JP7219434B2 - Method for producing cyclic siloxane compound, cyclic siloxane compound, composition, and heat-resistant material - Google Patents

Description

The present invention relates to a method for producing a cyclic siloxane compound, a cyclic siloxane compound, a composition, and a heat-resistant material.

Siloxane compounds represented by polysiloxane are functional chemicals and materials that are used in various industrial fields such as construction, electricity, automobiles, medical care, and daily necessities in the form of oils, rubbers, resins, etc. . In order to improve the functionality and performance of such siloxane compounds, there are methods for efficiently producing compounds having a cyclic siloxane structure with excellent thermal stability, etc., and methods for producing cyclic compounds with higher functionality and performance. Development of siloxane compounds is also an important issue.

Cyclic tetramer (cyclotetrasiloxane), which is one of the representative compounds among cyclic siloxane compounds, is an eight-membered ring compound containing four silicon atoms. Compounds having substituents such as groups, hydrogen atoms, etc. are known. Specific examples of general methods for producing cyclic siloxane compounds include (A) a method of hydrolyzing chlorosilanes (e.g., Patent Documents 1 and 2, Non-Patent Documents 1 and 2), and (B) chlorosilanes and Examples thereof include a method of reacting silanols in the presence of a base (for example, Patent Document 3, Non-Patent Documents 3 and 4).

On the other hand, a compound having a structure in which diagonal silicon atoms of cyclotetrasiloxane are bonded with oxysilyleneoxy groups is a bicyclic pentamer having five silicon atoms, bicyclo[3.3.3]pentasiloxane and having two cyclotetrasiloxane skeletons in the molecule, it is expected to have physical properties such as thermal stability superior to those of simple cyclotetrasiloxane compounds. As such a bicyclic pentamer compound, a compound having a substituent such as a phenyl group or a methyl group is known. (e.g., Patent Document 4, Non-Patent Documents 4 and 5), and (D) reaction of bicyclic oligosilane bicyclo[1.1.1]pentasilane with an oxidizing agent (m-chloroperbenzoic acid). A method (Non-Patent Literature 6) and the like have been reported.

Japanese Patent Publication No. 63-28893 JP-A-07-285974 JP-A-08-157487 U.S. Pat. No. 3,145,225

Chemistry of Organosilicon Compounds, p.206, Kagaku Dojin (1972) Organosilicon Chemistry, p.48,Walter de Gruyter (1986) Silicon,6,21(2014) J. Gen. Chem. USSR, 54, 306 (1984) Z. Anorg. Allg. Chem., 636, 1212 (2010) Chem. Commun., 54, 268 (2018)

However, in the above-described conventional production methods (A), (B), and (C), since chlorosilanes are used as raw materials, hydrolysis of the chlorosilanes tends to produce hydrogen chloride, which has a corrosive action. Not easy to handle. In addition, when the chlorosilanes are used for the reaction, hydrogen chloride and its salts are produced, and special attention must be paid to storage of raw materials, reaction vessels, disposal of wastes, and the like. Furthermore, in the above-mentioned conventional production method (D), when a bicyclic oligosilane is used as a raw material, the silicon-bonded substituent is limited to bulky ones, and the production of the raw material compound is not easy. There is a problem that an expensive oxidizing agent is required. That is, there is a demand for an efficient method for producing cyclic siloxane compounds.

The present invention has been made in view of the above circumstances, an efficient method for producing a cyclic siloxane compound, a novel cyclic siloxane compound obtained by the method for producing, a composition containing the compound, and An object of the present invention is to provide a heat-resistant material containing the composition.

As a result of intensive studies aimed at solving the above problems, the present inventors have found that by continuously reacting an acyloxysilane having 3 or 4 acyloxy groups with a silanol having 2 hydroxy groups, , and found that a cyclic siloxane compound can be produced efficiently, leading to the completion of the present invention.

（式（IIIＡ）中、ａ、ｂ、ｃ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、およびＲ⁶は、式（IＡ）、式（IIＡ１）、式（IIＡ２）における、ａ、ｂ、ｃ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、およびＲ⁶と同義である。）
［３］
前記アシロキシシランが、式（IＡ）で表されるアシロキシシランであり、
前記シラノールが、式（IIＡ１）、式（IIＡ２）、および式（IIＡ３）で表されるシラノールであり、
前記環状シロキサン化合物が、式（IＶＡ１）および／または（IＶＡ２）で表される化合物であり、
前記連続的に反応させる工程が、式（IIＡ１）で表されるシラノールを添加する工程１；前記工程１の後に、式（IIＡ２）で表されるシラノールを添加する工程２；および、前記工程２の後に、式（IIＡ３）で表されるシラノールを添加する工程３；を含む、［１］に記載の環状シロキサン化合物の製造方法。
Ｒ¹ _aＳｉ（ＯＣＯＲ²）_4-a （IＡ）
（式（IＡ）中、Ｒ¹は、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、Ｒ²は、炭素数１～３のアルキル基であり、ａは、０または１である。Ｒ¹およびＲ²の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）；
ＨＯ（ＳｉＲ³Ｒ⁴Ｏ）_bＨ （IIＡ１）
（式（IIＡ１）中、Ｒ³およびＲ⁴は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、ｂは、１～６の整数である。Ｒ³およびＲ⁴の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）；
ＨＯ（ＳｉＲ⁵Ｒ⁶Ｏ）_cＨ （IIＡ２）
（式（IIＡ２）中、Ｒ⁵およびＲ⁶は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、ｃは、１～６の整数である。Ｒ⁵およびＲ⁶の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）；
ＨＯ（ＳｉＲ⁷Ｒ⁸Ｏ）_dＨ （IIＡ３）
（式（IIＡ３）中、Ｒ⁷およびＲ⁸は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、ｄは、１～６の整数である。Ｒ⁷およびＲ⁸の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）；

