JP5030471B2 - Silicon-containing adamantane compounds - Google Patents

Description

  The present invention relates to a novel silicon-containing adamantane compound useful as a sealing material for functional materials and electronic materials, a coating agent, and a raw material for various industrial products.

  In recent years, sealants such as light-emitting diodes (LEDs) have been required to have higher heat resistance while maintaining transparency. Especially, sealants for near-ultraviolet and white LEDs have high output. Therefore, a material that can withstand the high heat and ultraviolet light deterioration of 400 nm or less is desired. Until now, epoxy resin has been used for such sealant materials, but no epoxy resin that can withstand the high heat and ultraviolet light degradation below 400 nm has been developed. Silicone is an alternative to epoxy resin. The use of resins has been studied.

  On the other hand, since adamantane derivatives have excellent heat resistance and transparency, they can be expected to be applied to highly functional materials such as heat resistant polymers and electronic materials such as semiconductor resists. Examples of such a polymer having adamantane in the main chain skeleton include a compound in which adamantanes are linked to each other (for example, Non-Patent Document 1). Although the polymer exhibits a relatively high thermogravimetric decrease temperature, the main chain is rigid, so it is extremely hard to use as a resin, and it is difficult to use the resin from the aspects of mechanical strength and operability. It is expected that.

Macromolecules, 2004, 37, 7069-7071

  As described above, it is considered that a polymer having an adamantane skeleton has a possibility of becoming an excellent LED encapsulant material from the viewpoint of heat resistance and transparency, but at present, such a polymer is practically used. It has not been converted.

  Therefore, the present invention is to provide an adamantane compound that is a polymer having an adamantane skeleton that is expected to be excellent in heat resistance and weather resistance, and that is not too hard and gives a polymer that is excellent in operability. Objective.

  The inventors of the present invention have intensively studied that the above object can be achieved by introducing an adamantane skeleton into a silicon resin. As a result, a novel silicon-containing adamantane compound obtained by hydrosilylating an adamantane derivative having an allyloxy group and a hydrosilane compound can be polymerized by a hydrosilylation reaction with an unsaturated bond-containing compound. The obtained polymer has high heat resistance, and it has been found that there is a possibility that it can be used in applications requiring various heat resistance including LED sealants, and the present invention has been completed.

  That is, the first present invention is a silicon-containing adamantane compound represented by the following formula (1).

[Wherein, R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a chlorine atom, and R ⁴ And R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, a fluorine atom, a chlorine atom, or a group represented by the following formula (2). is there.

^{Wherein, R 1, ^{R 2,} and ^{R 3} have the same meaning as ^R 1, ^{R 2,} and ^{R 3} in each Formula (1). }]
Examples of the silicon-containing adamantane compound of the first invention include a silicon-containing adamantane compound represented by the following formula (3).

[Wherein R ⁶ and R ⁷ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a chlorine atom, and R ⁸ and R ⁹ are each independently Are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, a fluorine atom, a chlorine atom, or a group represented by the following formula (4).

{Wherein, ^{R 6,} and ^{R 7} have the same meanings as ^{R 6,} and ^{R 7} in each Formula (3). }]
The second aspect of the present invention is the following formula (5).

（式中、Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ は、各々独立に水素原子、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、フェニル基、又は塩素原子である。）
で示されるヒドロシラン化合物とを、ヒドロシリル化触媒の存在下にヒドロシリル化反応させることを特徴とする前記式（１）で示されるケイ素含有アダマンタン化合物の製造方法である。

( Wherein R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an allyloxy group, a phenyl group, a fluorine atom, or a chlorine atom. .)
And an allyloxy compound represented by the following formula (6)

(In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a chlorine atom.)
And a hydrosilane compound represented by formula (1) in the presence of a hydrosilylation catalyst. The method for producing a silicon-containing adamantane compound represented by the formula (1) is characterized in that:

  The third aspect of the present invention is an adamantane-containing silicon polymer characterized in that the silicon-containing adamantane compound represented by the formula (3) and the unsaturated bond-containing compound are subjected to a hydrosilylation reaction in the presence of a hydrosilylation catalyst. It is a manufacturing method.

  The silicon-containing adamantane compound of the present invention can provide a polymer by utilizing a functional group bonded to a silicon atom of the compound. For example, the polymer itself may be polymerized by condensation polymerization. The silicon-containing adamantane compound of the present invention having a hydrosilyl group (Si—H group) can also be polymerized by a hydrosilylation reaction with an unsaturated bond-containing compound. The polymer thus obtained has excellent characteristics (for example, high heat resistance) resulting from having an adamantane skeleton, and the adamantane skeleton is not directly connected to the main chain, so that it does not become too hard. Easy to handle. It is also possible to control various physical properties of the polymer obtained by selecting an unsaturated bond-containing compound. Therefore, the silicon-containing adamantane compound of the present invention is useful as a raw material for various industrial polymer materials such as various functional materials, sealing materials for electronic materials, and coating agents. Furthermore, trifunctional or more functional silicon-containing adamantane compounds of the present invention can be used as a crosslinking agent.

  The silicon-containing adamantane compound of the present invention is a novel compound and can be produced using a corresponding adamantane as a raw material.

Hereinafter, the silicon-containing adamantane compound of the present invention and the reactants used in the production method thereof, reaction conditions, reaction procedures, products, and the like will be described in detail.
The silicon-containing adamantane compound of the present invention is represented by the following formula (1).

