TW201605934A - Organopolysiloxane and method of producing thereof - Google Patents

Abstract

An organopolysiloxane represented by the average unit formula: (R1SiO3/2)a(R1 2R2SiO1/2)b(O1/2SiR1 2R3-X-R3R1 2SiO1/2)c (R1 is a C1-12 alkyl group, C6-20 aryl group, or C7-20 aralkyl group; R2 is a C2-12 alkenyl group; R3 is a C2-12 alkylene group; however, at least 10 mol% of the total of R1-R3 is C6-20 aryl groups; X is a siloxy group or silphenylene group; a is a number of 0.65-0.90, b is a number of 0.04-0.29, c is a number of 0.01-0.07, and a + b + c = 1.00) in which organopolysiloxane resin blocks are linked by the abovementioned siloxy groups or silphenylene groups. This organopolysiloxane has a high refractive index, high transparency, and excellent handling properties.

Description

Organic polyoxyalkylene and manufacturing method thereof

The present invention relates to a novel organopolyoxane in which an organopolyoxane resin block is bonded by a decyloxy group or a fluorenylphenyl group, and a process for producing the same.

Patent Documents 1 to 3 disclose organic polyoxoxanes containing the formula: -(R ₂ SiO) _m - (wherein R is unsubstituted or substituted without an unsaturated aliphatic bond) a linear organopolyoxane block represented by a monovalent hydrocarbon group, m is an integer of 1 or more; and a general formula: R' ₃ SiO _1/2 (wherein R' is unsubstituted or substituted M unit represented by a monovalent hydrocarbon group, alkoxy group, or a hydroxyl group, and a Q unit represented by SiO _4/2 and/or a formula: R'SiO _3/2 (wherein R' is the same as above The T unit represented by the above, and at least two of all R' are an alkenyl organopolysiloxane resin block.

Patent Documents 1 to 3 do not care about organic polyoxyalkylene having high refractive index and high transparency. Further, in Patent Documents 1 to 3, there are problems in that vinyl diorganochlorosilane (M unit source), organic trichlorodecane (T unit source), and/or tetrachlorodecane (Q unit source), and the formula are as follows: An organopolyoxane is prepared by co-hydrolyzing and polymerizing α,ω-dichlorodiorganopolysiloxane represented by Cl(R ₂ SiO) _m-1 SiR ₂ Cl (wherein R and m are the same as above). Since the respective hydrolysis properties are different, it is difficult to control the molecular structure of the organopolyoxane, and the linear diorganopolyoxyalkylene block is introduced into the organopolyoxane resin block, and the above organic polyfluorene cannot be formed. An organopolysiloxane having a block of a linear diorganopolyoxyalkylene block as described above, or an α,ω- as a hydrolyzate of α,ω-dichlorodiorganopolyoxyalkylene oxide The hydroxydiorganopolyoxyalkylenes are polycondensed with each other to form an unreacted diorganopolyoxyalkylene which is not bonded to the block of the organopolyoxane resin.

On the other hand, Patent Document 4 describes a solvent-soluble organic polyoxane which is an organic polydecane resin having at least two alkenyl groups in one molecule and hydrogen bonded to a ruthenium atom at both ends of the molecular chain. Atomically blocked linear diorganopolyoxyalkylene is a hydrogenation reaction. However, there is a problem in that the obtained organic polysiloxane has a low refractive index or transparency, or is viscous and has poor workability.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-063538

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-106243

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-041428

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-242627

An object of the present invention is to provide an organopolysiloxane having a high refractive index, high transparency, and good handleability, which is obtained by linking a polyalkylene oxide resin block to a decyloxy group or a fluorenylphenyl group, and a process for producing the same. method.

The organopolyoxane of the present invention is characterized in that it 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 - XR ³ R ¹ ₂ SiO _1/2 ) _c {wherein, R ¹ is the same or different 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 an alkenyl group having 2 to 12 carbon atoms, and R ³ is an alkylene group having the same or different carbon number of 2 to 12, wherein at least 10 mol% of the total of R ¹ to R ³ is a carbon number of 6~ 20 aryl, X is of the formula (I): -SiR ⁴ ₂ O(R ⁴ ₂ SiO) _n SiR ⁴ ₂ -

(wherein R ⁴ is the same or different 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, and n is an integer of 0 to 5) Alkoxy group, or formula (II): -SiR ⁴ ₂ -C ₆ H ₄ -SiR ⁴ ₂ -

(wherein R ⁴ is the same as above) is a phenyl group, a is a number from 0.65 to 0.90, b is a number from 0.04 to 0.29, c is a number from 0.01 to 0.07, and a+b+c= Included by 1.00}, the oxime unit represented by the formula: R ¹ SiO _3/2 and the oxime unit represented by the formula: R ¹ ₂ R ² SiO _1/2 and the formula: R ¹ ₂ R ³ SiO ₁ silicon siloxane units of _{/ 2} indicates the siloxane silicone organopolysiloxane resin block (in the formula, R ^1, R ^2, and R ³ are as defined above) in the formula via R ³ and by the above silicon or silicon-alkoxy Stretch phenyl link.

