CA1059306A - Heat stable organopolysiloxane composition - Google Patents
Heat stable organopolysiloxane compositionInfo
- Publication number
- CA1059306A CA1059306A CA239,157A CA239157A CA1059306A CA 1059306 A CA1059306 A CA 1059306A CA 239157 A CA239157 A CA 239157A CA 1059306 A CA1059306 A CA 1059306A
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- CA
- Canada
- Prior art keywords
- cerium
- composition
- sample
- organopolysiloxane
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
-
- 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
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K5/54—Silicon-containing compounds
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
Abstract
ABSTRACT OF THE DISCLOSURE
A reaction product of an alkali metal siloxanolate having at least three organosiloxane units per molecule with a cerium salt of an organic carboxylic acid or cerium chloride and an organic carboxylic acid salt or alkoxy compound of zirconium, titanium or iron are added to organosiloxane polymers to improve the heat stability of the polymer.
A reaction product of an alkali metal siloxanolate having at least three organosiloxane units per molecule with a cerium salt of an organic carboxylic acid or cerium chloride and an organic carboxylic acid salt or alkoxy compound of zirconium, titanium or iron are added to organosiloxane polymers to improve the heat stability of the polymer.
Description
)S~ 3 ~ ~ ;
This invention relates to an organopolysiloxane composition exhibiting improved heat stability.
It is well known in the art that the heat stability of organopolysiloxane compositions; particularly fluids and rubbers based on essentially linear diorganosiloxalle yolymers, can be improved by incorporation therein of certain inorganic salts of iron, zirconium, cerium, manganese, nickel and the like.
The use of compounds of cerium as heat stability additives for SUC}l siloxane polymers is shown in Japanese Patent No. 283,598 and Japanese Patent No. 535,121 wherein oxides or hydroxides of cerium or aromatic carboxylic acid salts o cerium are incorporated in the siloxane polyr,ler.
~lowever, these metal salts are not compatible Wit]l the organopolysiloxane, hence, it is necessary to admix the metal salt with a small portion of the siloxane polymer employing a suitable solvent to form a paste which can then be admixed Wit}l the siloxane composition. However, even when such additional steps are taken, the dispersion of the metal salt is heterogeneous or insuficient.
It is well known in the art that the heterogeneous or insuf~icient ~ispersion of any heat stability additive throu~h siloxane polymers results in unsatisfactory or minimal improvement in the heat stability o-f ~he polymer.
This is particularly noted in liquid organopolysiloxanes having relatively low viscosity because the inorganic or organic salts of cerium form sediments and precipitates when added to liquid organosiloxane polymers and this is especially noted following storage of the liquid. One means proposed for overcoming or minimizing the separation of the ~`;~
`:
~l~5~3~6 ~
cerium compound from the liquid organopolysiloxane is found in U.S. Patent No. 3,008,901, wherein it is proposed to heat a specific cerium complex salt in a solution of a liquid organopolysiloxane having a minute amount of SiII groups and an aromatic hydrocarbon at 2~0 to 290C. witll concurrent air flow through the reaction mixture for one to four days.
The proposed reaction is intended to disperse the cerium compound in the form of a colloid in the organopolysiloxane or to dissolve the cerium compound in the organopolysiloxane thereby obtaining a heat-stable organopolysiloxane composition.
In the composition prepared in accordance with U.S. Patent ,~
No. 3,008,901, the amount of cerium compound compatible with ~, the organopolysiloxane is very small and because the cerium content is changed by slight changes in the reaction conditions, it is dificult to establish and maintain the cerium content at a predetermined or constant level. Thus, from the commercial or industrial viewpoint, this known technique is unsatisfactory or the continuous preparation of large quantities of heat-stable organopolysiloxane compositions. `
It has been found that the reaction product obtained by reaction o a cerium salt of an organic carboxylic acid with an alkali metal siloxanolate or by reaction of cerium chloride with an alkali metal siloxanolate exhibits excellent compatibility with an organopolysiloxane. . `
Novel heat-stable organopolysiloxane compositions are - obtained by incorporating such reaction products tllerein.
However, it has been found that after several months storage at room temperature or durlng use of the organopolysiloxane at elevated temperatures, partial sedimentation or precipitation of the cerium compound will reduce the transparency of the organopolysiloxane and the heat stability as well.
; 2-~ 3~ ~
The search for a compatible heat-stability additive system for organopolysiloxanes W]liCh remains stable on storage has continued and it is the primary object of this invention to introduce such a system. A -furtller object is to introduce organopolysiloxane rubbers ancL liquids based on essentially linear diorganosiloxane polymers exhibiting improved heat stability even after extendecl periods of storage. Other objects and advantages attained through this invention are disclosed in or will be apparent from the disclosure and claims following.
This invention relates to a mixture o (1) a reaction pro~uct of (a) an alkali metal siloxanolate having at least three organosiloxane units per molecule with (b) a cerium salt of an organlc carboxylic acid or cerium chloride and (2) a metal compound selected Erom the group consisting of organic carboxylic acid salts and alkoxy compoun~s of zirconium, titanium and iron. The foregoing r~lixture is incorporated into an organopolysiloxane composition to pro~uce a composition exhibiting superior heat stability.
The use of the mixture produces a synergistic effect when compared to the use of either component separately.
The organopolysiloxane composition employed herein is based on an essentially linear diorganosiloxane polymer of ~he unit formula RXSiO4 x when R is an alkyl radical of ;
less than seven carbon atoms, a phenyl radical, a beta-perfluoroalkylethyl radical of three to nine carbon atoms or an alkenyl radical of two to six carbon atoms and x has an average value of 1.98 to 2.01. Preferred as R groups are CH3, C2H5, C3E17, CF3CH2CH2, C6E15 and Cli2=CH and minor amounts (e.g. less than 2 percent) of the R groups can be o~her than . ... .. . . . .: ; , . .
. . . . . . . .