R ¹ , R ² and R ³ in the above formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a chlorine atom. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, and a hexyl group are particularly preferable from the viewpoint of easy handling of the compound. Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, A dodecyloxy group is mentioned. Among these, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group are preferable because of high reactivity of the compound, and a methoxy group, an ethoxy group, and a propoxy group are particularly preferable.

R ⁴ and R ⁵ in the formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, a fluorine atom, a chlorine atom, or It is a group represented by the formula (2).

^{Wherein, R ^1, R 2, ^{R 3} has the same meaning as ^{R 1,} R 2, ^{R 3} of formula (1). }
Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and among these, a methyl group and an ethyl group are particularly preferable because of good handling of the compound. Moreover, as a C1-C5 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group are mentioned, A methoxy group, an ethoxy group, and a propoxy group are preferable from the ease of handling of a compound.

  In the present invention, preferred compounds among the compounds represented by the formula (1) are specifically exemplified by 1,3-bis {3- (dimethylsilyl) propoxy} adamantane, 1,3-bis {3- (Diethylsilyl) propoxy} adamantane, 1,3-bis {3- (dihexylsilyl) propoxy} adamantane, 1,3-bis {3- (diphenylsilyl) propoxy} adamantane, 1,3-bis {3- (dimethoxy) Silyl) propoxy} adamantane, 1,3-bis {3- (trimethoxysilyl) propoxy} adamantane, 1,3-bis {3- (diethoxysilyl) propoxy} adamantane, 1,3-bis {3- (tri Ethoxysilyl) propoxy} adamantane, 1,3-bis {3- (dichlorosilyl) propoxy} adamantane, 1,3- {3- (trichlorosilyl) propoxy} adamantane, 1,3-bis {3- (dimethylsilyl) propoxy} -5,7-dimethyladamantane, 1,3-bis {3- (diethylsilyl) propoxy} -5 , 7-dimethyladamantane, 1,3-bis {3- (dihexylsilyl) propoxy} -5,7-dimethyladamantane, 1,3-bis {3- (diphenylsilyl) propoxy} -5,7-dimethyladamantane, 1,3-bis {3- (dimethoxysilyl) propoxy} -5,7-dimethyladamantane, 1,3-bis {3- (trimethoxysilyl) propoxy} -5,7-dimethyladamantane, 1,3-bis {3- (diethoxysilyl) propoxy} -5,7-dimethyladamantane, 1,3-bis {3- (triethoxysilyl) Propoxy} -5,7-dimethyladamantane, 1,3-bis {3- (dichlorosilyl) propoxy} -5,7-dimethyladamantane, 1,3-bis {3- (trichlorosilyl) propoxy} -5,7 -Dimethyladamantane, 1,3,5-tris {3- (dimethylsilyl) propoxy} adamantane, 1,3,5-tris {3- (diethylsilyl) propoxy} adamantane, 1,3,5-tris {3- (Dihexylsilyl) propoxy} adamantane, 1,3,5-tris {3- (diphenylsilyl) propoxy} adamantane, 1,3,5-tris {3- (dimethoxysilyl) propoxy} adamantane, 1,3,5- Tris {3- (trimethoxysilyl) propoxy} adamantane, 1,3,5-tris {3- (diethoxysilyl) ) Propoxy} adamantane, 1,3,5-tris {3- (triethoxysilyl) propoxy} adamantane, 1,3,5-tris {3- (dichlorosilyl) propoxy} adamantane, 1,3,5-tris { 3- (trichlorosilyl) propoxy} adamantane, 1,3,5,7-tetrakis {3- (dimethylsilyl) propoxy} adamantane, 1,3,5,7-tetrakis {3- (diethylsilyl) propoxy} adamantane, 1,3,5,7-tetrakis {3- (dihexylsilyl) propoxy} adamantane, 1,3,5,7-tetrakis {3- (diphenylsilyl) propoxy} adamantane, 1,3,5,7-tetrakis { 3- (dimethoxysilyl) propoxy} adamantane, 1,3,5,7-tetrakis {3- (trimeth) Cisilyl) propoxy} adamantane, 1,3,5,7-tetrakis {3- (diethoxysilyl) propoxy} adamantane, 1,3,5,7-tetrakis {3- (triethoxysilyl) propoxy} adamantane, 1, Examples include 3,5,7-tetrakis {3- (dichlorosilyl) propoxy} adamantane and 1,3,5,7-tetrakis {3- (trichlorosilyl) propoxy} adamantane.

  In the present invention, among the compounds represented by the formula (1), a silicon-containing adamantane compound represented by the following formula (3) is preferable from the viewpoint that hydrosilylation is possible.

R ⁶ and R ⁷ in the above formula (3) are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a chlorine atom. Examples of the alkyl group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms include those similar to R ^{1 to} R ³ in the formula (1).

R ⁸ and R ⁹ in Formula (3) are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, a fluorine atom, a chlorine atom, or the following It is group shown by Formula (4).

