient ( ⁇ ') may be formulated into a composition with other ingredients before or during step (2).
  • the alkoxy groups, which were reacted onto ingredient (A) in step (1) are reacted with other ingredients.
  • the other ingredients may comprise: (C) a condensation reaction catalyst, , ( ⁇ ') a crosslinker e.g. , an alkoxysilane or alkoxy functional polyorganosiloxane, where the crosslinker has alkoxy groups which are the same as at least 60 mol % of the alkoxy groups bonded to ingredient ( ⁇ ').
  • the condensation reaction catalyst (C) may differ from the transesterification catalyst used in step (1). Alternatively, the condensation reaction catalyst (C) may be the same as the transesterification catalyst (C), described above. When the condensation reaction catalyst is the same as the transesterification catalyst, such as when a titanate is used, it is not necessary to deactivate transesterification catalyst and/or add a separate condensation reaction catalyst, such as a tin catalyst.
  • Ingredient ( ⁇ ') is a crosslinker.
  • Ingredient ( ⁇ ') may comprise a silane of formula where each R6 is independently a monovalent hydrocarbon group
  • Ingredient ( ⁇ ') may comprise an acyloxysilane, such as an acetoxysilane.
  • Acetoxysilanes include a tetraacetoxysilane, an organotriacetoxysilane, a diorganodiacetoxysilane, or a combination thereof.
  • the acetoxysilane may contain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and tertiary butyl; alkenyl groups such as vinyl, allyl, or hexenyl; aryl groups such as phenyl, tolyl, or xylyl; aralkyl groups such as benzyl or 2-phenylethyl; and fluorinated alkyl groups such as 3,3,3- trifluoropropyl.
  • ingredient ( ⁇ ') may comprise organotriacetoxysilanes, for example mixtures containing methyltriacetoxysilane and ethyltriacetoxysilane.
  • the amount of the acetoxysilane in the composition may range from 0.5 to 15 parts by weight per 100 parts by weight of ingredient (A'); alternatively 3 to 10 parts by weight of acetoxysilane per 100 parts by weight of ingredient ( ⁇ ').
  • crosslinkers include alkoxysilanes, oximeosilanes, enoxysilanes, and combinations thereof.
  • Akoxysilane crosslinkers include dialkoxysilanes and trialkoxysilanes. Examples of trialkoxysilanes include methyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, or aminoethylaminopropyltrimethoxysilane. Dialkoxysilanes may also be used, such as methylvinyldimethoxysilane.
  • the amount of crosslinker may range from 0.5 parts to 15 parts, alternatively 2 parts to 8 parts, per 100 parts by weight of ingredient ( ⁇ ').
  • Ingredient (C) is a condensation reaction catalyst capable of curing the composition comprising ingredients ( ⁇ ') and ( ⁇ ').
  • condensation reaction catalysts include a carboxylate, a carboxylic acid, a carboxylic acid salt of metal, a tin compound, a titanium compound, or a zirconium compound, or a combination thereof.
  • ingredient (C) may be a carboxylate, a carboxylic acid, a carboxylic acid salt of metal, a tin compound, a chelated titanium compound, a titanate, or a combination thereof.
  • Ingredient (C) may comprise carboxylic acid salts of metals, ranging from lead to manganese inclusive, in the electromotive series of metals.
  • Suitable tin catalysts for ingredient (C) include tin (IV) compounds and tin (II) compounds.
  • tin (IV) compounds include dibutyl tin dilaurate (DBTDL), dimethyl tin dilaurate, di-(n-butyl)tin bis-ketonate, dibutyl tin diacetate, dibutyl tin maleate, dibutyl tin di acetylacetonate, dibutyl tin dimethoxide carbomethoxyphenyl tin tris-uberate, isobutyl tin triceroate, dimethyl tin dibutyrate, dimethyl tin di-neodeconoate (DMDTN), triethyl tin tartrate, dibutyl tin dibenzoate, butyltintri-2-ethylhexoate, a dioctyl tin diacetate, tin octylate, tin oleate, tin butyrate, tin naphthenate, dimethyl
  • tin (II) compounds include tin (II) salts of organic carboxylic acids such as tin (II) diacetate, tin (II) dioctanoate, tin (II) diethylhexanoate, tin (II) dilaurate, stannous salts of carboxylic acids such as stannous octoate, stannous oleate, stannous acetate, stannous laurate, and a combination thereof.