Preferably, in the average unit formula, R ² is a vinyl group, R ³ is an exoethyl group, and further preferably, in the formula (I), all of R ⁴ are an alkyl group having 1 to 12 carbon atoms. When n is 0.

The method for producing an organopolyoxane of the present invention is characterized in that (A) is an average unit formula: (R ¹ SiO _3/2 ) _d (R ¹ ₂ R ² SiO _1/2)e

(wherein R ¹ is the same or different 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; and R ² is an alkene having 2 to 12 carbon atoms; a base wherein 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 from 0.65 to 0.90, and e is a number from 0.10 to 0.35, and d + e = 1.00 ) The organic polydecane resin and (B) (B-1) represented by the formula: HR ⁴ ₂ SiO(R ⁴ ₂ SiO) _n SiR ⁴ ₂ H

(wherein R ⁴ is the same or different 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, and n is an integer of 0 to 5) Bis organic oxane or (B-2) formula: HR ⁴ ₂ Si-C ₆ H ₄ -SiR ⁴ ₂ H

The formula wherein (in the formula, R ⁴ is the same as above) is carried out by hydrogenation of a dinonylalkylbenzene.

It is preferable that R ² in the component (A) is a vinyl group, and it is preferable that n is 0 when all of R ⁴ in the component (B-1) are an alkyl group having 1 to 12 carbon atoms.

The organopolyoxyalkylene-based organopolyoxane resin block of the present invention is an organopolysiloxane having a high refractive index and high transparency, which is obtained by linking a decyloxy group or a fluorenylphenyl group. Further, the production method of the present invention has the feature of efficiently producing such a novel organopolyoxane.

First, the organopolyoxane of the present invention will be described in detail.

The organic polysiloxane is an average unit: (R ¹ SiO _3/2 ) _a (R ¹ ₂ R ² SiO _1/2 ) _b (O _1/2 SiR ¹ ₂ R ³ -XR ³ R ¹ ₂ SiO _{1 /2} ) _c is indicated.

In the formula, R ¹ is the same or different 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, it may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a cyclohexyl group, an octyl group or a decyl group. An alkyl group such as fluorenyl; an aryl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group; an aralkyl group such as a benzyl group, a phenethyl group or a phenylpropyl group. Further, at least 10 mol% of the total of R ¹ to R ³ is an aryl group having 6 to 20 carbon atoms, preferably a phenyl group. The reason for this is that the refractive index of the present organopolyoxyalkylene can be increased. Further, the formula: R ¹ SiO _3/2 siloxane units represented by Si the sum of carbon atoms R ¹ is preferably an aryl group of 6 to 20, and particularly preferably a phenyl group.

In the formula, R ² is an alkenyl group having 2 to 12 carbon atoms. Specifically, a vinyl group, an allyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, or an octenyl group is preferable, and a vinyl group is preferable.

In the formula, R ³ is the same or different alkylene group having 2 to 12 carbon atoms. Specifically, an ethyl group, a propyl group, an exo-propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and an octyl group are preferably exemplified, and an ethyl group is preferably extended.

Wherein X is of the formula (I): -SiR ⁴ ₂ O(R ⁴ ₂ SiO) _n SiR ⁴ ₂ -

The decyloxy group represented by the formula or the general formula (II): -SiR ⁴ ₂ -C ₆ H ₄ -SiR ⁴ ₂ -

The indicated phenylene.

In the formula, R ⁴ is the same or different 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 the above R ¹ can be exemplified. Further, in the formula (I), 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. The reason for this is that the refractive index or transmittance of the present organopolyoxyalkylene can be further increased.

In the formula, n is an integer in the range of 0 to 5, preferably an integer in the range of 0 to 4, and further preferably an integer in the range of 0 to 3. The reason for this is that if n is an integer within the above range, the refractive index of the organic polyoxyalkylene can be increased without lowering the refractive index. Further, in the case of the formula (I), when all of R ⁴ in the formula are an alkyl group having 1 to 12 carbon atoms, n is 0.

In the formula, 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 a number in the range of 0.01 to 0.07, and a+b+c=1.00. The reason is that when a is at least the lower limit of the above range, the thermal characteristics such as the hot melt property of the organopolyoxane resin block in the organopolysiloxane can be improved, and the upper limit of the above range is Hereinafter, the solubility of the organic polyoxane in an organic solvent can be improved, and the workability can be improved. Further, the reason is that if b is at least the lower limit of the above range, the organopolyoxyalkylene can be hardened by a hydrogenation reaction using an organopolysiloxane having a hydrogen atom bonded to a halogen atom, and On the other hand, when it is at most the upper limit of the above range, thermal properties such as hot meltability of the organopolyoxane resin block in the organic polysiloxane can be improved. Again, the reason is: if c In the above range, the thermal properties such as the hot melt property of the organopolyoxane resin block in the organic polysiloxane can be improved. On the other hand, if it is at most the upper limit of the above range, the organic polymerization can be improved. The operability of the oxirane.

