US20130231452A1 - Organopolysilmethylene-siloxane and a cured product thereof - Google Patents
Organopolysilmethylene-siloxane and a cured product thereof Download PDFInfo
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- US20130231452A1 US20130231452A1 US13/773,428 US201313773428A US2013231452A1 US 20130231452 A1 US20130231452 A1 US 20130231452A1 US 201313773428 A US201313773428 A US 201313773428A US 2013231452 A1 US2013231452 A1 US 2013231452A1
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- organopolysilmethylene
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- 0 *C([2*])([2*])C[Si]([1*])([1*])O[3*] Chemical compound *C([2*])([2*])C[Si]([1*])([1*])O[3*] 0.000 description 15
- REDKJHWGNDYPLH-UHFFFAOYSA-N CC(C)(O[Si](C)(C)O)C(C)(C1=CC=CC=C1)[Si](C)(C)O.CC(C)(O[Si](C)(C)O)[Si](C)(C)O Chemical compound CC(C)(O[Si](C)(C)O)C(C)(C1=CC=CC=C1)[Si](C)(C)O.CC(C)(O[Si](C)(C)O)[Si](C)(C)O REDKJHWGNDYPLH-UHFFFAOYSA-N 0.000 description 1
- APUVUMQAAYIFKD-UHFFFAOYSA-N CC(C)=NCCC[Si](C)(C)O.CO[Si](C)(CCCN=C(C)C)OC.CO[Si](CCCN=C(C)C)(OC)OC Chemical compound CC(C)=NCCC[Si](C)(C)O.CO[Si](C)(CCCN=C(C)C)OC.CO[Si](CCCN=C(C)C)(OC)OC APUVUMQAAYIFKD-UHFFFAOYSA-N 0.000 description 1
- NJSMDRRISXRSQA-UHFFFAOYSA-O CCC(CC)=NOC(C)(C)[SH+]C Chemical compound CCC(CC)=NOC(C)(C)[SH+]C NJSMDRRISXRSQA-UHFFFAOYSA-O 0.000 description 1
- MQPNGCZWCHFJDX-UHFFFAOYSA-N CCC(CC)=NO[Si](C)(ON=C(CC)CC)ON=C(CC)CC Chemical compound CCC(CC)=NO[Si](C)(ON=C(CC)CC)ON=C(CC)CC MQPNGCZWCHFJDX-UHFFFAOYSA-N 0.000 description 1
- VTDZAHJRMRMQNP-UHFFFAOYSA-N C[Si](C)(Cl)C[Si](C)(C)Cl Chemical compound C[Si](C)(Cl)C[Si](C)(C)Cl VTDZAHJRMRMQNP-UHFFFAOYSA-N 0.000 description 1
- VLEHOCIGBBIUDF-UHFFFAOYSA-N C[Si](C)(O)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O Chemical compound C[Si](C)(O)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O VLEHOCIGBBIUDF-UHFFFAOYSA-N 0.000 description 1
- KEKPTEWISUPTJA-UHFFFAOYSA-N C[Si](C)(O)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O.C[Si](C)(O)C[Si](C)(C)O[Si](C)(C[Si](C)(C)O)C[Si](C)(C)O.[H]O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O Chemical compound C[Si](C)(O)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O.C[Si](C)(O)C[Si](C)(C)O[Si](C)(C[Si](C)(C)O)C[Si](C)(C)O.[H]O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O KEKPTEWISUPTJA-UHFFFAOYSA-N 0.000 description 1
- MUAINRODZAVDFY-UHFFFAOYSA-N [H]O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O Chemical compound [H]O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O[Si](C)(C)C[Si](C)(C)O MUAINRODZAVDFY-UHFFFAOYSA-N 0.000 description 1
- XCLIHDJZGPCUBT-UHFFFAOYSA-N [H]O[Si](C)(C)O Chemical compound [H]O[Si](C)(C)O XCLIHDJZGPCUBT-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- 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
-
- 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
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to an organopolysilmethylene-siloxane composition which yields a cured product excellent in heat resistance, mechanical strength, electrical insulation property, electrical properties and water-proof property, and a cured product thereof.
- Curable silicone rubber compositions which cure to form a silicone rubber elastomer are well known and widely used as a gasket material for electric and electronic parts, a potting material, a coating material, a shaping material such as a molding material, a wire-covering material and automobile parts, on account of good properties of the compositions such as weathering resistance, heat resistance, and electrical insulation property.
- Curable silicone rubber compositions have siloxane bonds which are inherent in a silicone. A siloxane bond is ionic and, therefore, the curable silicone rubber compositions cannot exert the excellent properties of silicones such as chemical resistance, for instance, acid and alkali resistance, water-proof property and permeability for gas in extremely severe environments such as a hot and humid environment.
- Patent Literature 1 As a countermeasure for the afore-mentioned problem, a polymer is known where a part of its siloxane bonds is a silethylene bond (Patent Literature 1) or a silphenylene bond (Patent Literature 2).
- Patent Literature 2 a polymer where a part of its siloxane bonds is a silethylene bond (Patent Literature 1) or a silphenylene bond (Patent Literature 2).
- Patent Literatures 3 to 5 As a precursor for silicon carbide ceramics, a polydiarylsilmethylenes having silmethylene bonds are known from Patent Literatures 3 to 5. These polymers are crystalline, thermoplastic silicon polymers having a high melting point and are good in heat resistance, insulation property, electrical properties, chemical resistance and water-proof property. However, the polymer is poor in processability by molding and, therefore, is not practically used. Various efforts have been made to improve the processability by molding. For instance, Patent Literature 6 describes a mixture of a polydiarylsilmethylene with a silicone polymer. Patent Literatures 7 and 8 describe mixtures of a polydiarylsilmethylene with a polyalkylsilmethylene.
- Patent Literature 9 describes a method for preparing a film of a polydiarylsilmethylene on a substrate where a film of disilacyclobutane is formed on a substrate and is ring-opening polymerized using fine particles of metal.
- the thermoplastic diarylsilmethylene polymer is highly crystalline and, therefore, is difficult to be synthesized. Accordingly, the diarylsilmethylene polymer is expensive and bad in processability. Therefore, research has been made to adopt the diarylsilmethylene polymer as a precursor for silicon carbide ceramics.
- a thermosetting composition is not known which takes advantages of the properties as a polymer.
- the purpose of the present invention is to provide an condensation-curable organopolysilmethylene-siloxane, i.e., silicon polymer having a silmethylene bond; an organopolysilmethylene-siloxane composition which comprises a condensation-curable organopolysilmethylene-siloxane and, after cured, gives a product which has good heat resistance, electrical insulation property, water-proof property and processability by molding and low permeability for gas; and a cured product thereof.