  • organic carboxylic acids such as tin (II) diacetate, tin (II) dioctanoate, tin (II) diethylhexanoate, tin (II) dilaurate, stannous salts of carboxylic acids such as stannous octoate, stannous oleate, stannous acetate, stannous laurate, and a combination thereof.
  • organofunctional titanates include 1,3-propanedioxytitanium bis(ethylacetoacetate); 1,3-propanedioxytitanium bis (acetylacetonate); diisopropoxytitanium bis(acetylacetonate); 2,3-di-isopropoxy-bis(ethylacetate)titanium; titanium naphthenate; tetra-propyl titanate; tetrabutyltitanate; tetra-ethylhexyl titanate; tetraphenyltitanate; tetra-octadecyl titanate; tetra-butoxy titanium; tetra-isopropoxy titanium; ethyltriethanolaminetitanate; a betadicarbonyltitanium compound such as bis(acetylacetonyl)di-isopropyl titanate; or a combination thereof.
  • Siloxytitanates are exemplified by tetrakis(trimethylsiloxy)titanium, bis(trimethylsiloxy)bis(isopropoxy)titanium, or a combination thereof.
  • condensation reaction catalysts are disclosed in, for example, U.S. Patents 4,962,076; 5,051,455; and 5,053,442 and EP 1 746 133 paragraphs [0086] to [0122] for examples of condensation reaction catalysts.
  • the amount of ingredient (C) is sufficient to cure the composition.
  • the amount of ingredient (C) will vary depending on the selection of ingredients ( ⁇ '), ( ⁇ '), and (C), however, the amount of ingredient (C) may range from 0.001 parts to 3 parts, alternatively 0.005 parts to 2 parts, based on the weight of the composition.
  • Ingredient (C) may be one condensation reaction catalyst. Alternatively, ingredient (C) may comprise two or more different condensation catalysts.
  • the composition may optionally further comprise one or more additional ingredients.
  • additional ingredients may be selected from (D) a plasticizer, (E) a stabilizer, (F) a filler, (G) a filler treating agent, (H) an adhesion promoter, (I) a fungicide, (J) a rheological additive, (K) a flame retardant, (L) a pigment, (M) a co- catalyst, and a combination thereof.
  • Ingredient (D) is a plasticizer, which may be added to the composition to adjust the viscosity and slump properties of the composition and the mechanical properties, such as tensile strength and elongation, of a product obtained by curing the composition.
  • the plasticizer may have an average, per molecule, of at least one group of formula (V). (V) o
  • R represents a hydrogen atom or a monovalent organic group.
  • R may represent a branched or linear monovalent hydrocarbon group.
  • the monovalent organic group may be a branched or linear monovalent hydrocarbon group such as an alkyl group of 4 to 15 carbon atoms, alternatively 9 to 12 carbon atoms.
  • Suitable plasticizers may be selected from the group consisting of adipates, carboxylates, phthalates, and a combination thereof.
  • the plasticizer may have an average, per molecule, of at least two groups of formula (V) bonded to carbon atoms in a cyclic hydrocarbon.
  • the plasticizer may have general formula (VI):
  • group X represents a cyclic hydrocarbon group having 3 or more carbon atoms, alternatively 3 to 15 carbon atoms. (Subscript x may have a value ranging from 1 to 12.) Group X may be saturated or aromatic.
  • Each R" is independently a hydrogen atom or a branched or linear monovalent organic group.
  • the monovalent organic group for R" may be an alkyl group such as methyl, ethyl, or butyl. Alternatively, the monovalent organic group for R" may be an ester functional group.
  • Each R' is independently a branched or linear monovalent hydrocarbon group, such as an alkyl group of 4 to 15 carbon atoms.
  • organic plasticizers of formula (VI) may have a formula (VII), (VII), (IX), or (X) set forth below.
  • R' is as described above.
  • Formulae (VII) and (VIII) represent the cases where the cycloalkyl group in formula (VII) and the aryl group in formula (VIII) are unsubstituted.
  • Formulae (IX) and (X) show that the cycloalkyl group in formula (IX) and the aryl group in formula (X) may be replaced with organic groups in which one or more of the hydrogen atoms bonded to the member atoms, in the cycloalkyl group of formula (VII) or in the aryl group of formula (VIII), shown is replaced with another monovalent organic group represented by R'.
