WO2015194159A1 - Organopolysiloxane et son procédé de production - Google Patents

Organopolysiloxane et son procédé de production Download PDF

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WO2015194159A1
WO2015194159A1 PCT/JP2015/002991 JP2015002991W WO2015194159A1 WO 2015194159 A1 WO2015194159 A1 WO 2015194159A1 JP 2015002991 W JP2015002991 W JP 2015002991W WO 2015194159 A1 WO2015194159 A1 WO 2015194159A1
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group
sio
carbon atoms
organopolysiloxane
formula
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森田　好次
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東レ・ダウコーニング株式会社
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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

Definitions

  • the present invention relates to a novel organopolysiloxane in which an organopolysiloxane resin block is linked by a siloxy group or a silphenylene group, and a method for producing the same.
  • Patent Documents 1 to 3 the general formula: — (R 2 SiO) m — (wherein R is an unsubstituted or substituted monovalent hydrocarbon group having no unsaturated aliphatic bond, and m is 1
  • organopolysiloxane having a high refractive index and high transparency is indifferent.
  • SiR 2 Cl ⁇ -dichlorodiorganopolysiloxane represented by SiR 2 Cl (wherein R and m are the same as described above)
  • Due to the difference in decomposition performance it is difficult to control the molecular structure of the organopolysiloxane, the linear diorganopolysiloxane block is incorporated into the organopolysiloxane resin block, and the organopolysiloxane resin block becomes the linear diorganopolyester.
  • organopolysiloxane linked by siloxane block ⁇ , ⁇ -di B is Logistics organopolysiloxane hydrolyzate alpha, .omega.-hydroxy diorganopolysiloxane each other by condensation polymerization, there is a problem that the diorganopolysiloxane unreacted that does not bind to organopolysiloxane resin block is generated.
  • Patent Document 4 discloses hydrosilylation of an organopolysiloxane resin having at least two alkenyl groups in one molecule and a linear diorganopolysiloxane having both molecular chain ends blocked with silicon-bonded hydrogen atoms.
  • a solvent-soluble organopolysiloxane obtained by reaction is described.
  • the organopolysiloxane thus obtained has a low refractive index and transparency, and is viscous and poor in handling workability.
  • An object of the present invention is to provide an organopolysiloxane having a high refractive index, a high transparency, and a good handleability, in which organopolysiloxane resin blocks are linked by a siloxy group or a silphenylene group, and a method for producing the same. It is in.
  • the organopolysiloxane of the present invention has an average unit formula: (R 1 SiO 3/2) a ( R 1 2 R 2 SiO 1/2) b (O 1/2 SiR 1 2 R 3 -X-R 3 R 1 2 SiO 1/2) c ⁇
  • R 1 is the same or different and is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms
  • R 2 is 2 to 12 carbon atoms
  • R 3 is the same or different alkylene group having 2 to 12 carbon atoms, provided that at least 10 mol% of the total of R 1 to R 3 is an aryl group having 6 to 20 carbon atoms
  • X represents the general formula (I): -SiR 4 2 O (R 4 2 SiO) n SiR 4 2- (Wherein R 4 is the same or different, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to
  • An organopolysiloxane resin block composed of siloxane units (wherein R 1 , R 2 , and R 3 are the same as described above) is bonded to the siloxy group or the silphenylene group via R 3 in the formula. It is connected.
  • R 2 is preferably a vinyl group
  • R 3 is preferably an ethylene group.
  • n Is preferably 0.
  • R 1 are the same or different, an alkyl group having 1 to 12 carbon atoms, an aryl group, or aralkyl group having 7 to 20 carbon atoms having a carbon number 6 ⁇ 20, R 2 is 2 to 12 carbon atoms Provided that at least 10 mol% of the total of R 1 and R 2 is an aryl group having 6 to 20 carbon atoms, d is a number of 0.65 to 0.90, and e is 0.8.
  • (A) is preferably R 2 in component a vinyl group, also be the case, n represents 0 is an alkyl group of (B-1) R 4 is any number of 1 to 12 carbon atoms in the component preferable.
  • the organopolysiloxane of the present invention is a highly refractive and highly transparent organopolysiloxane in which organopolysiloxane resin blocks are linked by a siloxy group or a silphenylene group. Further, the production method of the present invention is characterized in that such a novel organopolysiloxane can be produced efficiently.