~ ~5~3~6 those defined above. All R groups can be the same or they can be different. Because of commercial availability, siloxanes wherein at least 50 percent of the R groups are methyl radicals are preferred The terminal units on the siloxane polymer can be -OH, R3Si-, RO-, Cli2=CH- and the like.
The composition of this invention can be used in a wide variety of fields, hence, the viscosity of the organopolysiloxane employed is not critical and can vary from low polymers (less than 5 cs. viscosity at 25C.) to high polymer gUMS
(greater than 5 x 106 cs. viscosity at 25C.).
The alkali metal siloxanolate containing at least three siloxane units per molecule employed as a reactant herein is known and includes, Eor example, potassium siloxanolate and sodium siloxanolate. These alkali metal siloxanolates can be produced by known methods such as the synthesis disclosed by W. T. Grubb and R. C. Ostoff in the J_urnal of the American Chemical Society, Vol. 77, page 1405, (1955). A preferred method of preparing the alkali metal siloxanolates comprises preparing a siloxanolate having alkali metal atoms on each of the terminal siloxane units of the molecule and further reacting such alkali metal siloxanolate with an essentially linear diorganopolysiloxane to form an alkali metal siloxanolate having alkali metal substituted siloxane units on only one of the terminal siloxane units in the molecule. Such alkali metal siloxanolates are preferred herein.
As is well known, alkali metal siloxanolates have ~ ;
from 1 to 3 organic groups attached to each Si through silicon-carbon bonds such as hydrocarbon radicals such as ; 30 methyl, ethyl, vinyl and phenyl and fluorinated hydrocarbon radicals such as trifluoropropyl.
~ .
3~ :
,.
The organic carboxylic acid cerium salt to be used herein for the synthesis of the componen~ ~1) of the heat-stability additive of this invention sllould be soluble in an aromatic hydrocarbon solvent or a chlorinated hydrocarbon solvent. Specific examples of operable cerium salts include cerium-2-ethylhexanoate and cerium naphthenate.
The reaction between the alkali metal siloxanolate and tlle organic carboxylic acid salt of cerium is generally ;
carried out in an aromatic hydrocarbon solvent or chlorinated hydrocarbon solvent at the reflux temperature of the solvent.
When the reaction is completed, any by-produced precipitate can be removed by filtration (or other appropriate means) and the solvent is removed by dlstillation. The reaction `
product is generally a liquid.
The reaction between alkali metal siloxanolate and cerium chloride is carried out in an alcohol solvent such as ethanol, isopropanol and butanol, or a mixture of an alcohol with an aromatic hydrocarbon solvent such as benzene and toluene. The reaction can be carried out at room temperature or at elevated temperatures up to the reflux temperature of the solvent. The reaction product may be filtered to remove any by-produced precipitate and the solvent is removed by distillation. The reaction procluct is a light yellow liquid.
The cerium chloride employed in the above-described reaction is subjected to an appropriate dehydrating treatment before the reaction and is employed in the anhydrous state.
The alkali metal siloxanolate employed in the reactions described above to produce the cerium compound (1) employed herein contains at least three siloxane units. It is preferred to employ an alkali metal siloxanolate containing organic ~ . .
~ 3 ~
substituents and exhibiting a viscosity (determined by the average number of units per molecule) similar to the chemical structure of the organopolysiloxane into ~hich the reaction product is to be incorporated to achieve ~ery high compatibility of the additive with the base siloxane polymer. -The zirconium, titanium or iron salt or an organic carboxylic acid employed as component ~2) of the heat stability additive composition is represented by the general O
formula M(OCR')y where M is zirconium, titanium or iron, R' is a monovalent hydrocarbon radical preferably containing .
less than 32 carbon atoms, and _ designates the atomic ~alence o the metal M. Examples of operable organic carboxylic acids include 2-ethylhexanoic acid, naphth~nic acid, oleic acid, lauric acid, stearic acid and the like.
The alkoxy compounds o zirconium, titanium or iron employed herein can be represented by the general ormula M~OR")y wheTe ~ and _ are as above deined and R" is a mono~alent hydrocarbon radical as defined or R' above.
The mixture of components ~1) and ~2) when added to an organopolysiloxane produce~ better heat stability and storage stability than can be achie~ed with component ~
above because of the synergistic effect of both components.
The component ~1) generally contains 0.5 to 5 percent by weight of cerium but can contain larger or smaller percentages of cerium. Component ~1) contains the organopoly-siloxane composition and is used in an amount suçh that the cerium content of the total composition is from 0.01 percent to Q.l percent by weight. ~hen the cerium content of the organopolysiloxane composition is within the stated range, k`.~
.
: ', : ,. . , ' ,, . . " . . . - , . . .:
~ 5~ 3~ ~
compositions exhibiting much reduced color development can be obtained.
In order to obtain a homogeneous distribution of components ~1) and (2) in the organopolysiloxane composition9 thus achieving maximum heat stability and storage stability, it is preferred that component (2) should be incorpora~ed in amounts such that the mole ratio of component (2) to ceriurn present in the composition is in the range from 0.5/1 to
This invention relates to an organopolysiloxane composition exhibiting improved heat stability.
It is well known in the art that the heat stability of organopolysiloxane compositions; particularly fluids and rubbers based on essentially linear diorganosiloxalle yolymers, can be improved by incorporation therein of certain inorganic salts of iron, zirconium, cerium, manganese, nickel and the like.
The use of compounds of cerium as heat stability additives for SUC}l siloxane polymers is shown in Japanese Patent No. 283,598 and Japanese Patent No. 535,121 wherein oxides or hydroxides of cerium or aromatic carboxylic acid salts o cerium are incorporated in the siloxane polyr,ler.
~lowever, these metal salts are not compatible Wit]l the organopolysiloxane, hence, it is necessary to admix the metal salt with a small portion of the siloxane polymer employing a suitable solvent to form a paste which can then be admixed Wit}l the siloxane composition. However, even when such additional steps are taken, the dispersion of the metal salt is heterogeneous or insuficient.