（式（IＶＡ１）、式（IＶＡ２）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、ａ、ｂ、ｃ、およびｄは、式（IＡ）、式（IIＡ１）、式（IIＡ２）、式（IIＡ３）における、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、ａ、ｂ、ｃ、およびｄと同義である。）
［４］
前記環状シロキサン化合物にアシロキシ基が残存している場合、当該環状シロキサン化合物に水または式（ＶIＡ）で表されるアルコールを反応させて、残存するアシロキシ基の少なくとも１つを、ヒドロキシ基またはアルコキシ基に変換する修飾工程をさらに含み、
前記アルコキシ基が、－ＯＲ⁹基（Ｒ⁹は、式（ＶIＡ）中のＲ⁹と同義である。）で表される、［１］～［３］のいずれかに記載の環状シロキサン化合物の製造方法。
Ｒ⁹ＯＨ （ＶIＡ）
（式（ＶIＡ）中、Ｒ⁹は、アルキル基、アリール基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基である。Ｒ⁹の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）
［５］
前記環状シロキサン化合物にアシロキシ基が残存している場合、当該環状シロキサン化合物に式（IIＡ４）で表されるシラノールを反応させて、残存するアシロキシ基の少なくとも１つを、シロキシ基に変換する修飾工程をさらに含み、
前記シロキシ基が、－ＯＳｉＲ¹⁰Ｒ¹¹Ｒ¹²基（Ｒ¹⁰、Ｒ¹¹、およびＲ¹²はそれぞれ、式（IIＡ４）中のＲ¹⁰、Ｒ¹¹、およびＲ¹²と同義である。）で表される、［１］～［３］のいずれかに記載の環状シロキサン化合物の製造方法。
Ｒ¹⁰Ｒ¹¹Ｒ¹²ＳｉＯＨ （IIＡ４）
（式（IIＡ４）中、Ｒ¹⁰、Ｒ¹¹、およびＲ¹²は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基である。Ｒ¹⁰、Ｒ¹¹、およびＲ¹²の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）
［６］
式（IＶＡ１）で表される環状シロキサン化合物と、式（IIＡ５）で表されるシラノールとを反応させる工程を含む、式（ＶＡ１）で表される環状シロキサン化合物の製造方法。

（式（IＶＡ１）中、Ｒ¹、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、およびＲ⁸は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、Ｒ²は、炭素数１～３のアルキル基であり、ａは、０であり、ｂ、ｃ、およびｄは、それぞれ独立に、１～６の整数である。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、およびＲ⁸の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）；
ＨＯ（ＳｉＲ¹³Ｒ¹⁴Ｏ）_eＨ （IIＡ５）
（式（IIＡ５）中、Ｒ¹³およびＲ¹⁴は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、ｅは、１～１０００の整数である。Ｒ¹³およびＲ¹⁴の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）；

（式（ＶＡ１）中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹³、Ｒ¹⁴、ｂ、ｃ、ｄ、およびｅはそれぞれ、式（IＶＡ１）および式（IIＡ５）におけるＲ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹³、Ｒ¹⁴、ｂ、ｃ、ｄ、およびｅと同義である。ｖは、１以上１００００以下の整数であり、末端のシリル基に結合している基は、アシロキシ基、ヒドロキシ基、またはアルコキシ基である。）
［７］
式（IＶＡ１）で表される環状シロキサン化合物と、式（IIＡ６）で表されるシラノールとを反応させる工程を含む、式（ＶＡ２）で表される環状シロキサン化合物の製造方法。

（式（IＶＡ１）中、Ｒ¹、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、およびＲ⁸は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、Ｒ²は、炭素数１～３のアルキル基であり、ａは、０であり、ｂ、ｃ、およびｄは、それぞれ独立に、１～６の整数である。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、およびＲ⁸の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）；

（式（IIＡ６）中、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、およびＲ²⁰は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、ｆ、ｇ、およびｈは、それぞれ独立に、１～６の整数である。Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、およびＲ²⁰の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）；

（式（ＶＡ２）中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈはそれぞれ、式（IＶＡ１）および式（IIＡ６）におけるＲ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈと同義である。ｗは、１以上１００００以下の整数であり、末端のシリル基に結合している基は、アシロキシ基、ヒドロキシ基、またはアルコキシ基である。）
［８］
前記式（IＶＡ１）で表される環状シロキサン化合物と、式（IIＡ６）で表されるシラノールとを反応させる工程において、式（IIＡ４）で表されるシラノールおよび／または式（IＡ２）で表されるアシロキシシランを添加し、式（ＶＡ３）、式（ＶＡ４）、および式（ＶＡ５）からなる群より選択される少なくとも１つの環状シロキサン化合物を得る、［７］に記載の製造方法。
Ｒ¹⁰Ｒ¹¹Ｒ¹²ＳｉＯＨ （IIＡ４）
（式（IIＡ４）中、Ｒ¹⁰、Ｒ¹¹、およびＲ¹²は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基である。Ｒ¹⁰、Ｒ¹¹、およびＲ¹²の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）；
Ｒ²¹Ｒ²²Ｒ²³ＳｉＯＣＯＲ²⁴ （IＡ２）
（式（IＡ２）中、Ｒ²¹、Ｒ²²、およびＲ²³は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、Ｒ²⁴は、炭素数１～３のアルキル基である。Ｒ²¹、Ｒ²²、およびＲ²³の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。）；

（式（ＶＡ３）中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈは、式（IＶＡ１）、式（IIＡ６）、および式（IIＡ４）におけるＲ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈと同義である。ｗ１は、１以上１００００以下の整数である。）；

（式（ＶＡ４）中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈは、式（IＶＡ１）、式（IIＡ６）、および式（IＡ２）におけるＲ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈと同義である。ｗ２は、１以上１００００以下の整数である。）；

（式（ＶＡ５）中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈは、式（IＶＡ１）、式（IIＡ６）、式（IIＡ４）、および式（IＡ２）におけるＲ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈと同義である。ｗ３は、０以上１００００以下の整数である。）
［９］
式（IIIＢ）、式（IＶＢ１）、式（IＶＢ２）、式（ＶＢ１）、式（ＶＢ２）、式（ＶＢ３）、または式（ＶＢ４）で表される、環状シロキサン化合物。

（式（IIIＢ）中、Ｒ^a1は、炭素数２～３のアルケニル基であり、Ｒ^a2、Ｒ^a3、Ｒ^a4、およびＲ^a5は、それぞれ独立に、炭素数１～６のアルキル基または炭素数６～１０のアリール基であり、Ｘ¹は、アセトキシ基、ヒドロキシ基、炭素数１～６のアルコキシ基、または炭素数３～２０のシロキシ基であり、ｉは、０または１であり、ｊ１およびｊ２は、それぞれ独立に、１～６の整数である。）；

（式（IＶＢ１）および式（IＶＢ２）中、Ｒ^a6、Ｒ^a7、Ｒ^a8、Ｒ^a9、Ｒ^a10、およびＲ^a11は、それぞれ独立に、炭素数１～６のアルキル基または炭素数６～１０のアリール基であり、Ｘ²は、アセトキシ基、ヒドロキシ基、炭素数１～６のアルコキシ基、または炭素数３～２０のシロキシ基であり、ｋ１、ｋ２、およびｋ３は、それぞれ独立に、１～６の整数である。）；

