bis(alkynyloxysilyl)alkanes, their manufacturing methods, and cured polysiloxane compositions

Abstract

This invention provides a bis(alkynoxysilyl)alkane, which is a novel compound having alkynoxysilyl groups at both ends of the alkane and having alkoxy or hydroxyl (silanol) groups bonded to silicon atoms. It effectively acts as an inhibitor of hydrosilylation reactions, has a high boiling point, low vapor pressure at room temperature, and excellent affinity for hydrosilylation-cured polysiloxane compositions. This invention is a bis(alkynoxysilyl)alkane, which is derived from the general formula: (where R) 1 is an alkynyl group with 5 to 12 carbon atoms, R 2 is an alkyl group or a hydrogen atom having 1 to 3 carbon atoms, R 3 is an alkyl group having 1 to 3 carbon atoms, a is 1, 2 or 3, b is 0, 1 or 2, and a+b is 2 or 3, wherein at least one b is 1 or 2, and n is an integer from 2 to 20.

Description

Technical Field

[0001] This invention relates to a bis(alkynyloxysilyl)alkane, a method for manufacturing the same, and a curable polysiloxane composition containing the same. Prior Technology

[0002] In curable polysiloxane compositions cured by hydrosilylation of a monovalent hydrocarbon group with an aliphatic unsaturated bond to a hydrogen atom bonded to a silicon atom, it is well known to formulate acetylenols such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-cyclohexane-1-ol in order to control their curability. In order to sufficiently suppress the hydrosilylation reaction during storage of the aforementioned compositions and to rapidly cure the aforementioned compositions by heating, it is known to formulate silane compounds obtained by silylating the aforementioned acetylenols (Patent Documents 1 to 3) or organosiloxanes obtained by silalkoxylating the aforementioned acetylenols (Patent Documents 4 and 5).

[0003] However, this type of formulation, which produces silane compounds by silylating ethynyl alcohol or organosiloxanes by siloxylating ethynyl alcohol, has issues such as a lack of compatibility with curable polysiloxanes, yellowing of the cured product, and uneven curing due to heating conditions, specifically heating temperature, the presence or absence of pressure reduction during heating, and hot air circulation.

[0004] On the other hand, Patent Document 6 discloses bis(alkynoxysilyl)alkanes, and Patent Document 7 discloses curable polysiloxane compositions containing them. However, Patent Documents 6 and 7 neither describe nor suggest bis(alkynoxysilyl)alkanes that further have alkoxy or hydroxyl (silanol) groups bonded with silicon atoms. [Known Technical Documents] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 59-133252 Patent Document 2: Japanese Patent Application Publication No. 61-000261 Patent Document 3: Japanese Patent Application Publication No. 64-011160 Patent Document 4: Japanese Patent Application Publication No. 52-093468 Patent Document 5: Japanese Patent Application Publication No. 64-051466 Patent Document 6: Japanese Patent Application Publication No. 04-036292 Patent Document 7: Japanese Patent Application Publication No. 04-161459 Summary of the Invention

[0006] [The problem that the invention aims to solve]

[0007] The present invention aims to provide a bis(alkynoxysilyl)alkane, which is a novel compound having alkynoxysilyl groups at both ends of the alkane and alkoxy or hydroxyl (silanol) groups bonded to silicon atoms. This compound effectively acts as an inhibitor of hydrosilylation, has a high boiling point, low vapor pressure at room temperature, and excellent affinity for hydrosilylation-cured polysiloxane compositions. Furthermore, another objective of the present invention is to provide a curable polysiloxane composition that exhibits uniform curability even under heating conditions. [Technical means to solve the problem]

[0008] The bis(alkynoxysilyl)alkane of this invention is derived from the general formula: [Chemical Formula 1] (In the formula, R1 is independently an alkynyl group with 5 to 12 carbon atoms, R2 is independently an alkyl group or hydrogen atom with 1 to 3 carbon atoms, R3 is independently an alkyl group with 1 to 3 carbon atoms, a is independently 1, 2 or 3, b is independently 0, 1 or 2, and a+b is 2 or 3, where at least one b is 1 or 2, and n is an integer from 2 to 20) represents.

[0009] In the above formula, R1 is preferably represented by the following formula: [Chemical Formula 2] The ynyl group represented, formula: [Chemical Formula 3] The ynyl group or formula represented is: [Chemical Formula 4] The alkynyl group it represents.

[0010] Furthermore, the method for manufacturing bis(alkynoxysilyl)alkanes of the present invention is characterized by making the general formula: [Chemical Formula 5] (In the formula, R3 is an alkyl group with 1 to 3 carbon atoms, X is a halogen atom, c is 2 or 3, and n is an integer from 2 to 20.) The bis(halosilyl)alkanes represented, and the formula: R 1OH (In the formula, R1 is an alkynyl group with 5 to 12 carbon atoms) The alkynols are subjected to dehydrohalogenation condensation, and then the resulting partial condensation product is reacted with water or an alkyl alcohol having 1 to 3 carbon atoms.

[0011] In the above manufacturing method, the preferred form of the alkynol is: [Chemical Formula 6] The alkynols represented are: [Chemical Formula 7] The alkynols represented, or the formula: [Chemical Formula 8] The alkynols referred to.

[0012] In addition, in the above manufacturing method, it is preferable to carry out the dehydrohalogenation condensation reaction in the presence of a hydrogen halide scavenger, and the hydrogen halide scavenger is preferably triethylamine, pyridine, methylpyridine, or diazabicycloundecene.

[0013] The bis(alkynyloxysilyl)alkanes of this invention are preferably used as inhibitors of silanization reactions.