  • Each R' may be an alkyl group such as methyl, ethyl, or butyl.
  • the monovalent organic group for R' may be an ester functional group.
  • Suitable plasticizers are known in the art and are commercially available.
  • the plasticizer may comprise a phthalate, such as: dibutyl phthalate, dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, bis(2-propylheptyl) phthalate, di(2-ethylhexyl) phthalate, dimethyl phthalate; diethyl phthalate; dibutyl phthalate, and bis(2-ethylhexyl) terephthalate; a cadicarboxylate such as 1,2, 4-benzenetricarboxylic acid, bis(2-ethylhexyl)-l,4- benzenedicarboxylate; 2-ethylhexyl methyl- 1,4-benzenedicarboxylate; 1,2 cyclohexanedicarboxylic acid, dinonyl ester, branched and linear;
  • a polymer plasticizer can be used.
  • the polymer plasticizer include alkenyl polymers obtained by polymerizing vinyl or allyl monomers by means of various methods; polyalkylene glycol esters such as diethylene glycol dibenzoate, triethylene glycol dibenzoate and pentaerythritol ester; polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; polyethers
  • polyether polyols each having a molecular weight of not less than 500 such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polystyrenes such as polystyrene and poly-alpha-methylstyrene; and polybutadiene, polybutene, polyisobutylene, butadiene acrylonitrile, and polychloroprene.
  • the plasticizers may be used either each alone or in combinations of two or more thereof.
  • a low molecular weight plasticizer and a higher molecular weight polymer plasticizer may be used in combination.
  • the amount of plasticizer may range from 5 to 150 parts by weight based on the combined weights of all ingredients in the composition.
  • Plasticizers are known in the art and are exemplified by those disclosed in EP 1 746 133 at paragraphs [0154] to [0161].
  • Optional ingredient (E) is a stabilizer.
  • Stabilizers include ultraviolet absorbers such as benzophenone compounds, benzotriazole compounds, salicylate compounds, substituted tolyl compounds, and metal chelate compounds; photostabilizers such as benzotriazole compounds, hindered amine compounds, benzoate compounds; and antioxidants such as hindered amines, hindered phenol antioxidants, monophenol antioxidants, bisphenol antioxidants, and polyphenol antioxidants. Examples of suitable stabilizers are disclosed in EP 1 746 133 at paragraphs [0170] to [0173]. Suitable stabilizers are known in the art and are commercially available.
  • suitable stabilizers include Irganox® 1010, Irganox® 245, Irgafos® 168 and 126, EB 50-866, and Tinuvin® 5060, all of which are commercially available from BASF Corporation of Florham Park, New Jersey, USA.
  • the exact amount of stabilizer depends on various factors including the type of stabilizer selected and the reactivity of the composition, however, the amount of stabilizer, when present, may range from 0.2 parts to 5 parts, per 100 parts by weight of ingredient ( ⁇ ').
  • Ingredient (F) is a filler, such as reinforcing filler, an extending filler, or a combination thereof.
  • a reinforcing filler when present, may be added in an amount ranging from 1% to 35%, alternatively 1% to 15%, based on the weight of the composition.
  • suitable reinforcing fillers include reinforcing silica fillers such as fume silica, silica aerogel, silica zerogel, and precipitated silica. Fumed silicas are known in the art and commercially available; fumed silica is sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts.
  • the extending filler when present, may be used in an amount ranging from 1% to 60%, alternatively 1% to 20%, based on the weight of the composition.
  • extending fillers include crushed quartz, aluminum oxide, magnesium oxide, calcium carbonate, zinc oxide, talc, diatomaceous earth, iron oxide, clays, titanium dioxide, zirconia, sand, carbon black, graphite, or a combination thereof.
  • Extending fillers are known in the art and commercially available; such as a ground silica sold under the name MIN-U-SIL by U.S. Silica of Berkeley Springs, WV.
  • One skilled in the art would recognize that the amounts of fillers disclosed are exemplary and not limiting. More or less filler may be used depending on the end use of the composition.
  • Semi- reinforcing fillers such as precipitated calcium carbonate fillers, may be used alone or in combination with other fillers.
  • a filler treating agent when present, may be used in an amount ranging from 0.1 % to 15 %, alternatively 0.5 % to 5 %, based on the weight of the composition.
  • the filler (F) may optionally be surface treated with ingredient (G).
