JP2018172499A - Bifunctional cage silsesquioxane derivative and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bifunctional cage silsesquioxane derivative having two functional groups each having a trimethoxysilyl group.SOLUTION: The present invention provides a bifunctional cage silsesquioxane derivative represented by a formula (1) [R's independently represent a divalent organic group; X is a single bond or a divalent organic group; two groups represented by -X-CH-CH-S-Y-Si-(O-CH)may be the same or different].SELECTED DRAWING: Figure 7

Description

  One embodiment of the present invention relates to a bifunctional cage silsesquioxane derivative and a method for producing the same.

  In recent years, silsesquioxane compounds have organic and inorganic units in their structures, and various functional groups can be introduced. Therefore, they have attracted attention as organic-inorganic hybrid materials, and many studies have been reported. Has been. It is known that the structure includes a random structure without a specific structure, a ladder structure that can determine the structure, and a cage structure. In particular, silsesquioxane having a cage structure has attracted attention as a semiconductor or an electronic material because it has excellent characteristics such as heat resistance, electrical insulation, and transparency.

  The cage silsesquioxane compound is composed of eight Si and is called T8. In this T8, all eight substituents on Si are converted to reactive substituents, ie 8-substituted T8, or one is converted to another reactive substituent, ie monosubstituted X-T8. A number of derivatives having different substituents have been commercialized.

In addition, among T8, a derivative in which two on Si are converted to other reactive substituents, that is, disubstituted 2X-T8, can accurately introduce silsesquioxane into the polymer main chain. Expected to be a polymer with characteristics that are not present.
Non-Patent Document 1 proposes 2X-T8 synthesized with aminopropyltrialkoxysilane and having two aminopropyl groups introduced at the p-position.
Non-patent document 2 proposes 2X-T8 synthesized using trichlorovinylsilane and having two vinyl groups introduced at the p-position.
Aminopropyltrialkoxysilane and trichlorovinylsilane used in Non-Patent Documents 1 and 2 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 glass coating or the like.
Furthermore, it is impossible to introduce a functional group that does not exist as a trialkoxysilane compound or a trichlorosilane compound.

Chemistry Letters, (2014), 43, 1532-1534. Polymer Chemistry, (2015), 6,7500-7504.

  An object of one embodiment of the present invention is to provide a bifunctional cage-type silsesquioxane derivative in which two functional groups having a novel trimethoxysilyl group are introduced, and a method for producing the same.

［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−Ｓｉ−（Ｏ−ＣＨ_３）_３で表される基は、互いに同一であっても、異なってもよい。］ The gist of the present invention is as follows.
[1] A bifunctional cage-type silsesquioxane derivative represented by the following general formula (1).

[In General Formula (1), R ¹ represents a linear or branched alkyl group, cycloalkyl group, or aryl group, and all six R ^{1 s} may be the same or a part or all of them. 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; 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- S—Y—Si— (O—CH ₃ ) ₃ may be the same as 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。］ [2] including a step of producing a bifunctional cage silsesquioxane derivative 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.

[In General Formula (2), R ¹ represents a linear or branched alkyl group, cycloalkyl group, or aryl group, and all six R ^{1 s} may be the same or a part or all of them. X may represent a single bond, an alkylene group having a straight 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 groups represented by —X—CH═CH ₂ may be the same as or different from each other. ]

[In 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, it is possible to provide a bifunctional cage-type silsesquioxane derivative in which two functional groups having a trimethoxysilyl group are introduced, and a method for producing the same.

The figure which shows each fraction division | segmentation of the manufacture example 1. FIG. The MALDI-TOF MS measurement result of each fraction of Production Example 1. ¹ H NMR spectrum of bisvinyl POSS in each fraction of Production Example 1. ¹³ C NMR spectrum of bisvinyl POSS in each fraction of Production Example 1. ²⁹ Si NMR spectrum of bisvinyl POSS in each fraction of Production Example 1. Regioisomer of bisvinyl POSS. The MALDI-TOF MS measurement result of Example 1. ¹ H NMR spectrum of production example 1 bisvinyl POSS. ¹ H NMR spectrum of Example 1. ¹³ C NMR spectrum of bisvinyl POSS of Production Example 1. ¹³ C NMR spectrum of Example 1. The ²⁹ Si NMR spectrum of the bis vinyl POSS of manufacture example 1. ²⁹ Si NMR spectrum of Example 1.