[0014] The cured polysiloxane composition of the present invention is characterized in that it contains the above-mentioned bis(alkynoxysilyl)alkanes, specifically containing at least... (A) An organopolysiloxane having at least two alkenyl groups in one molecule; (B) An organohydrogen polysiloxane having at least two silicon-bonded hydrogen atoms in one molecule. (C) The above-mentioned bis(alkynoxysilyl)alkanes, and (D) Catalyst for hydrosiliconization reaction Cured polysiloxane composition. [Invention Effects]

[0015] The bis(alkynoxysilyl)alkanes of this invention are novel compounds with alkynoxysilyl groups at both ends of the alkane and alkoxy or hydroxyl (silanol) groups bonded by silicon atoms. They are characterized by their effectiveness as inhibitors of hydrosilylation reactions, high boiling point, low vapor pressure at room temperature, and excellent affinity for hydrosilylation-cured polysiloxane compositions. Furthermore, the curable polysiloxane compositions of this invention exhibit uniform curing properties even under heating conditions. Simple Explanation of the Diagram

[0016] [Figure 1] is the 13C-NMR spectrum of the bis(alkynoxysilyl)alkanes prepared in Example 1. [Figure 2] is the 29Si-NMR spectrum of the bis(alkynoxysilyl)alkanes prepared in Example 1. [Figure 3] is the 13C-NMR spectrum of the bis(alkynoxysilyl)alkanes prepared in Example 2. [Figure 4] is the 29Si-NMR spectrum of the bis(alkynoxysilyl)alkanes prepared in Example 2. [Figure 5] is the 13C-NMR spectrum of the bis(alkynoxysilyl)alkanes prepared in Example 3. [Figure 6] is the 29Si-NMR spectrum of the bis(alkynoxysilyl)alkanes prepared in Example 3. [Figure 7] is the 13C-NMR spectrum of the bis(alkynoxysilyl)alkanes prepared in Example 4. [Figure 8] is the 29Si-NMR spectrum of the bis(alkynoxysilyl)alkanes prepared in Example 4. Implementation

[0017] <Di(alkynoxysilyl)alkanes>

[0018] First, the bis(alkynoxysilyl)alkanes of the present invention will be described in detail. The bis(alkynoxysilyl)alkane of this invention is derived from the general formula: [Chemical Formula 9] express.

[0019] In the formula, R1 is an alkyne group with 5 to 12 carbon atoms, such as a straight-chain or branched alkyne group represented by the formula: C mH 2m-3 (where m is an integer from 5 to 12), or an alkyne group containing a cyclic structure represented by the formula: C mH 2m-5 (where m is the same as above), preferably a branched alkyne group or an alkyne group containing a cyclic structure.

[0020] Specifically, for R1, the formula is: [Chemical Formula 10] When the branched alkynyl group is represented, the bis(alkynoxysilyl)alkane of the present invention is derived from the general formula: [Chemical Formula 11] express.

[0021] Additionally, for R1, the formula is: [Chemical Formula 12] When the branched alkynyl group is represented, the bis(alkynoxysilyl)alkane of the present invention is derived from the general formula: [Chemical Formula 13] express.

[0022] Additionally, for R1, the formula is: [Chemical Formula 14] When the branched alkynyl group is represented, the bis(alkynoxysilyl)alkane of the present invention is derived from the general formula: [Chemical Formula 15] express.

[0023] Furthermore, in the above formula, R2 is independently an alkyl group or a hydrogen atom having 1 to 3 carbon atoms. Examples of alkyl groups for R2 include methyl, ethyl, and propyl, with methyl being preferred.

[0024] Furthermore, R3 in the above formula is independently an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, or propyl, with methyl being preferred.

[0025] Furthermore, in the above formula, 'a' independently represents 1, 2, or 3 of the number of alkoxy groups bonded to silicon atoms at the end of the molecular chain. Additionally, in the above formula, 'b' independently represents 0, 1, or 2 of the number of alkoxy or hydroxy (silanol) groups bonded to silicon atoms at the end of the molecular chain. Furthermore, in the above formula, a+b is 2 or 3, and at least one 'b' is 1 or 2. This is because the bis(alkynoxysilyl)alkanes of the present invention, having at least one or two alkoxy or hydroxy (silanol) groups bonded to silicon atoms at the end of their molecular chains, can improve adhesion when formulated into curable polysiloxane compositions. Furthermore, the bis(alkynoxysilyl)alkanes of the present invention are preferably used as inhibitors of the hydrosiliconization reaction in hydrosiliconization-reactive curable polysiloxane compositions, and therefore preferably have at least four alkynoxy groups per molecule.

[0026] Furthermore, n in the above formula is an integer from 2 to 20, preferably an integer from 6 to 20 or an integer from 6 to 10. The reason is that if n is above the lower limit of the above range, the transparency is improved when it is incorporated into the polysiloxane composition. On the other hand, if it is below the upper limit of the above range, the hydrosiloxane reaction can be sufficiently suppressed even if it is incorporated in small amounts into the hydrosilicone-cured type of cured polysiloxane composition.

[0027] Examples of bis(alkynyloxysilyl)alkanes in this invention include compounds represented by the following formulas. [Chemical Formula 16] [Chemical Formula 17] [Chemical Formula 18] [Chemical Formula 19] [Chemical Formula 20] [Chemical Formula 21] [Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 24] [Chemical Formula 25] [Chemical Formula 26] [Chemical Formula 27] [Chemical Formula 28] [Chemical Formula 29] [Chemical Formula 30] [Chemical Formula 31] [Chemical Formula 32] [Chemical Formula 33] [Chemical Formula 34] [Chemical Formula 35] [Chemical Formula 36] [Chemical Formula 37] [Chemical Formula 38] [Chemical Formula 39] [Chemical Formula 40] [Chemical Formula 41] [Chemical Formula 42] [Chemical Formula 43] [Chemical Formula 44] [Chemical Formula 45] [Chemical Formula 46] [Chemical Formula 47] <Method for manufacturing bis(alkynoxysilyl)alkanes>

[0028] Next, the method for manufacturing the bis(alkynoxysilyl)alkane of the present invention will be described in detail. The manufacturing method of this invention is characterized by comprising: [Chemical Formula 48] The bis(halosilyl)alkanes represented, and the formula: R 1OH The alkynols represented undergo a dehydrohalogenation condensation reaction, and then the condensation product is reacted with water or an alkyl alcohol having 1 to 3 carbon atoms.