{Wherein, ^{R 6} and ^{R 7} have the same meanings as ^{R 6} and ^{R 7} in the formula (3)}
In the present invention, among the compounds represented by the formula (3), suitable compounds are specifically exemplified by 1,3-bis {3- (dimethylsilyl) propoxy} adamantane, 1,3-bis {3- (Diethylsilyl) propoxy} adamantane, 1,3-bis {3- (dihexylsilyl) propoxy} adamantane, 1,3-bis {3- (diphenylsilyl) propoxy} adamantane, 1,3-bis {3- (dimethoxy) Silyl) propoxy} adamantane, 1,3-bis {3- (dichlorosilyl) propoxy} adamantane, 1,3-bis {3- (dimethylsilyl) propoxy} -5,7-dimethyladamantane, 1,3-bis { 3- (diethylsilyl) propoxy} -5,7-dimethyladamantane, 1,3-bis {3- (dihexylsilyl) propo Si} -5,7-dimethyladamantane, 1,3-bis {3- (diphenylsilyl) propoxy} -5,7-dimethyladamantane, 1,3-bis {3- (dimethoxysilyl) propoxy} -5,7 -Dimethyladamantane, 1,3-bis {3- (dichlorosilyl) propoxy} -5,7-dimethyladamantane, 1,3,5-tris {3- (dimethylsilyl) propoxy} adamantane, 1,3,5- Tris {3- (diethylsilyl) propoxy} adamantane, 1,3,5-tris {3- (dihexylsilyl) propoxy} adamantane, 1,3,5-tris {3- (diphenylsilyl) propoxy} adamantane, 1, 3,5-tris {3- (dimethoxysilyl) propoxy} adamantane, 1,3,5-tris {3- (dichlorosilyl ) Propoxy} adamantane, 1,3,5,7-tetrakis {3- (dimethylsilyl) propoxy} adamantane, 1,3,5,7-tetrakis {3- (diethylsilyl) propoxy} adamantane, 1,3,5 , 7-tetrakis {3- (dihexylsilyl) propoxy} adamantane, 1,3,5,7-tetrakis {3- (diphenylsilyl) propoxy} adamantane, 1,3,5,7-tetrakis {3- (dimethoxysilyl) ) Propoxy} adamantane, 1,3,5,7-tetrakis {3- (dichlorosilyl) propoxy} adamantane and the like. Among these, 1,3-bis {3- (dimethylsilyl) propoxy} adamantane, 1,3-bis {3- (dihexylsilyl) propoxy} adamantane, 1,3-bis {3- (Diphenylsilyl) propoxy} adamantane, 1,3-bis {3- (dimethylsilyl) propoxy} -5,7-dimethyladamantane, 1,3-bis {3- (dihexylsilyl) propoxy} -5,7-dimethyl Adamantane, 1,3-bis {3- (diphenylsilyl) propoxy} -5,7-dimethyladamantane, 1,3,5-tris {3- (dimethylsilyl) propoxy} adamantane, 1,3,5-tris { 3- (dihexylsilyl) propoxy} adamantane, 1,3,5-tris {3- (diphenylsilyl) propoxy Adamantane is preferable.

  Although the manufacturing method of the silicon containing adamantane compound of this invention is not specifically limited, For example, it can manufacture suitably by the following methods.

  That is, it can be produced by reacting an allyloxy compound represented by the following formula (5) with a hydrosilane compound represented by the following formula (6) in the presence of a hydrosilylation catalyst.

( Wherein R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an allyloxy group, a phenyl group, a fluorine atom, or a chlorine atom. .)

(In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a chlorine atom.)
Specific examples of the allyloxy compound represented by the formula (5) include 1,3-bis (allyloxy) adamantane, 1,3-bis (allyloxy) -5-methyladamantane, and 1,3-bis (allyloxy). -5,7-dimethyladamantane, 1,3-bis (allyloxy) -5-ethyladamantane, 1,3-bis (allyloxy) -5,7-diethyladamantane, 1,3-bis (allyloxy) -5-fluoro Adamantane, 1,3-bis (allyloxy) -5,7-difluoroadamantane, 1,3-bis (allyloxy) -5-chloroadamantane, 1,3-bis (allyloxy) -5,7-dichloroadamantane, 1, 3,5-tris (allyloxy) adamantane, 1,3,5-tris (allyloxy) -7-methyladaman 1,3,5-tris (allyloxy) -7-ethyladamantane, 1,3,5-tris (allyloxy) -7-fluoroadamantane, 1,3,5-tris (allyloxy) -7-chloroadamantane, Examples include 1,3,5,7-tetrakis (allyloxy) adamantane. Among these, in particular, due to the high heat resistance of the silicon-containing adamantane compound, 1,3-bis (allyloxy) adamantane, 1,3-bis (allyloxy) -5-methyladamantane, 1,3-bis (allyloxy) -5, 7-dimethyladamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (allyloxy) -7-methyladamantane, 1,3,5,7-tetrakis (allyloxy) adamantane are preferred, 1,3-bis (allyloxy) adamantane, 1,3-bis (allyloxy) -5,7-dimethyladamantane, and 1,3,5-tris (allyloxy) adamantane are preferred.

  Specific examples of the hydrosilane compound represented by the formula (6) include dimethylsilane, trimethylsilane, diethylsilane, triethylsilane, dihexylsilane, trihexylsilane, diphenylsilane, triphenylsilane, dichlorosilane, and trichlorosilane. Can be mentioned. Of these, dihexylsilane and diphenylsilane are particularly preferred because of the high heat resistance of the silicon-containing adamantane compound. When the allyloxy compound is a bisallyloxy compound, the amount of the hydrosilane compound used is from 1.5 to 2.5 mol, particularly from 1.7 to 2.5 mol, based on 1 mol of the bisallyloxy compound. It is preferable to use 2.2 mol, and in the case of the trisallyloxy compound, it is preferable to use 2.5 to 3.5 mol, particularly 2.7 to 3.2 mol, with respect to 1 mol of the trisallyloxy compound. In the case of a tetrakisallyloxy compound, it is preferable to use 3.5 to 4.5 mol, particularly 3.7 to 4.2 mol, per 1 mol of the tetrakisallyloxy compound.