  • Ingredient (F) may be treated with ingredient (G) before being added to the composition, or in situ.
  • Ingredient (G) may comprise an alkoxysilane, an alkoxy-functional oligosiloxane, a cyclic polyorganosiloxane, a hydroxyl- functional oligosiloxane such as a dimethyl siloxane or methyl phenyl siloxane, or a fatty acid.
  • stearates include calcium stearate.
  • Suitable adhesion promoters may comprise alkoxysilanes of the formula R9qSi(ORlO)(4_q), where subscript q is 1, 2, or 3, alternatively q is 3.
  • R9 is independently a monovalent organofunctional group.
  • R ⁇ can be an epoxyfunctional group such as glycidoxypropyl or (epoxycyclohexyl)ethyl, an amino functional group such as aminoethylaminopropyl or aminopropyl, a methacryloxypropyl, or an unsaturated organic group.
  • Each RIO is independently a saturated hydrocarbon group of at least 1 carbon atom.
  • RIO may have 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms.
  • RIO is exemplified by methyl, ethyl, n-propyl, and iso-propyl.
  • adhesion promoters examples include glycidoxypropyltrimethoxysilane or hydrolysis products thereof.
  • the composition may comprise 2 % to 5 % of adhesion promoter based on the weight of the composition.
  • adhesion promoters and their amounts is exemplary and not limiting.
  • any suitable fungicide may be utilized as component (I).
  • suitable fungicide include, but are not limited to methyl benzimidazol-2-ylcarbamate (carbendazim), ⁇ , ⁇ '-oxybisphenoxarsine, 2-(4- thiazolyl)-benzimidazole, N-(fluorodichloromethylthio)phthalimide, diiodomethyl p-tolyl sulfone, if appropriate in combination with a UV stabilizer, such as 2,6-di(tert-butyl)-p-cresol, 3- iodo-2-propinyl butylcarbamate (IPBC), zinc 2-pyridinethiol 1 -oxide, triazolyl compounds such as [alpha] - [2-(4-chlorophenyl)ethyl] - [alpha] -( 1 , 1 -dimethylethyl)- 1 H- 1 ,2,4-triazole
  • the rheological additives include polyamides, silicone organic co-polymers based on polyols of polyethers or polyesters; non-ionic surfactants such as polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylates, copolymers or ethylene oxide (EO) and propylene oxide (PO), and silicone polyether copolymers; as well as silicone glycols.
  • non-ionic surfactants such as polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylates, copolymers or ethylene oxide (EO) and propylene oxide (PO), and silicone polyether copolymers; as well as silicone glycols.
  • EO ethylene oxide
  • PO propylene oxide
  • silicone polyether copolymers may enhance the adhesion of a sealant to substrates, particularly plastic
  • Suitable rheological additives are known in the art and are exemplified by those in EP 1 746 133 at paragraph [0165]. These include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate and barium stearate, and combinations thereof.
  • Flame retardants may include for example, carbon black, hydrated aluminum hydroxide, and silicates such as wollastonite, platinum and platinum compounds.
  • Pigments include carbon black, titanium dioxide, and PolyOne Stan-Tone Green, which is commercially available from PolyOne.
  • Ingredient (M) is a co-catalyst that may be added to the composition.
  • Suitable co- catalysts include but are not limited to lauryl amine, aminoethylaminopropyltrimethoxysilane, and combinations thereof.
  • aminoethylaminopropyltrimethoxysilane may be both a co-catalyst and a crosslinker.
  • the amount of ingredient (M) may range from 0.05 to 3 % based on the weight of the composition.
  • compositions described above are useful in various applications such as sealant and adhesive applications.
  • a sealant may be prepared by a method comprising: i) preparing a sealant composition using the method and ingredients described above, and ii) curing the sealant composition.
  • an adhesive may be prepared by a method comprising: i) preparing an adhesive composition using the method and ingredients described above, and ii) curing the adhesive composition.
  • DBTDL dibutyltin dilaurate
  • the ethoxy end-blocked polymer prepared in reference example 2 was exposed to a mixture of isobutyltrimethoxysilane (IBTMS) and a titanate transesterification catalyst . After the titanate/ IBTMS exposure, cure rate was gauged by addition of DBTDL and an amine (either lauryl amine or aminoethylaminopropyltrimethoxysilane). The resulting mixture was then exposed to moisture for cure.