Hereinafter, although one Embodiment of this invention is described, this invention is not limited by the following illustrations.
"Bifunctional cage-type silsesquioxane derivatives"
A bifunctional cage-type silsesquioxane derivative according to an embodiment is represented by the following general formula (1).

In the general formula (1), R ¹ represents a linear or branched alkyl group, cycloalkyl group, or aryl group, and the six R ^{1 s} may be the same or partially or completely 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 Represents an alkylene group having a straight chain 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 ₂ The groups represented by —S—Y—Si— (O—CH ₃ ) ₃ may be the same as or different from each other.

The bifunctional cage-type silsesquioxane derivative includes a cage-type silsesquioxane skeleton, and a functional group having reactivity is introduced into two of eight Si. In the compound represented by the general formula (1), the group represented by —R ¹ is non-reactive, and —X—CH ₂ —CH ₂ —S—Y—Si— (O—CH ₃ ) ₃ The represented group becomes reactive. Thereby, a bifunctional cage silsesquioxane derivative into which two functional groups having a methoxysilyl group are introduced can be provided.

The alkyl group represented by R ¹ preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and may have a linear or branched chain.
The cycloalkyl group represented by R ¹ preferably has 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms. Within this carbon number range, the cycloalkyl group may have a linear or branched alkyl group bonded to at least one carbon atom forming the carbocyclic ring.
The aryl group represented by R ¹ preferably has 6 to 14 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 8 carbon atoms. Within this carbon number range, the aryl group may have a linear or branched alkyl group bonded to at least one carbon atom forming the carbocyclic ring.
Examples of R ¹ include a methyl group, an ethyl group, an isobutyl group, a cyclohexyl group, an isooctyl group, and a phenyl group.
R ¹ is preferably an alkyl group having 1 to 12 carbon atoms or a phenyl group, and more preferably an alkyl group having 1 to 8 carbon atoms or a phenyl group.

In the general formula (1), all six R ^{1 s} may be the same or part or all different. All six R ¹ are preferably the same.

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, more preferably 3 to 6 carbon atoms. Within this carbon number range, the cycloalkylene group may have a linear or branched alkyl group bonded to at least one carbon atom forming the carbocyclic ring.
The arylene group represented by X preferably has 6 to 14 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 8 carbon atoms. Within this carbon number range, the arylene group may have a linear or branched alkyl group bonded to at least one carbon atom forming the carbocyclic ring.
Examples of X include a single bond, methylene group, ethylene group, n-propylene group, i-propylene group, n-butylene group, i-butylene group, sec-butylene group, t-butylene group, hexylene group and 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 or an alkylene group having 1 to 3 carbon atoms, and even more preferably a single bond.

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, more preferably 3 to 8 carbon atoms. Within this carbon number range, the cycloalkylene group may have a linear or branched alkyl group bonded to at least one carbon atom forming the carbocyclic ring.
The arylene group represented by Y preferably has 6 to 25 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 8 carbon atoms. Within this carbon number range, the arylene group may have a linear or branched alkyl group bonded to at least one carbon atom forming the carbocyclic 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, i- Examples include octylene group, 2-ethylhexylene group, 3-ethylhexylene group, 2-methylpentylene group, cyclohexylene group, and phenylene group.
Y is preferably an alkylene group having 1 to 25 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms.

In the general formula (1), two groups represented by —X—CH ₂ —CH ₂ —S—Y—Si— (O—CH ₃ ) ₃ may be the same as or different from each other. . The two groups represented by —X—CH ₂ —CH ₂ —S—Y—Si— (O—CH ₃ ) ₃ are preferably the same as each other.

In the general formula _{(1), -X-CH 2} -CH 2 -S-Y-Si- (O-CH 3) to the two silicon atoms of the eight silicon atoms constituting the silsesquioxane skeleton ₃ Are bonded, and R ¹ is bonded to the other six silicon atoms.
The position at which the group represented by —X—CH ₂ —CH ₂ —S—Y—Si— (O—CH ₃ ) ₃ is introduced into the silsesquioxane skeleton is not particularly limited, but is the same as the benzene ring. If a proper naming convention is applied, for example, it may be introduced into two adjacent Sis through one oxygen atom (o-position), or introduced into two Sis through an oxygen atom-Si-oxygen atom. It may be introduced (m-position), or may be introduced into two Sis located diagonally to each other (p-position). The compound represented by the general formula (1) may have any structure among these three types. Moreover, the compound containing at least 1 type of structure among 3 types, or the mixture containing 2 or more types of structures may be sufficient.