[0029] In the above bis(halosilyl)alkanes, R3 in the above formula is independently an alkyl group having 1 to 3 carbon atoms, which is methyl, ethyl, or propyl, preferably methyl.

[0030] In the above bis(halosilyl)alkanes, X in the above formula is an independent halogen atom, such as a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom.

[0031] Furthermore, in the above formula, c can be either 2 or 3, with 3 being preferable.

[0032] Furthermore, n in the above formula is an integer from 2 to 20, preferably an integer from 6 to 20 or an integer from 6 to 10. The reason is that if n is above the lower limit of the above range, the transparency is improved when the obtained bis(alkynoxysilyl)alkanes are formulated into polysiloxane compositions. On the other hand, if n is below the upper limit of the above range, the hydrosilicification reaction can be sufficiently suppressed even if a small amount of the obtained bis(alkynoxysilyl)alkanes are formulated into hydrosilicification-cured polysiloxane compositions.

[0033] Regarding this type of bis(halosilyl)alkanes, for example, the general formula can be cited as follows: HSiX cR 3 (3-c) (In the formula, R3 is an alkyl group with 1 to 3 carbon atoms, X is a halogen atom, and c is 2 or 3) The halosilanes represented With general formula: SiX cR 3 (3-c)(CH 2) n"-CH=CH 2 (In the formula, R3 is an alkyl group with 1 to 3 carbon atoms, X is a halogen atom, c is 2 or 3, and n" is an integer from 0 to 18) The method for the hydrosilylation reaction of the halosilane represented herein, or as disclosed in Japanese Patent Application Publication No. 2006-117532 (corresponding to US Patent No. 7,456,307), generally uses the following formula: CH₂=CH-(CH₂)n'-CH=CH₂ (In the formula, n' is an integer from 1 to 16) The diene compounds represented, and the general formula: HSiX cR 3 (3-c) (In the formula, R3 is an alkyl group with 1 to 3 carbon atoms, X is a halogen atom, and c is 2 or 3) The method for the hydrosilylation reaction of the halosilane represented. Furthermore, R3 and X in the above formula are the same as described above.

[0034] In addition, in the above-mentioned alkynols, R1 is an alkynyl group with 5 to 12 carbon atoms, such as straight-chain or branched alkynols represented by the formula: C mH 2m-3OH (where m is an integer from 5 to 12), or alkynols containing a cyclic structure represented by the formula: C mH 2m-5OH (where m is the same as above), preferably branched alkynols or alkynols containing a cyclic structure.

[0035] Specific examples can be given: [Chemical Formula 49] The branched alkynols represented, or the formula: [Chemical Formula 50] The branched alkynols represented, or the formula: [Chemical Formula 51] The term represents alkynols containing cyclic structures.

[0036] In the manufacturing method of the present invention, the bis(alkynyloxysilyl)alkanes of the present invention can be prepared by performing a dehalogenation hydrogen condensation reaction between bis(halosilyl)alkanes and alkynols. The amount of alkynol added relative to the bis(halosilyl)alkanes is preferably 1.0 to 5.0 mol relative to 1 mol of halogen atoms bonded to silicon atoms in the bis(halosilyl)alkanes, more preferably 1.0 to 2.0 mol.

[0037] The dehydrohalogenation condensation reaction is preferably carried out in the presence of a hydrogen halide scavenger, preferably triethylamine, pyridine, methylpyridine, or diazabicycloundecene. The amount of the hydrogen halide scavenger added is preferably 1.0 to 5.0 mol, more preferably 1.0 to 2.5 mol, relative to 1 mol of halogen atoms bonded to silicon atoms in the bis(halosilyl)alkanes.

[0038] The dehydrohalogenation condensation reaction is preferably carried out by dropping bis(halosilyl)alkanes into a reaction vessel containing alkynols and hydrogen halide promoters. Although the dehydrohalogenation reaction can also be carried out at room temperature, it is preferably carried out at the reflux temperature of the alkynol for at least 3 hours.

[0039] In the manufacturing method of the present invention, by reacting a portion of the condensation reactant obtained by the above-mentioned dehydrohalogenation condensation reaction with water or an alkyl alcohol having 1 to 3 carbon atoms, the residual silicon atoms bonded to halogen atoms in the aforementioned condensation reactant can be replaced with hydroxyl (silanol) or alkoxy groups, thereby preparing the bis(alkynoxysilyl)alkanes of the present invention. Examples of such alkyl alcohols include methanol, ethanol, and propanol, with methanol being preferred.

[0040] The bis(alkynoxysilyl)alkane system obtained by the manufacturing method of the present invention is given by the general formula: [Chemical Formula 53] The bis(alkynoxysilyl)alkanes represented (1) and the general formula: [Chemical Formula 54] The mixture of the bis(alkynyloxysilyl)alkanes (2) is used to obtain the mixture, wherein the ratio of the aforementioned bis(alkynyloxysilyl)alkanes (1) in the mixture is not limited, but is preferably 1% or more, 5% or more, 10% or more, or 20% or more, by means of the area percentage method based on the analysis chart of the gas chromatograph (hereinafter referred to as the analysis chart of GC). <Cureable Polysiloxane Composition>

[0041] Next, the curable polysiloxane composition of the present invention will be described in detail. The bis(alkynyloxysilyl)alkanes of this invention are useful as inhibitors of hydrosiliconization reactions. Therefore, the curable polysiloxane composition of this invention is a hydrosiliconization-cured type, characterized by containing the aforementioned bis(alkynyloxysilyl)alkanes. Specifically, examples may include at least the following: (A) An organopolysiloxane having at least two alkenyl groups in one molecule; (B) An organohydrogen polysiloxane having at least two silicon-bonded hydrogen atoms in one molecule. (C) The above-mentioned bis(alkynoxysilyl)alkanes, and (D) Catalyst for hydrosiliconization reaction Cured polysiloxane composition.