  • the organopolysiloxane of the present invention has an average unit formula: (R 1 SiO 3/2 ) a (R 1 2 R 2 SiO 1/2 ) b (O 1/2 SiR 1 2 R 3 —X—R 3 R 1 2 SiO 1/2 ) c It is represented by
  • R 1 is the same or different and is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, etc.
  • R 1 to R 3 examples include alkyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; and aralkyl groups such as benzyl, phenethyl, and phenylpropyl.
  • R 1 SiO 3/2 the siloxane unit represented by the formula: R 1 SiO 3/2 , R 1 is preferably an aryl group having 6 to 20 carbon atoms, particularly a phenyl group.
  • R 2 is an alkenyl group having 2 to 12 carbon atoms.
  • Specific examples include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, and an octenyl group, and a vinyl group is preferable.
  • R 3 is the same or different alkylene group having 2 to 12 carbon atoms. Specific examples include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, a hexylene group, a cyclohexylene group, and an octylene group, and an ethylene group is preferable.
  • X represents the general formula (I): -SiR 4 2 O (R 4 2 SiO) n SiR 4 2-
  • R 4 is the same or different and is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Specifically, the same group as R 1 is exemplified.
  • at least 10 mol% of all R 4 in the formula is preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably a phenyl group. This is because the refractive index and transmittance of the organopolysiloxane can be further increased.
  • n is an integer in the range of 0 to 5, preferably an integer in the range of 0 to 4, and more preferably an integer in the range of 0 to 3. This is because, when n is an integer within the above range, the transmittance can be improved without lowering the refractive index of the present organopolysiloxane.
  • n is preferably 0.
  • a is a number in the range of 0.65 to 0.90
  • b is a number in the range of 0.04 to 0.29
  • c is in the range of 0.01 to 0.07.
  • a + b + c 1.00. This is because when a is equal to or higher than the lower limit of the above range, the thermal properties such as hot melt properties due to the organopolysiloxane resin block in the present organopolysiloxane can be improved, and on the other hand, it is equal to or lower than the upper limit of the above range. This is because the solubility of the present organopolysiloxane in an organic solvent can be improved, and its handleability can be improved.
  • the present organopolysiloxane can be cured by a hydrosilylation reaction with a silicon atom-bonded hydrogen atom-containing organopolysiloxane. This is because the thermal properties such as hot melt properties can be improved by the organopolysiloxane resin block in the organopolysiloxane.
  • thermal properties such as hot melt properties due to the organopolysiloxane resin block in the organopolysiloxane can be improved. This is because the handling property of the organopolysiloxane can be improved.
  • Such an organopolysiloxane includes a siloxane unit represented by the formula: R 1 SiO 3/2 and a siloxane unit represented by the formula: R 1 2 R 2 SiO 1/2 and the formula: R 1 2 R 3 SiO.
  • An organopolysiloxane resin block composed of siloxane units represented by 1/2 (wherein R 1 , R 2 , and R 3 are the same as above) is bonded to the siloxy group or the above-mentioned siloxy group via R 3 in the formula It is connected by the above silphenylene group.
  • the refractive index (25 ° C.) of visible light (589 nm) of the organopolysiloxane is not limited, but is preferably 1.50 or more. This is because the organopolysiloxane can be suitably used for an optical material having a high refractive index.
  • (A) component is an average unit formula: (R 1 SiO 3/2 ) d (R 1 2 R 2 SiO 1/2 ) e It is a raw material for forming the organopolysiloxane resin block.
  • R 1 is the same or different, an alkyl group having 1 to 6 carbon atoms, an aryl group, or aralkyl group having 7 to 20 carbon atoms of 6 to 20 carbon atoms, the same groups as those exemplified .
  • at least 10 mol% of the total of R 1 and R 2 in the component (A) is preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably a phenyl group. This is because the organopolysiloxane obtained can have a higher refractive index, improved transparency, and improved handling.
  • R 1 SiO 3/2 R 1 is preferably an aryl group having 6 to 20 carbon atoms, particularly a phenyl group.
  • R 2 is an alkenyl group having 2 to 12 carbon atoms, the same groups are exemplified, preferably a vinyl group.
  • the component (A) has at least two alkenyl groups in one molecule, and the content thereof is 0.1 to 40 mol% of the total of R 1 and R 2 , preferably 0.5 to It is 40 mol%, particularly preferably in the range of 1 to 30 mol%.