"Production method of bifunctional cage silsesquioxane derivative"
Hereinafter, an example of a method for producing the bifunctional cage silsesquioxane derivative represented by the general formula (1) will be described. In addition, the bifunctional cage-type silsesquioxane derivative represented by the general formula (1) is not limited to those manufactured by the following manufacturing method.
As a manufacturing method of the bifunctional cage-type silsesquioxane derivative represented by General formula (1), the process manufactured using the silicon compound represented by following General formula (2) is included, for example.
Furthermore, it is preferable that this manufacturing method includes the process manufactured using the thiol compound represented by following General formula (3).
Preferably, the method includes a step of producing a bifunctional cage silsesquioxane derivative by reacting the silicon compound represented by the general formula (2) with the thiol compound represented by the general formula (3).

In the general formula (2), R ¹ represents a linear or branched alkyl group, cycloalkyl group, or aryl group, and the six R ^{1 s} may be all the same or partially or completely different X represents 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, Two groups represented by —X—CH═CH ₂ may be the same as 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 details are as described in the general formula (1).
X in the general formula (2) is a group introduced as X in the compound represented by the general formula (1), and details are as described in the general formula (1).

  As the silicon compound represented by the general formula (2), a compound represented by the following general formula (III) in which X is a single bond can be preferably used.

In the general formula (2), 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 bonding a thiol compound having a trimethoxysilyl group to this silicon compound by a thiolene reaction, two trimethoxysilyl 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 General Formula (3), Y represents a C1-C25 linear or branched alkylene group, a C3-C25 cycloalkylene group, or a C6-C25 arylene group.
Y in the general formula (3) is a group introduced as Y in the compound represented by the general formula (1), and details are as described in the general formula (1).

A radical initiator may be used in the reaction between the silicon compound represented by the general formula (2) and the thiol compound represented by the general formula (3).
The radical initiator is not particularly limited, and any of known thermal polymerization initiators and photopolymerization initiators 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, methyl ethyl ketone peroxide, and tertiary butyl peroxybenzoate; azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate, and azobiscyanovaleric acid Are preferably used, preferably azobisisobutyronitrile (AIBN).
Specific examples of the photopolymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, Triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropyl Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-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-trimethylpentylphosphine oxide, 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 preferably 0.1 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the compound represented by the general formula (2). is there.

The reaction between the silicon compound represented by the general formula (2) and the thiol compound represented by the general formula (3) is preferably performed in a solvent.
Although there is no restriction | limiting in particular in a solvent, It can select arbitrarily according to the solubility of the silicon compound represented by General formula (2), the thiol compound represented by General formula (3), and a 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, Examples include acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene, and ethyl acetate is preferable. These may be used alone or in combination of two or more.

Although reaction temperature changes with the polymerization initiator and solvent to be used, 40-90 degreeC is preferable from the reaction rate of thiol-ene reaction, and 60-80 degreeC is more preferable.
The structure of the bifunctional cage silsesquioxane derivative represented by the general formula (1) can be confirmed by a nuclear magnetic resonance apparatus (NMR) and / or mass spectrometry (MS).

"Method for producing vinyl-containing cage silsesquioxane derivatives"
Hereinafter, with respect to an example of the silicon compound represented by the general formula (2), a vinyl group-containing cage silsesquioxane derivative represented by the following general formula (III) in which X is a single bond in the general formula (2) Will be described.

In general formula (III), R ¹ represents a linear or branched alkyl group, cycloalkyl group, or aryl group, and six R ^{1 s} may be all the same, or partially or completely different May be.
R ¹ in the general formula (III) 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).

The compound represented by the general formula (III) represents disubstituted vinyl-T8. T8 is composed of eight Sis and is a generic name for highly symmetrical cage silsesquioxanes. Disubstitution means that two of the organic groups bonded to Si are two reactive substituents. In the case of the general formula (III), the reactive substituent is a vinyl group. The organic group is the same as R ¹ derived from alkoxysilane represented by the general formula (I) described later.
In addition, as for the position where the vinyl group is bonded, if the same naming rule as that of the benzene ring is applied, the o-position where the vinyl group is in two Si via one oxygen, oxygen-Si-oxygen via There are three types, the m-position where the vinyl group exists in the two Si, and the p-position which is a diagonal position. Each structure is shown in FIG. The compound represented by the general formula (III) may have any structure among these three types. Moreover, the compound containing at least 1 type of structure among 3 types, or the mixture containing 2 or more types of structures may be sufficient.