[0042] (A) is an organopolysiloxane having at least two alkenyl groups per molecule. Examples of alkenyl groups in (A) include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl groups having 2 to 12 carbon atoms, with vinyl, allyl, and hexenyl being preferred. Examples of groups in (A) that bond to silicon atoms, other than alkenyl groups, include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptenyl; aryl groups having 6 to 12 carbon atoms such as phenyl, tolyl, and xylyl; and aralkyl groups having 7 to 12 carbon atoms such as benzyl and phenethyl; with methyl being preferred. Furthermore, a small amount of hydroxyl and alkoxy groups having 1 to 3 carbon atoms, such as methoxy and ethoxy, may also be bonded to the silicon atoms in (A) without impairing the purpose of the invention.

[0043] The molecular structure of this component (A) is not limited; examples include linear, partially branched linear, branched, cyclic, or resinous structures. Examples of this component (A) include: dimethyl polysiloxanes with both ends of the molecular chain capped by dimethylvinylsiloxy groups; dimethylsiloxane-methyl vinylsiloxane copolymers with both ends of the molecular chain capped by trimethylsiloxy groups; dimethylsiloxane-methyl vinylsiloxane copolymers with both ends of the molecular chain capped by dimethylvinylsiloxy groups; dimethyl polysiloxanes with both ends of the molecular chain capped by dimethylhydrosiloxy groups; methyl vinyl polysiloxanes with both ends of the molecular chain capped by trimethylsiloxy groups; cyclic methyl vinyl polysiloxanes; cyclic methyl vinylsiloxane-dimethylsiloxane copolymers; copolymers containing siloxane units represented by the formula (CH₂=CH)(CH₃)₂SiO₁ / ₂ and siloxane units represented by the formula SiO₄ / ₂; and copolymers containing the formula (CH₂=CH)(CH₃). The copolymer of siloxane units represented by 2SiO 1 / 2 and siloxane units represented by the formula: CH 3SiO 3 / 2, including the formula: (CH 2=CH)(CH 3) 2SiO 1 / 2 and siloxane units represented by the formula: C 6H 5SiO 3 / 2, including the formula: (CH 3) 3SiO 1 / 2, siloxane units represented by the formula: (CH 2=CH)(CH 3) 2SiO 1 / 2 and siloxane units represented by the formula: SiO 4 / 2, including the formula: (CH 3) 3SiO 1 / 2, siloxane units represented by the formula: (CH 2=CH)(CH 3) 2SiO 1 / 2 and siloxane units represented by the formula: CH 3SiO The copolymer of siloxane units represented by 3 / 2, and copolymers including siloxane units represented by the formula: (CH 3) 3SiO 1 / 2, siloxane units represented by the formula: (CH 2=CH)(CH 3) 2SiO 1 / 2 and siloxane units represented by the formula: C 6H 5SiO 3 / 2.

[0044] (B) is an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and serves as a crosslinking agent for this composition. Examples of groups in (B) that bond to silicon atoms, other than hydrogen atoms, include alkyl groups with 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; aryl groups with 6 to 12 carbon atoms such as phenyl, tolyl, and xylyl; and aralkyl groups with 7 to 12 carbon atoms such as benzyl and phenethyl; methyl is preferred. Furthermore, a small amount of hydroxyl groups and alkoxy groups with 1 to 3 carbon atoms, such as methoxy and ethoxy, may also be bonded to the silicon atoms in (B) without prejudice to the purpose of this invention.

[0045] The molecular structure of this component (B) is not limited; examples include linear, partially branched linear, branched, cyclic, or resinous structures. Examples of this type of component (B) include: dimethyl polysiloxanes with both ends of the molecular chain capped by dimethylhydrosiloxane groups; dimethylsiloxane-methylhydrosiloxane copolymers with both ends of the molecular chain capped by trimethylsiloxane groups; dimethylsiloxane-methylhydrosiloxane copolymers with both ends of the molecular chain capped by dimethylhydrosiloxane groups; dimethyl polysiloxanes with both ends of the molecular chain capped by dimethylhydrosiloxane groups; methylhydropolysiloxanes with both ends of the molecular chain capped by trimethylsiloxane groups; cyclic methylhydropolysiloxanes; cyclic methylhydrosiloxane-dimethylsiloxane copolymers; copolymers containing silica units represented by the formula: H(CH3)2SiO1 / 2 and silica units represented by the formula: SiO4 / 2; and copolymers containing the formula: H(CH3)2SiO1 / 2. The copolymer of siloxane units represented by 1 / 2 and siloxane units represented by the formula: CH3SiO3 / 2, including siloxane units represented by the formula: H(CH3)2SiO1 / 2 and siloxane units represented by the formula: C6H5SiO3 / 2, including siloxane units represented by the formula: (CH3)3SiO1 / 2, siloxane units represented by the formula: H(CH3)2SiO1 / 2 and siloxane units represented by the formula: SiO4 / 2, including siloxane units represented by the formula: (CH3)3SiO1 / 2, siloxane units represented by the formula: H(CH3)2SiO1 / 2 and siloxane units represented by the formula: CH3SiO3 / 2, and including siloxane units represented by the formula: (CH3) A copolymer of siloxane units represented by 3SiO 1 / 2, siloxane units represented by the formula: H(CH 3) 2SiO 1 / 2, and siloxane units represented by the formula: C 6H 5SiO 3 / 2.

[0046] In this composition, the content of component (B) is not particularly limited, but preferably, relative to the total amount of alkenyl groups in component (A) of 1 mol, the amount of silicon atoms bonded to hydrogen atoms in component (B) is in the range of 0.1 to 20 mol, 0.5 to 10 mol, 0.5 to 5 mol, or 0.7 to 3 mol. This is because when the content of component (B) is above the lower limit of the above range, the composition will be sufficiently cured; on the other hand, when the content of component (B) is below the upper limit of the above range, the obtained cured product has good heat resistance.