  Moreover, as a hydrosilylation catalyst, the well-known compound used as a hydrosilylation catalyst can be used without a restriction | limiting, However, Rhodium type catalyst, a platinum type catalyst, a palladium type catalyst etc. are mentioned from the efficiency of hydrosilylation. Of these, chlorotris (triphenylphosphine) rhodium (I), dichloropalladium (II), hexachloroplatinic (IV) acid hexahydrate, and the like can be raised because of particularly easy availability. The amount of the hydrosilylation catalyst used is 0.00025 to 0.05 mol, particularly 0.0005 mol to 0.025 mol, based on 1 mol of the allyloxy compound used, from the viewpoint of the usefulness of the resulting silicon-containing adamantane compound. It is preferable to do this.

  The hydrosilylation of the allyloxy compound is preferably carried out in the presence of an organic solvent because of its good operability. The organic solvent used at this time is preferably an organic solvent that does not inhibit the hydrosilylation reaction. Specific examples include aromatic hydrocarbons such as benzene, toluene, xylene; diethyl ether, diisopropyl ether, di n-butyl ether, Examples include ethers such as tetrahydrofuran, cyclopentylmethyl ether, and dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide. Of these, aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, tetrahydrofuran, cyclopentyl methyl ether, and dioxane are preferable, particularly toluene. Tetrahydrofuran is preferred. Although the usage-amount of an organic solvent is not restrict | limited in particular, It is preferable that it is 1-100 mass times with respect to the allyloxy compound to be used from the ease of operativity, and is 2-50 mass times especially.

  The reaction at this time is preferably carried out by mixing each reaction reagent in a solvent. The reaction temperature is not particularly limited, but a sufficient conversion can be usually obtained at 0 to 120 ° C. Although the reaction time is not particularly limited, a sufficient conversion can be usually obtained in 1 to 60 hours.

  The method of purifying the crude silicon-containing adamantane compound thus obtained is not particularly limited, and can be purified by techniques such as recrystallization, distillation, reprecipitation, column chromatography and the like.

  The allyloxy compound represented by the formula (5) can be hydrosilylated even when a hydrosilane compound other than the hydrosilane compound represented by the formula (6) is used.

  Since the silicon-containing adamantane compound represented by the formula (1) of the present invention has a reactive silyl group to which an alkoxy group, a chlorine atom, a hydrogen atom, or the like is bonded, self-condensation reaction or condensation with other compounds It is a compound that can form a wide variety of polymers by reaction, addition reaction, etc., and is very useful. For example, in the formula (1), the compound having an alkoxysilyl group is a condensation method generally applied to an alkoxysilane compound, and is hydrolyzed in the presence of an acid catalyst or a base catalyst and water, followed by dehydration. It is possible to perform a self-condensation reaction by condensation. Moreover, the same condensation reaction can be performed with an alkoxysilane compound such as tetraethoxysilane, and a multi-crosslinked polymer can be constructed. In addition, since a similar condensation reaction can be performed with metal alkoxide compounds such as titanium tetraisopropoxide, it is also possible to construct adamantane-containing polymers containing different metal atoms.

  Further, the silicon-containing adamantane compound represented by the formula (3) gives an adamantane-containing silicon polymer by a hydrosilylation reaction in the presence of an unsaturated bond-containing compound and a hydrosilylation catalyst. As the unsaturated bond-containing compound used at this time, a known compound containing an unsaturated bond can be used without limitation, but the 1,4-represented by the following formula (7) from the good performance of the polymer obtained. A diethynylbenzene compound, a 1,3-diethynylbenzene compound represented by the following formula (8), a 1,4-divinylbenzene compound represented by the following formula (9), and a 1,3-diethylbenzene compound represented by the following formula (10) A divinylbenzene compound, a 2,5-norbornadiene compound represented by the following formula (11), and an allyloxy compound represented by the following formula (5) are preferably used.

(In formula, R < ¹⁰ > , R < ¹¹ > , R < ^12> , R < ^13> is respectively independently a hydrogen atom, a C1-C5 alkyl group, a C1-C5 alkoxy group, a fluorine atom, or a chlorine atom. )

{ Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ have the same meanings as R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in formula (7). }

{Wherein, ^{R 10,} R ^{11, R 12} and R ¹³ have the same meanings as R ^{10, R 11, R 12} and R ¹³ in the formula (7). }

{ Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ have the same meanings as R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in formula (7). }

{In formula, R < ^18> , R < ^19> , R < ^20> and R < ²¹ > are synonymous with R < ¹⁰ > , R < ¹¹ > , R < ¹² > , R < ¹³ > in said Formula (7). }

(Wherein, ^R 4, ^{R 5} are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an allyloxy group, a phenyl group, a fluorine atom or a chlorine atom. )
Examples of suitable compounds among the 1,4-diethynylbenzene compounds represented by the formula (7) include 1,4-diethynylbenzene, 2-methyl-1,4-diethynylbenzene, 2,6. -Dimethyl-1,4-diethynylbenzene, 2,3,5,6-tetramethyl-1,4-diethynylbenzene, 2-fluoro-1,4-diethynylbenzene, 2,6-difluoro-1, 4-diethynylbenzene, 2,3,5,6-tetrafluoro-1,4-diethynylbenzene and the like can be mentioned. Of these, 1,4-diethynylbenzene is particularly preferred because of its availability.

