JP2008063228A - Process for producing cage silsesquioxane having alkoxy group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for simply producing a cage silsesquioxane, particularly T-8 silsesquioxane of n=8 with high selectivity. <P>SOLUTION: The process for preparing a cage silsesquioxane having an alkoxy group comprises reacting one equivalent of a cage silsesquioxane having an Si-H bond with 30-40 equivalents of an alcohol at 20-30°C in the presence of a solvent and a base. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a cage silsesquioxane having an alkoxy group.

Silsesquioxane is a compound represented by the general formula (RSiO _3/2 ) _n and can be obtained by hydrolysis and polycondensation reaction of trifunctional silane. This silsesquioxane has a random structure, a ladder-like structure, a cage-like structure, an incomplete cage-like structure, and the like. Among these, ladder-shaped and cage-shaped silsesquioxanes have a clear molecular structure. Therefore, by using these as building blocks of a polymer, the structure of the polymer at the molecular level can be controlled. Polymers obtained using these compounds as building blocks have been reported to have advantages such as high mechanical strength and high heat resistance, and are expected to be highly functional materials.

  In recent years, cage silsesquioxane having an alkoxy group is said to have an optimum reaction rate when polymerizing and the like, and can be efficiently produced as a polymer, and is used as a low dielectric material and a low density material. There is a lot of research being conducted as possible.

The production method of the cage silsesquioxane includes a method of synthesizing by hydrolysis / polycondensation reaction of trifunctional silane (RSiX ₃ ) or tetrafunctional silane (SiX ₄ ), and an incomplete cage silsesquioxane, A method of synthesis by reaction with trichlorosilane is known. However, each method has a complicated reaction process, and it takes a long time to produce a low yield. Therefore, various synthesis methods have been studied to solve this problem.

For example, Patent Document 1 proposes a method for producing a cage silsesquioxane by reacting (SiO _3/2 ) ₈ H ₈ with a branched siloxane in the presence of a Karstedt catalyst.

Patent Document 2 proposes a method of producing a cage silsesquioxane by reacting alcohol or hydroxyarene in the presence of a transition metal, and Patent Document 3 polymerizes cyclic tetrasiloxane. Has proposed a method for producing a cage silsesquioxane.
Journal of Organometallic Chemistry 521 (1996) 391-393. JP 2001-48890 A Japanese Patent Application Laid-Open No. 2004-292643

  The method for producing a cage silsesquioxane described in Patent Document 1 can easily produce only a cage silsesquioxane. However, it is necessary to heat to 100 to 120 ° C., and there is a case in which danger is accompanied when mass synthesis is performed. In addition, the method for producing a cage silsesquioxane described in Patent Document 2 has a problem that it takes a long time and has a low yield compared to the method for producing a cage silsesquioxane described in Patent Document 1. .

  Furthermore, in the method for producing a cage silsesquioxane described in Patent Document 3, it is necessary to produce a cyclic tetrasiloxane as a precursor of a cage silsesquioxane, but it is possible to produce a cyclic tetrasiloxane. There is a problem that it is difficult to easily produce a cage silsesquioxane.

  The present invention has been made in view of the problems as described above, and the object thereof is to provide a cage-like silsesquioxane, in particular, an n = 8 T-8 silsesquioxane having an alkoxy group with high selectivity. It is to provide a method of manufacturing.

The present inventors have made extensive studies to solve the above problems. As a result, a cage silsesquioxane whose substituent is hydrogen (hereinafter referred to as “T ₈ ^H ”) is reacted easily at 20-30 ° C. in the presence of a solvent, an alcohol and a base, thereby having an alkoxy group. The present inventors have found that a cage silsesquioxane can be produced and have completed the present invention. More specifically, the present invention provides the following.

(1) Production of a cage silsesquioxane having an alkoxy group for producing a cage silsesquioxane represented by the following general formula (2) from a cage silsesquioxane represented by the following general formula (1) In the method, an alkoxy group for reacting 1 equivalent of the above-mentioned cage silsesquioxane represented by the following general formula (1) with 30 to 40 equivalents of alcohol or silanol at 20 to 30 ° C. in the presence of a solvent and a base. The manufacturing method of the cage silsesquioxane which has.

