JP6942996B2 - A method for producing a vinyl group-containing cage-type silsesquioxane derivative, a bifunctional cage-type silsesquioxane derivative, and a method for producing the same. - Google Patents

Description

One embodiment of the present invention relates to a method for producing a vinyl group-containing cage-type silsesquioxane derivative. Further, another embodiment of the present invention relates to a bifunctional cage type silsesquioxane derivative and a method for producing the same.

Generally, an organosilicon compound having three hydrolyzable groups represented by an alkoxide group has already been widely used as a silane coupling agent. It is known that the silsesquioxane compound obtained by hydrolyzing and then condensing this silane coupling agent has a random structure without a specific structure, a ladder structure capable of determining the structure, and a cage-type structure. .. In particular, silsesquioxane having a cage-shaped structure has excellent properties in heat resistance, electrical insulation, transparency, etc., and therefore has attracted attention as a semiconductor or electronic material, and many studies have been reported.

Of these, the cage-type silsesquioxane, which is composed of eight Sis and has high symmetry, is called T8. In this T8, a derivative in which all eight substituents on Si are converted to reactive substituents, that is, an eight-substituted T8, or one in which one is converted to another reactive substituent, that is, a mono-substituted XT8 Many derivatives with different substituents have been commercialized (Patent Documents 1 and 2).

Further, among these T8s, the derivative in which two on Si are converted into other reactive substituents, that is, the disubstituted 2X-T8, is, for example, two kinds of trialkoxysilanes or trichlorosilanes as in Non-Patent Document 1. It is known that it can be synthesized from compounds. However, when the reactive substituent is a vinyl group, vinyltrichlorosilane and alkyltrichlorosilane, which are raw materials for synthesis, are highly reactive with water and even react with water vapor in the atmosphere. In addition, hydrochloric acid gas generated as a by-product of the reaction is highly corrosive and requires special manufacturing equipment with a glass coating or the like. In addition, silanol produced from chlorosilane is likely to cause condensation in the presence of an acid, and in addition to the thermodynamically stable product, a by-product is generated by a kinetic reaction mechanism, and the yield of the target compound decreases. Tend to do. Therefore, in order to obtain the desired disubstituted 2X-T8 in good yield, it is necessary to devise the reaction conditions and the charging ratio of the reaction raw materials.

Recently, as in Non-Patent Documents 2 and 3, a method has been proposed in which a di-substituted 2X-T8 at the p-position is selectively synthesized from a mono-substituted X-T8 in two steps. Since the disubstituted 2X-T8 can precisely introduce silsesquioxane into the polymer main chain, a polymer having unprecedented characteristics is expected. However, since this method requires two steps for the synthesis of the raw material silane compound to the monosubstituted XT8, the result is a four-step production method. Further, when introduced into the polymer main chain, it is not considered that the di-substituted 2X-T8 at the o-position or the m-position necessarily causes a deterioration in characteristics, so that industrially selective p-position disubstituted 2X-T8 It is not restricted by the manufacturing method.

Further, since the methods of Non-Patent Documents 2 and 3 are synthesized from a trialkoxysilane or a trichlorosilane compound, they have the same problems as those of Non-Patent Document 1. Furthermore, it is not possible to introduce a functional group that does not exist as a trialkoxysilane or trichlorosilane compound.

Japanese Patent No. 5362160 Japanese Patent Application Laid-Open No. 2005-509042

Journal of Organometallic Chemistry, (1994), 483, 33-38 Chemistry Letters, (2014), 43, 1532 to 1534 Polymer Chemistry, (2015), 6,7500-7504

An industrially superior method for producing a disubstituted vinyl-T8 is provided, and one embodiment of the present invention is an object of providing a method for producing a vinyl group-containing cage-type silsesquioxane derivative. ..
Another object of another embodiment of the present invention is to provide a bifunctional cage-type silsesquioxane derivative into which two functional groups having a novel hydroxy group are introduced, and a method for producing the same.

Specific means for achieving the above-mentioned problems are as follows.
[1] A step of reacting an alkoxysilane represented by the following general formula (I), a vinyl alkoxysilane represented by the following general formula (II), and a basic compound in the presence of water, and a chromatography method. A method for producing a vinyl group-containing cage-type silsesquioxane derivative represented by the following general formula (III), which comprises a separation and purification step.

［一般式（Ｉ）中、Ｒ^１は炭素数１〜８のアルキル基又は炭素数６〜１４のアリール基を表す。Ｒ^２はそれぞれ独立して炭素数１〜８のアルキル基を表す。一般式（ＩＩ）中、Ｒ^３はそれぞれ独立して炭素数１〜８のアルキル基を表す。一般式（ＩＩＩ）中、Ｒ^１は一般式（Ｉ）と同じ炭素数１〜８のアルキル基又は炭素数６〜１４のアリール基を表す。］
［２］前記反応させる工程が生成物を酸で処理することを含む、上記［１］に記載のビニル基含有かご型シルセスキオキサン誘導体の製造方法。
［３］前記塩基性化合物が下記（ＩＶ）表される化合物である上記［１］又は［２］に記載のビニル基含有かご型シルセスキオキサン誘導体の製造方法。

[In the general formula (I), R ¹ represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms. R ² independently represents an alkyl group having 1 to 8 carbon atoms. In the general formula (II), R ³ independently represents an alkyl group having 1 to 8 carbon atoms. In the general formula (III), R ¹ represents the same alkyl group having 1 to 8 carbon atoms or the aryl group having 6 to 14 carbon atoms as in the general formula (I). ]
[2] The method for producing a vinyl group-containing cage-type silsesquioxane derivative according to the above [1], wherein the reaction step comprises treating the product with an acid.
[3] The method for producing a vinyl group-containing cage-type silsesquioxane derivative according to the above [1] or [2], wherein the basic compound is a compound represented by the following (IV).

