WO2007081431A1 - Compositions durcissables a la silicone contenant de la silice derivee de matiere biogene - Google Patents

Compositions durcissables a la silicone contenant de la silice derivee de matiere biogene Download PDF

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Publication number
WO2007081431A1
WO2007081431A1 PCT/US2006/044053 US2006044053W WO2007081431A1 WO 2007081431 A1 WO2007081431 A1 WO 2007081431A1 US 2006044053 W US2006044053 W US 2006044053W WO 2007081431 A1 WO2007081431 A1 WO 2007081431A1
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Prior art keywords
ingredient
composition
group
groups
curable silicone
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Jary Jensen
Tommy Detemmerman
Thierry Dessilly
Herschel Henry Reese
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Dow Silicones Corp
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Dow Corning Corp
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    • 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
    • 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
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy 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
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • This invention relates to curable silicone compositions and methods for their preparation and use.
  • the compositions contain silica filler derived from biogenic matter. Cured products of the compositions are capable of transmitting light or capable of being pigmented to a light color, or both.
  • Background [0003] Silica fillers derived from biogenic matter are known in the art. Previous attempts to incorporate them into curable silicone compositions have been unsuccessful because silica fillers derived from biogenic matter frequently impart black color to curable silicone compositions, and cured products thereof.
  • curable silicone compositions There is a need to reduce the cost of producing curable silicone compositions as compared to curable silicone compositions prepared using fumed and/or precipitated silica derived from crystalline silica, which may be mined or dredged. There is a need to produce curable silicone compositions containing silica derived from biogenic matter that cure to form cured products that are capable of transmitting light or capable of being pigmented to a light color, or both.
  • This invention relates to a curable silicone composition.
  • the curable silicone composition comprises: (I) 1% to 50% based on the weight of the composition of a non- colorant silica derived from biogenic matter and (II) 10% to 99% based on the weight of the composition of a silicone cure package.
  • the inventors surprisingly found a non-colorant silica derived from biogenic matter allows the cured product of the curable silicone composition to remain capable of transmitting light or capable of being pigmented to a light color, or both.
  • Non-colorant means any substance that imparts color to another material or mixture. The term colorant applies to black and white, as well as actual colors.
  • Non-colorant means a substance that imparts low or no color to a curable composition such that the cured product thereof is either capable of transmitting light or capable of being pigmented to a light color, or both.
  • non-colorant includes a substance that imparts some gray color to a transparent or translucent curable composition as long as the cured product thereof is also transparent or translucent when evaluated as in example 1, described below.
  • Translucent means capable of transmitting light but causing sufficient diffusion to eliminate perception of distinct images.
  • Transparent means capable of transmitting light so that objects or images can be perceived.
  • Capable of being pigmented to a light color means that the cured product may be a color other than black or gray, such as white or almond, when the composition contains no more than 10% of a pigment, such as titanium dioxide.
  • the curable silicone composition of this invention comprises (I) a non-colorant silica derived from biogenic matter in an amount sufficient to reduce the cost of production of the curable silicone composition (as compared to a comparable composition, which contains silica not derived from biogenic matter instead of the non-colorant silica derived from biogenic matter) but insufficient to render a cured product of the composition incapable of transmitting light or incapable of being pigmented to a light color, or both.
  • the curable silicone composition of this invention may comprise an amount ranging from 1% to 50%, alternatively 1% to 40%, alternatively 1% to 35%, alternatively 1% to 20%, alternatively 5% to 20%, alternatively 5% to 30%, and alternatively 10% to 20% of ingredient (I).
  • a cured product prepared from this composition including an amount ranging from 1 to 20% of ingredient (I) is capable of transmitting light.
  • a cured product prepared from the composition including an amount of ingredient (I) ranging from 1% to 50% or 1% to 35% is capable of being pigmented to a light color.
  • amounts of ingredient (I) ranging from 1% to 50% may be used in curable silicone rubber compositions, such as high consistency rubber compositions, as exemplified below.
  • amounts of ingredient (I) ranging from 1% to 35% may be used in sealant compositions, such as acetoxy curable silicone sealant compositions, as exemplified below, and other moisture curable silicone sealant compositions.
  • Ingredient (I) may be prepared by processes known in the art, for example, the process disclosed in U.S. Patent 6,406,678. This process involves soaking a biogenic material containing amorphous silica, such as rice hulls, in an oxidizing agent and thereafter burning the biogenic material at elevated temperature (above 500 0 C) but below the melting point of silica. Thereafter, the silica may be rinsed with water or mild acid solution. Before soaking, the biogenic material may be cleaned, softened, or both. The resulting silica may be white.
  • a biogenic material containing amorphous silica such as rice hulls
  • Non-colorant silica suitable for use as ingredient (I) may comprise rice hull ash, wheat chaff ash, oat bran ash, or a combination thereof; alternatively rice hull ash.
  • Ingredient (I) may be amorphous.
  • Ingredient (I) may have a BET surface area ranging from 150 to 350 m 2 /g, alternatively 250 to 400 m 2 /g.
  • Ingredient (I) may be white.
  • Ingredient (I) has high purity. For example, ingredient (I) may have purity greater than or equal to 99.5% SiO 2 , alternatively greater than or equal to 99.8%.
  • Sodium content may be less than 0.03%. Iron content may be less than 0.02%. Potassium content may be less than 0.01%.
  • Calcium content may be less than 0.01%. Water content may be 0.5% to 1.5%, alternatively 0.88% to 1.19%.