  Examples of suitable compounds among the 1,3-diethynylbenzene compounds represented by the formula (8) include 1,3-diethynylbenzene, 2-methyl-1,3-diethynylbenzene, 4-methyl. -1,3-diethynylbenzene, 5-methyl-1,3-diethynylbenzene, 2,5-dimethyl-1,3-diethynylbenzene, 4,5-dimethyl-1,3-diethynylbenzene, 2 , 4,5,6-tetramethyl-1,3-diethynylbenzene, 2-fluoro-1,3-diethynylbenzene, 4-fluoro-1,3-diethynylbenzene, 5-fluoro-1,3- Diethynylbenzene, 2,5-difluoro-1,3-diethynylbenzene, 4,5-difluoro-1,3-diethynylbenzene, 2,4,5,6-tetrafluoro-1,3-diethynylbenzene Etc. It can gel. Of these, 1,3-diethynylbenzene is particularly preferred from the standpoint of availability.

  Of the 1,4-divinylbenzene compounds represented by the formula (9), preferable examples are 1,4-divinylbenzene, 2-methyl-1,4-divinylbenzene, 2,6-dimethyl- 1,4-divinylbenzene, 2,3,5,6-tetramethyl-1,4-divinylbenzene, 2-fluoro-1,4-divinylbenzene, 2,6-difluoro-1,4-divinylbenzene, 2 3,5,6-tetrafluoro-1,4-divinylbenzene and the like. Of these, 1,4-divinylbenzene is particularly preferred from the standpoint of availability.

  Of the 1,3-divinylbenzene compounds represented by the formula (10), preferred examples include 1,3-divinylbenzene, 2-methyl-1,3-divinylbenzene, 4-methyl-1, 3-divinylbenzene, 5-methyl-1,3-divinylbenzene, 2,5-dimethyl-1,3-divinylbenzene, 4,5-dimethyl-1,3-divinylbenzene, 2,4,5,6- Tetramethyl-1,3-divinylbenzene, 2-fluoro-1,3-divinylbenzene, 4-fluoro-1,3-divinylbenzene, 5-fluoro-1,3-divinylbenzene, 2,5-difluoro-1 , 3-divinylbenzene, 4,5-difluoro-1,3-divinylbenzene, 2,4,5,6-tetrafluoro-1,3-divinylbenzene and the like. Of these, 1,3-divinylbenzene is particularly preferred because of its availability.

  Of the 2,5-norbornadiene compounds represented by the formula (11), suitable examples are 2,5-norbornadiene, 1-methyl-2,5-norbornadiene, 7-methyl-2,5-norbornadiene. 7,7-dimethyl-2,5-norbornadiene and the like. Of these, 2,5-norbornadiene is particularly preferred because of its availability.

  Of the allyloxy compounds represented by the formula (5), preferred examples include 1,3-bis (allyloxy) adamantane, 1,3-bis (allyloxy) -5-methyladamantane, and 1,3-bis. (Allyloxy) -5,7-dimethyladamantane, 1,3-bis (allyloxy) -5-ethyladamantane, 1,3-bis (allyloxy) -5,7-diethyladamantane, 1,3-bis (allyloxy)- 5-fluoroadamantane, 1,3-bis (allyloxy) -5,7-difluoroadamantane, 1,3-bis (allyloxy) -5-chloroadamantane, 1,3-bis (allyloxy) -5,7-dichloroadamantane 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (allyloxy) -7-methyl Adamantane, 1,3,5-tris (allyloxy) -7-ethyladamantane, 1,3,5-tris (allyloxy) -7-fluoroadamantane, 1,3,5-tris (allyloxy) -7-chloroadamantane, Examples include 1,3,5,7-tetrakis (allyloxy) adamantane. Of these, in particular, 1,3-bis (allyloxy) adamantane, 1,3-bis (allyloxy) -5-methyladamantane, 1,3-bis (allyloxy) -5,7-dimethyladamantane due to availability 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (allyloxy) -7-methyladamantane, 1,3,5,7-tetrakis (allyloxy) adamantane are preferred, Bis (allyloxy) adamantane, 1,3-bis (allyloxy) -5,7-dimethyladamantane, and 1,3,5-tris (allyloxy) adamantane are preferred.

  When these unsaturated bond-containing compounds are reacted with the silicon-containing adamantane compound represented by the above formula (3) which is a bishydrosilyl compound having two hydrosilyl groups, from the viewpoint of the usefulness of the resulting polymer, the bishydrosilyl compound 1 It is preferable to use 0.5 to 1.5 mol, particularly 0.75 to 1.25 mol, relative to mol. Moreover, when making it react with the silicon-containing adamantane compound shown by the said Formula (3) which is a tris hydrosilyl body which has three hydrosilyl groups, from a viewpoint of the usefulness of the polymer obtained, it is 0. It is preferable to use 3 to 1.0 mol, particularly 0.4 to 0.8 mol. Moreover, when making it react with the silicon-containing adamantane compound shown by the said Formula (3) which is a tetrakis hydrosilyl body which has four hydrosilyl groups, from a viewpoint of the usefulness of the polymer obtained, it is 0. It is preferable to use from 0.5 to 0.8 mol, particularly from 0.1 to 0.7 mol.