- an condensation-curable organopolysilmethylene-siloxane i.e., silicon polymer having a silmethylene bond
- an organopolysilmethylene-siloxane composition which comprises a condensation-curable organopolysilmethylene-siloxane and, after cured, gives a product which has good heat resistance, electrical insulation property, water-proof property and processability by molding and low permeability for gas
- the present inventors eagerly made research to attain the afore-mentioned purpose and have succeeded in synthesizing an organopolysilmethylene-siloxane having, in a molecule, at least two out of alkoxy groups, hydroxy groups and halogen atoms bonded to one or more silicon atoms and have found that the afore-mentioned organopolysilmethylene-siloxane is condensation-reacted, optionally using a particular curing agent and a curing catalyst, to give a useful cured product.
- the present invention provides an organopolysilmethylene-siloxane represented by the following general formula (1):
- R 1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group and a halogen atom
- R 2 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group, a halogen atom and (R 1 ) 3 SiCH 2 —
- R 3 is, independently of each other, a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms
- k is an integer of 1 to 100
- n is an integer of 1 to 1000; and having, in a molecule, at least two out of alkoxy groups, hydroxy groups and halogen atoms bonded to one or more silicon
- the present invention provides a method for preparing the aforesaid organopolysilmethylene-siloxane, comprising a step of hydrolyzing an organopolysilmethylene-siloxane represented by the following general formula (3):
- R 4 is, independently of each other, a group selected from the group consisting of a chlorine atom, a hydroxy group and an alkoxy group having 1 to 4 carbon atoms; R 1 , R 2 and k are as defined above and wherein k may be the same as or different from each other.
- the present invention provides an organopolysilmethylene-siloxane composition comprising
- R 1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group and a halogen atom, and m is an integer of 0 to 300; and having, in a molecule, at least two out of alkoxy groups, hydroxy groups and halogen atoms bonded to one or more silicon atoms,
- R is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms
- X is, independently of each other, a group selected from the group consisting of ketoxime, alkoxy, and 1-methylvinyloxy groups
- a is 0, 1, or 2;
- a cured product from the afore-mentioned composition is also provided.
- the organopolysilmethylene-siloxane composition of the present invention provides a cured product having excellent properties such as heat resistance, electrical insulation property, mechanical properties and optical properties.
- the cured product also shows low permeability for gas and excellent water-proof property and hydrolysis resistance even in extremely severe environments, whereas silicone rubbers do not show these properties.
- the organopolysilmethylene-siloxane composition of the present invention shows as good processability by molding as that of conventional silicone rubbers and, therefore, can be processed by conventional processing machinery such as a molding instrument.
- Molded products obtained from the organopolysilmethylene-siloxane composition of the present invention can be used in insulating materials, sealing materials, electric or electronic parts such as cables, packings, and connectors, automobile parts and semi-conductor devices, similarly to silicone rubbers. They can also be used for lenses or transparent sealing materials, taking advantages of its optical properties.
- FIG. 1 shows NMR spectra of the compound prepared in Example 1.
- Component (A) is an organopolysilmethylene-siloxane which is represented by the following general formula (1):
- R 3 is, independently of each other, a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; k is an integer of 1 to 100, preferably 1 to 50; n is an integer of 1 to 1000, preferably 1 to 100, more preferably 1 to 50; and
- R 1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10, preferably 1 to 6, carbon atoms other than an alkenyl group; alkoxy and hydroxy groups and a halogen atom.
- Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl, ethyl, propyl, isopropyl, and butyl groups; a cycloalkyl group such as a cyclohexyl group; an aryl group such as phenyl and tolyl groups; an aralkyl group such as benzyl and 2-phenylethyl groups; and the groups where a part or whole of their hydrogen atoms bonded to each one carbon atom are replaced with a halogen atom or a cyano group, such as a chlormethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl groups.
- methyl and phenyl groups are preferred.
- a methyl group is preferred for curing property of the composition and flexibility of the cured product.
- 50 mol % or more of R 1 is preferably a methyl group.
- R 2 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10, preferably 1 to 6, carbon atoms other than an alkenyl group; an alkoxy group and a hydroxy group, a halogen atom and (R 1 ) 3 SiCH 2 —.
- Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl, ethyl, propyl, isopropyl, and butyl groups; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl and tolyl groups; an aralkyl group such as a benzyl group and 2-phenylethyl group; and the groups where a part or whole of their hydrogen atoms bonded to each one carbon atom are replaced with a halogen atom or a cyano group, such as a chlormethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl groups.
- methyl and phenyl groups are preferred.
- a methyl group is preferred for curing property of the composition and flexibility of the cured product.
- 50 mol % or more of R 2 is preferably a methyl group.
- organopolysilmethylene-siloxane is preferably represented by the following formula (2):
- R 2 is, independently of each other, a group selected from the group consisting of a methyl group and Y(CH 3 ) 2 SiCH 2 —;
- R 3 is a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms;
- Y is a group selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms and a hydroxy group; and k and n are as defined above.
- the organopolysilmethylene-siloxane represented by the afore-mentioned formula (1) can be prepared by hydrolysis of an organopolysilmethyelene represented by the following formula (3) wherein the number of silmethylene units may be the same or different among the molecules. If required, a strong alkali such as KOH and NaOH is added after the hydrolysis to cause alkali polymerization and then the reaction mixture is washed with water and neutralized to obtain the organopolysilmethylene-siloxane of the present invention.
- a strong alkali such as KOH and NaOH
- R 4 is a chlorine atom, a hydroxy group or an alkoxy group having 1 to 4 carbon atoms and R 1 , R 2 and k are as defined above.
- organopolysilmethylene-siloxane represented by the afore-mentioned formula (1) examples include the following:
- the present invention also provides an organopolysilmethylene-siloxane composition
- an organopolysilmethylene-siloxane composition comprising (A) the organopolysilmethylene-siloxane represented by the afore-mentioned general formula (1); optionally, (C) a particular curing agent; and (D) a curing catalyst.
- the organopolysilmethylene-siloxane composition of the present invention may further comprise (B) an organopolysiloxane represented by the following general formula (4).
- Component (B) is an optional component which replaces a part of organopolysilmethylene-siloxane (A).
- Component (B) is represented by the following general formula (4):
- m is an integer of 0 to 300, preferably 0 to 100, more preferably 0 to 20 and has at least two out of alkoxy groups, hydroxy groups and halogen atoms bonded to one or more silicon atoms. Its viscosity at 25 degrees C. is preferably 1 to 1,000,000 mm 2 /s.
- R 1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10, preferably 1 to 6, carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group and a halogen atom.
- Examples of the monovalent hydrocarbon group include an alkyl group such as methyl, ethyl, propyl, isopropyl, and butyl groups; a cycloalkyl group such as a cyclohexyl group; an aryl group such as phenyl and tolyl groups; an aralkyl group such as benzyl and 2-phenylethyl groups; and the groups where a part or whole of their hydrogen atoms bonded to each one carbon atom are replaced with a halogen atom or a cyano group.
- at least two out of R 1 are selected from the group consisting of alkoxy and hydroxy groups and a halogen atom and the rest of R 1 is a methyl group.
- organopolysiloxane having hydroxy groups on both ends and represented by the following formula (6):
- R 1 is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group
- m is an integer of 0 to 300, preferably 0 to 100, more preferably 0 to 20.