  • the curable silicone composition of this invention cures to form a cured product that is capable of transmitting light.
  • the curing mechanism of the silicone cure package is not critical, for example, the composition may be moisture curable such as a one part or two part room temperature vulcanizing (RTV) composition, hydrosilylation curable such as a thermally curable one part composition or a two part composition that cures at ambient or elevated temperature, a peroxide curable composition, a radiation curable composition, or a combination thereof.
  • RTV room temperature vulcanizing
  • Ingredient (II) may comprise a moisture cure package.
  • the moisture cure package may comprise: 100 parts by weight of (A) a base polymer, an amount sufficient to cure the composition of (B) a crosslinking agent, and optionally an amount sufficient to accelerate curing of the composition of (C) a catalyst, where the ingredients and amounts are selected such that a cured product of the composition is capable of transmitting light or is capable of being pigmented to a light color, or both.
  • Ingredient (A) in the moisture cure package of this invention is a polyorganosiloxane having an average per molecule of at least two hydrolyzable substituents, such as halogen atoms, acetamido groups, acyloxy groups such as acetoxy, alkoxy groups, amido groups, amino groups, aminoxy groups, hydroxyl groups, oximo groups, ketoximo groups, methylacetamido groups, alkoxysilylhydrocarbylene groups, or a combination thereof.
  • the hydrolyzable substituents in ingredient (A) may be located at terminal, pendant, or both terminal and pendant positions.
  • Ingredient (A) may have a linear or branched structure.
  • Ingredient (A) may be a homopolymer or a copolymer.
  • Ingredient (A) may comprise an alkoxy-endblocked polydiorganosiloxane, a alkoxysilylhydrocarbylene-endblocked polydiorganosiloxane, a hydroxyl-endblocked polydiorganosiloxane, or a combination thereof.
  • Ingredient (A) may comprise a polydiorganosiloxane of Formula (I): where each R 1 is independently a hydrolyzable substituent, each R 2 is independently a monovalent organic group, each R 3 is independently an oxygen atom or a divalent hydrocarbon group, each a is independently 0, 1, or 2, and b is an integer having a value sufficient to provide the polydiorganosiloxane with a viscosity of at least 100 mPa-s at 25 0 C.
  • Formula (I) where each R 1 is independently a hydrolyzable substituent, each R 2 is independently a monovalent organic group, each R 3 is independently an oxygen atom or a divalent hydrocarbon group, each a is independently 0, 1, or 2, and b is an integer having a value sufficient to provide the polydiorganosiloxane with a viscosity of at least 100 mPa-s at 25 0 C.
  • Suitable hydrolyzable substituents for R 1 include, but are not limited to, a halogen atom, an acetamido group, an acetoxy group, an acyloxy group, an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, and a methylacetamido group.
  • Suitable organic groups for R 2 include, but are not limited to, monovalent substituted and unsubstituted hydrocarbon groups.
  • Examples of monovalent unsubstituted hydrocarbon groups for R 2 include, but are not limited to, alkyl such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; aryl such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl.
  • Examples of monovalent substituted hydrocarbon groups for R 2 include, but are not limited to, monovalent hal ⁇ genated hydrocarbon groups such as chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3 ,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3- nonafluorohexyl, and 8,8,8,7, 7-pentaf ⁇ uorooctyl; chlorinated cycloalkyl groups such as 2,2- dichlorocyclopropyl, 2,3-dichlorocyclopentyl; and fluorinated cycloalkyl groups such as 2,2- difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,
  • R 2 examples include, but are not limited to, hydrocarbon groups substituted with oxygen atoms such as glycidoxyalkyl, and hydrocarbon groups substituted with nitrogen atoms such as aminoalkyl and cyano-functional groups such as cyanoethyl and cyanopropyl.
  • each R 2 may be an alkyl group.
  • Ingredient (A) may comprise an ⁇ , ⁇ -difunctional-polydiorganosiloxane when, in Formula (I) above, each a is 2 and each R 3 is an oxygen atom.
  • ingredient (A) may have Formula (II): R 1 R 2 2 SiO-(R 2 2 SiO) b -SiR 2 2 R 1 , where R 1 and R 2 are as described above and b is an integer having a value ranging from 50 to 1 ,000, alternatively 200 to 700.
  • Ingredient (A) may comprise a hydroxyl-functional polydiorganosiloxane of the formula described above, in which each R 1 may be a hydroxyl group, each R 2 may be an alkyl group such as methyl, and b may have a value such that the hydroxyl functional polydiorganosiloxane has a viscosity of at least 100 mPa-s at 25 0 C.
  • b may have a value ranging from 50 to 700.
  • Exemplary hydroxy 1-endblocked polydiorganosiloxanes are hydroxyl -endblocked polydimethylsiloxanes.
  • Hydroxyl- endblocked polydiorganosiloxanes suitable for use as ingredient (A) may be prepared by methods known in the art, such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes.
  • Ingredient (A) may further comprise polydimethylsiloxanes endblocked on one terminal end by a triorganosilyl group, e.g.
  • the polydiorganosiloxanes having both hydroxyl end groups and triorganosilyl end groups may have more than 50%, alternatively more than 75%, of the total end groups as hydroxyl groups.
  • the amount of triorganosilyl group in the polymer may be used to regulate the modulus of the resulting cured sealant. Without wishing to be bound by theory, it is thought that higher concentrations of triorganosilyl end groups provide a lower modulus in cured sealants.