  Moreover, as a hydrosilylation catalyst, the well-known compound used as a hydrosilylation catalyst can be used without a restriction | limiting, However, Rhodium type catalyst, a platinum type catalyst, a palladium type catalyst etc. are mentioned from the efficiency of hydrosilylation. Of these, chlorotris (triphenylphosphine) rhodium (I), dichloropalladium (II), hexachloroplatinic (IV) acid hexahydrate, and the like can be raised because of particularly easy availability. From the viewpoint of the usefulness of the obtained adamantane-containing silicon polymer, the amount of the hydrosilylation catalyst used is 0.00025 to 0.05 mol, particularly 0.0005 mol to 0.025, relative to 1 mol of the silicon-containing adamantane compound used. It is preferable to use mol.

  Hydrosilylation of the silicon-containing adamantane compound and the unsaturated bond-containing compound may be performed in the presence of a hydrosilylation catalyst in the absence of a solvent or in an organic solvent. As the organic solvent in the case of using an organic solvent, those which do not inhibit the hydrosilylation reaction are preferable. Specific examples include aromatic hydrocarbons such as benzene, toluene and xylene; diethyl ether, diisopropyl ether, di-n -Ethers such as butyl ether, tetrahydrofuran, cyclopentyl methyl ether and dioxane; and amides such as N, N-dimethylformamide and N, N-dimethylacetamide. Of these, aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, tetrahydrofuran, cyclopentyl methyl ether, and dioxane are preferable, particularly toluene. Tetrahydrofuran is preferred. Although the usage-amount of an organic solvent is not restrict | limited in particular, It is preferable that it is 1-100 mass times with respect to the allyloxy compound to be used from the ease of operativity, and it is preferable that it is 2-50 mass times.

  At this time, the reaction is preferably carried out by mixing each reaction reagent in a solvent. The reaction temperature is not particularly limited, but a sufficient conversion can usually be obtained at 0 to 200 ° C. Although the reaction time is not particularly limited, a sufficient conversion can be usually obtained in 1 to 60 hours. In addition, the reaction temperature can be adjusted while arbitrarily adjusting the reaction rate by, for example, increasing the temperature stepwise according to the characteristics of the silicon-containing adamantane compound and the unsaturated bond-containing compound to be used.

  In preparing the adamantane-containing silicon polymer in the present invention, if necessary, a filler, a coupling agent, a flame retardant, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, an anti-coloring agent, a charge Various additives such as inhibitors, dyes, pigments, fragrances, and stabilizers can be mixed and used.

  Since the adamantane-containing silicon polymer obtained by such a method contains a silicon atom and an adamantane skeleton, it has excellent heat resistance and has a relatively flexible propylene unit, so that the resin obtained also has appropriate flexibility. is doing. For this reason, it has the advantage that the operativity at the time of using resin is good.

  The silicon-containing adamantane compound of the present invention can be suitably used for various plastic substrate raw materials, coating agent raw materials, adhesive raw materials, sealant raw materials and the like, taking advantage of the above characteristics.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

Production Example 1
Under a nitrogen stream, 100 g (0.594 mol) of 1,3-adamantanediol, 500 ml of N, N-dimethylformamide, and 1,3-adamantanediol 3 starting from allyl bromide in a 1000 ml four-necked flask 215.7 g (1.783 mol), which is a molar ratio, was added and stirred at room temperature. Then, 59.5 g (1.485 mol) of 60% sodium hydride (oily), which is 2.5 mol times the raw material 1,3-adamantanediol, was washed with n-hexane so that the reaction would not run away. Added carefully. After stirring for 4 hours, the reaction solution was analyzed by gas chromatography (hereinafter referred to as GC). As a result, the raw material 1,3-adamantanediol was not detected with GC purity, and 1-allyloxy-3-hydroxyadamantane was detected. Was 2%, impurities of unknown structure were 1%, and 1,3-bis (allyloxy) adamantane was 97%. The reaction solution was cooled to 10 ° C. or lower, and 300 ml of tap water was carefully added dropwise so that the temperature of the reaction solution did not exceed 20 ° C. Thereafter, 700 ml of methylene chloride was added to carry out a liquid separation operation, and then the methylene chloride layer was washed four times with 300 ml of ion-exchanged water. The methylene chloride layer was concentrated under reduced pressure to obtain 178 g of a yellow oil. To the resulting yellow oil, 0.32 g of Sumitomo Chemical Co., Ltd. trade name “Sumilyzer GM”, 0.32 g of “Sumilyzer TP-D” and 0.32 g of “Sumilyzer WX-R” were added as polymerization inhibitors. It was. Distillation under reduced pressure (120 ° C./1 mmHg) was performed to obtain 138 g of a transparent liquid (94% in terms of 1,3-adamantanediol). As a result of analyzing this liquid by GC, the content of 1,3-bis (allyloxy) adamantane was GC purity of 98%.