It is well known in the art that the heterogeneous or insuf~icient ~ispersion of any heat stability additive throu~h siloxane polymers results in unsatisfactory or minimal improvement in the heat stability o-f ~he polymer.
This is particularly noted in liquid organopolysiloxanes having relatively low viscosity because the inorganic or organic salts of cerium form sediments and precipitates when added to liquid organosiloxane polymers and this is especially noted following storage of the liquid. One means proposed for overcoming or minimizing the separation of the ~`;~
`:
~l~5~3~6 ~
cerium compound from the liquid organopolysiloxane is found in U.S. Patent No. 3,008,901, wherein it is proposed to heat a specific cerium complex salt in a solution of a liquid organopolysiloxane having a minute amount of SiII groups and an aromatic hydrocarbon at 2~0 to 290C. witll concurrent air flow through the reaction mixture for one to four days.
The proposed reaction is intended to disperse the cerium compound in the form of a colloid in the organopolysiloxane or to dissolve the cerium compound in the organopolysiloxane thereby obtaining a heat-stable organopolysiloxane composition.
In the composition prepared in accordance with U.S. Patent ,~
No. 3,008,901, the amount of cerium compound compatible with ~, the organopolysiloxane is very small and because the cerium content is changed by slight changes in the reaction conditions, it is dificult to establish and maintain the cerium content at a predetermined or constant level. Thus, from the commercial or industrial viewpoint, this known technique is unsatisfactory or the continuous preparation of large quantities of heat-stable organopolysiloxane compositions. `
It has been found that the reaction product obtained by reaction o a cerium salt of an organic carboxylic acid with an alkali metal siloxanolate or by reaction of cerium chloride with an alkali metal siloxanolate exhibits excellent compatibility with an organopolysiloxane. . `
Novel heat-stable organopolysiloxane compositions are - obtained by incorporating such reaction products tllerein.
However, it has been found that after several months storage at room temperature or durlng use of the organopolysiloxane at elevated temperatures, partial sedimentation or precipitation of the cerium compound will reduce the transparency of the organopolysiloxane and the heat stability as well.
; 2-~ 3~ ~
The search for a compatible heat-stability additive system for organopolysiloxanes W]liCh remains stable on storage has continued and it is the primary object of this invention to introduce such a system. A -furtller object is to introduce organopolysiloxane rubbers ancL liquids based on essentially linear diorganosiloxane polymers exhibiting improved heat stability even after extendecl periods of storage. Other objects and advantages attained through this invention are disclosed in or will be apparent from the disclosure and claims following.
This invention relates to a mixture o (1) a reaction pro~uct of (a) an alkali metal siloxanolate having at least three organosiloxane units per molecule with (b) a cerium salt of an organlc carboxylic acid or cerium chloride and (2) a metal compound selected Erom the group consisting of organic carboxylic acid salts and alkoxy compoun~s of zirconium, titanium and iron. The foregoing r~lixture is incorporated into an organopolysiloxane composition to pro~uce a composition exhibiting superior heat stability.
The use of the mixture produces a synergistic effect when compared to the use of either component separately.
The organopolysiloxane composition employed herein is based on an essentially linear diorganosiloxane polymer of ~he unit formula RXSiO4 x when R is an alkyl radical of ;
less than seven carbon atoms, a phenyl radical, a beta-perfluoroalkylethyl radical of three to nine carbon atoms or an alkenyl radical of two to six carbon atoms and x has an average value of 1.98 to 2.01. Preferred as R groups are CH3, C2H5, C3E17, CF3CH2CH2, C6E15 and Cli2=CH and minor amounts (e.g. less than 2 percent) of the R groups can be o~her than . ... .. . . . .: ; , . .
. . . . . . . .
~ ~5~3~6 those defined above. All R groups can be the same or they can be different. Because of commercial availability, siloxanes wherein at least 50 percent of the R groups are methyl radicals are preferred The terminal units on the siloxane polymer can be -OH, R3Si-, RO-, Cli2=CH- and the like.
The composition of this invention can be used in a wide variety of fields, hence, the viscosity of the organopolysiloxane employed is not critical and can vary from low polymers (less than 5 cs. viscosity at 25C.) to high polymer gUMS
(greater than 5 x 106 cs. viscosity at 25C.).
The alkali metal siloxanolate containing at least three siloxane units per molecule employed as a reactant herein is known and includes, Eor example, potassium siloxanolate and sodium siloxanolate. These alkali metal siloxanolates can be produced by known methods such as the synthesis disclosed by W. T. Grubb and R. C. Ostoff in the J_urnal of the American Chemical Society, Vol. 77, page 1405, (1955). A preferred method of preparing the alkali metal siloxanolates comprises preparing a siloxanolate having alkali metal atoms on each of the terminal siloxane units of the molecule and further reacting such alkali metal siloxanolate with an essentially linear diorganopolysiloxane to form an alkali metal siloxanolate having alkali metal substituted siloxane units on only one of the terminal siloxane units in the molecule. Such alkali metal siloxanolates are preferred herein.
As is well known, alkali metal siloxanolates have ~ ;
from 1 to 3 organic groups attached to each Si through silicon-carbon bonds such as hydrocarbon radicals such as ; 30 methyl, ethyl, vinyl and phenyl and fluorinated hydrocarbon radicals such as trifluoropropyl.
~ .
3~ :
,.
The organic carboxylic acid cerium salt to be used herein for the synthesis of the componen~ ~1) of the heat-stability additive of this invention sllould be soluble in an aromatic hydrocarbon solvent or a chlorinated hydrocarbon solvent. Specific examples of operable cerium salts include cerium-2-ethylhexanoate and cerium naphthenate.
The reaction between the alkali metal siloxanolate and tlle organic carboxylic acid salt of cerium is generally ;
carried out in an aromatic hydrocarbon solvent or chlorinated hydrocarbon solvent at the reflux temperature of the solvent.
When the reaction is completed, any by-produced precipitate can be removed by filtration (or other appropriate means) and the solvent is removed by dlstillation. The reaction `
product is generally a liquid.