The organic polyoxyalkylene is generally characterized by comprising: a fluorinated alkane unit represented by the formula: R ¹ SiO _3/2 and a fluorinated alkane unit represented by the formula: R ¹ ₂ R ² SiO _1/2 : an organopolyoxyalkylene resin block of a decane unit represented by R ¹ ₂ R ³ SiO _1/2 (wherein R ¹ , R ² , and R ³ are the same as defined above) via R ³ in the formula Further, it is bonded by the above decyloxy group or the above-mentioned phenylene group.

Further, the refractive index (25 ° C) of the visible light (589 nm) of the organic polysiloxane is not limited, and is preferably 1.50 or more. The reason for this is that the present organopolysiloxane can be applied to an optical material having a high refractive index.

Next, the method for producing the organopolyoxane of the present invention will be described in detail.

(A) component is an average unit: (R ¹ SiO _3/2 ) _d (R ¹ ₂ R ² SiO _1/2 ) _e is an organopolysiloxane resin for forming an organic polyoxyalkylene resin. The raw material of the block.

In the formula, R ¹ is the same or different 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 the same groups as described above can be exemplified. Further, 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. The reason for this is that the refractive index of the obtained organic polyoxyalkylene can be increased, transparency can be improved, and workability can be improved. Further, the formula: R ¹ SiO _3/2 siloxane units represented by Si the sum of carbon atoms R ¹ is preferably an aryl group of 6 to 20, and particularly preferably a phenyl group.

In the formula, R ² is an alkenyl group having 2 to 12 carbon atoms, and the same groups as described above are exemplified, and a vinyl group is preferred. Further, the component (A) has at least two alkenyl groups in one molecule, and the content thereof is 0.1 to 40 mol%, preferably 0.5 to 40 mol%, particularly preferably ¹ in total of R ¹ and R ² . ~30% of the range of moles. The reason for this is that when the content of the alkenyl group in the component (A) is within the above range, the hydrogenation reaction with the component (B) can be sufficiently carried out, and the alkenyl group can remain in the obtained organopolyoxane. .

In the formula, 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, and d + e = 1.00. The reason for this is that if d is at least the lower limit of the above range, thermal properties such as hot meltability of the organopolyoxane resin block in the obtained organopolyoxane can be improved, and if d is the above Below the upper limit of the range, the solubility of the obtained organic polyoxane in an organic solvent can be improved, and the workability can be improved. Further, when e is at least the lower limit of the above range, an alkenyl group may remain in the obtained organopolyoxane, and it can be carried out by using an organopolyoxane having a hydrogen atom bonded to a ruthenium atom. In the hydrogenation reaction, on the other hand, when e is at most the upper limit of the above range, thermal properties such as hot meltability of the organopolyoxane resin block in the obtained organic polysiloxane can be improved.

The trait of the component (A) at 25 ° C is not limited, for example, it is solid at 25 ° C or the viscosity is 10 mPa. Liquid above s.

The component (B) is a raw material for linking the above organopolyoxane resin, and is a compound of the formula (B-1): HR ⁴ ₂ SiO(R ⁴ ₂ SiO) _n SiR ⁴ ₂ H Or (B-2) Formula: bis ⁴ alkyl group represented by HR ⁴ ₂ Si-C ₆ H ₄ -SiR ⁴ ₂ H.

In the formula, R ⁴ is the same or different 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 the same group as the above R ¹ can be exemplified. Further, in the component (B-1), 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. The reason for this is that the refractive index or transmittance of the obtained organopolyoxane can be further increased.

In the formula, 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. The reason for this is that if n is an integer within the above range, the transmittance of the obtained organopolyoxane can be increased without lowering the refractive index. Further, in the component (B-1), it is preferred that when R ⁴ in the formula is an alkyl group having 1 to 12 carbon atoms, n is 0.

As the component (B-1), the following two organooxanes can be exemplified: 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

Further, as the component (B-2), the following dinonylalkylbenzene can be exemplified: H(CH ₃ ) ₂ Si-C ₆ H ₄ -Si(CH ₃ ) ₂ H

H(CH ₃ )(C ₆ H ₅ )Si-C ₆ H ₄ -Si(CH ₃ )(C ₆ H ₅ )H

H(C ₆ H ₅ ) ₂ Si-C ₆ H ₄ -Si(C ₆ H ₅ ) ₂ H

In the production method of the present invention, the amount of the component (B) to be added is not limited, and it is preferably the same as the alkenyl group 1 in the component (A), and the hydrogen atom bonded to the ruthenium atom in the component is not reached. The amount of 0.8 moles is more preferably in the range of 0.05 to 0.7 moles, more preferably in the range of 0.1 to 0.6 moles, and particularly preferably in the range of 0.2 to 0.5 moles. The amount. The reason for this is that the gelation of the obtained organic polyoxyalkylene can be suppressed, and the alkenyl group remains.