［一般式（ＩＶ）中、ＭはＬｉ、Ｎａ、Ｋからなる群より選択される少なくとも１種の金属元素を含む。］
［４］前記一般式（Ｉ）で表されるアルコキシシランと、一般式（ＩＩ）で表されるビニルアルコキシシランとのモル比率が８０：２０〜５０：５０である上記［１］〜［３］のいずれか一項に記載のビニル基含有かご型シルセスキオキサン誘導体の製造方法。
［５］前記クロマトグラフィー法が液体順相である上記［１］〜［４］のいずれか一項に記載のビニル基含有かご型シルセスキオキサン誘導体の製造方法。
［６］前記クロマトグラフィー法で用いる展開溶剤がヘキサンを含む有機溶剤である上記［１］〜［５］のいずれか一項に記載のビニル基含有かご型シルセスキオキサン誘導体の製造方法。

[In general formula (IV), M comprises at least one metal element selected from the group consisting of Li, Na, K. ]
[4] The molar ratio of the alkoxysilane represented by the general formula (I) to the vinyl alkoxysilane represented by the general formula (II) is 80:20 to 50:50. ]. The method for producing a vinyl group-containing cage-type silsesquioxane derivative according to any one of the above.
[5] The method for producing a vinyl group-containing cage-type silsesquioxane derivative according to any one of the above [1] to [4], wherein the chromatography method is a liquid normal phase.
[6] The method for producing a vinyl group-containing cage-type silsesquioxane derivative according to any one of the above [1] to [5], wherein the developing solvent used in the chromatography method is an organic solvent containing hexane.

［一般式（１）中、Ｒ^１は、直鎖または分岐鎖を有するアルキル基、シクロアルキル基、またはアリール基を表し、６個のＲ^１は、全て同一であっても、一部または全て異なってもよく、Ｘは、単結合、炭素数１〜８の直鎖または分岐鎖を有するアルキレン基、炭素数３〜８のシクロアルキレン基、または炭素数６〜１４のアリーレン基を表し、Ｙは、炭素数１〜２５の直鎖または分岐鎖を有するアルキレン基、炭素数３〜２５のシクロアルキレン基、または炭素数６〜２５のアリーレン基を表し、２個の−Ｘ−ＣＨ_２−ＣＨ_２−Ｓ−Ｙ−ＯＨで表される基は、互いに同一であっても、異なってもよい。] [7] A bifunctional cage-type silsesquioxane derivative represented by the following general formula (1).

[In the general formula (1), R ¹ represents an alkyl group having a linear or branched chain, a cycloalkyl group, or an aryl group, and six R ^1s are partially or all even if they are all the same. Although different, X represents a single bond, an alkylene group having a linear or branched chain having 1 to 8 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms, and Y Represents an alkylene group having a linear or branched chain having 1 to 25 carbon atoms, a cycloalkylene group having 3 to 25 carbon atoms, or an arylene group having 6 to 25 carbon atoms, and two -X-CH _{2-CH. The} groups represented by 2-SY-OH may be the same or different from each other. ]

［一般式（２）中、Ｒ^１は、直鎖または分岐鎖を有するアルキル基、シクロアルキル基、またはアリール基を表し、６個のＲ^１は、全て同一であっても、一部または全て異なってもよく、Ｘは、単結合、炭素数１〜８の直鎖または分岐鎖を有するアルキレン基、炭素数３〜８のシクロアルキレン基、または炭素数６〜１４のアリーレン基を表し、２個の−Ｘ−ＣＨ＝ＣＨ_２で表される基は、互いに同一であっても、異なってもよい。］

［一般式（３）中、Ｙは、炭素数１〜２５の直鎖または分岐鎖を有するアルキレン基、炭素数３〜２５のシクロアルキレン基、または炭素数６〜２５のアリーレン基を表す。］ [8] A step of reacting a silicon compound represented by the following general formula (2) with a thiol compound represented by the following general formula (3) to produce a bifunctional cage-type silsesquioxane derivative is included. A method for producing a bifunctional cage-type silsesquioxane derivative.