An example of a method for producing the compound represented by the general formula (III) will be described.
The compound represented by the general formula (III) can be obtained, for example, by reacting an alkylalkoxysilane and vinylalkoxysilane.
Specifically, an alkoxysilane represented by the following general formula (I), a vinylalkoxysilane represented by the following general formula (II), and a basic compound are reacted in the presence of water, and the reaction product is chromatographed. A compound represented by the general formula (III) can be obtained by separation and purification by a graphic method.

  In the said method, at least 1 sort (s) can be used among the alkoxysilanes represented with the following general formula (I).

In general formula (I), R ¹ represents a linear or branched alkyl group, cycloalkyl group, or aryl group, and R ² each independently represents an alkyl group.
R ¹ in the general formula (I) is a group introduced as R ^{1 in the} compound represented by the general formula (III), and further, as R ^{1 in the} compound represented by the general formula (1), The group to be introduced. The details are as described in the general formula (1).

In the general formula (I), R ² represents an alkyl group independently, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
The alkyl groups represented by R ² may each independently have a linear or branched chain, and may be acyclic or cyclic.
Examples of R ² include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, hexyl group, octyl group, 2 -An ethylhexyl group, 3-ethylhexyl group, etc. can be mentioned.
Among these, R ² is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, from the viewpoint of controlling reactivity.

As the compound represented by the general formula (I), for example, alkylalkoxysilanes such as isobutyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane can be used.
These may be used alone or in combination of two or more.
By synthesizing a compound represented by the general formula (III) using one of the alkylalkoxysilanes, a compound having the same R ¹ in the general formula (III) can be obtained.
By synthesizing a compound represented by the general formula (III) using two or more alkylalkoxysilanes having different R ¹ , a compound in which R ¹ is partially or entirely different in the general formula (III) can be obtained. it can.

  In the said method, at least 1 sort (s) can be used among the vinyl alkoxysilanes represented with the following general formula (II).

In the general formula (II), R ³ represents an alkyl group independently, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl groups represented by R ³ may each independently have a straight chain or branched chain, and may be acyclic or cyclic.
Examples of R ³ include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, hexyl group, octyl group, 2 -An ethylhexyl group, 3-ethylhexyl group, etc. can be mentioned. Among these, R ³ is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, from the viewpoint of controlling reactivity.

  As the compound represented by the general formula (II), for example, vinyl alkoxysilane such as vinyltrimethoxysilane can be used.

  In the above method, as the basic compound, a compound represented by the following general formula (IV) can be used.

  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 (OH) is preferable from the viewpoint of reactivity control and yield. Alkali metal hydroxides with slightly reduced basicity or nucleophilicity show good selectivity, and Si at the base of the reactive substituent X is preferentially eliminated. Among these, Li hydroxide has the lowest basicity and nucleophilicity, and is advantageous for obtaining a thermodynamically stable product according to the charging ratio of the silane raw material.

The reaction between the alkoxysilane represented by the general formula (I) and the vinylalkoxysilane represented by the general formula (III) is preferably performed in a solvent.
There is no particular limitation on the medium, but the alkoxysilane represented by the general formula (I) and the vinylalkoxysilane represented by the general formula (II) are highly compatible. On the other hand, a solvent having low compatibility with M (OH) of the general formula (IV), and in which M (OH) remains in the system without being dissolved when mixed is preferable. A uniformly dispersed silane feed is advantageous in providing a thermodynamically stable product. In addition, it is advantageous to give a thermodynamically stable product when the M (OH) concentration is constant at a low concentration in the system during the reaction.
Moreover, reaction can be advanced in water presence by adding water to a solvent. What is necessary is just to add water at 5-15 mass parts with respect to 100 mass parts in total of the alkoxysilane represented by general formula (I), and the vinyl alkoxysilane represented by general formula (III).