The catalyst for the hydrogenation reaction for promoting the above reaction is not limited, and examples thereof include a platinum-based catalyst, a ruthenium-based catalyst, and a palladium-based catalyst. In particular, in the case of remarkably promoting the hydrogenation reaction, a platinum-based catalyst is preferred. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenyl alkane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenyl alkoxylate complex is preferred. As the alkenyl decane, 1,3-divinyl-1,1,3,3-tetramethyldioxane and 1,3,5,7-tetramethyl-1,3 can be exemplified. , 5,7-tetravinylcyclotetraoxane, an alkenyl alkane obtained by substituting a part of a methyl group of the alkenyl alkoxysilane with a group such as an ethyl group or a phenyl group, the alkenyl group An alkenyl alkane obtained by substituting a vinyl group of a decane with a group such as an allyl group or a hexenyl group.

The amount of the catalyst for the hydrogenation reaction in the above-mentioned production method is not limited. For example, the catalyst metal is preferably 0.01 to 1,000 ppm by mass based on the total amount of the component (A) and the component (B). The amount in the range is particularly preferably in the range of 0.1 to 500 ppm. The reason for this is that if the amount of the catalyst for the hydrogenation reaction is at least the lower limit of the above range, the rhodium hydrogenation reaction can be sufficiently promoted, and if the amount of the catalyst for the rhodium hydrogenation reaction is less than the upper limit of the above range, Then, it becomes difficult to cause problems such as coloring of the obtained organic polyoxane.

The reaction conditions in the above production method are not limited, and the reaction can be promoted by heating. In the reaction system, when an aromatic solvent such as toluene or xylene or a solvent such as an aliphatic solvent such as heptane or hexane is used, the reaction temperature is preferably the reflux temperature of the solvent, and the organic solvent is not used. In the case of the case, the reaction temperature is preferably 200 ° C or lower. Further, in the reaction, by using an organic solvent, the viscosity of the reaction system can be lowered, and water can be removed from the reaction system by azeotropy or the like.

The organopolysiloxane-based organopolyoxane resin block obtained by this is linked by a decyloxy group or a fluorenylphenyl group, and is soluble in an aromatic solvent such as toluene or xylene; or a fat such as heptane or hexane. A solvent such as a family solvent. The properties at 25 ° C are not particularly limited, and examples thereof include a liquid form, a viscous liquid form, and a solid form.

Since the organopolysiloxane of the present invention contains an alkenyl group in the molecule, it can be hardened by forming an organic polyoxane having a hydrogen atom bonded to a halogen atom and a catalyst for hydrogenation reaction. A curable organopolyoxane composition having a moderate modulus of elasticity.

The organic polyoxosiloxane containing a hydrogen atom bonded to a halogen atom is represented by an average composition formula: R ⁵ _f H _g SiO _(4-fg)/2 . In the formula, R ⁵ is a monovalent hydrocarbon group having no aliphatic unsaturated bond, and the same group as the above R ¹ can be exemplified. Further, in the formula, f and g satisfy 0.7≦f≦2.1, 0.001≦g≦1.0, and 0.8≦f+g≦2.6, preferably 0.8≦f≦2, 0.01≦g≦1, 1≦f+ A positive number of g≦2.4.

The molecular structure of the organopolysiloxane is not particularly limited, and examples thereof include a linear chain, a part of a linear, branched, cyclic, or three-dimensional network having a branch, and preferably a part having a straight chain. Chain, branched, three-dimensional network structure. The organic polyoxyalkylene has a solid or liquid property at 25 ° C, preferably a viscosity of 10,000 mPa at 25 ° C. s or less, more preferably 0.1 to 5,000 mPa. Within the range of s, especially preferably 0.5~1,000mPa. Within the scope of s.

As such an organic polyoxane, a methyl methacrylate polyoxyalkylene at both ends of the molecular chain of the trimethyl decyloxy group is blocked, and a dimethyl hydrazine at both ends of the molecular chain of the trimethyl decyloxy group is blocked. An oxane-methylhydroquinone copolymer, a dimethylhydroquinoloxy group blocking the dimethylpolyoxane at both ends of the molecular chain, and a dimethylhydroquinoloxy group blocking the dimethyl group at both ends of the molecular chain a hydrazine-methylhydroperoxane copolymer, a methyl hydrooxane-diphenyl fluorene copolymer at both ends of a molecular chain of a trimethyl decyloxy group, and a trimethyl decyloxy group a copolymer of methylhydroquinoxane-diphenyloxirane-dimethyloxane at both ends of the molecular chain, a copolymer comprising (CH ₃ ) ₂ HSiO _1/2 unit and SiO _4/2 unit, A copolymer comprising (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units and (C ₆ H ₅ )SiO _3/2 units.

In the above composition, the content of the organopolyoxane is 0.1 to 10 moles, more preferably 0.1 to 10 moles, per mole of the hydrogen atom bonded to the ruthenium atom in the organopolysiloxane of the present invention. It is in the range of 0.1 to 5 moles, and more preferably 0.5 to 5 moles. The reason for this is that if the content of the organopolyoxane is less than the lower limit of the above range, the obtained composition is not sufficiently cured, and on the other hand, if it exceeds the upper limit of the above range, the obtained cured product is mechanically obtained. The feature is reduced.