[In the general formula (2), R ¹ represents an alkyl group having a linear or branched chain, a cycloalkyl group, or an aryl group, and six R ^1s are partially or all even if they are all the same. It may be different, where X represents a single bond, an alkylene group having a linear or branched chain with 1 to 8 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms, 2 The groups represented by -X-CH = CH ₂ may be the same or different from each other. ]

[In the general formula (3), Y represents an alkylene group having a linear or branched chain having 1 to 25 carbon atoms, a cycloalkylene group having 3 to 25 carbon atoms, or an arylene group having 6 to 25 carbon atoms. ]

According to one embodiment of the present invention, disubstituted vinyl-T8 can be produced in good yield by a one-step reaction using an inexpensive production facility.
According to another embodiment of the present invention, it is possible to provide a bifunctional cage-type silsesquioxane derivative into which two functional groups having a hydroxy group are introduced, and a method for producing the same.

The figure which shows each fraction division of Example 1. FIG. MALDI-TOF MS measurement results for each fraction of Example 1. ^{1 1} H NMR spectrum of each fraction of Example 1. ¹³ C NMR spectrum of each fraction of Example 1. ²⁹ Si NMR spectra of each fraction of Example 1. Positional isomer of bisvinyl POSS. MALDI-TOF MS measurement result of Example 2. 1H NMR spectrum of bisvinyl POSS of Example 1. ^{1 1} H NMR spectrum of Example 2. ¹³ C NMR spectrum of bisvinyl POSS of Example 1. ¹³ C NMR spectrum of Example 2. ²⁹ Si NMR spectrum of bisvinyl POSS of Example 1. ²⁹ Si NMR spectrum of Example 2.

Hereinafter, an embodiment of the present invention will be described, but the present invention is not limited by the following examples.
"Method for producing a cage-type silsesquioxane derivative containing a vinyl group"
(Compound represented by the general formula (I), alkoxysilane)
In the production method of the present invention, at least one of the compounds represented by the following general formula (I) is used.

In the general formula (I), R ¹ represents an alkyl group or an aryl group. It is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. The ^{alkyl group represented by R 1} may be linear or branched. Examples thereof include a methyl group, an ethyl group, an isobutyl group, a cyclohexyl group, an isooctyl group, a phenyl group and the like. In the general formula (I), R ² independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The ^{alkyl group represented by R 2} may be linear or branched. Specific examples of the alkyl group represented by R ^2, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl group, sec- butyl group, t- butyl group, Examples thereof include a hexyl group, an octyl group, a 2-ethylhexyl group, and a 3-ethylhexyl group. Among ^{them, the alkyl group represented by R 2} is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, and is an unsubstituted alkyl group having 1 to 4 carbon atoms from the viewpoint of controlling reactivity. Is more preferable.

(Compound represented by the general formula (II), vinyl alkoxysilane)

一般式（ＩＩ）において、Ｒ^３はそれぞれ独立してアルキル基を表し、炭素数１〜８のアルキル基であることが好ましく、炭素数１〜４のアルキル基であることがより好ましい。Ｒ^３で表されるアルキル基は直鎖状であっても分岐鎖状であってもよい。Ｒ^３で表されるアルキル基として具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、３−エチルヘキシル基等を挙げることができる。中でもＲ^３で表されるアルキル基は、反応性の制御の観点から、炭素数１〜８の無置換のアルキル基であることが好ましく、炭素数１〜４の無置換のアルキル基であることがより好ましい。

In the general formula (II), R ³ independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The ^{alkyl group represented by R 3} may be linear or branched. Specifically, the alkyl group represented by R ³ includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, and a t-butyl group. Examples thereof include a hexyl group, an octyl group, a 2-ethylhexyl group, and a 3-ethylhexyl group. Among them, it alkyl group represented by R ^3, from the viewpoint of controlling reactivity, be an unsubstituted alkyl group having 1 to 8 carbon atoms is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms Is more preferable.

(Compound represented by the general formula (III))

一般式（ＩＩＩ）の化合物は二置換ビニル−Ｔ８を表す。Ｔ８とは８つのＳｉから構成され、対称性の高いかご型シルセスキオキサンの総称である。二置換とは８つのＳｉに結合した有機基のうち、２つが反応性置換基であることを意味し、一般式（ＩＩＩ）の場合はビニル基となる。有機基は、一般式（Ｉ）に由来するＲ^１と同一のものとなる。また、ビニル基が結合している位置については、ベンゼン環と同じような命名則を当てはめれば、酸素を一つ介した２つのＳｉにビニル基があるｏ位、酸素−Ｓｉ−酸素を介した２つのＳｉにビニル基があるｍ位、さらに、対角の位置になるｐ位の３種類がある。本発明では、この３種類のうちいずれの構造でもよい。また、少なくとも３種のうち一つ以上の構造を含んでいればよい。

The compound of general formula (III) represents disubstituted vinyl-T8. T8 is a general term for cage-type silsesquioxane, which is composed of eight Sis and has high symmetry. The di-substituted means that two of the eight organic groups bonded to Si are reactive substituents, and in the case of the general formula (III), it is a vinyl group. The organic group is the same as ^{R 1} derived from the general formula (I). As for the position where the vinyl group is bonded, if the same naming rule as the benzene ring is applied, the o-position where the vinyl group is in two Sis via one oxygen and the oxygen-Si-oxygen are used. There are three types: m-position, which has a vinyl group on the two Sis, and p-position, which is diagonally located. In the present invention, any of these three types of structures may be used. In addition, it suffices to include at least one of three structures.