  • IBTMS isobutyltrimethoxysilane
  • amine either lauryl amine or aminoethylaminopropyltrimethoxysilane
  • IBTMS isobutyl-trimethoxysilane
  • TTBT tetrabutyl titanate
  • LA lauryl amine
  • LA lauryl amine
  • Example 1 was repeated, except that TTBT was eliminated. The composition did not cure after 24 hours.
  • Example 6 (comparative)
  • Example 2 was repeated, except that TTBT was eliminated. The composition did not cure after 24 hours.
  • Examples 3-4 show that the composition cures when a transesterification catalyst is added and the composition is aged to allow transesterification to occur.
  • Examples 5 and 6 show that cure takes too long for the composition to be commercially viable when the transesterification catalyst is omitted, indicating that the ethoxy groups on the ethoxy-end- blocked organic polymer remain on the polymer (i.e., transesterification to a methoxy-end- blocked organic polymer does not take place).
  • the ingredients were reacted under the following conditions.
  • the polyl pro ylene glycol
  • DBTDL was added and mixed for 15 minutes.
  • the end blocker, N ⁇ C-0-(CH2)3Si(OCH3)3 was added drop wise. After all the end blocker was added, the flask was heated. The contents of the flask were kept at 70 °C for 5 hours.
  • Diisodecyl phthalate (DIDP) plasticizer was then added, and the resulting mixture was stored at 50 °C for another 16 hours.
  • the mixture was a combination of DBTDL with aminoethylaminopropyltrimethoxysilane in a weight ratio 1.5 parts DBTDL to 1 part aminoethylaminopropyltrimethoxysilane.
  • the amounts of each ingredient were in weight parts per 10 weight parts of polymer used from Example 2 or Example 3.
  • the samples were evaluated for cure time and for swell gel according to reference example 1. The results are also in Table 1.
  • Examples 10 and 14 show that the ethoxy-end-blocked polymer can be cured to a similar extent as a corresponding methoxy-end-blocked polymer according to the transesterification process described herein.
  • the ingredients were reacted under the following conditions.
  • the polyl (propylene glycol) was weighed in a 3 neck flask with a dry nitrogen blanket. DBTDL was added and mixed for 15 minutes.
  • the end-blocker, N ⁇ C-0-(CH2)3Si(OCH3)3 was added drop wise. After all the end-blocker was added, the flask was heated. The contents of the flask were kept at 70 °C for 5 hours.
  • Samples were prepared by mixing the ingredients in Table 2 under the following conditions.
  • the methoxy- or ethoxy- end-blocked polymer was mixed with IBTMS and stored at RT or 50 °C for 24 hours.
  • the amounts of each ingredient were in weight parts per 10 weight parts of polymer used from Example 3, 4 or 5.
  • a mixture of DBTDL and aminoethylaminopropyltrimethoxysilane was mixed therewith.
  • the mixture contained 2 parts DBTDL per 1 part aminoethylaminopropyltrimethoxysilane and was added in an amount of 0.15 g mixture per 10 grams end-blocked polymer.
  • IBTES was isobutyltriethoxysilane and Tyzor 9000 was titanium tetra-t-butoxide, Ti(OtBu)4, where tBu represents a tert-butyl group.
  • Ti(OtBu)4 titanium tetra-t-butoxide
  • tBu represents a tert-butyl group.
  • Example 21 shows that transesterification occurs upon heating in this example, as evidenced by the comparable cure to the methoxy-end-blocked polymers in examples 15 and 16 when a transesterification catalyst and methoxysilane are used with the ethoxy-end-blocked polymer.
  • curable compositions containing methoxy capped organic polymers typically cured at a faster rate as compared to a similar composition containing an organic polymer capped with ethoxy groups (or other alkoxy groups having more than one carbon atom).