- polydimethylsiloxane having hydroxy groups on both ends preference is given to polydimethylsiloxane having hydroxy groups on both ends and copolymers having hydroxy groups on both ends and composed of polydimethylsiloxane and polymethylphenylsiloxane as each represented by the following formulas.
- m is as defined above and a total of p and q is an integer of 1 to 300, preferably 1 to 100, more preferably 1 to 20.
- the present organopolysilmethylene-siloxane composition comprises 1 to 100 parts by weight of component (A) and 0 to 99 parts by weight of component (B), preferably 30 to 100 parts by weight of component (A) and 0 to 70 parts by weight of component (B), relative to 100 parts by weight of a total of components (A) and (B). If the amount of component (A) is less than the afore-mentioned lower limit, the organopolysilmethylene-siloxane does not exert its properties such as water resistance and optical properties.
- Curing agent (C) condensates with organopolysilmethylene-siloxane (A) and organopolysiloxane (B) to form a cross-linking bond and yield a rubber elastomer with a three dimensional network.
- the curing agent of the present invention is an organosilicon compound represented by the following general formula (5) and/or partial hydrolysis condensate thereof,
- R is, independently of each other, a group selected from the group consisting of unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms
- X is, independently of each other, a group selected from the group consisting of ketoxime, alkoxy, and 1-methylvinyloxy groups and a is 0, 1, or 2;
- a partial hydrolysis condensate is an organopolysiloxane obtained by condensation among partially hydrolyzed organosilicon compounds.
- R is, independently of each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms.
- the monovalent hydrocarbon group include an alkyl group such as methyl, ethyl, propyl, isopropyl, and butyl groups; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as vinyl and allyl groups; an aryl group such as phenyl and tolyl groups; an aralkyl group such as benzyl and 2-phenylethyl groups; and the groups where a part or whole of the hydrogen atoms bonded to carbon atoms of the aforesaid groups are replaced with a halogen atom or a cyano group, such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl groups.
- organosilicon compound represented by formula (5) examples include ketoxime group-containing silanes such as methyltris(diethylketoxime)silane, methyltris (methyl ethylketoxime)silane, binyltris(methylethylketoxime)silane, and phenyltris(diethylketoxime)silane; alkoxy group-containing silanes such as trimethoxymethylsilane, trimethoxyphenylsilane, trimethoxyvinylsilane, triethoxymethylsilane, triethoxyphenylsilane, triethoxyvinylsilane, tetramethoxysilane and tetraethoxysilane; and 1-methylvinyloxy group-containing silanes such as tri(1-methylvinyloxy)methylsilane and tri(1-methylvinyloxy)phenylsilane.
- the curing agent of the present invention may be a
- Component (C) is usually added in an amount of 0 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, relative to 100 parts by weight of a total of the amounts of components (A) and (B).
- Component (C) is usually added in an amount of 0 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, relative to 100 parts by weight of a total of the amounts of components (A) and (B).
- Below the afore-mentioned lower limit storage stability and processability of the composition is so worse as to sometime cause gelation. If the amount exceeds the afore-mentioned upper limit, shrinkage after cured is so large that properties of the cured product obtained may be worse.
- Curing catalyst (D) is to promote condensation between components (A) and (B) with component (C).
- the curing catalyst include metal salts of carboxylic acids such as stannous octoate, cobalt octoate, manganese octoate, zinc octoate, stannous octaoate, stannous caprylate and stannous oleate; organotin compounds such as dibutyltindiacetate, dibutyltindioctoate, dibutyltindilaurate, dibutyltindioleate, diphenyltindiacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis(triethoxy)tin, and dioctyltindilaurate; titanate esters such as tetrabutyl titanate, tetra-1-ethylhexyl titanate and tetraisopropenyl titanate; oraganotit
- Me represents a methyl group.
- the curing catalyst may be blended in such an amount that the catalyst works effectively.
- the amount may be properly increased or decreased depending upon a desired curing rate.
- the amount may not be particularly restricted, but is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of total of components (A), (B) and (C).
- the organopolysilmethylene-siloxane composition of the present invention may comprise, in addition to the afore-mentioned components (A) to (D), a variety of functional additives, for instance, reinforcing fillers, heat stabilizers, antioxidants, ultraviolet rays absorbers, photo stabilizers, agents rendering conductivity, agents rendering adhesiveness, coloring agents, lubricants, plasticizers, anti-static agents, and flame retardants as long as the purposes and effects of the present invention are not impaired.
- a variety of functional additives for instance, reinforcing fillers, heat stabilizers, antioxidants, ultraviolet rays absorbers, photo stabilizers, agents rendering conductivity, agents rendering adhesiveness, coloring agents, lubricants, plasticizers, anti-static agents, and flame retardants as long as the purposes and effects of the present invention are not impaired.
- examples of the additives include reinforcing fillers such as fumed silica and precipitated silica; fillers such as diatom earth, graphite, aluminum oxide, mica, clay, carbon, titanium oxide and glass beads; conductive materials; pigments; lubricants; and polydimethylsiloxane as a mold release agent.
- the organopolysilmethylene-siloxane composition of the present invention can be obtained by blending the afore-mentioned components in a planetary mixer or Shinagawa mixer according to conventional methods.
- a curing method and curing conditions of the organopolysilmethylene-siloxane composition of the present invention may be conventional ones and may be selected, depending on types of compositions.
- the composition of the present invention cures with moisture in the atmosphere and, therefore shall be stored in an atmosphere where moisture is kept out. Curing is preferably performed at a temperature of 60 to 150 degrees C. and a humidity of 20 to 80% for 0.5 to 24 hours.
- the cured product of the organopolysilmethylene-siloxane composition of the present invention is excellent in mechanical strength, heat resistance, electrical insulation property, water-proof property, and optical properties; low in permeability for gas; and is most suitable as optical materials which particularly need transparency, such as LED lenses and sealing materials for LED.
- part or parts means part or parts by mass.
- a viscosity is a value measured at 25 degrees C. with a rotational viscometer, BM type ex Toki Sangyo Co., Ltd.
- the product obtained was analyzed by 1 H-NMR and was found to be organopolysilmethylene-siloxane (A1) represented by the following formula (8).
- the viscosity was 5 mm 2 /s.
- the NMR spectra of A1 are shown in FIG. 1 (NMR: JNM-LA300WB ex JOEL, 300 MHz, 1 H-NMR, DMSO-d as a deuterated solvent)
- reaction mixture was neutralized, filtered and, subsequently, stripped at 160 degrees C./5 mm Hg for 30 minutes to obtain the organopolysilmethylene-siloxane (A2) represented by the following formula (9).
- the viscosity was 20 mm 2 /s.
- organopolysilmethylene-siloxane (A1) prepared in Example 1 100 Parts of organopolysilmethylene-siloxane (A1) prepared in Example 1, 2.0 parts of tetraethoxysiloxane (C1) and 0.2 part of dibutyltindilaurate (D) were blended homogeneously to obtain an organopolysilmethylene-siloxane composition.