  • the content of the alkenyl group in the component (A) is within the above range, the hydrosilylation reaction with the component (B) can be sufficiently performed, and the alkenyl group in the resulting organopolysiloxane can be obtained. It is because it can be made to remain.
  • d is a number in the range of 0.65 to 0.90
  • e is a number in the range of 0.10 to 0.35
  • d + e 1.00.
  • an alkenyl group remains in the obtained organopolysiloxane, which can be hydrosilylated with a silicon atom-bonded hydrogen atom-containing organopolysiloxane, It is because thermal characteristics, such as hot-melt property by the organopolysiloxane resin block in the obtained organopolysiloxane, can be improved as it is below the upper limit of the said range.
  • compositions of such component (A) at 25 ° C. are not limited, but are, for example, solid at 25 ° C. or liquid with a viscosity of 10 mPa ⁇ s or more.
  • Component (B) is a raw material for linking the organopolysiloxane resin, and (B-1) general formula: HR 4 2 SiO (R 4 2 SiO) n SiR 4 2 H Or (B-2) general formula: HR 4 2 Si-C 6 H 4 -SiR 4 2 H It is bissilylbenzene represented by these.
  • R 4 is the same or different and is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and examples thereof are the same groups as R 1 above. Is done.
  • at least 10 mol% of all R 4 in the formula is preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably a phenyl group. This is because the refractive index and transmittance of the resulting organopolysiloxane can be further increased.
  • n is an integer in the range of 0 to 5, preferably an integer in the range of 0 to 4, and particularly preferably an integer in the range of 0 to 3. This is because when n is an integer within the above range, the transmittance can be improved without lowering the refractive index of the resulting organopolysiloxane.
  • n is preferably 0.
  • Examples of the component (B-1) include the following diorganosiloxanes. H (CH 3 ) 2 SiOSi (CH 3 ) 2 H H (CH 3 ) (C 6 H 5 ) SiOSi (CH 3 ) (C 6 H 5 ) H H (CH 3 ) 2 SiO [(CH 3 ) 2 SiO] Si (CH 3 ) 2 H H (CH 3 ) 2 SiO [(CH 3 ) (C 6 H 5 ) SiO] Si (CH 3 ) 2 H H (CH 3 ) 2 SiO [(C 6 H 5 ) 2 SiO] Si (CH 3 ) 2 H H (CH 3 ) (C 6 H 5 ) SiO [(CH 3 ) 2 SiO] Si (CH 3 ) (C 6 H 5 ) H.
  • the following bissilylbenzene is exemplified.
  • the amount of component (B) added is not limited, but the silicon-bonded hydrogen atom in this component is less than 0.8 mol relative to 1 mol of alkenyl group in component (A).
  • the amount is within the range of 0.05 to 0.7 mol, and more preferably within the range of 0.1 to 0.6 mol.
  • the amount is preferably in the range of 0.2 to 0.5 mol. This is because gelation of the resulting organopolysiloxane can be suppressed and alkenyl groups can remain.
  • the hydrosilylation reaction catalyst for promoting the above reaction is not limited, and examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts.
  • a platinum-based catalyst is preferable because the hydrosilylation reaction can be significantly accelerated.
  • the platinum-based catalyst include platinum fine powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex, particularly platinum-alkenylsiloxane complex. It is preferable.
  • alkenylsiloxane examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples include alkenyl siloxanes in which a part of the methyl groups of these alkenyl siloxanes are substituted with groups such as ethyl groups and phenyl groups, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with groups such as allyl groups and hexenyl groups. .
  • the addition amount of the hydrosilylation reaction catalyst in the above preparation method is not limited.
  • the catalyst metal is 0.01 to 1,000 ppm in mass units with respect to the total amount of the component (A) and the component (B).
  • the amount is preferably in the range, and particularly preferably in the range of 0.1 to 500 ppm. This is because when the amount of the hydrosilylation reaction catalyst is at least the lower limit of the above range, the hydrosilylation reaction can be sufficiently promoted. On the other hand, when it is below the upper limit of the above range, the resulting organopolysiloxane can be colored. This is because problems are less likely to occur.
  • reaction conditions in the above preparation method are not limited, and the reaction can be promoted by heating.