  • the present composition and method may provide the advantages of improved stability of the higher alkoxy functional organic polymer as compared to the same polymer with methoxy groups; ability to handle the higher alkoxy-end-blocked polymer at higher temperatures and/or for longer times in processing to allow for moisture removal from other sealant and/or adhesive ingredients such as precipitated CaC03, higher flash points for the higher alkoxy silanes and polymers end-blocked therewith, and improved availability of the ethoxy silane precursors, for example, for isocyanto silane preparation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)
  • Sealing Material Composition (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention a pour objet un procédé de modification de la vitesse de durcissement d'un produit durcissable par réaction de condensation impliquant la conversion des groupes alcoxy supérieurs sur l'ingrédient (A) en groupes alcoxy inférieurs (tels que des groupes méthoxy) au moyen des ingrédients (B) et (C). L'ingrédient (A) est un substrat (polymère) ayant une moyenne, par molécule, d'au moins deux groupes de blocage des terminaisons silyle fonctionnalisés par un groupe alcoxy supérieur. L'ingrédient (B) est un réactif ayant des groupes alcoxy inférieurs reliés au silicium. L'ingrédient (C) est un catalyseur de transestérification. On pense que les groupes alcoxy supérieurs sur l'ingrédient (A) durcissent trop lentement pour être utilisables dans de nombreux produits d'étanchéité et adhésifs durcissables à l'humidité. Tel qu'il est utilisé ici, le terme groupe alcoxy supérieur signifie un groupe alcoxy ayant plus d'atomes de carbone que le groupe alcoxy inférieur sur l'ingrédient (B). Par l'échange d'une partie ou de la totalité des groupes alcoxy supérieurs sur l'ingrédient (A) par des groupes alcoxy inférieurs provenant de l'ingrédient (B), on pense que la vitesse de durcissement d'une composition de produit d'étanchéité ou d'adhésif peut être augmentée. En outre, il peut être possible de réguler la vitesse de durcissement de la composition par la variation de la quantité des groupes alcoxy inférieurs présents. Et il peut être possible de réguler les propriétés physiques, telles que le module, par la variation des quantités des ingrédients (A) et (B) l'une par rapport à l'autre.
PCT/US2010/059536 2009-12-08 2010-12-08 Régulation de la vitesse de durcissement pour des polymères à terminaison bloquée par un alcoxysilyle Ceased WO2011072056A2 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018113937A1 (fr) * 2016-12-20 2018-06-28 Wacker Chemie Ag Procédé pour la préparation de polymères terminés par organyloxysilyle
WO2018141614A1 (fr) * 2017-01-31 2018-08-09 Basf Se Dispersion de particules de silicium oxydé dans un polyol
JP2020533421A (ja) * 2017-06-26 2020-11-19 ダウ シリコーンズ コーポレーション シリコーンポリエーテルコポリマー、それにより形成されるイソシアネート官能性シリコーンポリエーテルコポリマー、シリコーンポリエーテルウレタンコポリマー、それらを含むシーラント、および関連する方法

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4291316A (en) 1975-06-03 1981-09-22 Ricoh Co., Ltd. System for driving ink drop generator of ink-jet printer
US4889903A (en) 1988-08-03 1989-12-26 Basf Corporation Fast-cure polyurethane sealant composition containing titanium ester accelerators
WO1990006958A1 (fr) 1988-12-14 1990-06-28 Bramite Limited Polyurethanes modifies a la silicone
US4962076A (en) 1988-11-28 1990-10-09 Dow Corning Corporation Silicone sealants having reduced color
US5051455A (en) 1990-01-16 1991-09-24 Dow Corning Corporation Adhesion of silicone sealants
US5053442A (en) 1990-01-16 1991-10-01 Dow Corning Corporation Low modulus silicone sealants
US5489622A (en) 1993-06-11 1996-02-06 Three Bond Co., Ltd. Moisture- or anaerobic-curable and photocurable silicone compositions
EP0930605A2 (fr) 1998-01-14 1999-07-21 J. Hudson & Co. (Whistles) Ltd Sifflet