According to the manufacturing method of (1), since it can be made to react at the temperature close | similar to room temperature of 20-30 degreeC, it becomes possible to manufacture a cage silsesquioxane simply compared with the conventional method. . Further, T ₈ ^H, since it is possible to use those which are commercially available, can be produced a cage silsesquioxane having an alkoxy group only in one step. The synthesis time, yield and the like can be controlled by appropriately adjusting the amounts of alcohol, solvent and base.

Further, relative to 1 equivalent of T ₈ ^H, is reacted with 30-40 equivalents of alcohol, it is possible to shorten the reaction time and can improve the yield.

  (2) The cage silsesquioxane having the alkoxy group according to (1), wherein the cage silsesquioxane represented by the general formula (1) is reacted in the presence of a solvent, an alcohol and a base for 2 to 5 hours. Manufacturing method.

  According to the production method (2), silsesquioxane having an alkoxy group can be produced with high yield and high selectivity by reacting for 2 to 5 hours.

  (3) The cage silsesqui having an alkoxy group according to (1) or (2), wherein the alcohol is a primary alcohol, a secondary alcohol, a tertiary alcohol, or a silanol having 2 to 8 carbon atoms. Oxane production method.

  According to the production method (3), a cage silsesquioxane having an alkoxy group having 2 to 8 carbon atoms can be produced. Further, the alkoxy group is not limited to a straight chain, and may be a branched alkoxy group. Moreover, it is not limited to alcohol, Even if it is a silanol, it can manufacture easily.

  (4) The solvent is a cage silsesquioxane having an alkoxy group according to any one of (1) to (3), which is at least one solvent selected from the group consisting of benzene, toluene, and tetrahydrofuran. Production method.

According to the production method of (4), the solvent is not particularly limited as long as T ₈ ^H can be dissolved.

  (5) The method for producing a cage silsesquioxane having an alkoxy group according to any one of (1) to (4), wherein the pH of the base is 7 to 10.

  According to the production method of (5), the use of a weak base having a pH of 7 to 10 not only accelerates the reaction as a catalyst, but also decomposes a cage-like silsesquioxane having an alkoxy group produced. Can be prevented.

  (6) The method for producing a cage silsesquioxane having an alkoxy group according to any one of (1) to (5), wherein the base is diethylhydroxyamine.

  According to the production method (6), silsesquioxane having an alkoxy group can be produced with high yield and high selectivity by using diethylhydroxyamine which is a weak base.

  According to the method for producing a cage silsesquioxane having an alkoxy group of the present invention, a cage silsesquioxane having an alkoxy group can be produced in only one step without going through a complicated reaction route. Thereby, it became possible to produce a cage silsesquioxane having an alkoxy group with high yield and high selectivity.

The method for producing a cage silsesquioxane having an alkoxy group according to the present invention comprises reacting a cage silsesquioxane represented by the general formula (1) at 20 to 30 ° C. in the presence of a solvent, an alcohol and a base. A cage silsesquioxane having an alkoxy group represented by the general formula (2) is produced. Hereinafter, embodiments of the method for producing a cage silsesquioxane having an alkoxy group of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and within the scope of the object of the present invention, Changes can be made as appropriate.

The method for producing a cage silsesquioxane having an alkoxy group according to the present invention is a scheme represented by the following general formula (3), wherein T ₈ ^H is reacted with alcohol at 20 to 30 ° C. in the presence of a solvent and a base. Then, a cage silsesquioxane having an alkoxy group represented by the general formula (2) is produced (hereinafter referred to as “Q ₈ ^R ”). “R” in Q ₈ ^R refers to “R” in formula (2). Silanol may be used instead of alcohol.

Alcohol (ROH) reacts with T ₈ ^H to produce Q ₈ ^R. In the conventional method, the alcohol is mixed with 8 equivalents of alcohol with respect to 1 equivalent of T ₈ ^H. However, according to the present invention, 30 to 40 equivalents of alcohol are mixed according to the results of earnest research by the inventors. It was found that the reaction can be promoted and the yield can be improved. Therefore, it is preferable to mix 30 to 40 equivalents of alcohol with respect to 1 equivalent of T ₈ ^H. When the alcohol is less than 30 equivalents with respect to 1 equivalent of T ₈ ^H , the reaction rate becomes slow, and it becomes difficult to proceed the reaction at 20 to 30 ° C. Therefore, it is necessary to heat the reaction to complete the reaction in a short time, and there is a case where there is a danger in mass synthesis. On the other hand, even if the alcohol exceeds 40 equivalents with respect to 1 equivalent of T ₈ ^H , the reaction does not become faster, and the treatment after the completion of the reaction becomes complicated.