  • a solvent such as an aromatic solvent such as toluene or xylene; an aliphatic solvent such as heptane or hexane
  • the reaction temperature is preferably the reflux temperature of the solvent.
  • the viscosity of the reaction system can be reduced, and water can be dehydrated from the reaction system by azeotropic distillation or the like.
  • the organopolysiloxane thus obtained has an organopolysiloxane resin block linked by a siloxy group or a silphenylene group, an aromatic solvent such as toluene or xylene; an aliphatic solvent such as heptane or hexane, or the like. Soluble in solvent.
  • the property at 25 ° C. is not particularly limited, and examples thereof include liquid, viscous liquid, and solid.
  • the organopolysiloxane of the present invention has an alkenyl group in the molecule, it is cured with a silicon atom-bonded hydrogen atom-containing organopolysiloxane and a hydrosilylation reaction catalyst, and a cured product having an appropriate elastic modulus. It can be set as the curable organopolysiloxane composition which forms.
  • the silicon atom-bonded hydrogen atom-containing organopolysiloxane has an average composition formula: R 5 f H g SiO (4-f-g) / 2 It is represented by
  • R 5 is a monovalent hydrocarbon group having no aliphatic unsaturated bond, and examples thereof are the same groups as R 1 described above.
  • f and g are 0.7 ⁇ f ⁇ 2.1, 0.001 ⁇ g ⁇ 1.0, and 0.8 ⁇ f + g ⁇ 2.6, preferably 0.8 ⁇ f ⁇ 2, It is a positive number satisfying 0.01 ⁇ g ⁇ 1, 1 ⁇ f + g ⁇ 2.4.
  • the molecular structure of this organopolysiloxane is not particularly limited, and examples thereof include straight-chain, partially-branched straight-chain, branched-chain, cyclic, and three-dimensional network structures, and preferably a partially-branched straight-chain, Branched chain and three-dimensional network structure.
  • Such organopolysiloxane has a solid or liquid property at 25 ° C., and preferably has a viscosity at 25 ° C. of 10,000 mPa ⁇ s or less, more preferably within a range of 0.1 to 5,000 mPa ⁇ s, Particularly preferably, it is in the range of 0.5 to 1,000 mPa ⁇ s.
  • organopolysiloxane examples include a trimethylsiloxy group-capped methylhydrogen polysiloxane at both molecular chain ends, a trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer at both molecular chain terminals, and a dimethylhydrogensiloxy at both molecular chain terminals.
  • the content of the organopolysiloxane is 0.1 to 10 moles, preferably 0.1 to 5 moles of silicon-bonded hydrogen atoms with respect to 1 mole of alkenyl groups in the organopolysiloxane of the present invention.
  • the amount is particularly preferably in the range of 0.5 to 5 mol. This is because if the content of the organopolysiloxane is less than the lower limit of the above range, the resulting composition will not be sufficiently cured, whereas if it exceeds the upper limit of the above range, the resulting cured product will be machined. This is because the physical characteristics may be deteriorated.
  • the hydrosilylation reaction catalyst is a catalyst for accelerating the crosslinking reaction by the hydrosilylation reaction of the composition, and examples thereof include the hydrosilylation reaction catalyst as described above.
  • the content of the hydrosilylation reaction catalyst is a catalytic amount.
  • the catalyst metal in the catalyst is within a range of 0.01 to 1000 ppm by weight with respect to the composition.
  • the amount is preferably in the range of 0.1 to 500 ppm. This is because if the content of the catalyst for hydrosilylation reaction is less than the lower limit of the above range, the composition tends not to be cured sufficiently, whereas if the content exceeds the upper limit of the above range, the resulting curing is obtained. This is because problems such as coloring may occur in objects.
  • alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and phenylbutynol
  • Enyne compounds such as methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne
  • 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclo Reaction inhibitors such as tetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and benzotriazole
  • the content of the reaction inhibitor is not limited, but is preferably in the range of 0.0001 to 5 parts by weight with respect to 100 parts by weight of the composition.
  • the composition may contain an adhesion-imparting agent for improving its adhesion.
  • the adhesion-imparting agent is preferably an organosilicon compound having at least one alkoxy group bonded to a silicon atom in one molecule.
  • the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group is particularly preferable.