- the resulting composition was poured into a mold of 130 mm long ⁇ 170 mm wide X 2 mm deep and the mold was placed in a desiccator. Then, the composition was defoamed under a reduced pressure of 10 Torr for 10 minutes and left at 25 degrees C. and a relative humidity of 60% for one week to allow to cure.
- a cured product of the polysilmethylene of 1.0 mm thick was obtained. The properties of the cured product are shown in Table 1.
- organopolysilmethylene-siloxane (A2) prepared in Example 2 100 Parts of organopolysilmethylene-siloxane (A2) prepared in Example 2, 2.0 parts of methyltris(diethylketoxime)silane (C2) represented by the following formula (10) and 0.2 part of dibutyltindilaurate (D) were blended homogeneously to obtain an organopolysilmethylene-siloxane composition.
- a cured product of the organopolysilmethylene-siloxane was prepared, as in Example 3. The properties of the cured product are shown in Table 1.
- organopolysilmethylene-siloxane (A1) prepared in Example 1 30 parts of dimethylpolysiloxane (B1) represented by the following formula (11) and having a viscosity of 10 mm 2 /s and 0.2 part of dibutyltindilaurate (D) were blended homogeneously to obtain an organopolysilmethylene-siloxane composition.
- a cured product of the organopolysilmethylene-siloxane composition was prepared, as in Example 3. The properties of the cured product are shown in Table 1.
- organopolysilmethylene-siloxane (A2) prepared in Example 2 50 parts of dimethylpolysiloxane (B1) represented by the afore-mentioned formula (11) and having a viscosity of 25 mm 2 /s and 0.2 part of dibutyltindilaurate (D) were blended homogeneously to obtain an organopolysilmethylene-siloxane composition.
- a cured product of the polysilmethylene-polysiloxane composition was prepared, as in Example 3. The properties of the cured product are shown in Table 1.
- Appearance of a cured product is observed by the naked eye to evaluate discoloration and transparency.
- a tensile strength, an elongation, a density, a volume resistivity, an electrical breakdown strength, a specific inductive and a dielectric tangent are determined according to JIS K6249.
- Example 1 Comparative Properties after cured Example 3
- Example 4 Example 5
- Example 6 Example Appearance Colorless and Colorless and Colorless and Colorless and Colorless and transparent transparent transparent transparent transparent transparent transparent transparent transparent transparent transparent transparent transparent transparent hardness (Type A) 75 40 30 25 35 Tensile Strength in MPa 3 5 2 4 0.3 Elongation in % 30 120 160 180 150 Density 1.07 1.07 1.07 1.07 Water Vapor Permeability 15 19 22 25 55 in g/m 2 ⁇ 24 hr Volume Resistivity in T ⁇ ⁇ cm 50 22 25 26 5 Electrical Breakdown Strength 37 30 23 22 20 in KV/mm Specific Inductive (50 Hz) 2.99 3.00 2.90 2.90 2.77 Dielectric Tangent (50 Hz) 0.001 0.001 0.001 0.001 0.001 Hardness after heated at 150 79 45 35 28 40 degrees C. for 1000 hrs
- the cured products of the organopolysilmethylene-siloxanes of Examples 3 to 6 are transparent, excellent in mechanical strength and less permeable by water vapor.
- the cured product of the Comparative Example is worse in mechanical strength and more permeable by water vapor.
- the organopolysilmethylene-siloxane composition of the present invention provides a cured product excellent in mechanical properties, heat resistance, electrical insulation property, water resistance, and low permeability for gas; optical properties; and is very suitable as optical materials which particularly need transparency, such as LED lenses and sealing materials for LED.
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Abstract
Organopolysilmethylene-siloxane of the formula (1):
-
- wherein each R1 is, independently of one another, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group, and a halogen atom; each R2 is, independently of one another, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group, a halogen atom, and (R1)3SiCH2—, wherein each R3 is, independently of one another, a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; k is an integer of 1 to 100; and n is an integer of 1 to 1000; said organopolysilmethylene-siloxane having, in a molecule, at least two out of alkoxy groups, hydroxy groups, and halogen atoms bonded to one or more silicon atoms.
Description
- This application is a Divisional of copending application Ser. No. 12/860,682 filed on Aug. 20, 2010, which claims priority to Japanese Patent Application No. 2009-192209 filed on Aug. 21, 2009. The entire contents of all of the above applications is hereby incorporated by reference.
- The present invention relates to an organopolysilmethylene-siloxane composition which yields a cured product excellent in heat resistance, mechanical strength, electrical insulation property, electrical properties and water-proof property, and a cured product thereof.
- Curable silicone rubber compositions which cure to form a silicone rubber elastomer are well known and widely used as a gasket material for electric and electronic parts, a potting material, a coating material, a shaping material such as a molding material, a wire-covering material and automobile parts, on account of good properties of the compositions such as weathering resistance, heat resistance, and electrical insulation property. Curable silicone rubber compositions have siloxane bonds which are inherent in a silicone. A siloxane bond is ionic and, therefore, the curable silicone rubber compositions cannot exert the excellent properties of silicones such as chemical resistance, for instance, acid and alkali resistance, water-proof property and permeability for gas in extremely severe environments such as a hot and humid environment.
- As a countermeasure for the afore-mentioned problem, a polymer is known where a part of its siloxane bonds is a silethylene bond (Patent Literature 1) or a silphenylene bond (Patent Literature 2). However, the synthesis of these polymers and, accordingly, their mass production, are difficult and, therefore the polymers are expensive. Therefore, the polymers have been commercialized only in special applications or in special fields.
- As a precursor for silicon carbide ceramics, a polydiarylsilmethylenes having silmethylene bonds are known from Patent Literatures 3 to 5. These polymers are crystalline, thermoplastic silicon polymers having a high melting point and are good in heat resistance, insulation property, electrical properties, chemical resistance and water-proof property. However, the polymer is poor in processability by molding and, therefore, is not practically used. Various efforts have been made to improve the processability by molding. For instance,
Patent Literature 6 describes a mixture of a polydiarylsilmethylene with a silicone polymer. Patent Literatures 7 and 8 describe mixtures of a polydiarylsilmethylene with a polyalkylsilmethylene. Patent Literature 9 describes a method for preparing a film of a polydiarylsilmethylene on a substrate where a film of disilacyclobutane is formed on a substrate and is ring-opening polymerized using fine particles of metal. However, the thermoplastic diarylsilmethylene polymer is highly crystalline and, therefore, is difficult to be synthesized. Accordingly, the diarylsilmethylene polymer is expensive and bad in processability. Therefore, research has been made to adopt the diarylsilmethylene polymer as a precursor for silicon carbide ceramics. However, a thermosetting composition is not known which takes advantages of the properties as a polymer. -
- Patent Literature 1: JP National Phase Publication No. 01/030887
- Patent Literature 2: Japanese Patent Application Laid-Open No. Hei-5-320350
- Patent Literature 3: Japanese Patent Application Laid-Open No. Hei-8-109264
- Patent Literature 4: Japanese Patent Application Laid-Open No. Hei-8-109265
- Patent Literature 5: Japanese Patent Application Laid-Open No. Hei-8-109266
- Patent Literature 6: Japanese Patent Application Laid-Open No. Hei-9-227781
- Patent Literature 7: Japanese Patent Application Laid-Open No. Hei-9-227782
- Patent Literature 8: Japanese Patent Application Laid-Open No. Hei-9-227783
- Patent Literature 9: Japanese Patent No. 3069655
- The purpose of the present invention is to provide an condensation-curable organopolysilmethylene-siloxane, i.e., silicon polymer having a silmethylene bond; an organopolysilmethylene-siloxane composition which comprises a condensation-curable organopolysilmethylene-siloxane and, after cured, gives a product which has good heat resistance, electrical insulation property, water-proof property and processability by molding and low permeability for gas; and a cured product thereof.