The reaction between alkali metal siloxanolate and cerium chloride is carried out in an alcohol solvent such as ethanol, isopropanol and butanol, or a mixture of an alcohol with an aromatic hydrocarbon solvent such as benzene and toluene. The reaction can be carried out at room temperature or at elevated temperatures up to the reflux temperature of the solvent. The reaction product may be filtered to remove any by-produced precipitate and the solvent is removed by distillation. The reaction procluct is a light yellow liquid.
The cerium chloride employed in the above-described reaction is subjected to an appropriate dehydrating treatment before the reaction and is employed in the anhydrous state.
The alkali metal siloxanolate employed in the reactions described above to produce the cerium compound (1) employed herein contains at least three siloxane units. It is preferred to employ an alkali metal siloxanolate containing organic ~ . .
~ 3 ~
substituents and exhibiting a viscosity (determined by the average number of units per molecule) similar to the chemical structure of the organopolysiloxane into ~hich the reaction product is to be incorporated to achieve ~ery high compatibility of the additive with the base siloxane polymer. -The zirconium, titanium or iron salt or an organic carboxylic acid employed as component ~2) of the heat stability additive composition is represented by the general O
formula M(OCR')y where M is zirconium, titanium or iron, R' is a monovalent hydrocarbon radical preferably containing .
less than 32 carbon atoms, and _ designates the atomic ~alence o the metal M. Examples of operable organic carboxylic acids include 2-ethylhexanoic acid, naphth~nic acid, oleic acid, lauric acid, stearic acid and the like.
The alkoxy compounds o zirconium, titanium or iron employed herein can be represented by the general ormula M~OR")y wheTe ~ and _ are as above deined and R" is a mono~alent hydrocarbon radical as defined or R' above.
The mixture of components ~1) and ~2) when added to an organopolysiloxane produce~ better heat stability and storage stability than can be achie~ed with component ~
above because of the synergistic effect of both components.
The component ~1) generally contains 0.5 to 5 percent by weight of cerium but can contain larger or smaller percentages of cerium. Component ~1) contains the organopoly-siloxane composition and is used in an amount suçh that the cerium content of the total composition is from 0.01 percent to Q.l percent by weight. ~hen the cerium content of the organopolysiloxane composition is within the stated range, k`.~
.
: ', : ,. . , ' ,, . . " . . . - , . . .:
~ 5~ 3~ ~
compositions exhibiting much reduced color development can be obtained.
In order to obtain a homogeneous distribution of components ~1) and (2) in the organopolysiloxane composition9 thus achieving maximum heat stability and storage stability, it is preferred that component (2) should be incorpora~ed in amounts such that the mole ratio of component (2) to ceriurn present in the composition is in the range from 0.5/1 to
2.0/1.
When a metal compound (2) having a relatively low color developing property is employed, the organopolysiloxane composition will have a much reduced color development.
The organopolysiloxane composition of this invention may also contain inorganic fillers such a~ Fume silica, silica aerogel, precipitated silica, diatomaceous earth, powdered quartz and similar well-known fillers. Metal soaps, pigments~ vulcanizing agents and other s~andard and well-known additives may be present. For example, a room _ temperature vulcanizing silicone rubber stock having excellent heat stability can be prepared by incorporating in the organopolysiloxane composition containing the heat-stability "
additives (1) and ~2), an inorganic filler and a combination of a crosslinking agent such as trialkoxysilane, polyalkyl silicate, triacetoxy silane, trioxime silane and methyl-hydrogensiloxane polymer with a curing catalys~ such as metal salts of atty acids, more particularly, tin salts, or a platinum compound. Thermosetting or heat vulcanizing silicone rubber stocks are obtained by use of organic peroxides or other free radical producers added to the organopolysiloxane composition as is well known in the art.
When a metal compound (2) having a relatively low color developing property is employed, the organopolysiloxane composition will have a much reduced color development.
The organopolysiloxane composition of this invention may also contain inorganic fillers such a~ Fume silica, silica aerogel, precipitated silica, diatomaceous earth, powdered quartz and similar well-known fillers. Metal soaps, pigments~ vulcanizing agents and other s~andard and well-known additives may be present. For example, a room _ temperature vulcanizing silicone rubber stock having excellent heat stability can be prepared by incorporating in the organopolysiloxane composition containing the heat-stability "
additives (1) and ~2), an inorganic filler and a combination of a crosslinking agent such as trialkoxysilane, polyalkyl silicate, triacetoxy silane, trioxime silane and methyl-hydrogensiloxane polymer with a curing catalys~ such as metal salts of atty acids, more particularly, tin salts, or a platinum compound. Thermosetting or heat vulcanizing silicone rubber stocks are obtained by use of organic peroxides or other free radical producers added to the organopolysiloxane composition as is well known in the art.
3~6 ~:
The compositions o~ this invention are useful for a wide variety of purposes such as sealants, silicone rubber gaskets, hea-t stable silicone fluids for hydraulic systems and automobile brake systems, and in the many known areas wherein silicone fluids and rubbers are presently used.
The following examples illustrate the invention and do not limit the scope of the invention which is set forth in the claims. All parts and percentages in the examples are based on weight and all viscosities are measured at 25C.
PREPARATION OF SAMPLE I `
.
~ mploying the method of Grubb and Ostoff (J.A.C.S., Vol 77, p. 1405 [1955~) potassium siloxanolate was prepared from potassium hydroxide, hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane. Next, 67 g. of trimethylsilyl endblocked dimethylpolysiloxane having a viscosity of 20 cs.
and 3 g. of hexamethylphosphoramide were admixed with 33 g. of ~ ~, the potassium siloxanolate. The reaction mixture was heated at 115C. under nitrogen gas for one hour. Then, 120 g. of dehydrated xylene and 16 g. of cerium 2-ethylhexanoate were added to the reaction mixture and the reaction was carried orward at reflux for 2.5 hours. The reaction mixture was cooled to room temperature and neutralized by addition of 2 g, of trimethylchlorosilane. The precipitate was removed by filtration and the xylene solvent was distilled off and the ~;
reaction product obtained was a light yellow clear liquid.