  • ingredient (A) may comprise an alkoxysilylhydrocarbylene- endblocked polydiorganosiloxane, for example when in Formula (I) above each R 3 is divalent hydrocarbon group or a combination of a divalent hydrocarbon group and a divalent siloxane group.
  • R 3 may be an alkylene group such as ethylene, propylene, or hexylene; an arylene group such as phenylene, or an alkylarylene group such as:
  • Ingredient (A) can be a single base polymer or a combination comprising two or more base polymers that differ in at least one of the following properties: average molecular weight, siloxane units, sequence, and viscosity.
  • Alkoxysilylhydrocarbylene-endblocked polydiorganosiloxanes may be prepared by reacting a vinyl-terminated, polydimethylsiloxane with
  • Ingredient (A) may further comprise an MQ resin, which comprises siloxane units of the formulae R'xRVxSiOi/a and SiO 4 ⁇ , where R 1 and R 2 are as described above and each instance of x is 0, 1 , or 2.
  • the MQ resin may have a ratio of M units to Q units (M:Q) of 0.5 to 1.2.
  • a MQ resin may be prepared by treating a product produced by the silica hydrosol capping process of Daudt, etal. disclosed in U.S. Patent 2,676,182.
  • the method of Daudt, et al. involves reacting a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or a combination thereof, and recovering a product comprising M and Q units (MQ resin).
  • the resulting MQ resins may contain from 2 to 5 percent by weight of silicon-bonded hydroxyl groups.
  • Ingredient (B) in the moisture cure package is a crosslinker added to the curable silicone composition in an amount sufficient to cure the curable silicone composition without too much weight loss from condensation products of the curing reaction and insufficient to allow curing of the curable silicone composition during storage for several months in a moisture impermeable package.
  • the exact amount of ingredient (B) depends on various factors including the hydrolyzable substituents 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).
  • Ingredient (B) may comprise a silane crosslinker having hydrolyzable groups or partial or full hydrolysis products thereof.
  • silane crosslinkers may have the general formula (III) R 4 c Si(R 5 )4-c, where each R 4 is independently a monovalent hydrocarbon group such as an alkyl group; each R 5 is a hydrolyzable substituent, for example a halogen atom, an acetamido group, an acyloxy group such as acetoxy, an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, or a methylacetamido group; and c is 0, 1, 2, or 3.
  • each R 5 may be independently selected from hydroxyl, alkoxy, acetoxy, amide, or oxime.
  • ingredient (B) may be selected from an acyloxysilane, an alkoxysilane, a ketoximosilane, and an oximosilane.
  • 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.
  • a dialkoxysilane such as a dialkyldialkoxysilane
  • a trialkoxysilane such as an alkyltrialkoxysilane
  • a tetraalkoxysilane such as a tetraalkoxysilane
  • suitable trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and a combination thereof, and alternatively methyltrimethoxysilane.
  • tetraalkoxysilanes examples include tetraethoxysilane.
  • the amount of the alkoxysilane that is used in the curable silicone composition may range from 0.5 to 15 parts by weight per 100 parts by weight of ingredient (A).
  • alkoxysilane crosslinkers are disclosed in U.S. Patents 4,962.076; 5,051,455; and 5,053,442.
  • Ingredient (B) 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-phenyl ethyl; and fluorinated alkyl groups such as 3,3,3-trifluoropropyl.
  • ingredient (B) may comprise organotriacetoxysilanes, for example mixtures containing methyltriacetoxysilane and ethyltriacetoxysilane.
  • the amount of the acetoxysilane that is used in the curable silicone 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 (A).
  • Ingredient (C) is a catalyst that may optionally be added to the silicone cure package to accelerate curing.
  • Ingredient (C) in the moisture cure package may comprise a carboxylic acid salt of metal, a tin compound, a titanium compound, or a zirconium compound.
  • Ingredient (C) may comprise carboxylic acid salts of metals, ranging from lead to manganese inclusive, in the electromotive series of metals.
  • ingredient (C) may comprise a chelated titanium compound, a titanate such as a tetraalkoxytitanate, or a combination thereof.
  • suitable titanium compounds include, but are not limited to, diisopropoxytitaniurn bis(ethylacetoacetate), tetrabutoxy titanate, tetrabutyltitanate, tetraisopropyltitanate, and bis-(ethoxyacetoacetonate)diiso ⁇ ropoxy titanium (IV), and a combination thereof.
  • ingredient (C) may comprise a tin compound such as dibutyltin diacetate, dibutyltin dilaurate, dibutyl tin oxide, stannous octoate tin oxide, or a combination thereof.
  • catalysts are disclosed in U.S. Patents 4,962,076; 5,051 ,455; and 5,053,442.
  • ingredient (II) in the curable silicone composition may comprise a hydrosilylation cure package.
  • the hydrosilylation cure package may comprise: 100 parts by weight of (A') a base polymer, an amount sufficient to cure the composition of (B') a crosslinking agent, and an amount sufficient to initiate curing of the composition of (C) a catalyst, where the ingredients and amounts are selected such that a cured product of the composition is capable of transmitting light or capable of being pigmented to a light color, or both.
  • Ingredient (A') of the hydrosilylation cure package may comprise a polyorganosiloxane having an average of at least two aliphatically unsaturated organic groups per molecule.
  • Ingredient (A') may have a linear or branched structure.
  • Ingredient (A') may be a homopolymer or a copolymer.