- The present inventors eagerly made research to attain the afore-mentioned purpose and have succeeded in synthesizing an organopolysilmethylene-siloxane having, in a molecule, at least two out of alkoxy groups, hydroxy groups and halogen atoms bonded to one or more silicon atoms and have found that the afore-mentioned organopolysilmethylene-siloxane is condensation-reacted, optionally using a particular curing agent and a curing catalyst, to give a useful cured product.
- Namely, the present invention provides an organopolysilmethylene-siloxane represented by the following general formula (1):
- wherein R1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group and a halogen atom; R2 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group, a halogen atom and (R1)3SiCH2—, wherein R3 is, independently of each other, a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; k is an integer of 1 to 100; and n is an integer of 1 to 1000; and having, in a molecule, at least two out of alkoxy groups, hydroxy groups and halogen atoms bonded to one or more silicon atoms.
- Further, the present invention provides a method for preparing the aforesaid organopolysilmethylene-siloxane, comprising a step of hydrolyzing an organopolysilmethylene-siloxane represented by the following general formula (3):
- wherein R4 is, independently of each other, a group selected from the group consisting of a chlorine atom, a hydroxy group and an alkoxy group having 1 to 4 carbon atoms; R1, R2 and k are as defined above and wherein k may be the same as or different from each other.
- Furthermore, the present invention provides an organopolysilmethylene-siloxane composition comprising
- (A) 1 to 100 parts by weight of the aforesaid organopolysilmethylene-siloxane (1),
- (B) 0 to 99 parts by weight of an organopolysiloxane represented by the following general formula:
- wherein R1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group and a halogen atom, and m is an integer of 0 to 300; and having, in a molecule, at least two out of alkoxy groups, hydroxy groups and halogen atoms bonded to one or more silicon atoms,
- provided that a total of the amounts of (A) and (B) is 100 parts by weight; (C) 0 to 30 parts by weight of a curing agent which is an organosilicon compound represented by the following general formula:
-
RaSiX4-a (5) - and/or a partial hydrolysis condensate thereof,
- wherein R is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms; X is, independently of each other, a group selected from the group consisting of ketoxime, alkoxy, and 1-methylvinyloxy groups; and a is 0, 1, or 2; and
- (D) a catalytic amount of a curing catalyst.
- A cured product from the afore-mentioned composition is also provided.
- The organopolysilmethylene-siloxane composition of the present invention provides a cured product having excellent properties such as heat resistance, electrical insulation property, mechanical properties and optical properties. The cured product also shows low permeability for gas and excellent water-proof property and hydrolysis resistance even in extremely severe environments, whereas silicone rubbers do not show these properties. The organopolysilmethylene-siloxane composition of the present invention shows as good processability by molding as that of conventional silicone rubbers and, therefore, can be processed by conventional processing machinery such as a molding instrument. Molded products obtained from the organopolysilmethylene-siloxane composition of the present invention can be used in insulating materials, sealing materials, electric or electronic parts such as cables, packings, and connectors, automobile parts and semi-conductor devices, similarly to silicone rubbers. They can also be used for lenses or transparent sealing materials, taking advantages of its optical properties.
-
FIG. 1 shows NMR spectra of the compound prepared in Example 1. - The present invention will be further described below.
- (A) Organopolysilmethylene-Siloxane
- Component (A) is an organopolysilmethylene-siloxane which is represented by the following general formula (1):
- wherein R3 is, independently of each other, a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; k is an integer of 1 to 100, preferably 1 to 50; n is an integer of 1 to 1000, preferably 1 to 100, more preferably 1 to 50; and
- having, in a molecule, at least two out of alkoxy groups, hydroxy groups and halogen atoms bonded to one or more silicon atoms; and which preferably has a viscosity at 25 degrees C. of 1 to 1,000,000 mm2/s.
- In formula (1), R1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10, preferably 1 to 6, carbon atoms other than an alkenyl group; alkoxy and hydroxy groups and a halogen atom. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl, ethyl, propyl, isopropyl, and butyl groups; a cycloalkyl group such as a cyclohexyl group; an aryl group such as phenyl and tolyl groups; an aralkyl group such as benzyl and 2-phenylethyl groups; and the groups where a part or whole of their hydrogen atoms bonded to each one carbon atom are replaced with a halogen atom or a cyano group, such as a chlormethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl groups. Inter alia, methyl and phenyl groups are preferred. Particularly, a methyl group is preferred for curing property of the composition and flexibility of the cured product. Particularly, 50 mol % or more of R1 is preferably a methyl group.
- R2 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10, preferably 1 to 6, carbon atoms other than an alkenyl group; an alkoxy group and a hydroxy group, a halogen atom and (R1)3SiCH2—. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl, ethyl, propyl, isopropyl, and butyl groups; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl and tolyl groups; an aralkyl group such as a benzyl group and 2-phenylethyl group; and the groups where a part or whole of their hydrogen atoms bonded to each one carbon atom are replaced with a halogen atom or a cyano group, such as a chlormethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl groups. Inter alia, methyl and phenyl groups are preferred. Particularly, a methyl group is preferred for curing property of the composition and flexibility of the cured product. Particularly, 50 mol % or more of R2 is preferably a methyl group.
- Inter alia, the organopolysilmethylene-siloxane is preferably represented by the following formula (2):
- wherein R2 is, independently of each other, a group selected from the group consisting of a methyl group and Y(CH3)2SiCH2—; R3 is a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms;
- Y is a group selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms and a hydroxy group; and k and n are as defined above.
- The organopolysilmethylene-siloxane represented by the afore-mentioned formula (1) can be prepared by hydrolysis of an organopolysilmethyelene represented by the following formula (3) wherein the number of silmethylene units may be the same or different among the molecules. If required, a strong alkali such as KOH and NaOH is added after the hydrolysis to cause alkali polymerization and then the reaction mixture is washed with water and neutralized to obtain the organopolysilmethylene-siloxane of the present invention.
- wherein R4 is a chlorine atom, a hydroxy group or an alkoxy group having 1 to 4 carbon atoms and R1, R2 and k are as defined above.