The cerium concentration in the reaction product obtained was 1.2 percent. Next, ive parts of a naphtha solution of zirconium 2-ethylhexanoate (metal salt concentration, 53 percent) was added to 100 parts of the reaction product and the mixture was stirred to obtain a homogeneous solution.
~ S~ 3 ~ 6 PREPARATION OF SAMPL~ II
A mixture of 60 g. of the potassium siloxanolate prepared in the preparation of Sample I, and 0.5 g. of hexamethylphosphoramide was added to 120 g. of the 20 cs.
trimethylsilyl endblocked dimethylpolysiloxane employed abo~e.
The mixture was heated at 110C. for two hours under nitrogen.
Next, 100 g. of the mixture was dissolved in 150 g. of isopropanol and a solution of 2.5 g. of anhydrous cerium chloride in alcohol ~50 g. ethanol and 50 g. isopropanol) was added dropwise to the above solution with concurrent mixing. The resulting reaction mixture was filtered and the solvent removed by vacuum distillation at 40 to 50C. The remaining filtrate was again filtered to remove trace amounts of precipitate and a light yellow liquid reaction product containing 0.8 percent cerium was obtained. Next, 2.2 parts of tetrabutylzirconate was added to 100 parts of the above reaction product and the mixture was stirred to obtain a homogeneous solution.
PR~PARATION OF SAMPLE III
A solution was prepared by adding 70 g. of sodium trimethylsilanolate prepared according to the method disclosed by L. H. Sommer et al., J.A.C.S., Vol. 68, page 2282 (1946), to 25 g. of toluene. Then 100 g. of the 20 cs. dimethylpoly-siloxane employed in preparation of Sample I and 6.75 g. of dimethylformamide were added to the solution. The mixture was heated at 105 to 110C. for three hours and a 2.5 percent solution of 5.25 g. of anhydrous cerium chloride in n-bu~anol l was added dropwise to the reaction mixture with concurrent ;l stirring. The reaction mixture was treated in the same manner as in the case of Sample I and a light yellow liquid reaction , ~ C~SY 3~6 product containing a 1.7 percent concentration of cerium was obtained. Then, 4.1 parts of tetrabutyltitanate was added to 100 parts of the reaction product and the mixture was stirred to obtain a homogeneous solution.
PREPARATION OF SAMPLE IV
A mixture was prepared by adding 40 g. of the diméthylpolysiloxane employed in Sample I above and 2.7 g. of dimethyl formamide to a solution of 2.8 g. of the sodium trimethylsilanolate of Sample III in 10 g. of toluene. The mixture was reacted at 105-110C. for three hours. Then, 65 g. of xylene and 11.5 g of cerium 2-ethylhexanoate were added to the mixture and further reaction was carried forward -at reflux temperature for three hours. The reaction mixture was cooled to room temperature and neutralized by adding trimethylchlorosilane. The xylene and dimethylformamide were removed by vacuum distillation. The precipitate formed was removed by filtration and the liquid reaction product obtained had a cerium concentration of 1.3 percent. Then,
The compositions o~ this invention are useful for a wide variety of purposes such as sealants, silicone rubber gaskets, hea-t stable silicone fluids for hydraulic systems and automobile brake systems, and in the many known areas wherein silicone fluids and rubbers are presently used.
The following examples illustrate the invention and do not limit the scope of the invention which is set forth in the claims. All parts and percentages in the examples are based on weight and all viscosities are measured at 25C.
PREPARATION OF SAMPLE I `
.
~ mploying the method of Grubb and Ostoff (J.A.C.S., Vol 77, p. 1405 [1955~) potassium siloxanolate was prepared from potassium hydroxide, hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane. Next, 67 g. of trimethylsilyl endblocked dimethylpolysiloxane having a viscosity of 20 cs.
and 3 g. of hexamethylphosphoramide were admixed with 33 g. of ~ ~, the potassium siloxanolate. The reaction mixture was heated at 115C. under nitrogen gas for one hour. Then, 120 g. of dehydrated xylene and 16 g. of cerium 2-ethylhexanoate were added to the reaction mixture and the reaction was carried orward at reflux for 2.5 hours. The reaction mixture was cooled to room temperature and neutralized by addition of 2 g, of trimethylchlorosilane. The precipitate was removed by filtration and the xylene solvent was distilled off and the ~;
reaction product obtained was a light yellow clear liquid.
The cerium concentration in the reaction product obtained was 1.2 percent. Next, ive parts of a naphtha solution of zirconium 2-ethylhexanoate (metal salt concentration, 53 percent) was added to 100 parts of the reaction product and the mixture was stirred to obtain a homogeneous solution.
~ S~ 3 ~ 6 PREPARATION OF SAMPL~ II
A mixture of 60 g. of the potassium siloxanolate prepared in the preparation of Sample I, and 0.5 g. of hexamethylphosphoramide was added to 120 g. of the 20 cs.
trimethylsilyl endblocked dimethylpolysiloxane employed abo~e.
The mixture was heated at 110C. for two hours under nitrogen.
Next, 100 g. of the mixture was dissolved in 150 g. of isopropanol and a solution of 2.5 g. of anhydrous cerium chloride in alcohol ~50 g. ethanol and 50 g. isopropanol) was added dropwise to the above solution with concurrent mixing. The resulting reaction mixture was filtered and the solvent removed by vacuum distillation at 40 to 50C. The remaining filtrate was again filtered to remove trace amounts of precipitate and a light yellow liquid reaction product containing 0.8 percent cerium was obtained. Next, 2.2 parts of tetrabutylzirconate was added to 100 parts of the above reaction product and the mixture was stirred to obtain a homogeneous solution.