  • the group other than the alkoxy group bonded to the silicon atom of the organosilicon compound includes substituted or unsubstituted monovalent groups such as the alkyl group, the alkenyl group, the aryl group, the aralkyl group, and the halogenated alkyl group.
  • Hydrocarbon group glycidoxyalkyl group such as 3-glycidoxypropyl group, 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) Epoxy cyclohexyl alkyl group such as propyl group; Epoxy group-containing monovalent organic group such as oxiranyl alkyl group such as 4-oxiranylbutyl group and 8-oxiranyloctyl group; Acrylic such as 3-methacryloxypropyl group Group-containing monovalent organic group; a hydrogen atom is exemplified.
  • This organosilicon compound preferably has an alkenyl group or a silicon-bonded hydrogen atom. Moreover, since it can provide favorable adhesiveness to various types of substrates, the organosilicon compound preferably has at least one epoxy group-containing monovalent organic group in one molecule.
  • organosilicon compounds examples include organosilane compounds and organosiloxane oligomers.
  • organosilane compounds and organosiloxane oligomers.
  • molecular structure of the organosiloxane oligomer include linear, partially branched linear, branched, cyclic, and network, and in particular, linear, branched, and network. preferable.
  • organosilicon compounds examples include silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane;
  • a siloxane compound represented by the formula: (In the formula, k, m, p, and q are positive numbers.) The siloxane compound shown by these is illustrated.
  • the adhesion-imparting agent is preferably a low-viscosity liquid, and the viscosity is not limited, but is preferably in the range of 1 to 500 mPa ⁇ s at 25 ° C.
  • the content of the adhesion-imparting agent is not limited, but is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the total composition.
  • inorganic fillers such as silica, glass, alumina and zinc oxide; fine organic resin powders such as polymethacrylate resin; You may contain dye, a pigment, a flame-retarding agent, a solvent, etc.
  • the above composition cures at room temperature or by heating, but is preferably heated in order to cure quickly.
  • the heating temperature is preferably in the range of 50 to 250 ° C.
  • the cured product thus obtained is in the form of a rubber, in particular, a hard rubber or a flexible resin.
  • organopolysiloxane of the present invention and the production method thereof will be described in detail with reference to examples.
  • Example 1 In a reaction vessel, toluene 107.98 g, weight average molecular weight 1,560, average unit formula: (C 6 H 5 SiO 3/2 ) 0.75 [(CH 3 ) 2 (CH 2 ⁇ CH) SiO 1/2 ] 0.25 204.84 g of a 58.6% by weight toluene solution of an organopolysiloxane resin represented by the formula: H (CH 3 ) 2 SiOSi (CH 3 ) 2 H 3.37 g of disiloxane represented by the above formula (in an amount such that 0.2 mol of silicon-bonded hydrogen atoms in this component is 0.2 mol with respect to 1 mol of vinyl groups in the organopolysiloxane resin) at 112 ° C.
  • an organopolysiloxane resin represented by the formula: H (CH 3 ) 2 SiOSi (CH 3 ) 2 H 3.37 g of disiloxane represented by the above formula (in an amount such that 0.2 mol of silicon
  • This solid has the average unit formula: (C 6 H 5 SiO 3/2 ) 0.77 [(CH 3 ) 2 (CH 2 ⁇ CH) SiO 1/2 ] 0.20 [O 1/2 Si (CH 3 ) 2 —C 2 H 4 — (CH 3 ) 2 SiO (CH 3 ) 2 Si—C 2 H 4 — (CH 3 ) 2 SiO 1/2 ] 0.03
  • An organopolysiloxane resin block composed of siloxane units represented by 2 (—C 2 H 4 ) SiO 1/2 is represented by the formula: -(CH 3 ) 2 SiO (CH 3 ) 2 Si- It was found to be an organopolysiloxane linked by a siloxy group represented by:
  • Example 2 In a reaction vessel, 102.4 g of toluene, a mass average molecular weight of 1,560, and an average unit formula: (C 6 H 5 SiO 3/2 ) 0.75 [(CH 3 ) 2 (CH 2 ⁇ CH) SiO 1/2 ] 0.25 204.97 g of a 58.6% by weight toluene solution of an organopolysiloxane resin represented by the formula: H (CH 3 ) 2 SiO (C 6 H 5 ) 2 SiOSi (CH 3 ) 2 H 16.67 g of trisiloxane represented by the formula (in an amount such that the silicon atom-bonded hydrogen atom in this component is 0.4 mol with respect to 1 mol of the vinyl group in the organopolysiloxane resin) at 113 ° C.