  • the aliphatically unsaturated organic groups may be alkenyl exemplified by, but not limited to, vinyl, allyl, butenyl, and hexenyl.
  • the unsaturated organic groups may be alkynyl groups exemplified by, but not limited to, ethynyl, propynyl, and butynyl.
  • the aliphatically unsaturated organic groups in ingredient (A') may be located at terminal, pendant, or both terminal and pendant positions.
  • the remaining silicon-bonded organic groups in ingredient (A') may be monovalent organic groups free of aliphatic unsaturation.
  • These monovalent organic groups may have 1 to 20 carbon atoms, alternatively 1 to 10 carbon atoms, and are exemplified by, but not limited to alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl; cycloalkyl groups such as cyclohexyl; and aromatic groups such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl.
  • alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl
  • cycloalkyl groups such as cyclohexyl
  • aromatic groups such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl.
  • Ingredient (A') may comprise a polyorganosiloxane of Formula (IV): R 6 2 R 7 SiO(R 6 2 SiO) d (R 6 R 7 SiO) e SiR 6 2 R 7 , Formula (V): R 6 3 SiO(R 6 2 SiO) f (R 6 R 7 SiO) g SiR 6 3 , or a combination thereof.
  • each R 6 is independently a monovalent organic group firee of aliphatic unsaturation and each R 7 is independently an aliphatically unsaturated organic group
  • d has an average value ranging from 2 to 2000
  • e has an average value ranging from 0 to 2000
  • f has an average value ranging from 0 to 2000
  • g has an average value ranging from 2 to 2000.
  • Suitable monovalent organic groups for R 6 include, but are not limited to, alkyl such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; and aryl such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl.
  • Each R 7 is independently an aliphatically unsaturated monovalent organic group.
  • R 7 is exemplified by alkenyl groups such as vinyl, allyl, and butenyl and alkynyl groups such as ethynyl and propynyl.
  • Ingredient (A') may comprise polydiorganosiloxanes such as i) dimethylvinylsiloxy-terminated polydimethylsiloxane, ii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/memylvinylsiloxane) 3 iii) dimethylvinylsiloxy-terminated polymethylv ⁇ nylsiloxane, iv) trimethylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane), v) trimethylsiloxy-terminated polymethylvinylsiloxane, vi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylphenylsiloxane), vii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/diphenylsiloxane), viii) phenyl,methyl,vinyl-siloxa
  • Ingredient (A') may further comprise a resin such as an MQ resin consisting essentially of R 8 3 SiOi /2 units and S1O4/2 units, a TD resin consisting essentially of R 8 Si ⁇ 3 /2 units and R 8 2 Si ⁇ 2/2 units, an MT resin consisting essentially of R 8 3 SiOi /2 units and R 8 SiO 3 ⁇ units, an MTD resin consisting essentially of R 8 3SiOi/2 units, R 8 SiO 3 Q units, and R ⁇ SiO 2Z2 units, or a combination thereof.
  • a resin such as an MQ resin consisting essentially of R 8 3 SiOi /2 units and S1O4/2 units, a TD resin consisting essentially of R 8 Si ⁇ 3 /2 units and R 8 2 Si ⁇ 2/2 units, an MT resin consisting essentially of R 8 3 SiOi /2 units and R 8 SiO 3 ⁇ units, an MTD resin consisting essentially of R 8 3SiOi/2 units, R 8 SiO 3 Q units
  • Each R 8 is a monovalent organic group.
  • the monovalent organic groups represented by R 8 may have 1 to 20 carbon atoms. Examples of monovalent organic groups include, but are not limited to, monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups.
  • Monovalent hydrocarbon groups include, but are not limited to, alkyl such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; alkenyl such as vinyl, allyl, butenyl, and hexenyl; alkynyl such as ethynyl, propynyl, and butynyl; and aryl such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl.
  • the resin may contain an average of 3 to 30 mole percent of aliphatically unsaturated organic groups.
  • the aliphatically unsaturated organic groups may be alkenyl groups, alkynyl groups, or a combination thereof.
  • the mole percent of aliphatically unsaturated organic groups in the resin is the ratio of the number of moles of unsaturated group-containing siloxane units in the resin to the total number of moles of siloxane units in the resin, multiplied by 100.
  • Methods of preparing resins are well known in the art. For example, resin may be prepared by treating a resin copolymer produced by the silica hydrosol capping process of Daudt, et al. with at least an alkenyl-containing endblocking reagent. The method of Daudt et al, is disclosed in U.S.
  • the method of Daudt, et al. involves reacting a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or mixtures thereof, and recovering a copolymer having M and Q units.
  • a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or mixtures thereof.
  • the resulting copolymers generally contain from 2 to 5 percent by weight of hydroxyl groups.
  • the resin which typically contains less than 2 percent by weight of silicon-bonded hydroxyl groups, may be prepared by reacting the product of Daudt, et al. with an unsaturated organic group-containing endblocking agent and an endblocking agent free of aliphatic unsaturation, in an amount sufficient to provide from 3 to 30 mole percent of unsaturated organic groups in the final product.
  • endblocking agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable endblocking agents are known in the art and exemplified in U.S. Patents 4,584,355; 4,591 ,622; and 4,585,836. A single endblocking agent or a mixture of such agents may be used to prepare the resin.
  • Ingredient (A') can be a single base polymer or a combination comprising two or more base polymers that differ in at least one of the following properties: structure, viscosity, average molecular weight, siloxane units, and sequence.