  The alcohol used in the present invention is, for example, linear 1 having 2 to 8 carbon atoms such as ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol and the like. Examples include secondary alcohols having 2 to 8 carbon atoms such as secondary alcohol, 2-propanol (isopropyl alcohol), cyclohexyl alcohol, etc., tertiary alcohols having 2 to 8 carbon atoms such as tertiary butyl alcohol, and trimethylsilanol. Among these, ethanol, 1-octanol, isopropyl alcohol, cyclohexyl alcohol, tertiary butyl alcohol, and trimethylsilanol are preferably used.

In addition, the type of the solvent used in the present invention is not particularly limited as long as T ₈ ^H can be dissolved. As a solvent that easily dissolves T ₈ ^H , it is preferable to use, for example, a polar solvent such as benzene, toluene, tetrahydrofuran, etc. These may be used alone or in combination.

The base used in the present invention is preferably a weak base having a pH of 7 to 10, more preferably a weak base having a pH of 7.5 to 8.5. Not only can the reaction be promoted as a catalyst, but also decomposition of the produced Q ₈ ^R can be prevented. If the pH is less than 7, the reaction cannot be promoted as a catalyst, and the reaction time tends to be long. On the other hand, when the pH exceeds _{10, Q} ^{8 R} obtained from _T ^{8 H} is decomposed.

  As described above, the base used in the present invention is not particularly limited as long as the pH is 7 to 10, but for example, hydroxyamines having a long carbon chain such as diethylhydroxyamine and dipropylhydroxyamine are known. These various bases can be used, and these may be used alone or in combination.

By reacting T ₈ ^H with the alcohol as described above in the presence of the solvent and the base as described above, Q ₈ ^R can be produced with high yield and high selectivity. The reaction time can be appropriately changed depending on the type of “R” of Q ₈ ^R , but it is preferably 2 to 5 hours. By setting the reaction time to 2 to 5 hours, Q ₈ ^R can be produced with high yield and high selectivity. When the reaction time exceeds 5 hours, the peak of A in FIG. 1 increases and the peak of Q ₈ ^R (B in FIG. 1) decreases and the selectivity of Q ₈ ^R increases as shown in FIG. The fall yield also decreases. In addition to Q ₈ ^R , the peak of A in FIG. 1 also appears as a feature of the method for producing a cage silsesquioxane having an alkoxy group of the present invention. The peak A in FIG. 1 needs to be further studied, but is considered to be a Q ₈ ^R polymer. Therefore, when the isolated Q ₈ ^R is used after polymerization or the like, only the polymer of Q ₈ ^R (A in FIG. 1) may be produced by lengthening the reaction time. Thus, it is possible to omit the step of polymerizing the Q ₈ ^R, easily and quickly and at a lower dielectric material, it is possible to produce a polymer which can be a low density material Q ₈ ^R. The GPC chart in FIG. 1 is obtained by measuring the refractive index at a flow rate of 1.0 mL / min and a temperature of 33 ^° C. using tetrahydrofuran as an eluent.

In addition, by reacting T ₈ ^H with the alcohol as described above in the presence of the solvent and the base as described above, it is not necessary to react at a high temperature as in the prior art, and the reaction can be performed at 20 to 30 ° C. become. When the reaction temperature is less than 20 ° C., the reaction rate becomes slow and the reaction time takes. In addition, in order to shorten reaction time, such as when "R" of alcohol is bulky, it can also heat suitably as needed.

  Examples of the present invention will be described below. However, these examples are merely examples for suitably explaining the present invention, and do not limit the present invention.