PR~PARATION OF SAMPLE III
A solution was prepared by adding 70 g. of sodium trimethylsilanolate prepared according to the method disclosed by L. H. Sommer et al., J.A.C.S., Vol. 68, page 2282 (1946), to 25 g. of toluene. Then 100 g. of the 20 cs. dimethylpoly-siloxane employed in preparation of Sample I and 6.75 g. of dimethylformamide were added to the solution. The mixture was heated at 105 to 110C. for three hours and a 2.5 percent solution of 5.25 g. of anhydrous cerium chloride in n-bu~anol l was added dropwise to the reaction mixture with concurrent ;l stirring. The reaction mixture was treated in the same manner as in the case of Sample I and a light yellow liquid reaction , ~ C~SY 3~6 product containing a 1.7 percent concentration of cerium was obtained. Then, 4.1 parts of tetrabutyltitanate was added to 100 parts of the reaction product and the mixture was stirred to obtain a homogeneous solution.
PREPARATION OF SAMPLE IV
A mixture was prepared by adding 40 g. of the diméthylpolysiloxane employed in Sample I above and 2.7 g. of dimethyl formamide to a solution of 2.8 g. of the sodium trimethylsilanolate of Sample III in 10 g. of toluene. The mixture was reacted at 105-110C. for three hours. Then, 65 g. of xylene and 11.5 g of cerium 2-ethylhexanoate were added to the mixture and further reaction was carried forward -at reflux temperature for three hours. The reaction mixture was cooled to room temperature and neutralized by adding trimethylchlorosilane. The xylene and dimethylformamide were removed by vacuum distillation. The precipitate formed was removed by filtration and the liquid reaction product obtained had a cerium concentration of 1.3 percent. Then,
4.7 parts of an iron 2-ethylhexanoate solution in mineral spirits containing 11 percent iron was added to 100 parts of the reaction product. The mixture was stirred to obtain a homogeneous solution.
Example 1 1 kg. of dimethylpolysiloxane having a viscosity of 100 cs. was placed in a 2 liter beaker and 64.~ g. of the Sample I was incorporated in the dimethylpolysiloxane. A
homogeneous transparent solution designated Sample I-a was easily obtained.
As a control, 64 g. of the reaction product obtained before the addition of zirconium 2-ethylhexanoate in the 3~6 preparation of Sample I was added to l kg. of the dimethyl-polysiloxane having a viscosity of 100 cs. and a homogeneous transparent solution designated Sample I-b was obtained.
Samples I-a and I-b were placed in a hot air circulating oven maintained at 100C. The Sample I-b formed a white precipitate after three days in the oven. Sample I-a formed a white precipitate only after 17 days in the oven.
This clearly demonstrates the storage and heat stability achieved herein as compared to the closest prior art.
Example 2 1 kg. of dimethylpolysiloxane having a viscosity of 350 cs, was charged to a 2 liter capacity beaker and 96.2 g. `
of the product obtained in Sample II was incorporated therein to obtain a homogeneous transparent solution ~Sample II-a).
Employing the same method employed above, 96 g. of the reaction product obtained before the addition of ths tetrabutyl zirconate in the preparation of Sample II was added to 1 kg. of the 350 cs. dimethylpolysiloxane to obtain a homogeneous transparent solution (Sample II-b).
The Samples II-a and II-b were placed in a hot air circulating oven heated at 100C. A white precipitate formed in Sample II-b after 10 days in the oven whereas the white precipitate formed in Sample II-a only after 21 days in the oven.
Example_3 1 kg. of a copolymer of 60 mole percent phenyl-methylsiloxane units and 40 mole percent dimethylsiloxane units having a viscosity of 350 cs. was charged to a 2 liter beaker and 45.2 g. of the product of Sample III was easily ~ 59 3~ ~
incorporated into the polysiloxane to obtain a homogeneous transparent solution (Sample III-a).
~ nder the same conditions as above, 45 g. of the reaction product obtained before addition of the tetrabutyl-titanate in the preparation of Sample III was added to 1 kg.
of the phenylmethylsiloxane~dimethylsiloxane copolymer employed above to obtain a homogeneous transparent solution -(Sample III-b).
The Samples III-a and III-b were placed in a hot air circulating oven heated at 100C. A white precipitate formed ln Sample III-b after 12 days in the oven. In contrast, the Sample III-a remained in the oven or 23 days before a white precipitate was ormed.
~xample ~
1 kg. of a dimethylpolysiloxane having a viscosity of 100 cs. was charged to a 2 liter beaker. As in the previous examples, 59.3 g. of Sample IV was readily dispersed in the polysiloxane to obtain a homogeneous transparent solution (Sample IV-a).
As a control, 1 kg. of the 100 cs. dimethylpolysiloxane ~ was charged to a 2 liter beaker and 59 g. of the reaction ; product obtained beore the addition o iron-2-ethylhexanoate in preparing Sample IV was added to the dimethylpolysiloxane ` to obtain a transparent homogeneous solution ~Sample IV-b).
- The Samples IV-a and IV-b were placed in a room maintained at 20 to 23C. and a relative humidity of 50 to 70 percent. A white precipitate ormed in Sample IV-b a-fter 67 days. In contrast, a white precipitate formed in Sample IV-a only after 115 days.
' , :
~ o~
Example 5 A mixture of 150 g. of 100 cs. dimethylpolysiloxane and 3.3 g. of the reaction product obtained before addition of , zirconium 2-ethylhexanoate in preparation of Sample I was charged to a 300 ml. beaker to obtain Sample C.
3.3 g. of Sample I obtained after the addition of zirconium 2-ethylhexanoate was added to 150 g. of the 100 cs.
dimethylpolysiloxane to obtain Sample D.
4.8 g. of the reaction product obtained before the addition of tetrabutyl zirconate in preparing Sample II was added to 150 g. of the 100 cs. dimethylpolysiloxane to obtain Sample E.
4.8 g. of Sample II obtained after the addition of tetrabutyl ~irconate was added to 150 g. o the 100 cs.
dimethylpolysiloxane to obtain Sample F.