Example 1
In a 100 ml two-necked flask, 0.82 g (3.31 mmol) of 1,3-bis (allyloxy) adamantane obtained in Production Example 1 and 2.1 mol of 1,3-bis (allyloxy) adamantane were added with dihexylsilane. 1.38 g (6.91 mmol) which is double, 0.0046 g which is 0.0015 mol times the raw material 1,3-bis (allyloxy) adamantane of chlorotris (triphenylphosphine) rhodium (I) as a hydrosilylation catalyst (0.0049 mmol) and 10 ml of toluene were added and stirred at room temperature for 3 hours. The hydrosilylation catalyst was removed by silica gel column chromatography, and the solution was concentrated under reduced pressure to obtain 1.77 g of a colorless liquid. As a result of ¹ H-NMR spectrum, ¹³ C-NMR spectrum and elemental analysis of the obtained colorless liquid, the objective 1,3-bis {3- (dihexylsilyl) propoxy} adamantane was confirmed. The measurement results are shown below. The ¹ H-NMR spectrum was assigned based on the structural formula of the following formula (12), and the ¹³ C-NMR spectrum was assigned based on the structural formula of the following formula (13).

¹ H-NMR spectrum (in CDCl ₃ ): δ 3.66 (m, 2H, H _a ), δ 3.34 (t, 4H, H _h ), δ 2.28 (s, 2H, H _o ), 1.47 −1.74 (m, 16H, H _i , H _k , H _l , H _m , H _n ), 1.23-1.29 (m, 32H, H _c , H _d , H _e , H _f ), δ 0.86 (t, 12H, H _g ) 0.51-0.59 (m, 12H, H _b , H _j )
¹³ C-NMR spectrum (in CDCl ₃ ): δ 74.09 (C ₁₀ ), δ 63.06 (C ₇ ), δ 30.80, 35.49, 40.73, 45.52 (C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ ), δ 11.24, 14.12, 22.59, 24.59, 31.56, 33.03 (C ₁ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ ), δ 25 .84 (C ₈ ), δ 7.44 (C ₉ )
Elemental analysis value: As C ₄₀ H ₈₀ O ₂ Si ₂ Calculation value: C; 74.00, H; 12.42
Found: C; 73.70, H; 12.43
Example 2
In a 100 ml two-necked flask, 0.82 g (3.31 mmol) of 1,3-bis (allyloxy) adamantane obtained in Production Example 1, and 2.0 mol of 1,3-bis (allyloxy) adamantane with diphenylsilane. The amount is 1.22 g (6.63 mmol), 0.0049 g which is 0.0016 moles of 1,3-bis (allyloxy) adamantane, which is chlorotris (triphenylphosphine) rhodium (I) as a hydrosilylation catalyst. (0.0052 mmol) and 5 ml of toluene were added and stirred at room temperature for 2 hours. The hydrosilylation catalyst was removed by silica gel column chromatography, and the solution was concentrated under reduced pressure to obtain 1.77 g of a colorless liquid. As a result of ¹ H-NMR spectrum, ¹³ C-NMR spectrum and elemental analysis of the obtained colorless liquid, the objective 1,3-bis {3- (diphenylsilyl) propoxy} adamantane was confirmed. The measurement results are shown below. The ¹ H-NMR spectrum was assigned based on the structural formula of the following formula (14), and the ¹³ C-NMR spectrum was assigned based on the structural formula of the following formula (15).

¹ H-NMR spectrum (in CDCl ₃ ): δ 7.35, 7.30-7.38 (m, 20H, H _b , H _c , H _d ), δ 4.84 (t, 2H, H _a ), δ 3 .35 (s, 4H, H _e ), δ 2.24 (s, 2H, H _l ), 1.44-1.71 (m, 16H, H _f , H _h , H _i , H _j , H _k ) 1.09-1.15 (m, 4H, H _g )
¹³ C-NMR spectrum (in CDCl ₃ ): δ 127.94, 129.51, 134.35, 135.13 (C ₁ , C ₂ , C ₃ , C ₄ ), δ 74.10 (C ₈ ), δ 62. 55 (C ₅ ), δ 30.72, 35.40, 40.61, 45.38 (C ₉ , C ₁₀ , C ₁₁ , C ₁₂ ), δ 25.48 (C ₆ ), δ 8.49 (C ₇ )
Elemental analysis value: As C ₄₀ H ₄₈ O ₂ Si ₂ Calculation value: C; 77.87, H; 7.84
Found: C; 77.60, H; 8.00
Example 3
In a 50 ml two-necked flask, 0.46 g (0.71 mmol) of 1,3-bis {3- (dihexylsilyl) propoxy} adamantane obtained in Example 1 was used as an unsaturated bond-containing compound. -0.09 g (0.71 mmol) of diethynylbenzene and 1,3-bis {3- (dihexylsilyl) propoxy} adamantane, and chlorotris (triphenylphosphine) rhodium (I) as a hydrosilylation catalyst 0.0017 g (0.0018 mmol) which is 0.0025 mol times 1,3-bis {3- (dihexylsilyl) propoxy} adamantane and 5 ml of toluene were added and stirred at 70 ° C. for 24 hours. The hydrosilylation catalyst was removed by silica gel column chromatography, the solution was concentrated under reduced pressure, and then reprecipitated with chloroform-methanol to obtain 0.26 g of a transparent oil. The structure of the obtained polymer is considered to be represented by the following formula (16).

(Hex in the formula represents a hexyl group, and n is a quantity corresponding to the molecular weight.)
As a result of calculating the weight average molecular weight (Mw) and the molecular weight dispersion (Mw / Mn; the weight average molecular weight divided by the number average molecular weight) by gel permeation chromatography in terms of polystyrene, Mw is 9664 and Mw / Mn is 1. .81.