WO1999065966A1 (fr) 1998-06-12 1999-12-23 Schlegel Limited Compositions de polyurethannes ii
US6168253B1 (en) 1995-12-28 2001-01-02 Canon Kabushiki Kaisha Ink-jet head using sealant and ink-jet apparatus using the ink-jet head
US6169142B1 (en) 1998-06-17 2001-01-02 Shin Etsu Chemical Co., Ltd. Thermal conductive silicone rubber compositions and method of making
EP1101167A1 (fr) 1998-07-24 2001-05-23 Sun Microsystems, Inc. Technique et dispositif de reponse d'attribution de memoire pre-deterministe dans un systeme informatique
EP1746133A1 (fr) 2004-05-07 2007-01-24 Kaneka Corporation Composition durcissable améliorée en termes d'adhésivité
WO2008132236A2 (fr) 2007-05-01 2008-11-06 Dow Corning Corporation Polymères et compositions à base de polymère

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2292747T5 (es) * 2001-02-23 2014-04-10 Henkel Ag & Co. Kgaa Polímeros alcoxisililfuncionales mixtos

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4291316A (en) 1975-06-03 1981-09-22 Ricoh Co., Ltd. System for driving ink drop generator of ink-jet printer
US4889903A (en) 1988-08-03 1989-12-26 Basf Corporation Fast-cure polyurethane sealant composition containing titanium ester accelerators
US4962076A (en) 1988-11-28 1990-10-09 Dow Corning Corporation Silicone sealants having reduced color
WO1990006958A1 (fr) 1988-12-14 1990-06-28 Bramite Limited Polyurethanes modifies a la silicone
US5051455A (en) 1990-01-16 1991-09-24 Dow Corning Corporation Adhesion of silicone sealants
US5053442A (en) 1990-01-16 1991-10-01 Dow Corning Corporation Low modulus silicone sealants
US5489622A (en) 1993-06-11 1996-02-06 Three Bond Co., Ltd. Moisture- or anaerobic-curable and photocurable silicone compositions
US6168253B1 (en) 1995-12-28 2001-01-02 Canon Kabushiki Kaisha Ink-jet head using sealant and ink-jet apparatus using the ink-jet head
EP0930605A2 (fr) 1998-01-14 1999-07-21 J. Hudson & Co. (Whistles) Ltd Sifflet
WO1999065966A1 (fr) 1998-06-12 1999-12-23 Schlegel Limited Compositions de polyurethannes ii
US6169142B1 (en) 1998-06-17 2001-01-02 Shin Etsu Chemical Co., Ltd. Thermal conductive silicone rubber compositions and method of making
EP1101167A1 (fr) 1998-07-24 2001-05-23 Sun Microsystems, Inc. Technique et dispositif de reponse d'attribution de memoire pre-deterministe dans un systeme informatique
EP1746133A1 (fr) 2004-05-07 2007-01-24 Kaneka Corporation Composition durcissable améliorée en termes d'adhésivité
WO2008132236A2 (fr) 2007-05-01 2008-11-06 Dow Corning Corporation Polymères et compositions à base de polymère
WO2008132237A2 (fr) 2007-05-01 2008-11-06 Dow Corning Corporation Compositions à base de polymère

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018113937A1 (fr) * 2016-12-20 2018-06-28 Wacker Chemie Ag Procédé pour la préparation de polymères terminés par organyloxysilyle
CN110088161A (zh) * 2016-12-20 2019-08-02 瓦克化学股份公司 用于生产有机氧基甲硅烷基封端的聚合物的方法
US11421068B2 (en) 2016-12-20 2022-08-23 Wacker Chemie Ag Method for producing organyloxysilyl-terminated polymers
WO2018141614A1 (fr) * 2017-01-31 2018-08-09 Basf Se Dispersion de particules de silicium oxydé dans un polyol
CN110234671A (zh) * 2017-01-31 2019-09-13 巴斯夫欧洲公司 在多元醇中的氧化硅颗粒分散体
CN110234671B (zh) * 2017-01-31 2022-05-31 巴斯夫欧洲公司 在多元醇中的氧化硅颗粒分散体
US11479635B2 (en) 2017-01-31 2022-10-25 Basf Se Oxidic silicon particle dispersion in polyol
JP2020533421A (ja) * 2017-06-26 2020-11-19 ダウ シリコーンズ コーポレーション シリコーンポリエーテルコポリマー、それにより形成されるイソシアネート官能性シリコーンポリエーテルコポリマー、シリコーンポリエーテルウレタンコポリマー、それらを含むシーラント、および関連する方法
JP2020534376A (ja) * 2017-06-26 2020-11-26 ダウ シリコーンズ コーポレーション シリコーンポリエーテルコポリマー、その調製方法、およびそれを含むシーラント
JP7197518B2 (ja) 2017-06-26 2022-12-27 ダウ シリコーンズ コーポレーション シリコーンポリエーテルコポリマー、それにより形成されるイソシアネート官能性シリコーンポリエーテルコポリマー、シリコーンポリエーテルウレタンコポリマー、それらを含むシーラント、および関連する方法
JP7197517B2 (ja) 2017-06-26 2022-12-27 ダウ シリコーンズ コーポレーション シリコーンポリエーテルコポリマー、その調製方法、およびそれを含むシーラント

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