[Synthesis of T ₈ ^H ]
A 3L four-necked flask was attached with an Allen cooler, a gas introduction tube and a stir bar and dried, 1500 mL of hexane (1st grade manufactured by Wako Pure Chemical Industries), 350 mL of toluene (1st grade manufactured by Wako Pure Chemical Industries), 125 mL of methanol, Trichlorosilane (Shin-Etsu Chemical Co., Ltd.) added to 75 mL of iron (III) chloride (1st grade manufactured by Wako Pure Chemical Industries, Ltd.) and 74.4 g of 37% hydrochloric acid (1st grade manufactured by Wako Pure Chemical Industries, Ltd.) and placed in a 100 mL bironal flask while stirring 83 g (0.613 mo1) (manufactured by Kogyo Co., Ltd.) was blown from the gas introduction tube together with nitrogen over 5 hours.

After completion of the blowing, the mixture was stirred for 1 hour, iron (III) chloride was filtered through a glass filter, the aqueous layer was removed with a separatory funnel, 46 g of potassium carbonate (1st grade manufactured by Wako Pure Chemical Industries), calcium chloride (Wako Pure) 31 g of Yakuhin Kogyo grade 1) was added and stirred overnight. After potassium carbonate and calcium chloride were filtered off, the solvent was distilled off until the solution reached about 120 mL, and the precipitated white powder was filtered through a glass filter. The obtained filtrate was washed with hexane and dried under reduced pressure to obtain a white powder of T ₈ ^H (yield 23%).

[Manufacture of Q ₈ ^Et ]
In a 100 mL eggplant type flask, 0.5 g (1.16 × 10 ⁻³ mol) of T ₈ ^H , 50 mL of benzene, 1.76 g (3.83 × 10 ⁻² mol) of ethanol and 85% aqueous solution of diethylhydroxyamine (sum) 1 μL of Kojunyaku Kogyo Co., Ltd. grade 1) was mixed and stirred at 25 ° C. for 4 hours. After stirring, the solvent and the like were removed, and the residue was dissolved in tetrahydrofuran (1st grade manufactured by Wako Pure Chemical Industries) and fractionated by GPC. The GPC chart was as shown in FIG. The yield was 54%.

GPC used a system including an LC-6AD type liquid feed pump manufactured by Shimadzu Corporation and a RID-10A type differential refractive index detector. Tetrahydrofuran was used as an eluent, and a column of PLgel 10μ 100Å manufactured by Polymer Science at a flow rate of 1.0 mL / min and a temperature of 33 ^° C. was used.

Identification of Q ₈ ^Et is referred to as nuclear magnetic resonance (ECP500 type manufactured by JEOL) (hereinafter referred to as “NMR”), infrared absorption spectrum (FT / IR-6100 type manufactured by JASCO) (hereinafter referred to as “IR”). ), Elemental analysis (CHNOS type manufactured by PerkinElmer), differential thermal analysis (hereinafter referred to as “DTA”), and thermogravimetric analysis (TG-DTA2020S manufactured by Mac Science) (hereinafter referred to as “TG”). The speed was set at 10 ° C./min. NMR was measured as a deuterated chloroform solution (grade 1 manufactured by Wako Pure Chemical Industries, Ltd.). The chemical shift was based on tetramethylsilane (grade 1 manufactured by Wako Pure Chemical Industries, Ltd.), and IR was measured by the carbon tetrachloride solution method.

²⁹ SiNMR confirmed a sharp signal at −103 ppm, indicating that the cage structure was retained. Further, IR was found to have broad absorption at 1080 cm ⁻¹ and have a siloxane bond.

[Production of Q ₈ ^Oct ]
In a 100 mL eggplant-shaped flask, 0.5 g (1.16 × 10 ⁻³ mol) of T ₈ ^H , 50 mL of benzene, 4.98 g (3.83 × 10 ⁻² mol) of octanol, and 85% aqueous solution of diethylhydroxyamine (sum) 1 μL of Kojunyaku Kogyo Co., Ltd. grade 1) was mixed and stirred at 25 ° C. for 4 hours. After stirring, the solvent and the like were removed, and the residue was dissolved in tetrahydrofuran and fractionated by GPC. The GPC chart was as shown in FIG. The yield was 80%.