2.3 g. of the reaction product obtained before the addition of tetrabutyltitanate in preparing Sample III was added to 150 g. of the 100 cs. dimethylpolysiloxane to obtain Sample G.
2.3 g. of Sample III obtained after the addition of tetrabutyltitanate was added to 150 g. of the 100 cs. --dimethylpolysiloxane to obtain Sample H.
3.0 g. of the reaction product obtained before the addition of iron-2-ethylhexanoate in preparing Sample IV
was added to 150 g. of the 100 cs. dimethylpolysiloxane to obtain Sample J.
3.0 g, of Sample IV obtained after the addition of iron-2-ethylhexanoate was added to 150 g. of the 100 cs.
dimethylpolysiloxane to obtain Sample K.
~ 3 For comparison, 150 g. of the lO0 cs. dimethylpoly- :~
siloxane free of any additive was employed as Sample L.
The foregoing nine samples were heated for 48 hours -~
in a hot air circulating oven maintained at 250C. and the -.
change in viscosity and the weight loss were recorded.
Results obtained are set forth below in the Table. It can readily be seen that the compositions of this invention (Samples D. F, H and K) exhibit better heat resistance than the compositions containing only component (1) (Samples C, E, G and J), Viscosity Weight Loss (cs. at 25C.) ~percent) After 48 After 48 S~ Hours Heating Hours Heatin~
C 130 6.5 D 112 3.8 F 106 2.6 G 122 5.0 H 108 3.3 J 129 6.7 K 118 5,5 L Gelled after 24 17.0 hrs. heating .
Example 1 1 kg. of dimethylpolysiloxane having a viscosity of 100 cs. was placed in a 2 liter beaker and 64.~ g. of the Sample I was incorporated in the dimethylpolysiloxane. A
homogeneous transparent solution designated Sample I-a was easily obtained.
As a control, 64 g. of the reaction product obtained before the addition of zirconium 2-ethylhexanoate in the 3~6 preparation of Sample I was added to l kg. of the dimethyl-polysiloxane having a viscosity of 100 cs. and a homogeneous transparent solution designated Sample I-b was obtained.
Samples I-a and I-b were placed in a hot air circulating oven maintained at 100C. The Sample I-b formed a white precipitate after three days in the oven. Sample I-a formed a white precipitate only after 17 days in the oven.
This clearly demonstrates the storage and heat stability achieved herein as compared to the closest prior art.
Example 2 1 kg. of dimethylpolysiloxane having a viscosity of 350 cs, was charged to a 2 liter capacity beaker and 96.2 g. `
of the product obtained in Sample II was incorporated therein to obtain a homogeneous transparent solution ~Sample II-a).
Employing the same method employed above, 96 g. of the reaction product obtained before the addition of ths tetrabutyl zirconate in the preparation of Sample II was added to 1 kg. of the 350 cs. dimethylpolysiloxane to obtain a homogeneous transparent solution (Sample II-b).
The Samples II-a and II-b were placed in a hot air circulating oven heated at 100C. A white precipitate formed in Sample II-b after 10 days in the oven whereas the white precipitate formed in Sample II-a only after 21 days in the oven.
Example_3 1 kg. of a copolymer of 60 mole percent phenyl-methylsiloxane units and 40 mole percent dimethylsiloxane units having a viscosity of 350 cs. was charged to a 2 liter beaker and 45.2 g. of the product of Sample III was easily ~ 59 3~ ~
incorporated into the polysiloxane to obtain a homogeneous transparent solution (Sample III-a).
~ nder the same conditions as above, 45 g. of the reaction product obtained before addition of the tetrabutyl-titanate in the preparation of Sample III was added to 1 kg.
of the phenylmethylsiloxane~dimethylsiloxane copolymer employed above to obtain a homogeneous transparent solution -(Sample III-b).
The Samples III-a and III-b were placed in a hot air circulating oven heated at 100C. A white precipitate formed ln Sample III-b after 12 days in the oven. In contrast, the Sample III-a remained in the oven or 23 days before a white precipitate was ormed.
~xample ~
1 kg. of a dimethylpolysiloxane having a viscosity of 100 cs. was charged to a 2 liter beaker. As in the previous examples, 59.3 g. of Sample IV was readily dispersed in the polysiloxane to obtain a homogeneous transparent solution (Sample IV-a).
As a control, 1 kg. of the 100 cs. dimethylpolysiloxane ~ was charged to a 2 liter beaker and 59 g. of the reaction ; product obtained beore the addition o iron-2-ethylhexanoate in preparing Sample IV was added to the dimethylpolysiloxane ` to obtain a transparent homogeneous solution ~Sample IV-b).
- The Samples IV-a and IV-b were placed in a room maintained at 20 to 23C. and a relative humidity of 50 to 70 percent. A white precipitate ormed in Sample IV-b a-fter 67 days. In contrast, a white precipitate formed in Sample IV-a only after 115 days.
' , :
~ o~
Example 5 A mixture of 150 g. of 100 cs. dimethylpolysiloxane and 3.3 g. of the reaction product obtained before addition of , zirconium 2-ethylhexanoate in preparation of Sample I was charged to a 300 ml. beaker to obtain Sample C.
3.3 g. of Sample I obtained after the addition of zirconium 2-ethylhexanoate was added to 150 g. of the 100 cs.
dimethylpolysiloxane to obtain Sample D.
4.8 g. of the reaction product obtained before the addition of tetrabutyl zirconate in preparing Sample II was added to 150 g. of the 100 cs. dimethylpolysiloxane to obtain Sample E.
4.8 g. of Sample II obtained after the addition of tetrabutyl ~irconate was added to 150 g. o the 100 cs.
dimethylpolysiloxane to obtain Sample F.
2.3 g. of the reaction product obtained before the addition of tetrabutyltitanate in preparing Sample III was added to 150 g. of the 100 cs. dimethylpolysiloxane to obtain Sample G.
2.3 g. of Sample III obtained after the addition of tetrabutyltitanate was added to 150 g. of the 100 cs. --dimethylpolysiloxane to obtain Sample H.