(Compound represented by the general formula (IV))

本発明で用いる塩基性化合物は一般式（ＩＶ）で表される化合物であることが好ましい。
一般式（ＩＶ）において、ＭはＬｉ、Ｎａ、Ｋからなる群より選択される少なくとも１種の金属元素を含むものであれば特に制限はない。但し、反応性の制御や収率の観点から、Ｌｉであることが好ましい。塩基性や求核性がやや低下したアルカリ金属水酸化物は良い選択性を示し、反応性置換基Ｘの付け根のＳｉが優先的に脱離する。特にこのなかでＬｉ水酸化物は塩基性や求核性が最も低く、シラン原料の仕込み比に応じた熱力学的に安定な生成物を得るのに有利である。

The basic compound used in the present invention is preferably a compound represented by the general formula (IV).
In the general formula (IV), M is not particularly limited as long as it contains at least one metal element selected from the group consisting of Li, Na, and K. However, Li is preferable from the viewpoint of controlling reactivity and yield. Alkali metal hydroxides with slightly reduced basicity and nucleophilicity show good selectivity, and Si at the base of the reactive substituent X is preferentially eliminated. In particular, Li hydroxide has the lowest basicity and nucleophilicity among them, and is advantageous for obtaining a thermodynamically stable product according to the charging ratio of the silane raw material.

The medium for production is not particularly limited, but the alkoxysilane represented by the general formula (I) and the vinylalkoxysilane represented by the general formula (II) have high compatibility and are uniform when mixed. On the other hand, a solvent having low compatibility with M (OH) of the general formula (IV) and having M (OH) remaining in the system without being dissolved when mixed is preferable. The uniformly dispersed silane raw material is advantageous in providing a thermodynamically stable product. Further, it is advantageous that the M (OH) concentration remains constant in the system during the reaction to provide a thermodynamically stable product.
Further, by adding water to the solvent, the reaction can proceed in the presence of water. Water may be added in an amount of 5 to 15 parts by mass with respect to a total of 100 parts by mass of the alkoxysilane represented by the general formula (I) and the vinyl alkoxysilane represented by the general formula (III).

The molar ratio of the alkoxysilane represented by the general formula (I), which is a silane raw material, to the vinylalkoxysilane represented by the general formula (II) is not particularly limited as long as the disubstituted vinyl-T8 is produced. Assuming that a compound can be obtained statistically thermodynamically according to the charging ratio, when disubstituted vinyl-T8 is the target compound, 75:25 is the molar ratio expected to have the highest yield. Therefore, the molar ratio is preferably 90: 10 to 40:60. Further, considering that T8, monosubstituted vinyl-T8, and trisubstituted vinyl-T8 produced at the same time are removed by normal phase chromatography, 85: 15 to 45:55 is preferable. Further, 80:20 to 50:50 is preferable.

As described above, the medium for carrying out the synthesis preferably has low solubility in LiOH and is compatible with the silane raw material and water. Specifically, a mixed solvent of methanol and acetone is preferable. At this time, there is no particular limitation on the mixing ratio.
In addition, there is no particular limitation on the temperature at which the synthesis is carried out. However, from the viewpoint of shortening the reaction time, 30 to 56 ° C. is preferable, and 40 to 55 ° C. is more preferable.

A chromatography method may be used as a method for separating and purifying the disubstituted vinyl-T8 from the product after the reaction. As the chromatography method, normal phase liquid chromatography using a column containing silica particles as a filler is preferable. By using normal phase liquid chromatography, the T8, monosubstituted vinyl-T8, and trisubstituted vinyl-T8 produced can be discharged in order because the polarization states of the molecules are slightly different. Further, since the polarization of these molecules is small, the developing solvent is preferably a solvent containing hexane or petroleum ether, which has low polarity and is inexpensive.

"Bifunctional cage type silsesquioxane derivative"
The bifunctional cage-type silsesquioxane derivative according to one embodiment is characterized by being represented by the following general formula (1).

In the general formula (1), R ¹ represents an alkyl group having a linear or branched chain, a cycloalkyl group, or an aryl group, and the six R ^1s are all the same but partially or all different. X may represent a single bond, an alkylene group having a linear or branched chain having 1 to 8 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms, and Y represents an arylene group having 6 to 14 carbon atoms. represents an alkylene group or an arylene group having 6 to 25 carbon atoms, having a straight-chain or branched-chain having 1 to 25 carbon atoms, represented by two _{-X-CH 2 -CH 2 -S-} Y-OH The groups may be the same or different from each other.

The bifunctional cage-type silsesquioxane derivative contains a cage-type silsesquioxane skeleton, and a functional group exhibiting reactivity in 2 out of 8 Sis is introduced. In the compound represented by the general formula (1), a group unreactive represented by -R _^1, the groups represented by _{-X-CH 2 -CH 2 -S-} Y-OH is a reactive Will be shown. This makes it possible to provide a bifunctional cage-type silsesquioxane derivative in which two functional groups having a hydroxy group are introduced.