  • an organopolysiloxane resin represented by the formula: H (CH 3 ) 2 SiO (C 6 H 5 ) 2 SiOSi (CH 3 ) 2 H 16.67 g of
  • Example 3 In a reaction vessel, 74.23 g of toluene, the weight average molecular weight is 1,560, and the average unit formula: (C 6 H 5 SiO 3/2 ) 0.75 [(CH 3 ) 2 (CH 2 ⁇ CH) SiO 1/2 ] 0.25 170.65 g of a 58.6% by weight toluene solution of an organopolysiloxane resin represented by the formula: H (CH 3 ) 2 SiO [(C 6 H 5 ) 2 SiO] 2.5 Si (CH 3 ) 2 H Of diorganopolysiloxane represented by the formula (in which the silicon atom-bonded hydrogen atom in this component is 0.2 mol with respect to 1 mol of vinyl group in the organopolysiloxane resin); After azeotropic dehydration at 0 ° C., the mixture was cooled to room temperature.
  • organopolysiloxane resin represented by the formula: H (CH 3 ) 2 SiO [(C 6 H 5
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal in the complex is in mass with respect to the total amount of the organopolysiloxane resin and the diorganopolysiloxane). In an amount of 5 ppm per unit) and reacted at a toluene reflux temperature of 112 ° C. for 1.8 hours. Thereafter, the mixture was cooled to room temperature, mixed with 9.0 g of activated carbon, and filtered through a glass filter. The filtrate was heated to 30-40 mmHg and 95-105 ° C.
  • Example 4 In a reaction vessel, 149.67 g of toluene, the weight average molecular weight is 1,560, and the average unit formula is: (C 6 H 5 SiO 3/2 ) 0.75 [(CH 3 ) 2 (CH 2 ⁇ CH) SiO 1/2 ] 0.25 204.8 g of a 58.6% by weight toluene solution of an organopolysiloxane resin represented by the formula: H (CH 3 ) 2 Si—C 6 H 4 —Si (CH 3 ) 2 H 9.79 g of bis (dimethylsilyl) benzene represented by the formula (into this mol of alkenyl group in the organopolysiloxane resin, an amount of 0.4 mol of silicon-bonded hydrogen atoms in this component was added, After azeotropic dehydration at 113 ° C., the mixture was cooled to room temperature, followed by platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane resin
  • the resin and the above bis (dimethylsilyl) benzene were added in an amount of 5 ppm by mass unit) and reacted at a toluene reflux temperature of 112 ° C. for 2.6 hours, then cooled to room temperature and activated carbon. After mixing 9.6 g, the mixture was filtered through a glass filter, and the filtrate was heated and decompressed at 30 to 40 mmHg and 95 to 105 ° C. to distill off the toluene, and the refractive index was 1.5438 at 50 to 100 ° C. Melting .
  • Example 5 In a reaction vessel, toluene 52.83 g, weight average molecular weight 1,500, average unit formula: (C 6 H 5 SiO 3/2 ) 0.80 [(CH 3 ) 2 (CH 2 ⁇ CH) SiO 1/2 ] 0.20 221.50 g of a 54.2% by weight toluene solution of an organopolysiloxane resin represented by the formula: H (CH 3 ) 2 SiOSi (CH 3 ) 2 H 3.37 g of disiloxane represented by the formula (in an amount of 0.4 mol of silicon-bonded hydrogen atoms in this component with respect to 1 mol of vinyl group in the organopolysiloxane resin) was added at 113 ° C.