  • Ingredient (B ') Organohydrogenpolysiloxane
  • Ingredient (B') in the hydrosilylation cure package is an organohydrogenpolysiloxane having an average of at least two silicon-bonded hydrogen atoms per molecule.
  • the amount of ingredient (B') in the hydrosilylation cure package may range from 0.5 to 15 parts per 100 parts by weight of ingredient (A').
  • Ingredient (B') can be can be a homopolymer or a copolymer.
  • Ingredient (B') can have a linear, branched, cyclic, or resinous structure.
  • the silicon-bonded hydrogen atoms in ingredient (B') can be located at terminal, pendant, or at both terminal and pendant positions.
  • Ingredient (B') may comprise siloxane units including, but not limited to, HR 9 2 SiOi/2, R 9 3 SiO I/2 , HR 9 SiO 2 Z 2 , R 9 2 SiO M , R 9 SiO 3/2 , and SiO 4/2 units.
  • each R 9 is independently selected from monovalent organic groups free of aliphatic unsaturation.
  • Ingredient (B') may comprise a compound of the formula (VI) R 9 3 SiO(R 9 2 SiO) h (R 9 HSiO)iSiR 9 3 5
  • h has an average value ranging from 0 to 2000
  • i has an average value ranging from 2 to 2000
  • j has an average value ranging from 0 to 2000
  • k has an average value ranging from 0 to 2000.
  • Each R 9 is independently a monovalent organic group.
  • Suitable monovalent organic groups include alkyl such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; alkenyl such as vinyl, allyl, butenyl, and hexenyl; alkynyl such as ethynyl, propynyl, and butynyl; and aryl such as phenyl, tolyl, xylyl, benzyl, and 2- ⁇ henylethyl.
  • Ingredient (B ') is exemplified by a) dimethylhydrogensiloxy-terminated polydimethylsiloxane, b) dimethylhydrogensiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane), c) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, d) trimethylsiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane), e) trimethylsiloxy-terminated polymethylhydrogensiloxane, f) a resin consisting essentially of H(CHa) 2 SiO 1Z2 units and SiO 4Z2 units, and g) a combination thereof.
  • Ingredient (B') may be a combination of two or more organohydrogenpolysiloxanes that differ in at least one of the following properties: structure, average molecular weight, viscosity, siloxane units, and sequence. Ingredient (B') may be added in an amount ranging from 0.4 to 20% based on the weight of the hydrosilylation cure package.
  • Ingredient (C) of the hydrosilylation cure package is a hydrosilylation catalyst.
  • Ingredient (C) is added to the hydrosilylation cure package in an amount of 0.1 to 1000 ppm of platinum group metal, alternatively 1 to 500 ppm, alternatively 2 to 200, alternatively 5 to
  • Suitable hydrosilylation catalysts are known in the art and commercially available.
  • Ingredient (C) may comprise a platinum group metal selected from platinum, rhodium, ruthenium, palladium, osmium or indium metal or organometallic compound thereof, or a combination thereof.
  • Ingredient (C) is exemplified by compounds such as chloroplatinie acid, chloroplatinic acid hexahydrate, platinum dichloride, and complexes of said compounds with low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or coreshell type structure.
  • Complexes of platinum with low molecular weight organopolysiloxanes include l,3-diethenyl-l,l,3,3 -tetramethyldisiloxane complexes with platinum.
  • the catalyst may comprise 1,3-diethenyl-l, 1,3,3 -tetramethyldisiloxane complex with platinum.
  • the amount of catalyst may range from 0.04 to 0.4% based on the weight of the curable silicone composition.
  • Microencapsulated hydrosilylation catalysts and methods of preparing them are known in the art, as exemplified in U.S. Patent No. 4,766,176; and U.S. Patent No. 5,017,654.
  • ingredient (II) may comprise a peroxide cure package.
  • the peroxide cure package may comprise: 100 parts by weight of (A") a base polymer, optionally an amount sufficient to cure the composition of (B") a crosslinking agent, and an amount sufficient to accelerate curing of the composition of (C”) a catalyst, where the ingredients and amounts are selected such that a cured product of the composition is capable of transmitting light or capable of being pigmented to a light color, or both.
  • Ingredient (A") of the peroxide cure package comprises a polydiorganosiloxane having an average of at least two aliphatically unsaturated organic groups per molecule.
  • the polydiorganosiloxane may have a viscosity of at least 100 mPa-s at 25 °C.
  • the polydiorganosiloxane may comprise a polydiorganosiloxane gum having a viscosity, measured as Williams Plasticity Number in accordance with ASTM D-962 of greater than 100, which is equivalent to 4 x 10 6 mPa-s at 25 0 C.
  • viscosity may range from 125 to 200 Williams Plasticity number (corresponding to 10 x 10 6 to 80 x 10 6 mPa-s at 25 0 C).
  • the aliphatically unsaturated organic groups may be alkenyl exemplified by, but not limited to, vinyl, allyl, butenyl, and hexenyl.
  • the aliphatically unsaturated organic groups may be alkynyl groups exemplified by, but not limited to, ethynyl, propynyl, and butynyl.
  • the unsaturated organic groups in ingredient (A") may be located at terminal, pendant, or both terminal and pendant positions.
  • the remaining silicon-bonded organic groups in ingredient (A'") may be monovalent organic groups free of aliphatic unsaturation.