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

As described above, the medium for carrying out the synthesis is preferably a medium having low solubility in LiOH and compatible with the silane raw material and water. Specifically, a mixed solvent of methanol and acetone is preferable. At this time, the mixing ratio is not particularly limited.
Moreover, there is no restriction | limiting in particular in the temperature when implementing synthesis | combination. However, from the viewpoint of shortening the reaction time, 30 to 56 ° C is preferable, and 40 to 55 ° C is more preferable.

  A chromatographic method may be used as a method for separating and purifying disubstituted vinyl-T8 from the product after the reaction. The chromatography method is preferably normal phase liquid chromatography using a column having silica particles as a filler. By using normal phase liquid chromatography, the produced T8, monosubstituted vinyl-T8, and trisubstituted vinyl-T8 are slightly different in the polarization state of the molecules, and therefore can be sequentially discharged. Moreover, 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.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” is based on mass.

<Production Example 1>
In a 500 mL three-necked flask, 300 mL of acetone, 40 mL of methanol, and 5.60 mL of purified water were added, and a nitrogen atmosphere was provided with a Dimroth cooler, a thermometer, and a dropping funnel. 7.00 g of LiOH monohydrate was added as a basic compound, and the mixture was heated with an oil bath to 55 ° C. with stirring. In the dropping funnel, 49.00 g of isobutyltrimethoxysilane as an alkoxysilane represented by the general formula (I) and 13.56 g of vinyltrimethoxysilane as a vinylalkoxysilane represented by the general formula (II) were weighed, and 50 Slowly dropped over a period of minutes. After the dropwise addition, the liquid temperature was adjusted to 50 ° C., and the mixture was heated and stirred in a nitrogen atmosphere for 18 hours. After heating, the oil bath was removed and the mixture was allowed to cool to room temperature (25 ° C.). When 150 mL of 1N HCl solution was added, it became 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 with 100 mL of acetonitrile three times, 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 dried under reduced pressure with an oil pump to obtain 34.64 g of a white viscous product.

The resulting white viscous product was purified by fractionation.
For preparative purification using an intermediate pressure column, “LC-forte / R” manufactured by YMC Co., Ltd., and “Universal Column Premium (2L)” manufactured by Yamazen Corporation were used. Preparative conditions were 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 to the top of the column. While monitoring the outflow RI detection, each fraction was divided into outflow times as shown in FIG. 1, and for each fraction, the solvent was distilled off with an evaporator and dried under reduced pressure with an oil pump to obtain white crystals from each fraction. Table 1 shows the mass of white crystals obtained from each fraction.

MALDI-TOF MS analysis was performed on 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 observed values of white crystals obtained from each fraction and calculated values of vinyl POSS, bisvinyl POSS, and trisvinyl POSS. Fraction 2 was vinyl POSS, fraction 3 was the desired 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.

フラクション２のビニルＰＯＳＳの結果と比較すると、ビスビニルＰＯＳＳは２種のビニル基を持つことが分かる。

Compared with the results of the vinyl POSS of fraction 2, it can be seen that bisvinyl POSS has two types of vinyl groups.

<Example 1>
In a 20 mL three-necked flask equipped with a Dimroth cooler, thermometer, and nitrogen pipe, divinylhexaisobutyl POSS (POSS: cage oligosilsesquioxane; in general formula (2), R ¹ is an isobutyl group, X is a single bond; 1.0 g of fraction 3 bisvinyl POSS produced by the production method of Production Example 1; 4.0 mL of ethyl acetate (manufactured by Gordo Co., Ltd.); 0 of AIBN (azobisisobutyronitrile, Nihon Finechem Co., Ltd.) 0.009 g was added, and the mixture was stirred using a magnetic stirrer while bubbling nitrogen at room temperature (25 ° C.) for 15 to 20 minutes.
Next, while carrying out nitrogen bubbling on this three-necked flask, the liquid temperature was heated to 40 ° C. in an oil bath, and then (3-mercaptopropyl) trimethoxysilane (HS— (CH 2) 3 — (CH 3 O) 3; In the general formula (3), 0.54 mL of Y is a propyl group (manufactured by Shin-Etsu Chemical Co., Ltd.) was weighed and dropped into a gas tight syringe. After the addition, the reaction mixture was heated to 76 to 78 ° C. and stirred for 4 hours under reflux conditions. 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. The obtained white solid was washed with 20 mL of acetonitrile, The mixture was filtered using 5C filter paper and dried under reduced pressure using a rotary evaporator to obtain 0.30 g of white crystals (yield: 37%).