（式（ＶＢ１）中、Ｒ^a12、Ｒ^a13、Ｒ^a14、Ｒ^a15、Ｒ^a16、Ｒ^a17、Ｒ^a18、およびＲ^a19は、それぞれ独立に、炭素数１～６のアルキル基またはアリール基であり、ｌ１、ｌ２、ｌ３、およびｌ４は、それぞれ独立に、１～６の整数であり、ｘは、１以上１００００以下の整数であり、末端のシリル基に結合している基は、アセトキシ基、ヒドロキシ基、またはアルコキシ基である。）；

（式（ＶＢ２）中、Ｒ^a20、Ｒ^a21、Ｒ^a22、Ｒ^a23、Ｒ^a24、Ｒ^a25、Ｒ^a26、Ｒ^a27、Ｒ^a28、Ｒ^a29、Ｒ^a30、およびＲ^a31は、それぞれ独立に、炭素数１～６のアルキル基または炭素数６～１０のアリール基であり、ｍ１、ｍ２、ｍ３、ｍ４、ｍ５、およびｍ６は、それぞれ独立に、１～６の整数であり、ｙは、１以上１００００以下の整数であり、末端のシリル基に結合している基は、アセトキシ基、ヒドロキシ基、またはアルコキシ基である。）；

（式（ＶＢ３）中、Ｒ^a32、Ｒ^a33、Ｒ^a34、Ｒ^a35、Ｒ^a36、Ｒ^a37、Ｒ^a38、Ｒ^a39、Ｒ^a40、Ｒ^a41、Ｒ^a42、Ｒ^a43、Ｒ^a44、Ｒ^a45、およびＲ^a46は、それぞれ独立に、炭素数１～６のアルキル基または炭素数６～１０のアリール基であり、ｍ７、ｍ８、ｍ９、ｍ１０、ｍ１１、およびｍ１２は、それぞれ独立に、１～６の整数であり、ｙ１は、０以上１００００以下の整数である。）；

（式（ＶＢ４）中、Ｒ^a47、Ｒ^a48、Ｒ^a49、Ｒ^a50、Ｒ^a51、Ｒ^a52、Ｒ^a53、Ｒ^a54、Ｒ^a55、Ｒ^a56、Ｒ^a57、Ｒ^a58、Ｒ^a59、Ｒ^a60、Ｒ^a61、Ｒ^a62、Ｒ^a63、およびＲ^a64は、それぞれ独立に、炭素数１～６のアルキル基または炭素数６～１０のアリール基であり、ｍ１３、ｍ１４、ｍ１５、ｍ１６、ｍ１７、およびｍ１８は、それぞれ独立に、１～６の整数であり、ｙ２は、０以上１００００以下の整数である。）
［１０］
式（ＶＡ１）、式（ＶＡ２）、式（ＶＡ３）、式（ＶＡ４）、および式（ＶＡ５）からなる群より選択される少なくとも一つの環状シロキサン化合物を含む組成物。

（式（ＶＡ１）中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹³、およびＲ¹⁴は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、ｂ、ｃ、およびｄは、それぞれ独立に、１～６の整数であり、ｅは、１～１０００の整数である。Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹³、およびＲ¹⁴の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。ｖは、１以上１００００以下の整数であり、末端のシリル基に結合している基は、アシロキシ基、ヒドロキシ基、またはアルコキシ基である。）；

（式（ＶＡ２）中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、およびＲ²⁰は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈは、それぞれ独立に、１～６の整数である。Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、およびＲ²⁰の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。ｗは、１以上１００００以下の整数であり、末端のシリル基に結合している基は、アシロキシ基、ヒドロキシ基、またはアルコキシ基である。）；

（式（ＶＡ３）中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、およびＲ²⁰は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈは、それぞれ独立に、１～６の整数である。Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、およびＲ²⁰の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。ｗ１は、１以上１００００以下の整数である。）；

（式（ＶＡ４）中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、およびＲ²³は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈは、それぞれ独立に、１～６の整数である。Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、およびＲ²³の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。ｗ２は、１以上１００００以下の整数である。）；

（式（ＶＡ５）中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、およびＲ²³は、それぞれ独立に、アルキル基、アリール基、アルケニル基、およびアラルキル基からなる群より選ばれる炭素数１～１２の炭化水素基であり、ｂ、ｃ、ｄ、ｆ、ｇ、およびｈは、それぞれ独立に、１～６の整数である。Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、およびＲ²³の炭素原子に結合した水素原子は、反応に関与しない基で置換されていてもよい。ｗ３は、０以上１００００以下の整数である。）
［１１］
式（ＶＢ１）、式（ＶＢ２）、式（ＶＢ３）、および式（ＶＢ４）からなる群より選択される少なくとも一つの環状シロキサン化合物を含む組成物。

（式（ＶＢ１）中、Ｒ^a12、Ｒ^a13、Ｒ^a14、Ｒ^a15、Ｒ^a16、Ｒ^a17、Ｒ^a18、およびＲ^a19は、それぞれ独立に、炭素数１～６のアルキル基またはアリール基であり、ｌ１、ｌ２、ｌ３、およびｌ４は、それぞれ独立に、１～６の整数であり、ｘは、１以上１００００以下の整数であり、末端のシリル基に結合している基は、アセトキシ基、ヒドロキシ基、またはアルコキシ基である。）；

（式（ＶＢ２）中、Ｒ^a20、Ｒ^a21、Ｒ^a22、Ｒ^a23、Ｒ^a24、Ｒ^a25、Ｒ^a26、Ｒ^a27、Ｒ^a28、Ｒ^a29、Ｒ^a30、およびＲ^a31は、それぞれ独立に、炭素数１～６のアルキル基または炭素数６～１０のアリール基であり、ｍ１、ｍ２、ｍ３、ｍ４、ｍ５、およびｍ６は、それぞれ独立に、１～６の整数であり、ｙは、１以上１００００以下の整数であり、末端のシリル基に結合している基は、アセトキシ基、ヒドロキシ基、またはアルコキシ基である。）；

（式（ＶＢ３）中、Ｒ^a32、Ｒ^a33、Ｒ^a34、Ｒ^a35、Ｒ^a36、Ｒ^a37、Ｒ^a38、Ｒ^a39、Ｒ^a40、Ｒ^a41、Ｒ^a42、Ｒ^a43、Ｒ^a44、Ｒ^a45、およびＲ^a46は、それぞれ独立に、炭素数１～６のアルキル基または炭素数６～１０のアリール基であり、ｍ７、ｍ８、ｍ９、ｍ１０、ｍ１１、およびｍ１２は、それぞれ独立に、１～６の整数であり、ｙ１は、０以上１００００以下の整数である。）；