GPC used a system including an LC-6AD type liquid feed pump manufactured by Shimadzu Corporation and a RID-10A type differential refractive index detector. Tetrahydrofuran was used as an eluent, and a column of PLgel 10μ 100Å manufactured by Polymer Science at a flow rate of 1.0 mL / min and a temperature of 33 ^° C. was used.

Q ₈ ^Oct was identified by NMR, IR, elemental analysis, DTA and TG. ²⁹ SiNMR confirmed a sharp signal at −103 ppm, indicating that the cage structure was retained. Further, IR was found to have broad absorption at 1080 cm ⁻¹ and have a siloxane bond.

[Production of Q ₈ ^i-Pr ]
In a 100 mL eggplant type flask, 0.5 g (1.16 × 10 ⁻³ mol) of T ₈ ^H , 50 mL of benzene, 2.30 g (3.83 × 10 ⁻² mol) of ² -propanol and 85% aqueous solution of diethylhydroxyamine 1 μL of Wako Pure Chemical Industries grade 1 was mixed and stirred at 25 ° C. for 4 hours. After stirring, the solvent and the like were removed, and the residue was dissolved in tetrahydrofuran and fractionated by GPC. The GPC chart was as shown in FIG. The yield was 87%.

GPC used a system including an LC-6AD type liquid feed pump manufactured by Shimadzu Corporation and a RID-10A type differential refractive index detector. Tetrahydrofuran was used as an eluent, and a column of PLgel 10μ 100Å manufactured by Polymer Science at a flow rate of 1.0 mL / min and a temperature of 33 ^° C. was used.

Q ₈ ^i-Pr was identified by NMR, IR, elemental analysis, DTA and TG. ²⁹ SiNMR confirmed a sharp signal at −104 ppm, indicating that the cage structure was retained. Further, IR was found to have a broad absorption at 1070 cm ⁻¹ and have a siloxane bond.

[Production of Q ₈ ^t-Bu ]
In a 100 mL eggplant type flask, 0.5 g (1.16 × 10 ⁻³ mol) of T ₈ ^H , 50 mL of benzene, 2.83 g (3.83 × 10 ⁻² mol) of ethanol, and 85% aqueous solution of diethylhydroxyamine (sum) 1 μL of 1st grade manufactured by Kojun Pharmaceutical Co., Ltd. was mixed and stirred at 70 ° C. for 10 hours. After stirring, the solvent and the like were removed, and the residue was dissolved in tetrahydrofuran and fractionated by GPC. The GPC chart was as shown in FIG. The yield was 83%.

GPC used a system including an LC-6AD type liquid feed pump manufactured by Shimadzu Corporation and a RID-10A type differential refractive index detector. Tetrahydrofuran was used as an eluent, and a column of PLgel 10μ 100Å manufactured by Polymer Science at a flow rate of 1.0 mL / min and a temperature of 33 ^° C. was used.

Q ₈ ^t-Bu was identified by NMR, IR, elemental analysis, DTA and TG. ²⁹ Si NMR confirmed a sharp signal at −108 ppm, indicating that the cage structure was retained. Further, IR was found to have broad absorption at 1080 cm ⁻¹ and have a siloxane bond.

[Production of Q ₈ ^Cy ]
In a 100 mL eggplant-shaped flask, 0.5 g (1.16 × 10 ⁻³ mol) of T ₈ ^H , 50 mL of benzene, 3.83 g (3.83 × 10 ⁻² mol) of cyclohexanol and 85% aqueous solution of diethylhydroxyamine ( 1 μL of Wako Pure Chemical Industries grade 1) was mixed and stirred at 25 ° C. for 4 hours. After stirring, the solvent and the like were removed, and the residue was dissolved in tetrahydrofuran and fractionated by GPC. The GPC chart was as shown in FIG. The yield was 80%.

GPC used a system including an LC-6AD type liquid feed pump manufactured by Shimadzu Corporation and a RID-10A type differential refractive index detector. Tetrahydrofuran was used as an eluent, and a column of PLgel 10μ 100Å manufactured by Polymer Science at a flow rate of 1.0 mL / min and a temperature of 33 ^° C. was used.