The catalyst for hydrogenation reaction is used as a catalyst for promoting the crosslinking reaction by the hydrogenation reaction of the above composition, and the catalyst for hydrogenation reaction as described above can be exemplified. In the above composition, the content of the catalyst for the hydrogenation reaction of the rhodium is the amount of the catalyst, specifically, relative to the upper In the composition, the catalytic metal in the catalyst is preferably in an amount of from 0.01 to 1000 ppm by weight, and particularly preferably in an amount of from 0.1 to 500 ppm. The reason for this is that if the content of the catalyst for the hydrogenation reaction does not reach the lower limit of the above range, the composition tends not to be sufficiently cured. On the other hand, if the upper limit of the above range is exceeded, the obtained The problem of hardening coloring and other issues.

Further, in the above composition, as other optional components, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and benzene may be contained. Alkynyl alcohols such as butylbutynol; alkenyl compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexene-1-yne; 1,3,5,7 -tetramethyl-1,3,5,7-tetravinylcyclotetraoxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrazepine Reaction inhibitors such as alkane and benzotriazole. The content of the reaction inhibitor is not limited, and is preferably in the range of 0.0001 to 5 parts by weight based on 100 parts by weight of the above composition.

Further, the composition may further contain an adhesion-imparting agent for improving the adhesion. As the adhesion-imparting agent, an organic ruthenium compound having at least one alkoxy group bonded to a ruthenium atom in one molecule is preferable. The alkoxy group may, for example, be a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a methoxyethoxy group, and more preferably a methoxy group. Further, the group other than the alkoxy group bonded to the ruthenium atom of the organic ruthenium compound may, for example, be substituted or not, such as the above alkyl group, the above alkenyl group, the above aryl group, the above aralkyl group, or the above halogenated alkyl group. Substituting a monovalent hydrocarbon group; a glycidoxyoxy group such as 3-glycidoxypropyl or 4-glycidoxybutyl; 2-(3,4-epoxycyclohexyl)ethyl, 3-( Epoxycyclohexylalkyl group such as 3,4-epoxycyclohexyl)propyl; epoxy group such as 4-oxiranylbutyl group, 8-oxiranyloctyl group, etc. One-valent organic group; one-valent organic group containing propylene fluorenyl group such as 3-methylpropenyloxypropyl group; hydrogen atom. Preferably, the organic ruthenium compound contains an alkenyl group or a hydrogen atom bonded to a ruthenium atom. Further, in order to impart good adhesion to various substrates, it is preferred that the organic ruthenium compound contains at least one monovalent organic group containing an epoxy group in one molecule.

Examples of such an organic ruthenium compound include an organic decane compound and an organic siloxane oxide oligomer. The molecular structure of the organic siloxane oxide oligomer is exemplified by a linear chain, a part of a linear chain having a branch, a branch, a ring, or a network, and more preferably a linear or branched chain. Mesh. As such an organic phosphonium compound, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxy group can be exemplified. a decane compound such as propyltrimethoxydecane; a oxoxane compound containing at least one of an alkenyl group or a hydrogen atom bonded to a ruthenium atom and an alkoxy group bonded to a ruthenium atom in one molecule, and at least one a mixture of a decane compound or a oxoxane compound bonded to an alkoxy group of a halogen atom and at least one of a hydroxyl group and an alkenyl group having a bonded ruthenium atom in one molecule;

(wherein, k, m, and p are positive numbers) represented by a oxoxane compound;

The formula (wherein k, m, p, and q are positive numbers) represents a oxoxane compound.

The adhesion-imparting agent is preferably a low-viscosity liquid, and the viscosity thereof is not limited, and is preferably 1 to 500 mPa at 25 ° C. Within the scope of s. Further, in the above composition, the content of the adhesion-imparting agent is not limited, and is preferably in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the total of the composition.

Further, in the above composition, as long as the object of the present invention is not impaired, The component may further contain: an inorganic filler such as cerium oxide, glass, aluminum oxide or zinc oxide; a fine powder of an organic resin such as a polymethacrylate resin; a heat-resistant agent, a dye, a pigment, a flame retardant imparting agent, a solvent, etc. .

The above composition is cured by room temperature or heating, and heating is preferably carried out in order to rapidly harden it. The heating temperature is preferably in the range of 50 to 250 °C. The cured product obtained thereby is in the form of a rubber, in particular, a hard rubber or a resin having flexibility.

[Examples]

The organic polyoxyalkylene of the present invention and a method for producing the same will be described in detail by way of examples.