（式（ＶＢ４）中、Ｒ^a47、Ｒ^a48、Ｒ^a49、Ｒ^a50、Ｒ^a51、Ｒ^a52、Ｒ^a53、Ｒ^a54、Ｒ^a55、Ｒ^a56、Ｒ^a57、Ｒ^a58、Ｒ^a59、Ｒ^a60、Ｒ^a61、Ｒ^a62、Ｒ^a63、およびＲ^a64は、それぞれ独立に、炭素数１～６のアルキル基または炭素数６～１０のアリール基であり、ｍ１３、ｍ１４、ｍ１５、ｍ１６、ｍ１７、およびｍ１８は、それぞれ独立に、１～６の整数であり、ｙ２は、０以上１００００以下の整数である。）
［１２］
［１０］又は［１１］に記載の組成物を含む、耐熱性材料。 That is, this application provides the following inventions.
[1]
An acyloxysilane having 3 or 4 —OCOR groups (a plurality of Rs are each independently a monovalent hydrocarbon group) is successively treated with a silanol having 2 —OH groups. A method for producing a cyclic siloxane compound having a cyclic siloxane with a ring skeleton formed by -Si-O- bonds, comprising a step of reacting.
[2]
The acyloxysilane is an acyloxysilane represented by formula (IA),
The silanols are silanols represented by formulas (IIA1) and (IIA2),
The cyclic siloxane compound is a compound represented by formula (IIIA),
The step of continuously reacting comprises step 1 of adding a silanol represented by formula (IIA1); and step 2 of adding a silanol represented by formula (IIA2) after step 1; A method for producing a cyclic siloxane compound according to [1].
^{R1aSi (} _OCOR2 ) _4-a (IA)
(In formula (IA), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; R ² is a and a is 0 or 1. The hydrogen atoms bonded to the carbon atoms of R ¹ and R ² may be substituted with groups that do not participate in the reaction.);
HO ^{( SiR3R4O} ) _bH (IIA1)
(In formula (IIA1), R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and b is , an integer of 1 to 6. The hydrogen atoms bonded to the carbon atoms of R ³ and R ⁴ may be substituted with groups that do not participate in the reaction.);
HO ^{( SiR5R6O} ) _cH (IIA2)
(In formula (IIA2), R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and c is , an integer of 1 to 6. The hydrogen atoms bonded to the carbon atoms of R ⁵ and R ⁶ may be substituted with groups that do not participate in the reaction.);

(In formula (IIIA), a, b, c, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are a , b, c, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ .)
[3]
The acyloxysilane is an acyloxysilane represented by formula (IA),
The silanols are silanols represented by formulas (IIA1), (IIA2), and (IIA3),
The cyclic siloxane compound is a compound represented by formula (IVA1) and/or (IVA2),
The step of reacting continuously includes step 1 of adding a silanol represented by formula (IIA1); step 2 of adding a silanol represented by formula (IIA2) after step 1; and step 2. followed by step 3 of adding a silanol represented by formula (IIA3).
^{R1aSi (} _OCOR2 ) _4-a (IA)
(In formula (IA), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; R ² is a and a is 0 or 1. The hydrogen atoms bonded to the carbon atoms of R ¹ and R ² may be substituted with groups that do not participate in the reaction.);
HO ^{( SiR3R4O} ) _bH (IIA1)
(In formula (IIA1), R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and b is , an integer of 1 to 6. The hydrogen atoms bonded to the carbon atoms of R ³ and R ⁴ may be substituted with groups that do not participate in the reaction.);
HO ^{( SiR5R6O} ) _cH (IIA2)
(In formula (IIA2), R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and c is , an integer of 1 to 6. The hydrogen atoms bonded to the carbon atoms of R ⁵ and R ⁶ may be substituted with groups that do not participate in the reaction.);
HO ^{( SiR7R8O} ) _dH (IIA3)
(In formula (IIA3), R ⁷ and R ⁸ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and d is , an integer of 1 to 6. The hydrogen atoms bonded to the carbon atoms of R ⁷ and R ⁸ may be substituted with groups that do not participate in the reaction.);

(In formula (IVA1) and formula (IVA2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , a, b, c, and d are represented by formula (IA) , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , a, b, c, and d in formula (IIA1), formula (IIA2), and formula (IIA3) synonymous.)
[4]
When an acyloxy group remains in the cyclic siloxane compound, the cyclic siloxane compound is reacted with water or an alcohol represented by the formula (VIA) to replace at least one of the remaining acyloxy groups with a hydroxy group or an alkoxy group. further comprising a modification step of converting to
The cyclic siloxane compound according to any one of [1] to [3], wherein the alkoxy group is represented by -OR ⁹ group (R ⁹ has the same definition as R ⁹ in formula (VIA)). Production method.
^R9OH (VIA)
(In formula (VIA), R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, and an aralkyl group. The hydrogen atom bonded to the carbon atom of R ⁹ is It may be substituted with a group that does not participate in the reaction.)
[5]
A modification step of reacting the cyclic siloxane compound with a silanol represented by the formula (IIA4) to convert at least one of the remaining acyloxy groups into siloxy groups when the cyclic siloxane compound has residual acyloxy groups. further comprising
the siloxy group is represented by a —OSiR ¹⁰ R ¹¹ R ¹² group (R ¹⁰ , R ¹¹ and R ¹² have the same meanings as R ¹⁰ , R ¹¹ and R ¹² in Formula (IIA4)); A method for producing a cyclic siloxane compound according to any one of [1] to [3].
^{R10R11R12SiOH ( IIA4} )
(In formula (IIA4), R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; The hydrogen atoms bonded to the carbon atoms of R ¹⁰ , R ¹¹ and R ¹² may be substituted with groups that do not participate in the reaction.)
[6]
A method for producing a cyclic siloxane compound represented by formula (VA1), comprising a step of reacting a cyclic siloxane compound represented by formula (IVA1) with a silanol represented by formula (IIA5).

(In formula (IVA1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group. a selected hydrocarbon group having 1 to 12 carbon atoms, R ² is an alkyl group having 1 to 3 carbon atoms, a is 0, b, c, and d are each independently 1 to is an integer of 6. The hydrogen atoms bonded to the carbon atoms of ^{R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are substituted with groups that do not participate in the reaction. is also good.);
HO ^{( SiR13R14O} ) _eH (IIA5)
(In formula (IIA5), R ¹³ and R ¹⁴ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and e is , an integer of 1 to 1000. The hydrogen atoms bonded to the carbon atoms of R ¹³ and R ¹⁴ may be substituted with groups that do not participate in the reaction.);

(In formula (VA1), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹³ , R ¹⁴ , b, c, d, and e represent formula (IVA1) and formula (IIA5), respectively. ) is synonymous with R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹³ , R ¹⁴ , b, c, d and e in v is an integer of 1 or more and 10000 or less , the group attached to the terminal silyl group is an acyloxy group, a hydroxy group, or an alkoxy group.)
[7]
A method for producing a cyclic siloxane compound represented by formula (VA2), comprising a step of reacting a cyclic siloxane compound represented by formula (IVA1) with a silanol represented by formula (IIA6).