  • an organopolysiloxane resin represented by the formula: H (CH 3 ) 2 SiOSi (CH 3 ) 2 H 3.37 g
  • disiloxane represented by the formula in an amount of 0.4 mol of silicon-bonded hydrogen atoms in this component with
  • This solid has the average unit formula: (C 6 H 5 SiO 3/2 ) 0.82 [(CH 3 ) 2 (CH 2 ⁇ CH) SiO 1/2 ] 0.15 [O 1/2 Si (CH 3 ) 2 —C 2 H 4 — (CH 3 ) 2 SiO (CH 3 ) 2 Si—C 2 H 4 — (CH 3 ) 2 SiO 1/2 ] 0.03
  • An organopolysiloxane resin block composed of siloxane units represented by 2 (—C 2 H 4 ) SiO 1/2 is represented by the formula: -(CH 3 ) 2 SiO (CH 3 ) 2 Si- It was found to be an organopolysiloxane linked by a siloxy group represented by:
  • Example 6 In a reaction vessel, 74.23 g of toluene, the weight average molecular weight is 1,560, and the average unit formula: (C 6 H 5 SiO 3/2 ) 0.75 [(CH 3 ) 2 (CH 2 ⁇ CH) SiO 1/2 ] 0.25 170.60 g of a 58.6% by weight toluene solution of an organopolysiloxane resin represented by the formula: H (CH 3 ) 2 SiO [(C 6 H 5 ) 2 SiO] 2.5 Si (CH 3 ) 2 H
  • the diorganopolysiloxane represented by the formula (2) was added in an amount of 26.50 g (amount of silicon atom-bonded hydrogen atoms in this component of 0.4 mol per mol of the vinyl group in the organopolysiloxane resin), 113 After azeotropic dehydration at 0 ° C., the mixture was cooled to room temperature.
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum metal in the complex is in mass with respect to the total amount of the organopolysiloxane resin and the diorganopolysiloxane). In an amount of 5 ppm per unit) was added, and the mixture was reacted at 112 ° C. with toluene reflux for 12 hours. Then, after cooling to room temperature and mixing 12.0g of activated carbon, it filtered with the glass filter. The filtrate was heated to 30-40 mmHg and 95-105 ° C. under reduced pressure to remove toluene, and melted at a refractive index of 1.5490, 50 ° C.-100 ° C.
  • the organopolysiloxane of the present invention is an organopolysiloxane in which organopolysiloxane resin blocks are linked by a siloxy group or a silphenylene group, has a high refractive index, is highly transparent, and is easy to handle. Hydrosilylation reaction can be performed by alkenyl group in the molecule, so it can be used as an adhesive for electric and electronic, potting agent, protective coating agent, underfill agent, especially because the cured product has high light transmittance. It is suitable as an adhesive, potting agent, protective coating agent and underfill agent for semiconductor elements for optical applications.

Abstract

　La présente invention concerne un organopolysiloxane représenté par la formule unitaire moyenne R1SiO3/2)a(R1 2R2SiO1/2)b(O1/2SiR1 2R3-X-R3R1 2SiO1/2)c (où R1 est un groupe alkyle en C1 à C12, un groupe aryle en C6 à C20, ou un groupe aralkyle en C7 à C20 ; R2 est un groupe alcényle en C2 à C12 ; R3 est un groupe alkylène en C2 à C12 ; cependant, au moins 10 % en moles du total de R1 à R3 sont des groupes aryle en C6 à C20 ; X est un groupe siloxy ou un groupe silphénylène ; a représente un nombre de 0,65 à 0,90, b représente un nombre de 0,04 à 0,29, c représente un nombre de 0,01 à 0,07, et a + b + c = 1,00), dans laquelle des blocs de résine d'organopolysiloxane sont liés par les susdits groupes siloxy ou groupes silphénylène. Cet organopolysiloxane a un indice de réfraction élevé, une grande transparence et d'excellentes propriétés de manipulation.
PCT/JP2015/002991 2014-06-20 2015-06-16 Organopolysiloxane et son procédé de production WO2015194159A1 (fr)

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WO2016152073A1 (fr) * 2015-03-20 2016-09-29 Dow Corning Toray Co., Ltd. Organopolysiloxane, son procédé de production, et composition de silicone durcissable
JP2017039885A (ja) * 2015-08-21 2017-02-23 信越化学工業株式会社 付加硬化型オルガノポリシロキサン組成物及び半導体装置
CN110330653A (zh) * 2019-07-05 2019-10-15 北京化工大学 一种耐高温高折射率的主链含亚苯基的钛杂化硅树脂、其制备方法及应用
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JP2017039885A (ja) * 2015-08-21 2017-02-23 信越化学工業株式会社 付加硬化型オルガノポリシロキサン組成物及び半導体装置
CN110330653A (zh) * 2019-07-05 2019-10-15 北京化工大学 一种耐高温高折射率的主链含亚苯基的钛杂化硅树脂、其制备方法及应用
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