In the general formula (1), R ¹ represents an alkyl group having a straight chain or a branched chain, a cycloalkyl group, or an aryl group.
Alkyl group represented by R ¹ is preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, which may have a straight or branched chain.
The ^{cycloalkyl group represented by R 1} preferably has 3 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms. Within this range of carbon numbers, the cycloalkyl group may have an alkyl group having a straight chain or a branched chain bonded to at least one carbon atom forming a carbon ring.
The ^{aryl group represented by R 1} preferably has 6 to 14 carbon atoms, more preferably 6 to 12 carbon atoms, and further preferably 6 to 8 carbon atoms. Within this range of carbon numbers, the aryl group may have an alkyl group having a linear or branched chain bonded to at least one carbon atom forming a carbon ring.
Examples of R ¹ include a methyl group, an ethyl group, an isobutyl group, a cyclohexyl group, an isooctyl group, a phenyl group and the like.
R ¹ is preferably an alkyl group or a phenyl group having 1 to 12 carbon atoms, and more preferably an alkyl group or a phenyl group having 1 to 8 carbon atoms.

In the general formula (1), the six R ^1s may be all the same, or partly or all different. It is preferable that all six R ^{1s are the same.}

In the general formula (1), X represents a single bond, an alkylene group having a linear or branched chain having 1 to 8 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms. ..
The alkylene group represented by X preferably has 1 to 8 carbon atoms, more preferably 1 to 3 carbon atoms, and may have a straight chain or a branched chain.
The cycloalkylene group represented by X preferably has 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms. Within this carbon number range, the cycloalkylene group may have an alkyl group having a straight chain or a branched chain bonded to at least one carbon atom forming a carbon ring.
The arylene group represented by X preferably has 6 to 14 carbon atoms, more preferably 6 to 12 carbon atoms, and further preferably 6 to 8 carbon atoms. Within this carbon number range, the arylene group may have an alkyl group having a straight chain or a branched chain bonded to at least one carbon atom forming a carbon ring.
Examples of X include a single bond, a methylene group, an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, an i-butylene group, a sec-butylene group, a t-butylene group, a hexylene group and an octylene group. , I-octylene group, 2-ethylhexylene group, 3-ethylhexylene group, 2-methylpentylene group, cyclohexylene group, phenylene group and the like.
X is preferably a single bond, an alkylene group having 1 to 8 carbon atoms or a phenylene group, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms, and even more preferably a single bond.

In the general formula (1), Y represents an alkylene group having a linear or branched chain having 1 to 25 carbon atoms, a cycloalkylene group having 3 to 25 carbon atoms, or an arylene group having 6 to 25 carbon atoms.
The alkylene group represented by Y preferably has 1 to 25 carbon atoms, more preferably 1 to 8 carbon atoms, and may have a straight chain or a branched chain.
The cycloalkylene group represented by Y preferably has 3 to 25 carbon atoms, and more preferably 3 to 8 carbon atoms. Within this carbon number range, the cycloalkylene group may have an alkyl group having a straight chain or a branched chain bonded to at least one carbon atom forming a carbon ring.
The arylene group represented by Y preferably has 6 to 25 carbon atoms, more preferably 6 to 14 carbon atoms, and further preferably 6 to 8 carbon atoms. Within this carbon number range, the arylene group may have an alkyl group having a straight chain or a branched chain bonded to at least one carbon atom forming a carbon ring.
Examples of Y include methylene group, ethylene group, n-propylene group, i-propylene group, n-butylene group, i-butylene group, sec-butylene group, t-butylene group, hexylene group, octylene group and i-. Examples thereof include an octylene group, a 2-ethylhexylene group, a 3-ethylhexylene group, a 2-methylpentylene group, a cyclohexylene group, a phenylene group and the like.
Y is preferably an alkylene group having 1 to 25 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms.

In the general formula (1), the _{groups represented by the two -X-CH 2} -CH 2-SY-OH may be the same or different from each other. _{It is preferable that the groups represented by the two} -X-CH ₂ -CH 2-SY-OH are the same as each other.

In the general formula (1), silsesquioxane skeleton eight _{-X-CH 2 -CH 2 -S-} Y-OH group is bonded, represented by the two silicon atoms of the silicon atoms constituting ^{, R 1} is bonded to the other 6 silicon atoms.
Position groups represented silsesquioxane skeleton _{-X-CH 2 -CH 2 -S-} Y-OH is introduced is not particularly limited, for example, of two adjacent via one oxygen atom It may be introduced into Si (position o), it may be introduced into two Sis via an oxygen atom-Si-oxygen atom (position m), or it may be introduced into two Sis located diagonally to each other. Good (p rank).

"Manufacturing method of bifunctional cage type silsesquioxane derivative"
Hereinafter, an example of a method for producing a bifunctional cage-type silsesquioxane derivative represented by the general formula (1) will be described. The bifunctional cage-type silsesquioxane derivative represented by the general formula (1) is not limited to that produced by the following production method.
The method for producing the bifunctional cage-type silsesquioxane derivative represented by the general formula (1) includes, for example, a step of producing using a silicon compound represented by the following general formula (2).
Further, this production method preferably includes a step of producing using a thiol compound represented by the following general formula (3).
Preferably, a step of reacting a silicon compound represented by the general formula (2) with a thiol compound represented by the general formula (3) to produce a bifunctional cage-type silsesquioxane derivative is included.