(In formula (IVA1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group. a selected hydrocarbon group having 1 to 12 carbon atoms, R ² is an alkyl group having 1 to 3 carbon atoms, a is 0, b, c, and d are each independently 1 to is an integer of 6. The hydrogen atoms bonded to the carbon atoms of ^{R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are substituted with groups that do not participate in the reaction. is also good.);

(In formula (IIA6), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a carbon selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group. a hydrocarbon group of numbers 1 to 12, f, g and h are each independently an integer of 1 to 6. R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ A hydrogen atom attached to a carbon atom may be substituted with a group that does not participate in the reaction.);

⁽ in formula (VA2), R ³ , R ⁴ , R 5 , R ⁶ , R ⁷ , R ⁸ , R ^{15 , R 16 ,} R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , b, c, d, f , g, and h are R ³ , R ⁴ , R ⁵ , R 6 , R ⁷ , R ⁸ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , ^{R 19 in} formula (IVA1) and formula (IIA6), respectively. , R ²⁰ , b, c, d, f, g, and h, w is an integer of 1 or more and 10000 or less, and the group bonded to the terminal silyl group is an acyloxy group or a hydroxy group. , or an alkoxy group.)
[8]
In the step of reacting the cyclic siloxane compound represented by the formula (IVA1) with the silanol represented by the formula (IIA6), the silanol represented by the formula (IIA4) and/or the silanol represented by the formula (IA2) The production method according to [7], wherein acyloxysilane is added to obtain at least one cyclic siloxane compound selected from the group consisting of formula (VA3), formula (VA4), and formula (VA5).
^{R10R11R12SiOH ( IIA4} )
(In formula (IIA4), R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; The hydrogen atoms bonded to the carbon atoms of R ¹⁰ , R ¹¹ and R ¹² may be substituted with groups that do not participate in the reaction.);
^{R21R22R23SiOCOR24 ( IA2 )}
(in formula (IA2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; and R ²⁴ is an alkyl group having 1 to 3 carbon atoms.The hydrogen atoms bonded to the carbon atoms of ^{R 21} , R ²² and R ²³ may be substituted with groups that do not participate in the reaction.) ;

(In formula (VA3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 10 , R 11 , R 12 , R 15 , R 16 , R 17 , R 18} , ^{R 19 ,} R ²⁰ , b, c, d, f, g, and h are R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , b, c, d, f, g, and h w1 is 1 or more and 10,000 is an integer below.);

(In formula (VA4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 15 , R 16 , R 17 , R 18} , R ¹⁹ , R ²⁰ , R ²¹ , ^{R 22 ,} R ²³ , b, c, d, f, g, and h are R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , b, c, d, f, g, and h w2 is 1 or more and 10,000 is an integer below.);

(In formula (VA5), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 10 , R 11 , R 12 , R 15 , R 16 , R 17 , R 18} , ^{R 19 ,} R ²⁰ , R ²¹ , R ²² , R ²³ , b, c, d, f, g, and h are R ³ , R in Formula (IVA1), Formula (IIA6), Formula (IIA4), and Formula (IA2) ⁴ , R5, ^{R6 , R7} , ^R8 , R10, R11, ^R12 , ^R15 , ^R16 , ^{R17 , R18} , ^R19 , ^R20 , ^R21 , ^R22 , ^{R23 ,} (synonymous with b, c, d, f, g, and h. w3 is an integer of 0 or more and 10,000 or less.)
[9]
A cyclic siloxane compound represented by formula (IIIB), formula (IVB1), formula (IVB2), formula (VB1), formula (VB2), formula (VB3), or formula (VB4).

(In formula (IIIB), R ^a1 is an alkenyl group having 2 to 3 carbon atoms, and R ^a2 , R ^a3 , R ^a4 , and R ^a5 are each independently an alkyl group having 1 to 6 carbon atoms or a carbon an aryl group having 6 to 10 numbers, X ¹ is an acetoxy group, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or a siloxy group having 3 to 20 carbon atoms, i is 0 or 1, j1 and j2 are each independently an integer of 1 to 6.);

(In formula (IVB1) and formula (IVB2), R ^a6 , R ^a7 , R ^a8 , R ^a9 , R ^a10 and R ^a11 are each independently an alkyl group having 1 to 6 carbon atoms or a X ² is an acetoxy group, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or a siloxy group having 3 to 20 carbon atoms, k1, k2, and k3 are each independently 1 is an integer of ~6.);

(in formula (VB1), R ^a12 , R ^a13 , R ^a14 , R ^a15 , R ^a16 , R ^a17 , R ^a18 , and R ^a19 are each independently an alkyl group or an aryl group having 1 to 6 carbon atoms; , l1, l2, l3, and l4 are each independently an integer of 1 to 6, x is an integer of 1 or more and 10000 or less, and the group bonded to the terminal silyl group is an acetoxy group, a hydroxy group or an alkoxy group);

(In formula (VB2), ^Ra20 , ^Ra21 , ^Ra22 , Ra23, ^Ra24 , ^Ra25 , ^Ra26 , ^Ra27 , ^Ra28 , ^{Ra29 , Ra30} , and ^Ra31 are each independently a carbon an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, m1, m2, m3, m4, m5, and m6 are each independently an integer of 1 to 6, and y is 1 or more It is an integer of 10000 or less, and the group bonded to the terminal silyl group is an acetoxy group, a hydroxy group, or an alkoxy group.);

(in formula (VB3), ^Ra32 , ^Ra33 , ^Ra34 , ^Ra35 , Ra36, ^Ra37 , ^Ra38 , ^Ra39 , ^Ra40 , ^Ra41 , ^Ra42 , ^Ra43 , ^Ra44 , ^Ra45 , ^and R ^a46 is each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m7, m8, m9, m10, m11, and m12 are each independently is an integer, and y1 is an integer of 0 or more and 10000 or less.);

(In formula (VB4) ^{, Ra47} , ^Ra48 , ^Ra49 , ^Ra50 , ^Ra51 , ^Ra52 , ^Ra53 , ^Ra54 , ^{Ra55, Ra56} , ^Ra57 , ^Ra58 , ^Ra59 , ^Ra60 , R ^a61 , R ^a62 , R ^a63 , and R ^a64 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m13, m14, m15, m16, m17, and m18 are , are each independently an integer of 1 to 6, and y2 is an integer of 0 or more and 10000 or less.)
[10]
A composition comprising at least one cyclic siloxane compound selected from the group consisting of formula (VA1), formula (VA2), formula (VA3), formula (VA4), and formula (VA5).