  • These monovalent organic groups are exemplified by, but not limited to alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl; cycloalkyl groups such as cyclohexyl; and aromatic groups such as phenyl, toly], xylyl, benzyl, and 2-phenylethyl.
  • Ingredient (A") may comprise a polydiorganosiloxane of Formula (IX): R 1 ⁇ R 1 ' SiO(R 9 2 SiO) m (R 9 R' 1 SiO) n SiR ⁇ R 11 , Formula (X): R 10 3 SiO(R 10 2SiO) o (R 10 R n SiO)pSiR 10 3, or a combination thereof. [0060] In formulae (IX) and (X),.
  • each R 10 is independently a monovalent organic group free of aliphatic unsaturation
  • each R 1 ' is independently an aliphatically unsaturated organic group
  • m has an average value of at least 2
  • n may be 0 or a positive number
  • o may be 0 or a positive number
  • p has an average value of at least 2, with the proviso that the subscripts have values sufficient to give the polydiorganosiloxanes of formulae (IX) and (X) Williams Plasticity Numbers greater than 100.
  • Suitable monovalent organic groups for R 10 include, but are not limited to, alkyl such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; and aryl such as phenyl, tolyl, xylyl, benzyl, and 2- phenylethyl.
  • Each R 1 ' is independently an aliphatically unsaturated monovalent organic group.
  • R 11 is exemplified by alkenyl groups such as vinyl, allyl, and butenyl and alkynyl groups such as ethynyl and propynyl.
  • Ingredient (A") may be a combination of two or more polydiorganosiloxanes that differ in at least one of the following properties: structure, average molecular weight, viscosity, siloxane units, and sequence.
  • Optional Ingredient (B") Cr osslinking Agent Ingredient (B") a crosslinking agent may optionally be added to the peroxide cure package to improve compression set of a silicone elastomer prepared by curing this composition. The amount of ingredient (B") in the composition may range from 0 to 15 parts per 100 parts by weight of ingredient (A").
  • Ingredient (B") may comprise a polydiorganohydrogensiloxane having an average of at least two silicon-bonded hydrogen atoms per molecule.
  • Ingredient (B") may comprise a polydiorganohydrogensiloxane of the formula (XI) R 12 3 SiO(R 12 2 SiO) q (R 12 HSiO) r SiR I2 3 ,
  • q has an average value ranging from 0 to 2000
  • r has an average value ranging from 2 to 2000
  • s has an average value ranging from 0 to 2000
  • t has an average value ranging from 0 to 2000
  • Each R 12 is independently a monovalent organic group.
  • Suitable monovalent organic groups include alkyl such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; alkenyl such as vinyl, allyU butenyl, and hexenyl; alkynyl such as ethynyl, propynyl, and butynyl; and aryl such as phenyl, tolyl, xylyl, benzyl, and 2- phenylethyl.
  • Ingredient (B") is exemplified by i) dimethylhydrogensiloxy-terminated polydimethylsiloxane, ii) dimethylhydrogensiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane), iii) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, iv) trimethylsiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane), v) trimethylsiloxy-terminated polymethylhydrogensiloxane, vi) a combination thereof.
  • Ingredient (B) may be a combination of two or more polydiorganohydrogensiloxanes that differ in at least one of the following properties: structure, average molecular weight, viscosity, siloxane units, and sequence.
  • Ingredient (C") in the peroxide cure package comprises a peroxide compound.
  • the amount of ingredient (C") added to the composition depends on the specific peroxide compound selected for ingredient (C"), however, the amount may range from 0.2 to 5 parts per 100 parts by weight of ingredient (A").
  • peroxide compounds suitable for ingredient (C") include, but are not limited to 2,4-dichlorobenzoyl peroxide, dicumyl peroxide, and a combination thereof; as well as combinations of such a peroxide with a benzoate compound such as tertiary-butyl perbenzoate.
  • Suitable peroxide cure packages are known in the art, and are disclosed in, for example, U.S. Patent 4,774,281.
  • the fume silica filler in the composition of U.S. Patent 4,774,281 may be partially replaced by ingredient (I).
  • Optional Ingredients are known in the art, and are disclosed in, for example, U.S. Patent 4,774,281.
  • the fume silica filler in the composition of U.S. Patent 4,774,281 may be partially replaced by ingredient (I).
  • Optional Ingredients are known in the art, and are disclosed in, for example, U.S. Patent 4,774,281.
  • the curable silicone compositions of this invention may further comprise one or more additional ingredients in addition to ingredients (I) and (II), provided that the ingredient and amount thereof does not render a cured product of the composition incapable of transmitting light.
  • the composition may further comprise an additional ingredient selected from the group consisting of (III) a reinforcing filler, (IV) an extending filler, (V) a conductive filler (e.g., electrically conductive, thermally conductive, or both), (VI) a filler treating agent, (VII) a stabilizer (e.g., a hydrosilylation cure stabilizer, a heat stabilizer, or a UV stabilizer), (VIII) a plasticizer, (IX), an extender (sometimes referred to as a secondary plasticizer or processing aid), (X) an adhesion promoter, (XI) a fungicide, (XII) a rheological additive, (XIII) a flame retardant, (XIV) a pigment, and a combination thereof
  • ingredient (HI) a reinforcing filler
  • ingredient (I) may be added in addition to ingredient (I) in an amount ranging from 1% to 35%, alternatively 1% to 15%, based on the weight of the composition when the composition will be formulated such that it cures to form a high consistency rubber.