In the general formula (2), R ¹ represents an alkyl group having a linear or branched chain, a cycloalkyl group, or an aryl group, and the six R ^1s are all the same but partially or all different. X may represent a single bond or an alkylene group having a linear or branched chain having 1 to 8 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms. The two groups represented by -X-CH = CH ₂ may be the same or different from each other.

^{R 1} in the general formula (2) ^{is a group introduced as R 1 in the} compound represented by the general formula (1), and the details are as described in the general formula (1).
Further, X in the general formula (2) is a group introduced as X in the compound represented by the general formula (1), and the details are as described in the general formula (1).

As an example of the silicon compound represented by the general formula (2), the silicon compound represented by the following general formula (III) in which X is a single bond in the general formula (2) can be preferably used. The details of the general formula (III) are as described above.

In the general formula (2), the two _{groups represented by −X—CH = CH 2} may be the same as or different from each other. The two groups represented by -X-CH = CH ₂ are preferably the same as each other.

The silicon compound represented by the general formula (2) has two vinyl groups. By binding a thiol compound having a hydroxy group to this silicon compound by a thiolene reaction, two hydroxy groups can be introduced into the silicon compound represented by the general formula (2). As the thiol compound, a thiol compound represented by the general formula (3) can be used.

In the general formula (3), Y represents an alkylene group having a linear or branched chain having 1 to 25 carbon atoms, a cycloalkylene group having 3 to 25 carbon atoms, or an arylene group having 6 to 25 carbon atoms.
Y in the general formula (3) is a group introduced as Y in the compound represented by the general formula (1), and the details are as described in the general formula (1).

A radical initiator may be used in the reaction of the silicon compound represented by the general formula (2) with the thiol compound represented by the general formula (3).
The radical initiator is not particularly limited, but any known thermal polymerization initiator and photopolymerization initiator can be used.
Specific examples of the thermal polymerization initiator include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2, Organic peroxides such as 5-dimethylhexane-2,5-dihydroperoxide, methylethylketone peroxide, tertiary butylperoxybenzoide; azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate, and azobiscyanovaleric acid. Etc. are preferably used, preferably azobisisobutyronitrile (AIBN).
Specific examples of the photopolymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, and the like. Triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropyl) Phenyl) -2-hydroxy-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2) -Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphos Examples include finoxide and oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone).
These radical initiators may be used alone or in combination of two or more.
The amount of the initiator added is 0.1 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass, based on 100 parts by mass of the compound represented by the general formula (2).

The reaction between the silicon compound represented by the general formula (2) and the thiol compound represented by the general formula (3) is preferably carried out in a solvent.
The solvent is not particularly limited, but can be arbitrarily selected depending on the solubility of the silicon compound represented by the general formula (2), the thiol compound represented by the general formula (3), and the polymerization initiator.
Specific examples of the solvent include methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, etc. Examples thereof include acetonitrile, tetrahydrofuran (THF), dimethylformamide, chloroform, toluene and the like, and ethyl acetate is preferable. These may be used alone or in combination of two or more.

The reaction temperature varies depending on the polymerization initiator and solvent used, but is preferably 40 to 90 ° C., more preferably 60 to 80 ° C. from the reaction rate of the thiol-ene reaction.
The structure of the bifunctional cage-type silsesquioxane derivative represented by the general formula (1) can be confirmed by a nuclear magnetic resonance apparatus (NMR) and / or mass spectrometry (MS).

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "%" is based on mass.

"Manufacture of cage-type silsesquioxane derivatives containing vinyl groups"
<Example 1>
Acetone (300 mL), methanol (40 mL), and purified water (5.60 mL) were added to a 500 mL three-necked flask, and a Dimroth condenser, a thermometer, and a dropping funnel were provided to create a nitrogen atmosphere. 7.00 g of LiOH monohydrate was added as a basic compound, and the mixture was heated in an oil bath with stirring so that the liquid temperature became 55 ° C. 49.00 g of isobutyltrimethoxysilane as the alkoxysilane represented by the general formula (I) and 13.56 g of vinyltrimethoxysilane as the vinyl alkoxysilane represented by the general formula (II) were weighed in the dropping funnel, and 50 It was slowly added dropwise over a minute. After the dropping, the liquid temperature was set to 50 ° C., and the mixture was heated and stirred in a nitrogen atmosphere for 18 hours. After heating, the oil bath was removed, the mixture was allowed to cool to room temperature (25 ° C.), and 150 mL of 1N HCl solution was added to make the mixture cloudy. The mixture was stirred as it was for 1 hour, and the supernatant was removed by inclining. The remaining white viscous substance was washed 3 times with 100 mL of acetonitrile, and then hexane was added to dissolve the white viscous substance. This solution was quantitatively transferred to a 500 mL flask, the solvent was distilled off with an evaporator, and the solution was dried under reduced pressure with an oil pump to obtain 34.64 g of a white viscous substance.