Q ₈ ^Cy was identified by NMR, IR, elemental analysis, DTA and TG. ²⁹ SiNMR confirmed a sharp signal at −104 ppm, indicating that the cage structure was retained. Further, IR was found to have broad absorption at 1080 cm ⁻¹ and have a siloxane bond.

[Manufacturing of Q ₈ ^TMS ]
In a 100 mL eggplant-shaped flask, 0.5 g (1.16 × 10 ⁻³ mol) of T ₈ ^H , 50 mL of benzene, 3.45 g (3.83 × 10 ⁻² mol) of trimethylsilanol and 85% aqueous solution of diethylhydroxyamine ( 1 μL of Wako Pure Chemical Industries grade 1) was mixed and stirred at 25 ° C. for 10 hours. After stirring, the solvent and the like were removed, and the residue was dissolved in tetrahydrofuran and fractionated by GPC. The GPC chart was as shown in FIG. The yield was 54%.

GPC used a system including an LC-6AD type liquid feed pump manufactured by Shimadzu Corporation and a RID-10A type differential refractive index detector. Tetrahydrofuran was used as an eluent, and a column of PLgel 10μ 100Å manufactured by Polymer Science at a flow rate of 1.0 mL / min and a temperature of 33 ^° C. was used.

Q ₈ ^TMS was identified by NMR, IR, elemental analysis, DTA and TG. ^{In 29} SiNMR, sharp signals were confirmed at 13 ppm and −109 ppm, and it was found that the cage structure was retained.

FIGS. 2 and 3 show the TG and DTA of the above-described Q ₈ ^Et , Q ₈ ^Oct , Q ₈ ^i-Pr , Q ₈ ^t-Bu , Q ₈ ^Cy , and Q ₈ ^TMS . From Figures 2 and ^{_{3, Q 8 TMS, Q 8}} Et, Q 8 Cy, Q 8 i-Pr, Q 8 Oct, it can be seen that there is a heat resistance in the order of ^{Q 8 t-Bu.}

Table 1 summarizes the alcohols, reaction times, reaction temperatures, etc. used for Q ₈ ^Et , Q ₈ ^Oct , Q ₈ ^i-Pr , Q ₈ ^t-Bu , Q ₈ ^Cy and Q ₈ ^TMS described above. .

From Table 1, it can be seen that it can be reacted with a bulky alcohol such as tertiary butyl alcohol or trimethylsilanol, and a silsesquioxane having a bulky alkoxy group can be easily produced. It can also be seen that Q ₈ ^R can be produced with high yield and high selectivity.

It is a GPC chart after reaction completion. Q 8 Et, Q 8 Oct, a diagram showing a TG of Q 8 i over Pr, Q 8 t-Bu, Q 8 Cy, Q 8 TMS. Q 8 Et, Q 8 Oct, illustrates the DTA of Q 8 i over Pr, Q 8 t-Bu, Q 8 Cy, Q 8 TMS.

Claims (6)

In the method for producing a cage silsesquioxane having an alkoxy group for producing a cage silsesquioxane represented by the following general formula (2) from a cage silsesquioxane represented by the following general formula (1):
In the presence of a solvent and a base, the cage-like silsesquioxane represented by the following general formula (1) and a cage having an alkoxy group for reacting 30 to 40 equivalents of alcohol or silanol at 20 to 30 ° C A method for producing silsesquioxane.

  The production of a cage silsesquioxane having an alkoxy group according to claim 1, wherein the cage silsesquioxane represented by the general formula (1) is reacted in the presence of a solvent, an alcohol and a base for 2 to 5 hours. Method.   The method for producing a cage silsesquioxane having an alkoxy group according to claim 1 or 2, wherein the alcohol is a primary alcohol, secondary alcohol, tertiary alcohol or silanol having 2 to 8 carbon atoms. .   The method for producing a cage silsesquioxane having an alkoxy group according to any one of claims 1 to 3, wherein the solvent is at least one solvent selected from the group consisting of benzene, toluene, and tetrahydrofuran.   The method for producing a cage silsesquioxane having an alkoxy group according to any one of claims 1 to 4, wherein the pH of the base is 7 to 10. The method for producing a cage silsesquioxane having an alkoxy group according to any one of claims 1 to 5, wherein the base is diethylhydroxyamine.

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