  • suitable reinforcing fillers include reinforcing silica fillers not derived from biogenic matter such as fume silica, silica aerogel, silica zerogel, and precipitated silica. Fumed silicas not derived from biogenic matter are known in the art and commercially available; fumed silica sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts .
  • the composition may optionally further comprise ingredient (IV) an extending filler 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.
  • the composition may optionally further comprise ingredient (VI), a filler treating agent in an amount ranging from 0.1% to 15%, alternatively 0.5% to 5%, based on the weight of the composition.
  • Ingredient (I), and when present ingredients (III), (IV) 5 and (V) may optionally be surface treated with ingredient (VI).
  • Ingredients (I) 5 (III), (IV), and (V) may be treated with ingredient (VI) before being added to the composition, or in situ.
  • Ingredient (VI) 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.
  • Stabilizers for hydrosilylation cure packages are exemplified by acetylenic alcohols such as methyl butynol, ethynyl cyclohexanol, dimethyl hexynol, 1 , 1 -dimethyl-2-propynyl)oxy)trimethylsilane, methyl(tris(l , 1 -dimethyl-2- propynyloxy))silane, and a combination thereof; cycloalkenylsiloxanes such as methyivinylcyclosiloxanes exemplified by l,3,5 5 7-tetramethyl-l,3,5 5 7- tetravinylcyclotetrasiloxane, l ⁇ S ⁇ -tetxamemyl-l ⁇ S ⁇ -tetrahexenylcyclotetrasiloxane, and a combination thereof ; ene-yne compounds such as 3-methyl-3-penten
  • the stabilizer may comprise phenyl butynol.
  • Suitable hydrosilylation cure package stabilizers are disclosed by, for example, U.S. Patents 3,445,420; 3,989,667; 4,584,361; and 5,036,117.
  • the amount of stabilizer added to the curable silicone composition will depend on the particular stabilizer used and the composition and amount of ingredient (II). However, the amount of hydrosilylation cure package stabilizer may range from 0.0025% to 0.025% based on the weight of the curable silicone composition.
  • the curable silicone composition may comprise more than one cure package. For example a dual cure package that is both moisture curable and hydrosilylation curable is within the scope of this invention.
  • One skilled in the art would be able to select ingredients and amounts thereof in each cure package described above to prepare a cured product that has a desired consistency, such as a rubber or gel.
  • the curable silicone composition may be prepared as a one part composition, for example, by combining all ingredients by any convenient means, such as mixing.
  • the curable silicone composition may be prepared as a multiple part composition in which the crosslinking agent and catalyst are stored in separate parts, and the parts are combined shortly before use of the composition.
  • a two part curable silicone composition may be prepared by combining ingredients comprising (A) 5 (C), and any optional ingredients in a first part by any convenient means such as mixing.
  • a second part may be prepared by combining ingredients comprising (A), (B), and any optional ingredients by any convenient means such as mixing.
  • the non-colorant silica derived from biogenic matter may be added to the first part, the second part, or both.
  • the ingredients may be combined at ambient or elevated temperature and under ambient or anhydrous conditions, depending on the silicone cure package selected.
  • One skilled in the art would be able to prepare a curable silicone composition without undue experimentation.
  • Method of Using the Curable Silicone Composition [0077] Curable silicone compositions prepared according to this invention have various uses. One skilled in the art would be able to select ingredients to formulate a composition, for example, for use as a sealant or a curable silicone rubber composition, based on the description herein without undue experimentation.
  • Base Polymer 1 was ⁇ , ⁇ -dihydroxy-polydimethylsiloxane.
  • Base Polymer 2 was dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane).
  • Base Polymer 3 was dimethylvinylsiloxy-terminated polydimethylsiloxane.
  • Base Polymer 4 is dimethylvinylsiloxy-terminated polydimethylsiloxane.
  • Base Polymer 5 is dimethylvinyl-siloxy terminated, poly(dimethylsiloxane/methylvinylsiloxane).
  • Treating Agent 1 is hexamethyldisilazane.
  • Crosslinker 1 was a mixture of methyltriacetoxysilane and ethyltriacetoxysilane.
  • Crosslinker 2 is poly(dimethylsiloxane/methylhydrogensiloxane) with methyl silsesquioxane.
  • Catalyst 1 was dibutyltin diacetate.
  • Catalyst 2 is 1 ,3-diethenyl-l ,1,3,3 -tetramethyldisiloxane complex with platinum.
  • Silica was StratoSilTM, which is commercially available from International Silica
  • Plasticizer 1 was hydroxy-terminated poly(dimethylsiloxane/methylvinylsiloxane).
  • Plasticizer 2 was hydroxy-terminated polydimethylsiloxane.
  • Stabilizer 1 was ethynyl cyclohexanol.
  • Curable silicone sealant compositions were prepared by mixing the ingredients in
  • Table 1 for 1 minute using a whip mixer and de-airing the resulting mixtures under vacuum for 1 minute.
  • the samples were packaged in plastic screw cap containers.
  • Example 1 shows that the Silica appears to be a semi-reinforcing filler in this formulation. The Silica is non-colorant in this formulation.
  • Example 2 High Consistency Rubber Composition
  • Samples were prepared by mixing the ingredients in Table 2 under a nitrogen atmosphere with a small amount of ammonium carbonate (to accelerate silanol condensation between silanol groups on the plasticizers and the Silica) until the Silica was incorporated to form a base. Thereafter 1.2 parts of a 2,4-dichlorobenzoylperoxide catalyst per hundred parts of the base were mixed together to form a curable silicone composition.