- Examples of the organopolysilmethylene-siloxane represented by the afore-mentioned formula (1) include the following:
- The present invention also provides an organopolysilmethylene-siloxane composition comprising (A) the organopolysilmethylene-siloxane represented by the afore-mentioned general formula (1); optionally, (C) a particular curing agent; and (D) a curing catalyst. The organopolysilmethylene-siloxane composition of the present invention may further comprise (B) an organopolysiloxane represented by the following general formula (4).
- (B) Organopolysiloxane
- Component (B) is an optional component which replaces a part of organopolysilmethylene-siloxane (A). Component (B) is represented by the following general formula (4):
- wherein m is an integer of 0 to 300, preferably 0 to 100, more preferably 0 to 20 and has at least two out of alkoxy groups, hydroxy groups and halogen atoms bonded to one or more silicon atoms. Its viscosity at 25 degrees C. is preferably 1 to 1,000,000 mm2/s.
- In the afore-mentioned formula, R1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10, preferably 1 to 6, carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group and a halogen atom. Examples of the monovalent hydrocarbon group include an alkyl group such as methyl, ethyl, propyl, isopropyl, and butyl groups; a cycloalkyl group such as a cyclohexyl group; an aryl group such as phenyl and tolyl groups; an aralkyl group such as benzyl and 2-phenylethyl groups; and the groups where a part or whole of their hydrogen atoms bonded to each one carbon atom are replaced with a halogen atom or a cyano group. Preferably, at least two out of R1 are selected from the group consisting of alkoxy and hydroxy groups and a halogen atom and the rest of R1 is a methyl group.
- Inter alia, preferred is the organopolysiloxane having hydroxy groups on both ends and represented by the following formula (6):
- wherein R1 is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, m is an integer of 0 to 300, preferably 0 to 100, more preferably 0 to 20.
- In particular, preference is given to polydimethylsiloxane having hydroxy groups on both ends and copolymers having hydroxy groups on both ends and composed of polydimethylsiloxane and polymethylphenylsiloxane as each represented by the following formulas.
- wherein m is as defined above and a total of p and q is an integer of 1 to 300, preferably 1 to 100, more preferably 1 to 20.
- The present organopolysilmethylene-siloxane composition comprises 1 to 100 parts by weight of component (A) and 0 to 99 parts by weight of component (B), preferably 30 to 100 parts by weight of component (A) and 0 to 70 parts by weight of component (B), relative to 100 parts by weight of a total of components (A) and (B). If the amount of component (A) is less than the afore-mentioned lower limit, the organopolysilmethylene-siloxane does not exert its properties such as water resistance and optical properties.
- (C) Curing Agent
- Curing agent (C) condensates with organopolysilmethylene-siloxane (A) and organopolysiloxane (B) to form a cross-linking bond and yield a rubber elastomer with a three dimensional network. The curing agent of the present invention is an organosilicon compound represented by the following general formula (5) and/or partial hydrolysis condensate thereof,
-
RaSiX4-a (5) - wherein R is, independently of each other, a group selected from the group consisting of unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms; X is, independently of each other, a group selected from the group consisting of ketoxime, alkoxy, and 1-methylvinyloxy groups and a is 0, 1, or 2; and
- having at least two groups selected from the group consisting of ketoxime, alkoxy, and 1-methylvinyloxy groups. A partial hydrolysis condensate is an organopolysiloxane obtained by condensation among partially hydrolyzed organosilicon compounds.
- In formula (5), R is, independently of each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group such as methyl, ethyl, propyl, isopropyl, and butyl groups; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as vinyl and allyl groups; an aryl group such as phenyl and tolyl groups; an aralkyl group such as benzyl and 2-phenylethyl groups; and the groups where a part or whole of the hydrogen atoms bonded to carbon atoms of the aforesaid groups are replaced with a halogen atom or a cyano group, such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl groups. Particularly, methyl, ethyl, vinyl and phenyl groups are preferred.
- Examples of the organosilicon compound represented by formula (5) include ketoxime group-containing silanes such as methyltris(diethylketoxime)silane, methyltris (methyl ethylketoxime)silane, binyltris(methylethylketoxime)silane, and phenyltris(diethylketoxime)silane; alkoxy group-containing silanes such as trimethoxymethylsilane, trimethoxyphenylsilane, trimethoxyvinylsilane, triethoxymethylsilane, triethoxyphenylsilane, triethoxyvinylsilane, tetramethoxysilane and tetraethoxysilane; and 1-methylvinyloxy group-containing silanes such as tri(1-methylvinyloxy)methylsilane and tri(1-methylvinyloxy)phenylsilane. The curing agent of the present invention may be a partial hydrolysis condensate of the afore-mentioned organosilicon compounds. These curing agents may be used alone or in combination of two or more of them.
- Component (C) is usually added in an amount of 0 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, relative to 100 parts by weight of a total of the amounts of components (A) and (B). Below the afore-mentioned lower limit, storage stability and processability of the composition is so worse as to sometime cause gelation. If the amount exceeds the afore-mentioned upper limit, shrinkage after cured is so large that properties of the cured product obtained may be worse.
- (D) Curing Catalyst
- Curing catalyst (D) is to promote condensation between components (A) and (B) with component (C). Examples of the curing catalyst include metal salts of carboxylic acids such as stannous octoate, cobalt octoate, manganese octoate, zinc octoate, stannous octaoate, stannous caprylate and stannous oleate; organotin compounds such as dibutyltindiacetate, dibutyltindioctoate, dibutyltindilaurate, dibutyltindioleate, diphenyltindiacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis(triethoxy)tin, and dioctyltindilaurate; titanate esters such as tetrabutyl titanate, tetra-1-ethylhexyl titanate and tetraisopropenyl titanate; oraganotitanium compounds such as tetra(organosiliconate)titanium; titanium chelates such as triethanolamine titanate and titanium acetylacetonate; and alkoxy aluminum compounds. The curing catalyst may be a 2-guanidyl group-containing silane as follows.
- In the formulas, Me represents a methyl group.
- The curing catalyst may be blended in such an amount that the catalyst works effectively. The amount may be properly increased or decreased depending upon a desired curing rate. The amount may not be particularly restricted, but is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of total of components (A), (B) and (C).
- Other Components
- The organopolysilmethylene-siloxane composition of the present invention may comprise, in addition to the afore-mentioned components (A) to (D), a variety of functional additives, for instance, reinforcing fillers, heat stabilizers, antioxidants, ultraviolet rays absorbers, photo stabilizers, agents rendering conductivity, agents rendering adhesiveness, coloring agents, lubricants, plasticizers, anti-static agents, and flame retardants as long as the purposes and effects of the present invention are not impaired. For instance, examples of the additives include reinforcing fillers such as fumed silica and precipitated silica; fillers such as diatom earth, graphite, aluminum oxide, mica, clay, carbon, titanium oxide and glass beads; conductive materials; pigments; lubricants; and polydimethylsiloxane as a mold release agent.