[Example 1]

The reaction vessel was charged with 107.98 g of toluene and a mass average molecular weight of 1,560. The average unit formula: (C ₆ H ₅ SiO _3/2 ) _0.75 [(CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 ] _0.25 The organic polyfluorene oxide resin has a 58.6 mass% toluene solution of 204.84 g, and the formula: H(CH ₃ ) ₂ SiOSi(CH ₃ ) ₂ H represents dioxane 3.37 g (relative to the above organopolyoxane) The vinyl group 1 mol in the resin, the hydrogen atom bonded to the ruthenium atom in the present component was 0.2 mol, and was azeotropically dehydrated at 112 ° C, and then cooled to room temperature. Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of dioxane was 5 ppm by mass unit, and the reaction was carried out at a reflux temperature of toluene of 111 ° C for 1.7 hours. Thereafter, toluene was distilled off by heating under reduced pressure of 1 mmHg and 117 ° C to obtain a solid having a refractive index of 1.5395, which was melted at 50 ° C to 100 ° C to be a transparent liquid, and was white at room temperature. It can be seen that the solid system has an 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 ] is represented by _0.03 and contains the formula: C ₆ H ₅ SiO _3/2 a oxoxane unit represented by the formula: (CH ₃ ) ₂ (CH ₂ =CH) SiO _1/2 represented by a oxoxane unit and a formula: (CH ₃ ) ₂ (-C ₂ H ₄ )SiO _1/2 The organopolyoxane resin block of the oxoxane unit represented by the formula is an organopolyoxane in which a decyloxy group represented by the formula: -(CH ₃ ) ₂ SiO(CH ₃ ) ₂ Si- is bonded.

[Embodiment 2]

The reaction unit was charged with 102.4 g of toluene and a mass average molecular weight of 1,560. The 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 mass% toluene solution of the organopolysiloxane resin, and 16.67 g of a trioxane represented by H(CH ₃ ) ₂ SiO(C ₆ H ₅ ) ₂ SiOSi(CH ₃ ) ₂ H ( It is azeotropically dehydrated at 113 ° C and then cooled to room temperature with respect to the vinyl 1 mol in the above organopolysiloxane resin, the hydrogen atom bonded to the ruthenium atom in the present component is 0.4 mol. . Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of trioxane was 5 ppm in mass units, and the reaction was carried out at a reflux temperature of toluene of 111 ° C for 2 hours. Thereafter, the mixture was cooled to room temperature, and 9.0 g of activated carbon was mixed, followed by filtration using a glass filter. Toluene was distilled off by heating and depressurizing the filtrate at 30 to 40 mmHg and 95 to 105 ° C to obtain a solid having a refractive index of 1.5422, melting at 50 to 100 ° C to form a transparent liquid, and white at room temperature. It can be seen that the solid system is of the average unit formula: (C ₆ H ₅ SiO _3/2 ) _0.80 [(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(C ₆ H ₅ ) ₂ SiO(CH ₃ ) ₂ Si-C ₂ H ₄ -(CH ₃ ) ₂ SiO _1/2 ] _0.05 , and contains: a _oxoxane unit represented by C ₆ H ₅ SiO _3/2 and a oxime unit represented by the formula: (CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 and a formula: (CH ₃ ) ₂ (- The organopolyoxane resin block of the oxirane unit represented by C ₂ H ₄ )SiO _1/2 is represented by the formula: -(CH ₃ ) ₂ SiO(C ₆ H ₅ ) ₂ SiO(CH ₃ ) ₂ Si- The organopolyoxane in which the decyloxy groups are bonded.

[Example 3]

Into the reaction vessel, 74.23 g of toluene and an average molecular weight of 1,560 were introduced: (C ₆ H ₅ SiO _3/2 ) _0.75 [(CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 ] _0.25 The organic polyfluorene oxide resin has a 58.6 mass% toluene solution of 170.65 g, and an average formula: H(CH ₃ ) ₂ SiO[(C ₆ H ₅ ) ₂ SiO] _2.5 Si(CH ₃ ) ₂ H 13.34 g of a decane (relative to the vinyl 1 mol in the above organopolysiloxane resin, the hydrogen atom bonded to the ruthenium atom in the composition is 0.2 mol), and azeotropically dehydrated at 114 ° C After that, it was cooled to room temperature. Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of the diorganopolyoxyalkylene oxide was 5 ppm in terms of mass units, and the reaction was carried out at a reflux temperature of toluene of 112 ° C for 1.8 hours. Thereafter, the mixture was cooled to room temperature, and 9.0 g of activated carbon was mixed, followed by filtration using a glass filter. Toluene was distilled off by heating and depressurizing the filtrate at 30 to 40 mmHg and 95 to 105 ° C to obtain a solid having a refractive index of 1.5462, melting at 50 to 100 ° C to form a transparent liquid, and white at room temperature. Understood, the solid system 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[(C ₆ H ₅ ) ₂ SiO] _2.5 (CH ₃ ) ₂ Si-C ₂ H ₄ -(CH ₃ ) ₂ SiO _1/2 ] _0.03 , and includes The oxime unit represented by C ₆ H ₅ SiO _3/2 and the oxime unit represented by the formula: (CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 and the formula: (CH ₃ ) ₂ (-C ₂ H ₄ ) The organopolyoxyalkylene resin block of the oxoxane unit represented by SiO _1/2 is of the formula: -(CH ₃ ) ₂ SiO[(C ₆ H ₅ ) ₂ SiO] _2.5 (CH ₃ ) An organopolyoxane in which a decyloxy group represented by ₂ Si- is bonded.