(In formula (VA1), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹³ , and R ¹⁴ are each independently selected from an alkyl group, an aryl group, an alkenyl group, and an aralkyl group. a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of b, c, and d each independently being an integer of 1 to 6, and e being an integer of 1 to 1,000 ^. , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹³ and R ¹⁴ may be substituted with groups that do not participate in the reaction, and v is 1 or more. It is an integer of 10000 or less, and the group bonded to the terminal silyl group is an acyloxy group, a hydroxy group, or an alkoxy group.);

(In formula (VA2), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent an alkyl a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of groups, aryl groups, alkenyl groups, and aralkyl groups, and b, c, d, f, g, and h each independently represent 1 to 6 The hydrogen atoms bonded to the carbon atoms of ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R15 , ^R16 , ^R17 , ^R18 , ^R19 , and ^R20 are , may be substituted with a group that does not participate in the reaction, w is an integer of 1 or more and 10000 or less, and the group bonded to the terminal silyl group is an acyloxy group, a hydroxy group, or an alkoxy group. );

(in formula (VA3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 10 , R 11 , R 12 , R 15 , R 16 , R 17 , R 18 ,} R ¹⁹ , and Each R ²⁰ is independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and b, c, d, f, g and h each independently represents an integer of 1 to 6. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R 10 , R ¹¹ , R ¹² , R ¹⁵ , R ¹⁶ , R ^{17 ,} Hydrogen atoms bonded to carbon atoms of R ¹⁸ , R ¹⁹ and R ²⁰ may be substituted with groups that do not participate in the reaction, w1 is an integer of 1 or more and 10000 or less);

(in formula (VA4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 15 , R 16 , R 17 , R 18 ,} R 19 , R ²⁰ , ^{R 21 ,} R ²² , and R ²³ is each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and b, c, d, f, g and h each independently represents an integer of 1 to 6. R ³ , R ^{4 ,} R ⁵ , R ⁶ , R ⁷ , R 8 , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , hydrogen atoms bonded to carbon atoms of R ²¹ , R ²² and R ²³ may be substituted with groups that do not participate in the reaction, w2 is an integer of 1 or more and 10000 or less);

(In formula (VA5), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 10 , R 11 , R 12 , R 15 , R 16 , R 17 , R 18} , ^{R 19 ,} R ²⁰ , R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; , d, f, g, and h are each independently an integer of 1 to 6. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² , Hydrogen atoms bonded to carbon atoms of R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ may be substituted with groups that do not participate in the reaction. w3 is an integer from 0 to 10000.)
[11]
A composition comprising at least one cyclic siloxane compound selected from the group consisting of formula (VB1), formula (VB2), formula (VB3), and formula (VB4).

(in formula (VB1), R ^a12 , R ^a13 , R ^a14 , R ^a15 , R ^a16 , R ^a17 , R ^a18 , and R ^a19 are each independently an alkyl group or an aryl group having 1 to 6 carbon atoms; , l1, l2, l3, and l4 are each independently an integer of 1 to 6, x is an integer of 1 or more and 10000 or less, and the group bonded to the terminal silyl group is an acetoxy group, a hydroxy group or an alkoxy group);

(In formula (VB2), ^Ra20 , ^Ra21 , ^Ra22 , Ra23, ^Ra24 , ^Ra25 , ^Ra26 , ^Ra27 , ^Ra28 , ^{Ra29 , Ra30} , and ^Ra31 are each independently a carbon an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, m1, m2, m3, m4, m5, and m6 are each independently an integer of 1 to 6, and y is 1 or more It is an integer of 10000 or less, and the group bonded to the terminal silyl group is an acetoxy group, a hydroxy group, or an alkoxy group.);

(in formula (VB3), ^Ra32 , ^Ra33 , ^Ra34 , ^Ra35 , Ra36, ^Ra37 , ^Ra38 , ^Ra39 , ^Ra40 , ^Ra41 , ^Ra42 , ^Ra43 , ^Ra44 , ^Ra45 , ^and R ^a46 is each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m7, m8, m9, m10, m11, and m12 are each independently is an integer, and y1 is an integer of 0 or more and 10000 or less.);

(In formula (VB4) ^{, Ra47} , ^Ra48 , ^Ra49 , ^Ra50 , ^Ra51 , ^Ra52 , ^Ra53 , ^Ra54 , ^{Ra55, Ra56} , ^Ra57 , ^Ra58 , ^Ra59 , ^Ra60 , R ^a61 , R ^a62 , R ^a63 , and R ^a64 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m13, m14, m15, m16, m17, and m18 are , are each independently an integer of 1 to 6, and y2 is an integer of 0 or more and 10000 or less.)
[12]
A heat-resistant material comprising the composition according to [10] or [11].

ADVANTAGE OF THE INVENTION According to this invention, the efficient manufacturing method of a cyclic siloxane compound, the novel cyclic siloxane compound obtained by the manufacturing method, the composition containing the compound, and the heat resistant material containing the composition can be provided. .

Although the present invention will be described in detail below, the present invention is not limited to this, and various modifications are possible without departing from the scope of the invention.

[Method for producing cyclic siloxane compound]
The production method of the present invention includes a step of continuously reacting an acyloxysilane having 3 or 4 —OCOR groups (hereinafter also referred to as acyloxy groups) with a silanol having 2 —OH groups. , and --Si--O-- bonds to produce a cyclic siloxane compound.
The number of cyclic siloxanes having a ring skeleton formed by —Si—O— bonds contained in the cyclic siloxane compound is not particularly limited as long as it is one or more.

The acyloxysilanes used in the present invention are silane compounds having 3 or 4 --OCOR groups, with 3 or 4 --OCOR groups on the silicon atom. When the acyloxysilane has three --OCOR groups, the remaining silicon-bonded substituent is any organic group. R in the —OCOR group is any monovalent hydrocarbon group, preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms.
As acyloxysilanes used in the present invention, acyloxysilanes represented by the formula (IA) are suitable.
^{R1aSi (} _OCOR2 ) _4-a (IA)
In formula (IA), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group;
R ² is an alkyl group having 1 to 3 carbon atoms,
a is 0 or 1;

The number of carbon atoms in R ¹ is preferably 1 to 10, more preferably 1 to 8, in the case of an alkyl group, and preferably 6 to 10, more preferably 6 to 8, in the case of an aryl group. and in the case of an alkenyl group, it is preferably 2 to 10, more preferably 2 to 8. Examples of alkyl groups include methyl, ethyl, propyl, butyl, and hexyl groups. Aryl groups include, for example, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of alkenyl groups include vinyl groups, propenyl groups, and hexenyl groups. Aralkyl groups include, for example, a benzyl group and a naphthylmethyl group.
The number of carbon atoms in R ² is preferably 1-2. Examples of R ² include a methyl group and an ethyl group.
The hydrogen atoms bonded to the carbon atoms of R ¹ and R ² may be substituted with groups that do not participate in the reaction. The number of substituents may be one or more, and all hydrogen atoms bonded to carbon atoms may be substituted.
Groups that do not participate in the reaction include, for example, chlorine atoms, fluorine atoms, and alkoxy groups.