Example 4
In a 50 ml two-necked flask, 1.85 g (3.00 mmol) of 1,3-bis {3- (diphenylsilyl) propoxy} adamantane obtained in Example 2 was used as an unsaturated bond-containing compound. Ethynylbenzene is equimolar 0.38 g (3.02 mmol) with 1,3-bis {3- (diphenylsilyl) propoxy} adamantane, and hexachloroplatinic (IV) acid hexahydrate is 1,3 as hydrosilylation catalyst. -0.015 g (0.0028 mmol) which is 0.0093 mol times bis {3- (diphenylsilyl) propoxy} adamantane, 1 drop of isopropyl alcohol and 4 ml of tetrahydrofuran were added, and the mixture was stirred at room temperature for 20 hours. The hydrosilylation catalyst was removed by silica gel column chromatography, the solution was concentrated under reduced pressure, and then reprecipitated with chloroform-ethanol to obtain 1.73 g of a tan solid. The structure of the obtained polymer is considered to be represented by the following formula (17).

(Ph in the formula represents a phenyl group, and n is a quantity corresponding to the molecular weight.)
As a result of calculating the weight average molecular weight (Mw) and molecular weight dispersion (Mw / Mn; weight average molecular weight divided by number average molecular weight) by gel permeation chromatography in terms of polystyrene, Mw was 6079 and Mw / Mn was 1. .52. Also, under a nitrogen stream, 5% thermogravimetric decrease temperature (Td ₅ ) and 10% thermogravimetric decrease temperature (Td ₁₀ ) were measured by thermogravimetric analysis. As a result, Td ₅ was 265 ° C. and Td ₁₀ was 359 ° C. there were.

Example 5
The same operation was carried out except that the hydrosilylation catalyst used in Example 4 was changed to chlorotris (triphenylphosphine) rhodium (I) to obtain 1.48 g of a tan solid. The structure of the obtained polymer is considered to be the same as in Example 4. As a result of calculating the weight average molecular weight (Mw) and the molecular weight dispersion (Mw / Mn; weight average molecular weight divided by the number average molecular weight) by gel permeation chromatography in terms of polystyrene, Mw was 6440 and Mw / Mn was 1. .60. Further, under a nitrogen stream, the results of measurement of 5% thermogravimetric decrease temperature (Td ₅ ) and 10% thermogravimetric decrease temperature (Td ₁₀ ) by thermogravimetric analysis showed that Td ₅ was 341 ° C. and Td ₁₀ was 384 ° C. there were.

Example 6
In a 50 ml two-necked flask, 1.77 g (2.87 mmol) of 1,3-bis {3- (diphenylsilyl) propoxy} adamantane obtained in Example 2 was used as an unsaturated bond-containing compound. 0.74 g (3.01 mmol) of (allyloxy) adamantane, 1.05 mol times 1,3-bis {3- (diphenylsilyl) propoxy} adamantane, and hexachloroplatinum (IV) acid hexahydrate as a hydrosilylation catalyst Was added to 0.021 g (0.041 mmol), 0.014 mol times 1,3-bis {3- (diphenylsilyl) propoxy} adamantane, 1 drop of isopropyl alcohol and 10 ml of tetrahydrofuran, and the mixture was stirred at room temperature for 45 hours. . The hydrosilylation catalyst was removed by silica gel column chromatography, the solution was concentrated under reduced pressure, and then reprecipitated with chloroform-ethanol to obtain 0.73 g of a tan solid. The structure of the obtained polymer is considered to be represented by the following formula (18).

(Ph in the formula represents a phenyl group, and n is a quantity corresponding to the molecular weight.)
As a result of calculating the weight average molecular weight (Mw) and molecular weight dispersion (Mw / Mn; weight average molecular weight divided by number average molecular weight) by gel permeation chromatography in terms of polystyrene, Mw was 3780, and Mw / Mn was 1. .25. Further, under a nitrogen stream, the measurement of 5% thermogravimetric decrease temperature (Td ₅ ) and 10% thermogravimetric decrease temperature (Td ₁₀ ) by thermogravimetric analysis revealed that Td ₅ was 340 ° C. and Td ₁₀ was 371 ° C. there were.

Claims (4)

A silicon-containing adamantane compound represented by the following formula (1):

[Wherein, R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a chlorine atom, and R ⁴ And R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, a fluorine atom, a chlorine atom, or a group represented by the following formula (2). is there.

^{Wherein, R 1, ^{R 2,} and ^{R 3} have the same meaning as ^R 1, ^{R 2,} and ^{R 3} in each Formula (1). }] A silicon-containing adamantane compound represented by the following formula (3).

[Wherein R ⁶ and R ⁷ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a chlorine atom, and R ⁸ and R ⁹ are each independently Are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, a fluorine atom, a chlorine atom, or a group represented by the following formula (4).

{Wherein, ^{R 6,} and ^{R 7} have the same meanings as ^{R 6,} and ^{R 7} in each Formula (3). }] Following formula (5)

( Wherein R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an allyloxy group, a phenyl group, a fluorine atom, or a chlorine atom. .)
And an allyloxy compound represented by the following formula (6)

(In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a chlorine atom.)
The method for producing a silicon-containing adamantane compound represented by the formula (1) according to claim 1, wherein a hydrosilylation reaction is performed in the presence of a hydrosilylation catalyst.

A method for producing an adamantane-containing silicon polymer, comprising subjecting a silicon-containing adamantane compound represented by formula (3) according to claim 2 and an unsaturated bond-containing compound to a hydrosilylation reaction in the presence of a hydrosilylation catalyst.