[Example 4]

Into the reaction vessel, 149.67 g of toluene and a mass average molecular weight of 1,560 were introduced: (C ₆ H ₅ SiO _3/2 ) _0.75 [(CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 ] _0.25 a 58.6 mass% toluene solution of an organic polyoxymethane resin, 204.8 g, of the formula: H(CH ₃ ) ₂ Si-C ₆ H ₄ -Si(CH ₃ ) ₂ H represented by bis(dimethylalkylalkyl)benzene 9.79 g (relative to the alkenyl group 1 mol in the above organopolysiloxane resin, the hydrogen atom bonded to the ruthenium atom in the present component is 0.4 mol), and azeotropically dehydrated at 113 ° C, followed by cooling To room temperature. Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of bis(dimethylalkylalkyl)benzene was 5 ppm by mass unit, and the reaction was carried out at a reflux temperature of toluene of 112 ° C for 2.6 hours. Thereafter, the mixture was cooled to room temperature, and 9.6 g of activated carbon was mixed, followed by filtration using a glass filter. The filtrate was heated and decompressed at 30 to 40 mmHg and 95 to 105 ° C, and toluene was distilled off to obtain a solid having a refractive index of 1.5438, melting at 50 to 100 ° C to form a transparent liquid, and white at room temperature. It can be seen that the solid system has an average unit formula: (C ₆ H ₅ SiO _3/2 ) _0.79 [(CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 ] _0.16 [O _1/2 Si(CH ₃ ) ₂ - C ₂ H ₄ -(CH ₃ ) ₂ Si-C ₆ H ₄ -Si(CH ₃ ) ₂ -C ₂ H ₄ -(CH ₃ ) ₂ SiO _1/2 ] _0.05 , and contains: C ₆ H _{5 a} siloxane unit represented by SiO _3/2 and a oxime unit represented by the formula: (CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 and a formula: (CH ₃ ) ₂ (-C ₂ H ₄ ) The organopolyoxane resin block of the oxirane unit represented by SiO _1/2 is represented by the formula: -(CH ₃ ) ₂ Si-C ₆ H ₄ -Si(CH ₃ ) ₂ - An organic polyoxyalkylene linked by a phenyl group.

[Example 5]

The reaction vessel was charged with 52.83 g of toluene and an average unit mass of 1,500 mass average molecular weight: (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 mass toluene solution of the organopolysiloxane resin, and 3.37 g of a dioxane represented by H(CH ₃ ) ₂ SiOSi(CH ₃ ) ₂ H (relative to the above organopolyoxane) The vinyl group 1 mol in the resin, the hydrogen atom bonded to the ruthenium atom in the present component was 0.4 mol, and was azeotropically dehydrated at 113 ° C, and then cooled to room temperature. Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of dioxane was 5 ppm in mass units, and the reaction was carried out at a reflux temperature of toluene of 113 ° C for 1 hour. Then, toluene was distilled off by heating and decompressing at 30 to 40 mmHg and 100 ° C to obtain a solid having a refractive index of 1.5436, melting at 50 to 100 ° C to form a transparent liquid, and white at room temperature. It can be seen that the solid system has an 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 ] is represented by _0.03 and contains the formula: C ₆ H ₅ SiO _3/2 a oxoxane unit represented by the formula: (CH ₃ ) ₂ (CH ₂ =CH) SiO _1/2 represented by a oxoxane unit and a formula: (CH ₃ ) ₂ (-C ₂ H ₄ )SiO _1/2 The organopolyoxane resin block of the oxoxane unit represented by the formula is an organopolyoxane in which a decyloxy group represented by the formula: -(CH ₃ ) ₂ SiO(CH ₃ ) ₂ Si- is bonded.

[Embodiment 6]

Into the reaction vessel, 74.23 g of toluene and an average molecular weight of 1,560 were introduced: (C ₆ H ₅ SiO _3/2 ) _0.75 [(CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 ] _0.25 The organic polyfluorene oxide resin has a 58.6 mass% toluene solution of 170.60 g, and the formula: H(CH ₃ ) ₂ SiO[(C ₆ H ₅ ) ₂ SiO] _2.5 Si(CH ₃ ) ₂ H 26.50 g of a decane (relative to the vinyl 1 mol in the above organopolysiloxane resin, the hydrogen atom bonded to the ruthenium atom in the present component is 0.4 mol), and azeotropically dehydrated at 113 ° C After that, it was cooled to room temperature. Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of the diorganopolyoxyalkylene oxide was 5 ppm in terms of mass units, and the reaction was refluxed at 112 ° C for 12 hours. Thereafter, the mixture was cooled to room temperature, and 12.0 g of activated carbon was mixed, followed by filtration using a glass filter. Toluene was distilled off by heating and depressurizing the filtrate at 30 to 40 mmHg and 95 to 105 ° C to obtain a solid having a refractive index of 1.5490, melting at 50 to 100 ° C to form a transparent liquid, and white at room temperature. It can be seen that the solid system has an average unit formula: (C ₆ H ₅ SiO _3/2 ) _0.79 [(CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 ] _0.16 [O _1/2 Si(CH ₃ ) ₂ - C ₂ H ₄ -(CH ₃ ) ₂ SiO[(C ₆ H ₅ ) ₂ SiO] _2.5 (CH ₃ ) ₂ Si-C ₂ H ₄ -(CH ₃ ) ₂ SiO _1/2 ] _0.05 , and includes The oxime unit represented by C ₆ H ₅ SiO _3/2 and the oxime unit represented by the formula: (CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 and the formula: (CH ₃ ) ₂ (-C ₂ H ₄ ) The organopolyoxyalkylene resin block of the oxoxane unit represented by SiO _1/2 is of the formula: -(CH ₃ ) ₂ SiO[(C ₆ H ₅ ) ₂ SiO] _2.5 (CH ₃ ) An organopolyoxane in which a decyloxy group represented by ₂ Si- is bonded.