Specific examples of acyloxysilanes represented by formula (IA) include methyltriacetoxysilane, ethyltriacetoxysilane, propyltriacetoxysilane, butyltriacetoxysilane, hexyltriacetoxysilane, decyltriacetoxysilane, phenyl triacetoxysilane, tolyltriacetoxysilane, naphthyltriacetoxysilane, vinyltriacetoxysilane, propenyltriacetoxysilane, benzyltriacetoxysilane, naphthyltriacetoxysilane, methyltris(trifluoroacetoxy)silane, tetraacetoxysilane.
In addition, the acyloxysilane represented by formula (IA) can be obtained as a commercial product.

The silanol used in the present invention is a silanol with two --OH groups and has two --OH groups on the silicon atom.
The silanols used in the present invention preferably include silanols represented by formulas (IIA1), (IIA2) and (IIA3).
HO ^{( SiR3R4O} ) _bH (IIA1)
HO ^{( SiR5R6O} ) _cH (IIA2)
HO ^{( SiR7R8O} ) _dH (IIA3)

In formulas (IIA1) to (IIA3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group. It is a selected hydrocarbon group having 1 to 12 carbon atoms, and b, c, and d are each independently an integer of 1 to 6.

The preferred number of carbon atoms and specific examples of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as those described for R ¹ in formula (IA) above.
Hydrogen atoms bonded to carbon atoms of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be substituted with groups that do not participate in the reaction. The number of substituents may be one or more, and all hydrogen atoms bonded to carbon atoms may be substituted. Groups that do not participate in the reaction include, for example, chlorine atoms, fluorine atoms, and alkoxy groups.
Also, b, c and d are each independently preferably 1 to 4, more preferably 1 to 3.
Specific examples of silanols represented by formulas (IIA1), (IIA2), and (IIA3) include dimethylsilanediol, diethylsilanediol, dipropylsilanediol, hexylmethylsilanediol, and methylphenylsilanediol. , diphenylsilanediol, ditolylsilanediol, tetramethyl-1,3-disiloxane-1,3-diol, tetraphenyl-1,3-disiloxane-1,3-diol, hexamethyl-1,3,5- trisiloxane-1,5-diol, octamethyl-1,3,5,7-tetrasiloxane-1,7-diol.

In the production method of the present invention, “continuously reacting silanols having two —OH groups” means that each —OH group in the silanol having two —OH groups and two molecules of acyloxy A stepwise reaction is carried out to form a -Si-O- bond between each Si of the silane and to react the product with at least one molecule of a silanol having two -OH groups. point to
A specific method for continuously reacting silanols having two —OH groups is, for example, a system in which an acyloxysilane having three or four —OCOR groups is A method of reacting by adding silanol in two or more stages; to a system in which acyloxysilane having 3 or 4 -OCOR groups is present, silanol is gradually added using a dropping funnel, syringe, etc. method.
By continuously reacting an acyloxysilane represented by the formula (IA) and a silanol represented by the formulas (IIA1) and (IIA2), a cyclic siloxane compound represented by the following formula (IIIA) is obtained. manufactured.

In formula (IIIA), a, b, c, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are a, Same as b, c, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ . Preferred examples and specific examples of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in formula (IIIA) are the same as those shown for R ¹ in formula (IA).

Furthermore, the cyclic siloxane compound represented by formula (IIIA) is continuously reacted with a silanol represented by formula (IIA3) to obtain a cyclic compound represented by formula (IVA1) and/or formula (IVA2). A siloxane compound is produced.

In formulas (IVA1) and (IVA2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , a, b, c, and d are represented by formula (IA), formula R 1 , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , a, b, c, ^and d in (IIA1), formula (IIA2), and formula (IIA3) be. Preferred and specific examples of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in formulas (IVA1) and (IVA2) are represented by R ¹ in formula (IA). is the same as

The reaction steps for producing formula (IIIA) and formula (IVA1) and/or (IVA2) are stepwise reactions accompanied by elimination of carboxylic acid, and generally the intermediate product is isolated and purified. A cyclic siloxane compound can be produced by a one-pot reaction operation in which raw materials are added in sequence without continuous addition.
For example, when tetraacyloxysilane is used as the acyloxysilane represented by formula (IA), silanols represented by formulas (IIA1) and (IIA2) are sequentially reacted as shown in Scheme 1 below to obtain Compounds of formula (IIIA) with four acyloxy groups can be prepared in one pot. Furthermore, when the reaction solution containing the compound represented by the formula (IIIA) thus produced is reacted with a silanol represented by the formula (IIA3), the formula (IVA1) having two or four acyloxy groups and/or A compound represented by (IVA2) can be prepared in one pot from tetraacyloxysilane.

In order to efficiently produce the compound represented by the formula (IIIA), the acyloxysilane represented by the formula (IA) is reacted with the silanol represented by the formulas (IIA1) and (IIA2) in order. (amount of substance of formula (IA): amount of substance of formula (IIA1): amount of substance of formula (IIA2)) is ideally set to 1:0.5:0.5, but There may be an error in the ratio, and the error in the molar ratio is preferably within 30%, more preferably within 20%, and even more preferably within 10%.
Further, in order to efficiently produce the compounds represented by formula (IVA1) and/or formula (IVA2), the acyloxysilane represented by formula (IA) is added with formula (IIA1), formula (IIA2), and the silanol represented by the formula (IIA3) are ideally reacted in order at a molar ratio of 1:0.5:0.5:0.5, but there is an error in the molar ratio. The error in the molar ratio is preferably within 30%, more preferably within 20%, and even more preferably within 10%.