  The obtained white crystals were dissolved in THF (tetrahydrofuran; manufactured by Wako Pure Chemical Industries, Ltd.), and subjected to gel permeation chromatography (GPC) using “Chromamaster” manufactured by Hitachi High-Technologies Corporation. The white crystals had a weight average molecular weight (Mw) in terms of polystyrene of 1140 and a number average molecular weight (Mn) of 1132, 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 result is shown in FIG. A peak of Na ⁺ adduct was observed in the circled portion of FIG. Table 3 shows the observed value of Na ⁺ adduct of the obtained white crystals (MALDI-TOF MS result) and the calculated value (Exact Mass) of hexaisobutyl-2 [(3-trimethoxysilylpropyl) thio] ethyl POSS. . The observed value of the Na ⁺ adduct is larger by the atomic weight of Na (22.99). As a result, the obtained white crystals were confirmed to be hexaisobutyl-2 [(3-trimethoxysilylpropyl) thio] ethyl POSS.

For structural identification for hexa isobutyl-2 [(3-trimethoxysilyl propyl) thio] ethyl POSS, to dissolve the resulting white crystals CDCl _3, using a Bruker ^"Avance300", 1 ^{H, 13} C and ²⁹ Si NMR were measured.
The measurement conditions are as follows.
⁽¹ H NMR)
Observation nucleus: ¹ H
Resonance frequency: 300 MHz
Measurement temperature: 25 ° C
Reference substance: Tetramethylsilane ( ¹³ C NMR)
Observation nucleus: ¹³ C
Resonance frequency: 75 MHz
Measurement temperature: 25 ° C
Reference substance: Tetramethylsilane ( ²⁹ Si NMR)
Observation nucleus: ²⁹ Si
Resonance frequency: 60 MHz
Measurement temperature: 25 ° C
Reference substance: Tetramethylsilane

Of the measurement results of ¹ H, ¹³ C and ²⁹ Si NMR of bisvinyl POSS of Production Example 1, the peak portion derived from the vinyl group is shown in FIGS. 8, 10, and 12.
The measurement results of ¹ H, ¹³ C and ²⁹ Si NMR of hexaisobutyl-2 [(3-trimethoxysilylpropyl) thio] ethyl POSS of Example 1 are shown in FIG. 9, FIG. 11 and FIG. 13, respectively.
^{From the 1} H NMR chart, the peak (FIG. 8) derived from the vinyl group of the raw material bisvinyl POSS confirmed at around 6 ppm disappears, and in the ¹ H NMR chart after the reaction shown in FIG. A peak around .6 ppm was confirmed.
^{From the 13} C NMR chart, it was confirmed that 129.7 ppm derived from the vinyl group of the raw material bisvinyl POSS and peaks near 136.0 ppm (FIG. 10) disappeared. In the ¹³ C NMR chart after the reaction shown in FIG. A new peak derived from a methoxy group was confirmed at 50.5 ppm.
^{Also from the 29} Si NMR chart, a peak around −81.5 ppm (FIG. 12) derived from the vinyl group of the raw material bisvinyl POSS disappeared, and in the ²⁹ Si NMR chart after the reaction shown in FIG. A new peak in the vicinity of −42.4 ppm was confirmed.

The structure of the white crystal synthesized as described above was confirmed to be represented by the following general formula (4).

Claims (2)

A bifunctional cage silsesquioxane derivative represented by the following general formula (1).

[In General Formula (1), R ¹ represents a linear or branched alkyl group, cycloalkyl group, or aryl group, and all six R ^{1 s} may be the same or a part or all of them. 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; 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- S—Y—Si— (O—CH ₃ ) ₃ may be the same as or different from each other. ] A bifunctional cage comprising a step of producing a bifunctional cage silsesquioxane derivative by reacting a silicon compound represented by the following general formula (2) with a thiol compound represented by the following general formula (3) For producing a type silsesquioxane derivative.

[In General Formula (2), R ¹ represents a linear or branched alkyl group, cycloalkyl group, or aryl group, and all six R ^{1 s} may be the same or a part or all of them. X may represent a single bond, an alkylene group having a straight 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 groups represented by —X—CH═CH ₂ may be the same as or different from each other. ]

[In 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. ]

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