The obtained white viscous product was separated and purified.
"LC-forte / R" manufactured by YMC Co., Ltd. was used for preparative purification using a medium pressure column, and "Universal Column Premium (2L)" manufactured by Yamazen Corporation was used as the column. The preparative condition was 10 mL / min, and the developing solvent was hexane. 2.64 g of white viscous material was dissolved in 1.47 g of hexane and charged directly onto the top of the column. While monitoring the outflow RI detection, each fraction was divided into fractions at the outflow time as shown in FIG. 1, the solvent was distilled off with an evaporator for each fraction, and the solvent was dried under reduced pressure with an oil pump to obtain white crystals from each fraction. The masses of white crystals obtained from each fraction are shown in Table 1.

MALDI-TOF MS analysis was performed on the white crystals obtained from fractions 2 to 4 using "AutoFlex" manufactured by Bruker Daltonics. The results are shown in FIG. From FIG. 2, peaks of H + and Na + adducts were observed.
Table 2 shows the observed values of white crystals obtained from each fraction and the calculated values of vinyl POSS (POSS; cage-type oligomeric SilSesquioxanes), bisvinyl POSS, and trisvinyl POSS. Fraction 2 was vinyl POSS, fraction 3 was the target bisvinyl POSS, and fraction 4 was trisvinyl POSS.

For Bisubiniru POSS, in order to investigate the binding position of the vinyl group, by dissolving the white crystals obtained from fractions 1-5 in CDCl ₃ (deuterated chloroform), using a Bruker ^"Avance300", 1 H, ¹³ C and ²⁹ Si NMR were measured. The measurement results are shown in FIGS. 3, 4, and 5, respectively.

Comparing with the result of vinyl POSS of fraction 2, it can be seen that bisvinyl POSS has two kinds of vinyl groups. However, as shown in FIG. 6, which two of the three possible structures cannot be determined from these NMR results.

"Manufacturing of bifunctional cage-type silsesquioxane derivative"
<Example 2>
In a 20 mL three-necked flask, bisvinylhexaisobutyry POSS (POSS: cage-type oligosilsesquioxane; R ¹ is an isobutyl group and X is a single bond in the general formula (2); fraction 3 produced by the production method of Example 1 above. Bisvinyl POSS) (1.0 g), ethyl acetate (manufactured by Gordo Co., Ltd.) (4.0 mL), and AIBN (azobisisobutyronitrile, manufactured by Japan Finechem Co., Ltd.) (0.017 g) were added. This three-necked flask was equipped with a Dimroth condenser, a thermometer, and a nitrogen pipe, and the mixture was stirred at room temperature (25 ° C.) for 15 to 20 minutes using a magnetic stirrer together with nitrogen bubbling.
Next, after heating this three-necked flask in an oil bath so that the liquid temperature becomes 40 ° C., 6-mercapto-1-hexanol (HS- (CH ₂ ) _6- OH; Y in the general formula (3) is a hexylene group. (Manufactured by Tokyo Chemical Industry Co., Ltd.) was weighed 0.37 mL into a gas tight syringe and dropped.
After the dropwise addition, the reaction mixture was heated to 76-78 ° C. and stirred under reflux conditions for 4 hours. After stirring, the three-necked flask was removed from the oil bath and allowed to cool to room temperature, the reaction product was quantitatively transferred to a 100 mL flask, and the solvent was distilled off with an evaporator. After washing the obtained white solid with 20 mL of acetonitrile, No. The mixture was filtered using 5C filter paper and dried under reduced pressure using a rotary evaporator to obtain 1.0 g of white crystals (yield: 77%).

The obtained white crystals were dissolved in THF (tetrahydrofuran; manufactured by Wako Pure Chemical Industries, Ltd.), and gel permeation chromatography (GPC) was performed using "Chromaster" manufactured by Hitachi High-Technologies Corporation. The white crystals had a polystyrene-equivalent weight average molecular weight (Mw) of 975 and a number average molecular weight (Mn) of 964, and showed a clean monodispersity (Mw / Mn = 1.0).

The obtained white crystals were subjected to MALDI-TOF MS analysis using "AutoFlex" manufactured by Bruker Daltonics. The results are shown in FIG. ^{A peak of Na +} adduct was observed in the circled part in FIG. 7. ^{Observed value of Na +} adduct of the obtained white crystal (MALDI-TOF MS result) and calculated value of hexaisobutyl-2 [(6-hydroxyhexyl) thio] ethyl POSS (Exact Mass) and its Na ⁺ adduct The calculated values (Na ⁺ adduct) are shown in Table 3. The observed value of Na ⁺ adduct is larger by the atomic weight of Na (22.99). As a result, it was confirmed that the obtained white crystals were hexaisobutyl-2 [(6-hydroxyhexyl) thio] ethyl POSS.