- The organopolysilmethylene-siloxane composition of the present invention can be obtained by blending the afore-mentioned components in a planetary mixer or Shinagawa mixer according to conventional methods. A curing method and curing conditions of the organopolysilmethylene-siloxane composition of the present invention may be conventional ones and may be selected, depending on types of compositions. The composition of the present invention cures with moisture in the atmosphere and, therefore shall be stored in an atmosphere where moisture is kept out. Curing is preferably performed at a temperature of 60 to 150 degrees C. and a humidity of 20 to 80% for 0.5 to 24 hours.
- The cured product of the organopolysilmethylene-siloxane composition of the present invention is excellent in mechanical strength, heat resistance, electrical insulation property, water-proof property, and optical properties; low in permeability for gas; and is most suitable as optical materials which particularly need transparency, such as LED lenses and sealing materials for LED.
- The present invention will be described below more in detail by referring to the Examples and Comparative Examples, but shall not be limited thereto. In the following description, “part” or “parts” means part or parts by mass. A viscosity is a value measured at 25 degrees C. with a rotational viscometer, BM type ex Toki Sangyo Co., Ltd.
- 1000 Grams (3.01 mols) of the chlorine atom containing silmethylene of the following formula (7) were dissolved in 800 grams of xylene and added dropwise at 60 degrees C. to a solvent mixture composed of 500 grams of water and 250 grams of xylene to hydrolyze. Then, the reaction mixture was aged at room temperature for 3 hours, the formed acid was separated and removed. The organic phase was washed with water, filtered and stripped at 160 degrees C./5 mmHg for 30 minutes.
- The product obtained was analyzed by 1H-NMR and was found to be organopolysilmethylene-siloxane (A1) represented by the following formula (8). The viscosity was 5 mm2/s. The NMR spectra of A1 are shown in
FIG. 1 (NMR: JNM-LA300WB ex JOEL, 300 MHz, 1H-NMR, DMSO-d as a deuterated solvent) - 1000 Grams (3.01 mols) of chlorine atom-containing silmethylene of the afore-mentioned formula (7) were dissolved in 800 grams of xylene and added dropwise to a solvent mixture composed of 500 grams of water and 250 grams of xylene at a temperature of 60 degrees C. to hydrolyze. Then, the reaction mixture was aged at room temperature for 3 hours, and the formed acid was separated. The remaining mixture was washed with water and subjected to azeotropic dehydration at 140 degrees C. To this polysilmethylene having terminal hydroxyl groups on both ends added was 0.2 gram of KOH, followed by alkali polymerization at 140 degrees C. for 10 hours. Then, the reaction mixture was neutralized, filtered and, subsequently, stripped at 160 degrees C./5 mm Hg for 30 minutes to obtain the organopolysilmethylene-siloxane (A2) represented by the following formula (9). The viscosity was 20 mm2/s.
- 100 Parts of organopolysilmethylene-siloxane (A1) prepared in Example 1, 2.0 parts of tetraethoxysiloxane (C1) and 0.2 part of dibutyltindilaurate (D) were blended homogeneously to obtain an organopolysilmethylene-siloxane composition. The resulting composition was poured into a mold of 130 mm long×170 mm wide X 2 mm deep and the mold was placed in a desiccator. Then, the composition was defoamed under a reduced pressure of 10 Torr for 10 minutes and left at 25 degrees C. and a relative humidity of 60% for one week to allow to cure. A cured product of the polysilmethylene of 1.0 mm thick was obtained. The properties of the cured product are shown in Table 1.
- 100 Parts of organopolysilmethylene-siloxane (A2) prepared in Example 2, 2.0 parts of methyltris(diethylketoxime)silane (C2) represented by the following formula (10) and 0.2 part of dibutyltindilaurate (D) were blended homogeneously to obtain an organopolysilmethylene-siloxane composition. A cured product of the organopolysilmethylene-siloxane was prepared, as in Example 3. The properties of the cured product are shown in Table 1.
- 70 Parts of organopolysilmethylene-siloxane (A1) prepared in Example 1, 30 parts of dimethylpolysiloxane (B1) represented by the following formula (11) and having a viscosity of 10 mm2/s and 0.2 part of dibutyltindilaurate (D) were blended homogeneously to obtain an organopolysilmethylene-siloxane composition. A cured product of the organopolysilmethylene-siloxane composition was prepared, as in Example 3. The properties of the cured product are shown in Table 1.
- 50 Parts of organopolysilmethylene-siloxane (A2) prepared in Example 2, 50 parts of dimethylpolysiloxane (B1) represented by the afore-mentioned formula (11) and having a viscosity of 25 mm2/s and 0.2 part of dibutyltindilaurate (D) were blended homogeneously to obtain an organopolysilmethylene-siloxane composition. A cured product of the polysilmethylene-polysiloxane composition was prepared, as in Example 3. The properties of the cured product are shown in Table 1.
- 100 Parts of dimethylpolysiloxane (B1) represented by the afore-mentioned formula (11) and having a viscosity of 25 mm2/s, 2.0 parts of tetraethoxysilane (C1) and 0.2 part of dibutyltindilaurate (D) were blended homogeneously to obtain an organopolysiloxane composition. A cured product of the organopolysiloxane was prepared, as in Example 3.
- The properties of the cured products were evaluated in the following methods. Results are shown in Table 1.
- Appearance of a cured product is observed by the naked eye to evaluate discoloration and transparency.
- (2) Hardness is determined with a durometer of type A in accordance with Japanese Industrial Standards (JIS) K6253.
- (3) A tensile strength, an elongation, a density, a volume resistivity, an electrical breakdown strength, a specific inductive and a dielectric tangent are determined according to JIS K6249.
- (4) Water vapor permeability is determined according to JIS Z0208.
-
TABLE 1 Comparative Properties after cured Example 3 Example 4 Example 5 Example 6 Example Appearance Colorless and Colorless and Colorless and Colorless and Colorless and transparent transparent transparent transparent transparent Hardness (Type A) 75 40 30 25 35 Tensile Strength in MPa 3 5 2 4 0.3 Elongation in % 30 120 160 180 150 Density 1.07 1.07 1.07 1.07 1.07 Water Vapor Permeability 15 19 22 25 55 in g/m2 · 24 hr Volume Resistivity in TΩ · cm 50 22 25 26 5 Electrical Breakdown Strength 37 30 23 22 20 in KV/mm Specific Inductive (50 Hz) 2.99 3.00 2.90 2.90 2.77 Dielectric Tangent (50 Hz) 0.001 0.001 0.001 0.001 0.001 Hardness after heated at 150 79 45 35 28 40 degrees C. for 1000 hrs - As seen in Table 1, the cured products of the organopolysilmethylene-siloxanes of Examples 3 to 6 are transparent, excellent in mechanical strength and less permeable by water vapor. The cured product of the Comparative Example is worse in mechanical strength and more permeable by water vapor.
- The organopolysilmethylene-siloxane composition of the present invention provides a cured product excellent in mechanical properties, heat resistance, electrical insulation property, water resistance, and low permeability for gas; optical properties; and is very suitable as optical materials which particularly need transparency, such as LED lenses and sealing materials for LED.