  • Sample 4 was cured and evaluated for tensile strength, % elongation, specific gravity, durometer, tear strength, and compression set at 22 hours and 177 0 C. The results are in Table 3. Table 3
  • a composition was prepared by mixing 571.9 parts Base Polymer 4, 26 parts water, 0.9 parts Plasticizer 1, and 39.4 parts Treating Agent 1 for 5 minutes. Thereafter, 131.5 parts Silica was added and mixed until incorporated. Thereafter, 23.7 parts Treating Agent 1 and 131.5 parts Silica were added and mixed until the Silica is incorporated. Thereafter, another 131.5 parts Silica were added and mixed until incorporated. Thereafter 13.2 parts Treating Agent 1 were added and mixed. The resulting mixture is heated at 160 °C for 1 hour and 45 minutes. Thereafter, 200.1 parts Base Polymer 4, 105.2 parts Base Polymer 5, 0.5 parts Stabilizer 1, and 14.9 parts Crosslinker 2 were added. The resulting mixture was mixed for 15 minutes and stored in a metal can.
  • Using a non-colorant silica derived from biogenic matter in a curable silicone composition may provide the benefits of reduced cost (as compared to a curable silicone composition containing only fillers derived from non-biogenic matter) while maintaining translucency or transparency of the curable silicone composition and cured products thereof.
  • the non-colorant silica derived from biogenic matter may be used in combination with silica derived from other sources to reduce cost.
  • the non-colorant silica derived from biogenic matter may be used to replace all or a portion of silica in commercially available products.
  • such products include moisture curable products such as DOW CORNING® 732, 3330, 3-7132 Premium, 3440, 1199, and 899; and hydrosilylation curable products such as DOW CORNING® SYLGARD® 182, 184, and 186, all of which are available from Dow Corning Corporation of Midland, Michigan, U.S.A. to reduce cost without impairing capability of transmitting light.
  • moisture curable products such as DOW CORNING® 732, 3330, 3-7132 Premium, 3440, 1199, and 899
  • hydrosilylation curable products such as DOW CORNING® SYLGARD® 182, 184, and 186, all of which are available from Dow Corning Corporation of Midland, Michigan, U.S.A. to reduce cost without impairing capability of transmitting light.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention a trait à une composition durcissable à la silicone qui forme, en durcissant, une silicone durcie translucide ou transparente. Ladite composition comprend : (I) de 1 % à 50 % en poids de la composition d’une silice sans colorant dérivée d’une matière biogène et (II) de 10 % à 99 % en poids de la composition d’un système de durcissement de la silicone.
PCT/US2006/044053 2006-01-05 2006-11-14 Compositions durcissables a la silicone contenant de la silice derivee de matiere biogene Ceased WO2007081431A1 (fr)

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WO2016000690A1 (fr) * 2014-06-30 2016-01-07 Günter Gäbler Matériaux avec une proportion de silicates séparés à partir de plantes, notamment du dioxyde de silicium (sio2)
US9284454B2 (en) 2006-11-30 2016-03-15 Formformform Ltd. Room temperature curable silicone elastomer composition
WO2017144035A1 (fr) * 2016-02-24 2017-08-31 Green Sugar Ag Procédé de fixation de métaux, de métaux de transition et de leurs oxydes sur des matériaux siliceux d'origine végétale et utilisation de ces matériaux siliceux modifiés en tant que catalyseur et additif pour des peintures, vernis, matières plastiques, élastomères et colles
RU2705956C1 (ru) * 2018-11-27 2019-11-12 Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "КОМИ научный центр Уральского отделения Российской академии наук" Эпоксидный компаунд, наполненный биогенным кремнеземом
DE102014014177B4 (de) * 2014-09-19 2020-03-26 Green Sugar Ag Verwendung von pflanzenbasierten Silikaten als Additiv zur Verbesserung der stofflichen Eigenschaften von Mischungen

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9284454B2 (en) 2006-11-30 2016-03-15 Formformform Ltd. Room temperature curable silicone elastomer composition
WO2016000690A1 (fr) * 2014-06-30 2016-01-07 Günter Gäbler Matériaux avec une proportion de silicates séparés à partir de plantes, notamment du dioxyde de silicium (sio2)
DE102014014177B4 (de) * 2014-09-19 2020-03-26 Green Sugar Ag Verwendung von pflanzenbasierten Silikaten als Additiv zur Verbesserung der stofflichen Eigenschaften von Mischungen
WO2017144035A1 (fr) * 2016-02-24 2017-08-31 Green Sugar Ag Procédé de fixation de métaux, de métaux de transition et de leurs oxydes sur des matériaux siliceux d'origine végétale et utilisation de ces matériaux siliceux modifiés en tant que catalyseur et additif pour des peintures, vernis, matières plastiques, élastomères et colles
CN109121416A (zh) * 2016-02-24 2019-01-01 绿糖股份公司 用于将金属、过渡金属及其氧化物固定在植物来源的硅酸盐材料的方法，经改性的硅酸盐材料作为催化剂和作为颜料、漆料、塑料、弹性体和胶黏剂的添加剂的用途
RU2705956C1 (ru) * 2018-11-27 2019-11-12 Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "КОМИ научный центр Уральского отделения Российской академии наук" Эпоксидный компаунд, наполненный биогенным кремнеземом

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