For structural identification of hexaisobutyl-2 [(6-hydroxyhexyl) thio] ethyl POSS, the obtained white crystals were _{dissolved in CDCl 3} (deuterated chloroform), and Bruker's "Avance 300" was used. ¹ H, ¹³ C and ²⁹ Si NMR were measured.
The measurement conditions are as follows.
( ^{1 1} H NMR)
Observation nucleus: ¹ H
Resonance frequency: 300MHz
Measurement temperature: 25 ° C
Reference substance: Tetramethylsilane ( ¹³ C NMR)
Observation nucleus: ¹³ C
Resonance frequency: 75MHz
Measurement temperature: 25 ° C
Reference substance: Tetramethylsilane ( ²⁹ Si NMR)
Observation nucleus: ²⁹ Si
Resonance frequency: 60MHz
Measurement temperature: 25 ° C
Reference substance: Tetramethylsilane

^{The peak portions derived from the vinyl group are extracted from the measurement results of H, 13} C and ²⁹ Si NMR of the bisvinyl POSS obtained in Example 1, and are shown in FIGS. 8, 10 and 12, respectively.
^{The measurement results of 1} H, ¹³ C and ²⁹ Si NMR of hexaisobutyl-2 [(6-hydroxyhexyl) thio] ethyl POSS obtained in Example 2 are shown in FIGS. 9, 11 and 13, respectively.
^{From the 1} H NMR chart, the peak of the vinyl group (FIG. 8) of the raw material bisvinyl POSS confirmed at around 6 ppm disappeared, and the peak at around 3.6 ppm derived from the hydroxyl group shown in FIG. 9 was confirmed.
^{From the 13} C NMR chart, the disappearance of the peaks (FIG. 10) around 129.7 ppm and 136.0 ppm derived from the vinyl group of the raw material bisvinyl POSS was confirmed, and 25.4 ppm, 28.6 ppm, 29 shown in FIG. 11 were confirmed. A total of 6 peaks derived from 6-hydroxyhexyl were confirmed at .4 ppm, 31.6 ppm, 32.6 ppm, and 62.7 ppm.
^{From the 29} Si NMR chart, the peak around -81.5 ppm (FIG. 12) derived from the vinyl group of the raw material bisvinyl POSS disappeared, and the peak around -70.1 ppm derived from the 6-hydroxyhexyl group shown in FIG. 13 disappeared. A peak was confirmed.

From the above, it was confirmed that the structure of the white crystal synthesized in Example 2 is represented by the following chemical formula (4).

Claims (7)

A step of reacting an alkoxysilane represented by the following general formula (I), a vinyl alkoxysilane represented by the following general formula (II), and LiOH in the presence of water, a separation and purification step by a chromatography method, and the like. A method for producing a vinyl group-containing cage-type silsesquioxane derivative represented by the following general formula (III).

[In the general formula (I), R ¹ represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms. R ² independently represents an alkyl group having 1 to 8 carbon atoms.
In the general formula (II), R ³ independently represents an alkyl group having 1 to 8 carbon atoms.
In the general formula (III), R ¹ represents the same alkyl group having 1 to 8 carbon atoms or the aryl group having 6 to 14 carbon atoms as in the general formula (I). ] The method for producing a vinyl group-containing cage-type silsesquioxane derivative according to claim 1, wherein the reaction step comprises treating the product with an acid. Formula and alkoxysilane represented by (I), 80 and a vinyl alkoxysilane represented by the general formula (II) in a molar ratio: 20 to 50: reacted with 50, according to claim 1 or 2 A method for producing a cage-type silsesquioxane derivative containing a vinyl group. The method for producing a vinyl group-containing cage-type silsesquioxane derivative according to any one of claims 1 to 3 , wherein the chromatography method is a liquid normal phase. The method for producing a vinyl group-containing cage-type silsesquioxane derivative according to any one of claims 1 to 4 , wherein the developing solvent used in the chromatography method is an organic solvent containing hexane. A bifunctional cage-type silsesquioxane derivative represented by the following general formula (1).

[In the general formula (1), R ¹ represents an alkyl group having a linear or branched chain, a cycloalkyl group, or an aryl group, and six R ^1s are partially or all even if they are all the same. It may be different, where X represents a single bond and Y is an alkylene group having a linear or branched chain having 1 to 25 carbon atoms, a cycloalkylene group having 3 to 25 carbon atoms, or an arylene having 6 to 25 carbon atoms. represents a group, a group represented by the two _{-X-CH 2 -CH 2 -S-} Y-OH can be the same as each other or may be different. ] A bifunctional cage-type silsesquioxane derivative represented by the following general formula (1) by reacting a silicon compound represented by the following general formula (2) with a thiol compound represented by the following general formula (3). A method for producing a bifunctional cage-type silsesquioxane derivative, which comprises a step of producing the same.

[In the general formula (2), R ¹ represents an alkyl group having a linear or branched chain, a cycloalkyl group, or an aryl group, and six R ^1s are partially or all even if they are all the same. may be different, X is, to table a single bond. ]

[In the general formula (3), Y represents an alkylene group having a linear or branched chain having 1 to 25 carbon atoms, a cycloalkylene group having 3 to 25 carbon atoms, or an arylene group having 6 to 25 carbon atoms. ]

[In the general formula (1), R ¹ represents an alkyl group having a linear or branched chain, a cycloalkyl group, or an aryl group, and six R ^1s are partially or all even if they are all the same. It may be different, where X represents a single bond and Y is an alkylene group having a linear or branched chain having 1 to 25 carbon atoms, a cycloalkylene group having 3 to 25 carbon atoms, or an arylene having 6 to 25 carbon atoms. represents a group, a group represented by the two _{-X-CH 2 -CH 2 -S-} Y-OH can be the same as each other or may be different. ]

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