Claims (6)
1. An organopolysilmethylene-siloxane composition comprising:
(A) 1 to 100 parts by weight of an organopolysilmethylene-siloxane represented by the following general formula (1):
wherein: R1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group, and a halogen atom; R2 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group, a halogen atom, and (R1)3SiCH2—; R3 is, independently of each other, a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; k is an integer of 1 to 100; and n is an integer of 1 to 1000, said organopolysilmethylene-siloxane having, in a molecule, at least two out of alkoxy groups, hydroxy groups, and halogen atoms bonded to one or more silicon atoms;
(B) 0 to 99 parts by weight, provided that a total of the amounts of (A) and (B) is 100 parts by weight, of an organopolysiloxane represented by the following general formula:
wherein R1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group, and a halogen atom, and m is an integer of 0 to 300; and having, in a molecule, at least two out of alkoxy groups, hydroxy groups and halogen atoms bonded to one or more silicon atoms;
(C) 1 to 30 parts by weight of a curing agent which is an organosilicon compound represented by the following general formula:
RaSiX4-a (5)
RaSiX4-a (5)
and/or a partial hydrolysis condensate thereof, wherein R is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms; X is, independently of each other, a group selected from the group consisting of ketoxime, alkoxy, and 1-methylvinyloxy groups; and a is 0, 1, or 2; and
(D) a catalytic amount of a curing catalyst.
2. An organopolysilmethylene-siloxane composition comprising
(A) 30 to 100 parts by weight of the organopolysilmethylene-siloxane according to claims 1 ;
(B) 0 to 70 parts by weight of the organopolysiloxane according to claim 1 , provided that a total of the amounts of (A) and (B) is 100 parts by weight;
(C) 1 to 30 parts by weight of the curing agent according to claim 1 ; and
(D) a catalytic amount of a curing catalyst.
3. The organopolysilmethylene-siloxane composition according to claim 1 , wherein the organopolysiloxane (B) is represented by the following formula (6):
wherein R1 is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group and m is an integer of 0 to 300.
4. A cured organopolysilmethylene-siloxane product from an organopolysilmethylene-siloxane composition comprising:
(A) 1 to 100 parts by weight of an organopolysilmethylene-siloxane represented by the following general formula (1):
wherein: R1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group, and a halogen atom; R2 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group, a halogen atom, and (R1)3SiCH2—; R3 is, independently of each other, a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; k is an integer of 1 to 100; and n is an integer of 1 to 1000, said organopolysilmethylene-siloxane having, in a molecule, at least two out of alkoxy groups, hydroxy groups, and halogen atoms bonded to one or more silicon atoms;
(B) 0 to 99 parts by weight, provided that a total of the amounts of (A) and (B) is 100 parts by weight, of an organopolysiloxane represented by the following general formula:
wherein R1 is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group, an alkoxy group, a hydroxy group, and a halogen atom, and m is an integer of 0 to 300; and having, in a molecule, at least two out of alkoxy groups, hydroxy groups and halogen atoms bonded to one or more silicon atoms;
(C) 1 to 30 parts by weight of a curing agent which is an organosilicon compound represented by the following general formula:
RaSiX4-a (5)
RaSiX4-a (5)
and/or a partial hydrolysis condensate thereof, wherein R is, independently of each other, a group selected from the group consisting of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms; X is, independently of each other, a group selected from the group consisting of ketoxime, alkoxy, and 1-methylvinyloxy groups; and a is 0, 1, or 2; and
(D) a catalytic amount of a curing catalyst.
5. The organopolysilmethylene-siloxane composition according to any one of claims 1 to 3 , wherein the organopolysilmethylene-siloxane is represented by the following formula (2):
wherein R2 is, independently of each other, a group selected from the group consisting of a methyl group and Y(CH3)2SiCH2—, R3 is a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Y is a group selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms and a hydroxy group, k is an integer of 1 to 100, and n is an integer of 1 to 1000.
6. An insulating material, a sealing material, an electric part, an electronic part, or an automobile part comprising the cured organopolysilmethylene-siloxane product according to claim 4 .
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US12/860,682 US8497024B2 (en) | 2009-08-21 | 2010-08-20 | Organopolysilmethylene-siloxane and a cured product thereof |
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JP5287935B2 (en) * | 2011-06-16 | 2013-09-11 | 東レ株式会社 | Phosphor-containing sheet, LED light-emitting device using the same, and manufacturing method thereof |
US10211380B2 (en) | 2011-07-21 | 2019-02-19 | Cree, Inc. | Light emitting devices and components having improved chemical resistance and related methods |
US10686107B2 (en) | 2011-07-21 | 2020-06-16 | Cree, Inc. | Light emitter devices and components with improved chemical resistance and related methods |
TW201312807A (en) | 2011-07-21 | 2013-03-16 | Cree Inc | Light emitter device packages, components, and methods for improved chemical resistance and related methods |
US9496466B2 (en) | 2011-12-06 | 2016-11-15 | Cree, Inc. | Light emitter devices and methods, utilizing light emitting diodes (LEDs), for improved light extraction |
US9343441B2 (en) | 2012-02-13 | 2016-05-17 | Cree, Inc. | Light emitter devices having improved light output and related methods |
US9240530B2 (en) | 2012-02-13 | 2016-01-19 | Cree, Inc. | Light emitter devices having improved chemical and physical resistance and related methods |
JP5814175B2 (en) * | 2012-04-16 | 2015-11-17 | 信越化学工業株式会社 | Thermosetting silicone resin composition for LED reflector, LED reflector and optical semiconductor device using the same |
JP5756054B2 (en) | 2012-04-16 | 2015-07-29 | 信越化学工業株式会社 | Thermosetting resin composition for LED reflector, LED reflector and optical semiconductor device using the same |
KR101767085B1 (en) | 2014-09-30 | 2017-08-10 | 삼성에스디아이 주식회사 | Curable organo polysiloxane composition, encapsulant, and electronic device |
CN104788678B (en) * | 2015-04-24 | 2018-01-19 | 浙江润禾有机硅新材料有限公司 | A kind of vinyl silicone oil containing alkylen structures and preparation method thereof |
JP6402690B2 (en) * | 2015-07-31 | 2018-10-10 | 信越化学工業株式会社 | Organopolysilmethylenesiloxane composition |
US9751989B2 (en) | 2015-12-22 | 2017-09-05 | Shin-Etsu Chemical Co., Ltd. | Condensation curable resin composition and semiconductor package |
WO2017183259A1 (en) * | 2016-04-22 | 2017-10-26 | 株式会社Adeka | Silicon-containing curable composition and cured object obtained therefrom |
KR101931454B1 (en) * | 2017-12-29 | 2018-12-20 | 박성원 | Photo-curable resin compositions and article using the same |
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JP5294414B2 (en) | 2013-09-18 |
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US20110046319A1 (en) | 2011-02-24 |
EP2289978B1 (en) | 2015-03-11 |
CN101993540A (en) | 2011-03-30 |
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