3.0 g. of the reaction product obtained before the addition of iron-2-ethylhexanoate in preparing Sample IV
was added to 150 g. of the 100 cs. dimethylpolysiloxane to obtain Sample J.
3.0 g, of Sample IV obtained after the addition of iron-2-ethylhexanoate was added to 150 g. of the 100 cs.
dimethylpolysiloxane to obtain Sample K.
~ 3 For comparison, 150 g. of the lO0 cs. dimethylpoly- :~
siloxane free of any additive was employed as Sample L.
The foregoing nine samples were heated for 48 hours -~
in a hot air circulating oven maintained at 250C. and the -.
change in viscosity and the weight loss were recorded.
Results obtained are set forth below in the Table. It can readily be seen that the compositions of this invention (Samples D. F, H and K) exhibit better heat resistance than the compositions containing only component (1) (Samples C, E, G and J), Viscosity Weight Loss (cs. at 25C.) ~percent) After 48 After 48 S~ Hours Heating Hours Heatin~
C 130 6.5 D 112 3.8 F 106 2.6 G 122 5.0 H 108 3.3 J 129 6.7 K 118 5,5 L Gelled after 24 17.0 hrs. heating .
Claims (5)
1. A composition consisting essentially of (1) a reaction product of an alkali metal siloxanolate containing an average of at least three siloxane units per molecule with a cerium salt of an organic carboxylic acid or cerium chloride and (2) at least one metal compound selected from the group consisting of organic carboxylic acid salts and alkoxy compounds of zirconium, titanium and iron.
2. A composition consisting of an organopolysiloxane composition having incorporated therein as a heat-stability additive a mixture of (1) a reaction product of an alkali metal siloxanolate having an average of at least three siloxane units per molecule with a cerium salt of an organic carboxylic acid or cerium chloride and (2) at least one metal compound selected from the group consisting of organic carboxylic acid salts and alkoxy compounds of zirconium, titanium and iron.
3. The composition of claim 2 wherein the organopolysiloxane composition is a liquid organopolysiloxane.
4. The composition of claim 2 wherein the organopolysiloxane is a room temperature vulcanizing silicone rubber stock or a heat vulcanizing silicone rubber stock.
5. The composition of claim 2 wherein component (1) contains an amount of 0.5 to 5 percent by weight of cerium and the mole ratio of component (2) to cerium present in the composition is from 0.5/1 to 2.0/1.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP13962274A JPS5312541B2 (en) | 1974-12-06 | 1974-12-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1059306A true CA1059306A (en) | 1979-07-31 |
Family
ID=15249560
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA239,157A Expired CA1059306A (en) | 1974-12-06 | 1975-11-07 | Heat stable organopolysiloxane composition |
Country Status (7)
Country | Link |
---|---|
JP (1) | JPS5312541B2 (en) |
BE (1) | BE836339A (en) |
CA (1) | CA1059306A (en) |
DE (1) | DE2554498C2 (en) |
FR (1) | FR2293462A1 (en) |
GB (1) | GB1534709A (en) |
SU (1) | SU795497A3 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10336913B2 (en) | 2013-08-28 | 2019-07-02 | Dow Corning Toray Co., Ltd. | Curable silicone composition, cured product thereof, and optical semiconductor device |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5099006A (en) * | 1988-01-14 | 1992-03-24 | Rhone-Poulenc Inc. | Alkoxy-type derivative compounds and process for preparing alkoxy-type derivatives of trivalent group 3b metals |
JP2838208B2 (en) * | 1988-03-29 | 1998-12-16 | 東レ・ダウコーニング・シリコーン株式会社 | Transparent flame-retardant silicone rubber composition |
DE4204200A1 (en) * | 1992-02-13 | 1993-08-19 | Daimler Benz Ag | Liq. useful as heat transfer and insulating media - comprises mixt. of poly-alpha-olefin(s) and/or isoparaffin(s) with poly:di:methyl:siloxane(s) and/or poly:alkyl -/poly:aryl:siloxane(s) |
JPH09183904A (en) * | 1995-12-28 | 1997-07-15 | Toray Dow Corning Silicone Co Ltd | Organopolysiloxane composition |
JP4565491B2 (en) * | 2003-04-15 | 2010-10-20 | 東レ・ダウコーニング株式会社 | Thermally conductive addition-curable liquid silicone rubber composition |
JP7365798B2 (en) * | 2019-07-03 | 2023-10-20 | ダウ・東レ株式会社 | Silicone gel composition, cured product thereof, electronic component encapsulant, electronic component, and method for protecting semiconductor chips |
-
1974
- 1974-12-06 JP JP13962274A patent/JPS5312541B2/ja not_active Expired
-
1975
- 1975-11-07 CA CA239,157A patent/CA1059306A/en not_active Expired
- 1975-12-03 GB GB49627/75A patent/GB1534709A/en not_active Expired
- 1975-12-04 DE DE2554498A patent/DE2554498C2/en not_active Expired
- 1975-12-04 SU SU752195656A patent/SU795497A3/en active
- 1975-12-05 BE BE162495A patent/BE836339A/en not_active IP Right Cessation
- 1975-12-05 FR FR7537299A patent/FR2293462A1/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10336913B2 (en) | 2013-08-28 | 2019-07-02 | Dow Corning Toray Co., Ltd. | Curable silicone composition, cured product thereof, and optical semiconductor device |
Also Published As
Publication number | Publication date |
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GB1534709A (en) | 1978-12-06 |
DE2554498C2 (en) | 1984-11-29 |
JPS5166344A (en) | 1976-06-08 |
SU795497A3 (en) | 1981-01-07 |
DE2554498A1 (en) | 1976-06-10 |
BE836339A (en) | 1976-06-08 |
FR2293462A1 (en) | 1976-07-02 |
JPS5312541B2 (en) | 1978-05-01 |
FR2293462B1 (en) | 1978-05-12 |
AU8657675A (en) | 1977-05-19 |
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