[0047] (C) The bis(alkynyloxysilyl)alkanes are as described above.

[0048] In this composition, the content of component (C) is not particularly limited. Relative to the total amount of components (A) to (D), this component is present in an amount ranging from 10 to 5,000 ppm, 10 to 1,000 ppm, or 10 to 500 ppm by mass. This is because when the content of component (C) is above the lower limit of the aforementioned range, the curing of this composition can be sufficiently suppressed; on the other hand, when the content of component (C) is below the upper limit of the aforementioned range, the curability of the obtained composition will not be impaired.

[0049] Component (D) is a catalyst used to promote the hydrosilylation reaction of this composition. Examples of components (D) include platinum-based catalysts, palladium-based catalysts, and rhodium-based catalysts, with platinum-based catalysts being preferred. Examples of platinum-based catalysts include chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, alcohol-modified chloroplatinic acid, platinum olefin complexes, platinum carbonyl complexes, platinum alkenylsiloxane complexes, platinum diketone complexes; high-energy line-activated catalysts or photoactivated catalysts such as (methylcyclopentadienyl)trimethylplatinum (IV), bis(2,4-pentanedione)platinum (II), and bis(acetylacetone)platinum (II). In addition, among the platinum-based alkenyl silicate complexes, examples of alkenyl silicate compounds include: 1,3-divinyltetramethyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane, and dimethylvinylsilalkoxy-terminated methyl (3,3,3-trifluoropropyl)siloxane oligomers.

[0050] The content of component (D) refers to the amount of catalyst used to promote the hydrosiliconization reaction of this composition. Specifically, relative to the total amount of components (A) to (D), the catalyst metal in this component is expressed in the following quantities by mass: 0.1 to 1,000 ppm, 0.1 to 500 ppm, 5 to 500 ppm, 0.1 to 300 ppm, or 5 to 300 ppm. This is because if the content of component (D) is above the lower limit of the above range, it promotes the curing of this composition; on the other hand, if it is below the upper limit of the above range, the obtained cured product is less likely to produce problems such as coloring.

[0051] In this composition, as long as it does not impair the purpose of the present invention, it may contain other organic polysiloxanes, inorganic fillers, tackifiers, flame retardants, organic solvents, etc., as any other components other than components (A) and (B). [Example]

[0052] The present invention, including bis(alkynoxysilyl)alkanes, their manufacturing methods, and curable polysiloxane compositions containing them, is described in more detail using examples. Furthermore, the present invention is not limited to the following examples. <Example 1>

[0053] A 1000 mL four-necked flask equipped with a stirrer, reflux cooler, thermometer, and dropping funnel was purged with nitrogen. 2-Methyl-3-butyn-2-ol (148.91 g, 1.770 mol), toluene (222 g), and 4-methylpyridine (243.69 g, 2.617 mol) were then added dropwise through the dropping funnel over 30 minutes. The reaction was carried out at reflux for 9 hours. Subsequently, methanol (7.921 g, 0.247 mol) was added through the dropping funnel, and the reaction was further carried out at reflux. A large amount of water was added to the resulting reaction solution to dissolve the byproduct salts. The organic layer was then separated and washed five times with water. Low-boiling-point components were removed from the obtained organic layer by vacuum distillation, yielding 89.41 g of a pale yellow liquid with a GC purity of 81.2%. This GC purity was calculated based on the peak areas of the principal components in the GC chromatogram. Analysis of the pale yellow liquid using 13C-NMR and 29Si-NMR revealed that it was produced by the formula: [Chemical Formula 55] The peak area ratio of the GC chromatogram for 1-[tris(1,1-dimethyl-2-butynoxy)silyl-2-[bis(1,1-dimethyl-2-butynoxy)methoxysilyl]ethane is 15% and the formula is: [Chemical Formula 56] The mixture represented is a mixture with a peak area ratio of 85% in the GC chromatogram of 1,2-bis[tris(1,1-dimethyl-2-butynoxy)silyl]ethane. The boiling point of this mixture is above 300°C. <Example 2>

[0054] A 500 mL four-necked glass flask equipped with a stirrer, reflux cooler, thermometer, and dropping funnel was purged with nitrogen. 2-Methyl-3-butyn-2-ol (62.96 g, 0.749 mol), toluene (100 g), and 4-methylpyridine (103.34 g, 1.110 mol) were then added dropwise through the dropping funnel over 30 minutes. The reaction was then carried out at reflux for 10 hours. Subsequently, methanol (3.569 g, 0.111 mol) was added through the dropping funnel, and the reaction was further carried out at reflux. A large amount of water was added to the resulting reaction solution to dissolve the byproduct salts. The organic layer was then separated and washed five times with water. Low-boiling-point components were removed from the obtained organic layer by vacuum distillation, yielding 39.06 g of a pale yellow liquid with a GC purity of 61.5%. This GC purity was calculated based on the peak area of ​​the principal component in the GC chromatogram. Analysis of the pale yellow liquid by 13C-NMR and 29Si-NMR revealed that it was produced by the formula: [Chemical Formula 57] The peak area ratio of the GC chromatogram for 1-[tris(1,1-dimethyl-2-butynoxy)silyl-6-[bis(1,1-dimethyl-2-butynoxy)methoxysilyl]hexane is 33% and the formula is: [Chemical Formula 58] The mixture represented is a mixture with a peak area ratio of 67% in the GC chromatogram of 1,6-bis[tris(1,1-dimethyl-2-butynoxy)silyl]hexane. The boiling point of this mixture is above 300°C. <Example 3>