[Industrial availability]

The organopolyoxyalkylene-based organopolyoxane resin block of the present invention is an organopolysiloxane having a high refractive index, high transparency, and good handleability, which is obtained by linking a decyloxy group or a fluorenylphenyl group. It is melted by heating, and can be used for the hydrogenation reaction of an alkenyl group in a molecule, so that it can be used as an adhesive for electric and electronic materials, a potting agent, a protective coating agent, an underfill, and especially a light-transmitting agent. In the case of a higher rate, it is suitable as an adhesive for a semiconductor component for optical use, a potting agent, a protective coating agent, and an underfill.

Claims (8)

An organopolymethoxyalkane having 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 -XR ³ R ¹ ₂ SiO _1/2 ) _c { wherein R ¹ is the same or different 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, and R ² is carbon The alkenyl group having 2 to 12, R ³ being the same or different alkylene group having 2 to 12 carbon atoms, wherein at least 10 mol% of the total of R ¹ to R ³ is an aryl group having 6 to 20 carbon atoms. X is a general formula (I): -SiR ⁴ ₂ O(R ⁴ ₂ SiO) _n SiR ⁴ ₂ - (wherein R ⁴ is the same or different alkyl group having 1 to 12 carbon atoms, and the carbon number is 6 to 20 An aryl group, or an aralkyl group having 7 to 20 carbon atoms, n is an integer represented by 0 to 5, or a formula (II): -SiR ⁴ ₂ -C ₆ H ₄ -SiR ⁴ ₂ - (wherein R ⁴ is the same as above) is a phenyl group, a is a number from 0.65 to 0.90, b is a number from 0.04 to 0.29, c is a number from 0.01 to 0.07, and a+b+c= Included by 1.00}, and include a formula: a _oxoxane unit represented by R ¹ SiO _3/2 and a fluorinated alkane unit represented by the formula: R ¹ ₂ R ² SiO _1/2 and a formula: R ¹ ₂ R ³ SiO An organopolyoxyalkylene resin block of _1/2 represented by a siloxane unit (wherein R ¹ , R ² , and R ³ is the same as above) and is bonded to the above decyloxy group or the above-mentioned phenylene group through R ³ in the formula. The organopolyoxane of claim 1, wherein in the average unit formula, R ² is a vinyl group and R ³ is an exoethyl group. The organopolyoxane of claim 1 or 2, wherein in the case of the formula (I), when all of R ⁴ are an alkyl group having 1 to 12 carbon atoms, n is 0. The organopolyoxane of claim 1 or 2, wherein the visible light (589 nm) has a refractive index (25 ° C) of 1.50 or more. The organopolyoxane of claim 3, wherein the visible light (589 nm) has a refractive index (25 ° C) of 1.50 or more. A method for producing an organopolyoxane according to claim 1, which comprises (A) an average unit formula: (R ¹ SiO _3/2 ) _d (R ¹ ₂ R ² SiO _1/2 ) _e (wherein R ¹ is the same or different 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, and R ² is an alkenyl group having 2 to 12 carbon atoms, wherein 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, e is a number of 0.10 to 0.35, and d + e = 1.00) The organic polydecane resin and (B) (B-1) have the formula: HR ⁴ ₂ SiO(R ⁴ ₂ SiO) _n SiR ⁴ ₂ H (wherein R ⁴ is the same or different carbon number 1 to 12) An alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, n is an integer of 0 to 5, or a compound of the formula (B-2): HR ⁴ _{2 is a} hydrogenation reaction of a dinonylalkylbenzene represented by Si-C ₆ H ₄ -SiR ⁴ ₂ H (wherein R ⁴ is the same as defined above). The method for producing an organopolyoxane according to claim 6, wherein R ² in the component (A) is a vinyl group. The method for producing an organopolyoxane according to claim 6 or 7, wherein, in the case where all of R ⁴ in the component (B-1) are an alkyl group having 1 to 12 carbon atoms, n is 0.