[0055] A 100 mL four-necked glass flask equipped with a stirrer, reflux cooler, thermometer, and dropping funnel was purged with nitrogen. 2-Methyl-3-butyn-2-ol (3.42 g, 0.041 mol), toluene (20 g), and diazabicycloundecene (8.80 g, 0.058 mol) were added and mixed for 10 minutes. Then, 1,6-bis(trichlorosilyl)hexane (2.00 g, 0.0057 mol) was added dropwise through the dropping funnel over 30 minutes, and the mixture was allowed to react at reflux for 3 hours. A large amount of water was added to the resulting reaction solution to dissolve the byproduct salts. The organic layer was then separated and washed five times with water. Low-boiling components were removed by vacuum distillation of the obtained organic layer, yielding 1.63 g of a pale yellow liquid with a GC purity of 85.6%. This GC purity was calculated based on the peak area of ​​the principal component in the GC chromatogram. The pale yellow liquid, as determined by 13C-NMR and 29Si-NMR analyses, is of the following formula: [Chemical Formula 59] The peak area ratio (10%) of the GC chromatogram for 1-[tris(1,1-dimethyl-2-butynoxy)silyl-6-[bis(1,1-dimethyl-2-butynoxy)hydroxysilyl]hexane is shown in the formula: [Chemical Formula 60] The mixture represented is a mixture with a peak area ratio of 90% in the GC chromatogram of 1,6-bis[tris(1,1-dimethyl-2-butynoxy)silyl]hexane. The boiling point of this mixture is above 300°C. <Example 4>

[0056] A 1000 mL four-necked glass flask equipped with a stirrer, reflux cooler, thermometer, and dropping funnel was purged with nitrogen. 2-Methyl-3-butyn-2-ol (118.00 g, 1.403 mol), toluene (201 g), and 4-methylpyridine (196.68 g, 2.112 mol) were added and mixed for 10 minutes. Then, 1,10-bis(trichlorosilyl)decane (83.06 g, 0.203 mol) was added dropwise through the dropping funnel over 30 minutes. The reaction was then carried out at reflux for 14 hours. Subsequently, methanol (6.342 g, 0.198 mol) was added through the dropping funnel, and the reaction was further carried out at reflux. A large amount of water was added to the resulting reaction solution to dissolve the byproduct salts. The organic layer was then separated and washed five times with water. Low-boiling-point components were removed from the obtained organic layer by vacuum distillation, yielding 88.57 g of a pale yellow liquid with a GC purity of 43.8%. This GC purity was calculated based on the peak areas of the principal components in the GC chromatogram. Analysis of the pale yellow liquid using 13C-NMR and 29Si-NMR revealed that it was produced by the formula: [Chemical Formula 61] The peak area ratio of the GC chromatogram for 1-[tris(1,1-dimethyl-2-butynoxy)silyl-10-[bis(1,1-dimethyl-2-butynoxy)methoxysilyl]octane is 38% and the formula is: [Chemical Formula 62] The mixture represented is a mixture with a peak area ratio of 62% in the GC chromatogram of 1,10-bis[tris(1,1-dimethyl-2-butynoxy)silyl]octane. The boiling point of this mixture is above 300°C. <Comparative Example 1>

[0057] A 1000 mL four-necked flask equipped with a stirrer, reflux cooler, thermometer, and dropping funnel was purged with nitrogen. 2-Methyl-3-butyn-2-ol (130.50 g, 1.546 mol), toluene (204 g), and 4-methylpyridine (211.90 g, 2.275 mol) were then added dropwise through the dropping funnel. The reaction mixture was then refluxed for 8 hours. A large amount of water was added to the resulting reaction solution to dissolve the byproduct salts. The organic layer was then separated and washed five times with water. Low-boiling components were removed by vacuum distillation of the organic layer, yielding 92.74 g of a pale yellow liquid with a GC purity of 90.4%. This GC purity was calculated based on the peak area of ​​the principal component in the GC chromatogram. The pale yellow liquid, as determined by 13C-NMR and 29Si-NMR analyses, is of the following formula: [Chemical Formula 63] The term refers to 1,6-bis[bis(1,1-dimethyl-2-propynoxy)methylsilyl]hexane. Its boiling point is above 300°C. <Comparison of evaporation rates under hot air>

[0058] To confirm the volatility of the following samples under hot air conditions, 1 g was measured in each 5 cm diameter aluminum cup and dried in a hot air circulating oven under the conditions described in Table 1. The volatile content (mass %) was then determined. The results are recorded in Table 1. Sample 1: 1-Ethynylcyclohexane-1-ol (boiling point = 174℃) Sample 2: Tris[(1,1-dimethyl-2-propynyl)oxy]methylsilane (boiling point = 245℃) Sample 3: The mixture prepared in Example 2 (boiling point = above 300°C)

[0059] [Table 1] Drying conditions Volatilization (mass %) Sample 1 60℃, 2 hours 100 70℃, 2 hours 100 80℃, 2 hours 100 Sample 2 60℃, 2 hours 87 70℃, 2 hours 100 80℃, 2 hours 100 Sample 3 60℃, 2 hours 0.26 70℃, 2 hours 0.32 80℃, 2 hours 0.35

[0060] Based on the results in Table 1, it can be confirmed that the bis(alkynyloxysilyl)alkanes of the present invention have significantly lower volatility in the hot air circulating oven compared to existing silanization reaction inhibitors such as 1-ethynyl-cyclohexane-1-ol or tris[(1,1-dimethyl-2-propynyl)oxy]methylsilane, and therefore have higher vapor pressure at room temperature. <Examples 5 to 12, Comparative Examples 2 to 5>

[0061] Curable polysiloxane compositions were prepared using the following ingredients according to the compositions recorded in Tables 2 and 3.

[0062] As component (A), the following organic polysiloxanes are used. (a1): In average unit form: [(CH 2=CH)(CH 3) 2SiO 1 / 2] 0.05[(CH 3) 3SiO 1 / 2] 0.39(SiO 4 / 2) 0.56(HO 1 / 2) 0.02 The indicated organic polysiloxane (a2): Formula: (CH 2=CH)(CH 3) 2SiO[(CH 3) 2SiO] 500Si(CH 3) 2(CH=CH 2) The indicated organic polysiloxane (a3): Formula: (CH 2=CH)(CH 3) 2SiO[(CH 3) 2SiO] 800Si(CH 3) 2(CH=CH 2) The indicated organic polysiloxane

[0063] As component (B), the following organic polysiloxanes are used. (b1): In average unit form: [H(CH 3) 2SiO 1 / 2] 0.67(SiO 4 / 2) 0.33 The indicated organic polysiloxane (b2): Formula: H(CH 3) 2SiO[(CH 3) 2SiO] 37[(CH 3)HSiO] 37Si(CH 3) 2H The indicated organic polysiloxane (b3): ​​In average unit form: (C 6H 5SiO 3 / 2) 0.4[H(CH 3) 2SiO 1 / 2) 0.6 The indicated organic polysiloxane

[0064] As component (C) and its comparison, the following compounds are used. (c1): Tris[(1,1-dimethyl-2-propynyl)oxy]methylsilane (c2): The mixture prepared in Example 1 (c3): The mixture prepared in Example 2 (c4): The mixture prepared in Example 3 (c5): The mixture prepared in Example 4 (c6): 1,6-bis[bis(1,1-dimethyl-2-propynoxy)methylsilyl]hexane prepared in Comparative Example 1

[0065] As component (D), the following catalysts are used. (d1): Solution of 1,3-divinyltetramethyldisiloxane complex of Pt (0 valence). (d2): Bis(acetylene)platinum(II)

[0066] Use the following ingredients as other ingredients. (e1): In average unit form: [(CH 3) 3SiO 1 / 2] 0.44(SiO 4 / 2) 0.56(HO 1 / 2) 0.02 The indicated organic polysiloxane is a white solid at room temperature. (f1): The condensation product of a methyl vinyl siloxane oligomer with silyl groups at both ends of its molecular chain and 3-glycidoxypropyltrimethoxysilane. (g1): Toluene <Cure Characteristics>

[0067] For the curable polysiloxane composition, the curing properties were measured using a vulcanizing apparatus (PREMIERMDR, Alpha Technologies) at a specific temperature for 600 seconds, following the method specified in JIS K 6300-2:2001 "Uncured rubber - Physical properties - Part 2: Method for calculating vulcanization properties using a vibration vulcanization tester". The examples in Table 2 were measured at 150°C, while the compositions in Table 3 were measured at 100°C. Furthermore, for the composition in Table 3, the composition was measured after irradiation with 365 nm ultraviolet light at a dose of 10 J / cm². Additionally, for the compositions in Table 2, the obtained liquid composition was thinly coated onto a PET film, dried in a hot air circulating oven set to 70°C for 1 hour, and then the curing properties were measured again at 150°C to evaluate the stability of the curing delay agent. Furthermore, during the measurement, approximately 5 g of the curable thermoplastic polysiloxane composition was measured, clamped in a 50 µm thick PET film, and then placed on the lower mold. The measurement began when the upper mold was closed. A rubber R-type mold was used, with an amplitude angle of 0.53°, a vibration frequency of 100 times / minute, and a maximum torque range of 230 kgf·cm. As for the measurement results, for the compositions in Table 2, the time required for the torque value to exceed 1 dNm was recorded in seconds (TS-1). For the compositions in Table 3, since the minimum torque is not less than 1 dNm, the time required for the torque value to exceed 2 dNm was recorded in seconds (TS-2). <Adhesion>

[0068] On a 25 mm × 75 mm aluminum plate, approximately 500 mg of the curable polysiloxane composition from Table 2 was applied at four locations. Next, a 1 mm thick 10 mm square glass wafer was placed on top of the composition, and the plate was heated at 150°C for 1 hour to cure. After cooling to room temperature, the shear strength (adhesive strength) of the wafer was measured using a shear strength testing device (Bond Tester SS-100KP manufactured by Nishishin Shoji Co., Ltd.). <Haze of solidified products>

[0069] The curable polysiloxane composition in Table 3 was irradiated with ultraviolet light at a dose of 4 J / cm² at a wavelength of 365 nm, and then cured at 100°C for 1 hour to obtain a film with a thickness of 200 µm. The haze value of the obtained cured film was measured using a spectrophotometer CM-5 (made by Konica Minolta). <Preparation of Cured Polysiloxane Compositions (1)>

[0070] Each component was measured according to the mixing amounts listed in Table 2, and stirred using a dental mixer to obtain a liquid-curing polysiloxane composition at room temperature. Furthermore, the initial curing characteristics of each component, the curing characteristics after forming a film and being exposed to 70°C, and the adhesive strength of the cured product are shown in Table 2.

[0071] [Table 2] Example Comparative example 5 6 7 8 2 3 4 Cured polysiloxane composition Composition (parts by mass) (A) (a1) 42.6 42.6 42.6 42.6 42.6 42.6 42.6 (a2) 52 52 52 52 52 52 52 (B) (b1) 2.1 2.1 2.1 2.1 2.1 2.1 2.1 (b2) 3.4 3.4 3.4 3.4 3.4 3.4 3.4 (C) (c1) 0 0 0 0 0 0.05 0.03 (c2) 0.05 0 0 0 0 0 0 (c3) 0 0.05 0 0 0 0 0 (c4) 0 0 0.05 0 0 0 0 (c5) 0 0 0 0.05 0 0 0 (c6) 0 0 0 0 0.05 0 0 (D) (d1) The amount of platinum atoms in the composition is 6 ppm by mass. TS-1 (seconds) Early stage 67 53 56 49 30 115 42 70℃, 1 hour. 30 50 53 45 35 34 Curing After being exposed in a thin film Adhesive strength (MPa) 5.7 6.1 5.1 6.3 4.1 3.9 4.2

[0072] As shown in Table 2, the curable polysiloxane composition of the present invention does not lose its curing delay effect even when exposed to a certain amount of hot air in the form of a thin film. Furthermore, it is evident that the cured product obtained from the curable polysiloxane composition of the present invention exhibits superior adhesion compared to the comparative example. Based on these results, it is clear that the bis(alkynyloxysilyl)alkane of the present invention can be used not only as an inhibitor of the hydrosiliconization reaction but also as a tackifier to improve the adhesion of the curable polysiloxane composition. <Preparation of Cured Polysiloxane Compositions (2)>

[0073] The components were measured according to the mixing amounts listed in Table 3, and a homogeneous liquid-curable polysiloxane composition was obtained by stirring with a Sany motor. The freshly prepared liquid composition was coated onto a film (manufactured by Nipper Corporation, FSC-6) coated with a fluorinated polysiloxane release agent to a thickness of 120 µm or 300 µm. The film was then dried in a hot air circulating oven set to 70°C for 5 minutes to remove toluene, thereby obtaining a film-curable polysiloxane composition with a thickness of 100 µm or 200 µm. Then, the same release film (manufactured by Nipper Corporation, FSC-6) was applied over the obtained film composition and rolled together to create a three-layer laminate consisting of a release film, a film-curable polysiloxane composition, and a release film. Furthermore, all the film compositions listed in Table 3 can be heated at 100°C for further processing, including thickness adjustment, thus maintaining their thermoplasticity. The initial curing characteristics of each component, storage stability at 50°C, and haze values ​​of the cured product composed of each component are shown in Table 3.

[0074] [Table 3] Example Comparative example 9 10 11 12 5 Cured polysiloxane composition Composition (parts by mass) (A) (a1) 10.2 10.2 10.2 10.2 10.2 (a3) 30.1 30.1 30.1 30.1 30.1 (B) (b1) 1.5 1.5 1.5 1.5 1.5 (C) (c1) 0 0 0 0 0.045 (c2) 0.045 0 0 0 0 (c3) 0 0.045 0 0 0 (c4) 0 0 0.045 0 0 (c5) 0 0 0 0.045 0 (D) (d2) The amount of platinum atoms in the composition is 16 ppm by mass. (E) (e1) 55.7 55.7 55.7 55.7 55.7 (F) (f1) 0.3 0.3 0.3 0.3 0.3 (G) (g1) 17 17 17 17 17 TS-2 (seconds) 283 153 70 165 98 Gelation time at 50℃ (days) 25 25 65 28 14 Haze of cured product (T=200 µm, %) 0.83 0.27 0.40 0.20 0.21

[0075] As shown in Table 3, during the preparation of cured polysiloxane compositions, in the process of removing diluent solvents using hot air, some or all of the hydrosiliconization reaction inhibitors in the cured polysiloxane composition containing general hydrosiliconization reaction inhibitors (Comparative Example 5) volatilize, making it difficult to ensure the storage stability of the obtained cured polysiloxane composition. However, the cured polysiloxane compositions containing the bis(alkynyloxysilyl)alkanes of the present invention (Examples 9 to 12) exhibit excellent storage stability. In addition, a comparison between Examples 9 and Examples 10 to 12 shows that, compared to the component with an ethylene backbone (c2), the component with a hexene backbone (c3), or the component with a decene backbone (c4) or (c5) can improve the transparency of the cured polysiloxane composition. [Industrial Applicability]

[0076] The bis(alkynyloxysilyl)alkanes of this invention are novel compounds with alkynyloxysilyl groups at both ends of the alkane and alkoxy or hydroxyl (silanol) groups bonded by silicon atoms. Due to their high boiling point and low vapor pressure at room temperature, they have excellent affinity for curable polysiloxane compositions. Therefore, they are useful as inhibitors of hydrosilicification reactions for use in hydrosilicification-curable polysiloxane compositions.

[0077] none

Claims

1. A bis(alkynyloxysilyl)alkane, represented by the general formula: [Chemical Formula 1] (wherein, R1 is independently an alkynyl group having 5 to 12 carbon atoms, R2 is independently an alkyl or hydrogen atom having 1 to 3 carbon atoms, R3 is independently an alkyl group having 1 to 3 carbon atoms, a is independently 1, 2 or 3, b is independently 0, 1 or 2, and a+b is 2 or 3, wherein at least one b is 1 or 2, and n is an integer from 2 to 20).

2. As claimed in item 1, a bis(alkynoxysilyl)alkane, wherein R1 is an alkynyl group represented by formula: [Chemical Formula 2], formula: [Chemical Formula 3], or formula: [Chemical Formula 4].

3. A method for producing a bis(alkynyloxysilyl)alkane, wherein the bis(alkynyloxysilyl)alkane is the bis(alkynyloxysilyl)alkane as claimed in claim 1, characterized in that a bis(halosilyl)alkane represented by the general formula: [Chemical Formula 5] (where R 3 is independently an alkyl group having 1 to 3 carbon atoms, X is independently a halogen atom, c is independently 2 or 3, and n is an integer from 2 to 20) and an alkynol represented by the formula: R 1OH (where R 1 is an alkynyl group having 5 to 12 carbon atoms) undergo a dehydrohalogenation condensation reaction, and then the obtained partial condensation product is reacted with water or an alkyl alcohol having 1 to 3 carbon atoms.

4. The manufacturing method of claim 3, wherein the alkynol is represented by formula: [Chemical Formula 6], formula: [Chemical Formula 7], or formula: [Chemical Formula 8].

5. The manufacturing method of claim 3, wherein the dehydrohalogenation condensation reaction is carried out in the presence of a hydrogen halide scavenger.

6. The manufacturing method of claim 5, wherein the hydrogen halide scavenger is triethylamine, pyridine, methylpyridine, or diazabicycloundecene.

7. The bis(alkynyloxysilyl)alkanes of claim 1 or 2 are inhibitors of the hydrogenation reaction.

8. A silane-cured, hydrostere-cured, cured polysiloxane composition containing a bis(alkynyloxysilyl)alkane as claimed in claim 1 or 2.

9. A curable polysiloxane composition comprising at least (A) an organopolysiloxane having at least two alkenyl groups in one molecule, (B) an organohydrogen polysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, (C) a bis(alkynyloxysilyl)alkane as claimed in claim 1 or 2, and (D) a catalyst for a silane hydrotreating reaction.

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