The reaction process of Scheme 1 is, in terms of reaction mechanism, a nucleophilic substitution reaction of silanol with acyloxysilane to form a Si--O--Si bond accompanied by elimination of carboxylic acid.
The reactivity of acyloxysilane increases stepwise in the order of monoacetoxysilane<diacetoxysilane<triacetoxysilane<tetraacetoxysilane. When reacting at a molar ratio of , a trisiloxane compound having acyloxy groups at both ends (a compound schematically represented by ABA) is selectively produced.
When the above trisiloxane compound is further reacted with silanediol B, the acyloxy group and the hydroxyl group react to form a tetrasiloxane compound, after which the intramolecular cyclization reaction proceeds rapidly, resulting in a cyclotetra having a cyclic tetramer structure. A siloxane compound is selectively produced.
Since this cyclotetrasiloxane compound has an acyloxy group on the diagonally positioned silicon atom, it can further react with silanediol, and the acyloxy group bonded to one of the silicon atoms becomes a hydroxy group. After the reaction, the acyloxy group bonded to the other silicon atom reacts intramolecularly with the remaining hydroxy group to form a [3.3.3] pentasiloxane compound having a bicyclic pentamer structure.
In the final reaction process to produce a [3.3.3]pentasiloxane compound with a bicyclic pentamer structure, the progress of the intermolecular reaction, which is a side reaction, is suppressed, and the target intramolecular reaction is preferentially progressed. Therefore, it is preferable to adjust the concentration of the reaction solution. By adjusting the concentration of the reaction solution to be appropriately low, it is possible to increase the selectivity for the intramolecular reaction and improve the yield of the bicyclic pentamer.

The step of reacting the silanols represented by formulas (IIA1) to (IIA3) can also be carried out in the presence of a reaction accelerator such as a base.
Regarding the presence or absence and amount of a base, etc., it may be adjusted appropriately according to the reactivity and combination of raw materials. It is preferred to add a reaction accelerator.
In addition, it is possible to control the type of product depending on the presence or absence of a base. For example, in the reaction system of tetraacyloxysilane, the cyclic siloxane represented by formula (IIIA) has When a silanol is reacted, a compound represented by formula (IVA1) can be produced in the presence of a base, and a compound represented by formula (IVA2) can be produced as the main product in the absence of a base.
The base is not particularly limited, and examples thereof include organic bases such as pyridine, triethylamine, diisopropylethylamine, dicyclohexylmethylamine, and dimethylaniline; inorganic bases such as sodium carbonate and potassium carbonate; ions having a basic group such as an amino group. exchange resins; inorganic compounds such as silica; basic zeolites containing alkali metals;

When an acyloxy group remains in a cyclic siloxane compound obtained by continuously reacting an acyloxysilane with a silanol, a modification step of converting the acyloxy group of the cyclic siloxane compound into a hydroxy group, an alkoxy group, or a siloxy group. can be provided to
For example, when an acyloxy group (-OCOR ² group) remains in the cyclic siloxane compound represented by formula (IIIA), formula (IVA1), or formula (IVA2), formula (IIIA), formula (IVA1), or formula Water or the formula (VIA) is added to the cyclic siloxane compound represented by (IVA2):
^R9OH (VIA)
A cyclic siloxane compound in which at least one of the remaining acyloxy groups is converted to a hydroxy group or an alkoxy group (--OR ⁹ group) can be produced by reacting an alcohol represented by.

In formula (VIA), R ⁹ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of alkyl groups, aryl groups and aralkyl groups.
When R ⁹ is a hydrocarbon group, the preferred number of carbon atoms and specific examples thereof include those shown in the description of R ¹ in formula (IA) above. Also, some or all of the hydrogen atoms bonded to carbon atoms may be substituted with groups that do not participate in the reaction, such as chlorine atoms, fluorine atoms, and alkoxy groups.
Accordingly, specific examples of alcohols having those groups include methanol, ethanol, isopropyl alcohol, butanol, hexanol.
Cyclic siloxane compounds having an alkoxy group are less reactive to water and the like than compounds having an acyloxy group, and thus have high storage stability.

Further, when an acyloxy group (-OCOR ² group) remains in the cyclic siloxane compound represented by formula (IIIA), formula (IVA1), or formula (IVA2), formula (IIIA), formula (IVA1), Or formula (IIA4) to the cyclic siloxane compound represented by formula (IVA2):
^{R10R11R12SiOH ( IIA4} )
It is also possible to produce a cyclic siloxane compound in which at least one of the remaining acyloxy groups is converted to a siloxy group (--OSiR ¹⁰ R ¹¹ R ¹² group) by reacting a silanol represented by the following.

In formula (IIA4), R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group. . Preferred numbers of carbon atoms and specific examples of R ¹⁰ , R ¹¹ and R ¹² are the same as those shown for R ¹ in formula (IA). Also, the hydrogen atoms bonded to the carbon atoms of R ¹⁰ , R ¹¹ and R ¹² may be substituted with groups that do not participate in the reaction.
The number of substituents may be one or more, and all hydrogen atoms bonded to carbon atoms may be substituted.
Groups that do not participate in the reaction include, for example, chlorine atoms, fluorine atoms, and alkoxy groups.

Specific examples of the silanol represented by formula (IIA4) include trimethylsilanol, triethylsilanol, tert-butyldimethylsilanol, dimethylphenylsilanol, methyldiphenylsilanol and triphenylsilanol.

Water, alcohol represented by formula (VA1), or formula ( The molar ratio of silanol (water, alcohol, or silanol/cyclic siloxane compound) represented by IIA4) can be selected arbitrarily, and the From the viewpoint of improving the yield, it is usually 0.4 or more and 50 or less, preferably 0.5 or more and 30 or less, and more preferably 0.5 or more and 20 or less.

A compound having a plurality of cyclic siloxane skeletons is produced by reacting a cyclic siloxane compound represented by the formula (IVA1) (where a is 0) with a silanol having two hydroxy groups. can. This reaction may be carried out continuously, or may be carried out starting from a cyclic siloxane compound represented by the formula (IVA1) (where a is 0).
Examples of the silanol having two hydroxy groups include a silanol represented by the formula (IIA5):
HO ^{( SiR13R14O} ) _eH (IIA5)
(In formula (IIA5), R ¹³ and R ¹⁴ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and e is , an integer of 1 to 1000. The hydrogen atoms bonded to the carbon atoms of R ¹³ and R ¹⁴ may be substituted with groups that do not participate in the reaction.)
and can produce a cyclic siloxane compound represented by the formula (VA1), which is a compound having a plurality of cyclic siloxane skeletons.

In formula (IIA5), R ¹³ and R ¹⁴ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of alkyl groups, aryl groups, alkenyl groups and aralkyl groups. The preferred number of carbon atoms and specific examples of R ¹³ and R ¹⁴ are the same as those shown for R ¹ in formula (IA).
Also, the carbon atoms of R ¹³ and R ¹⁴ may be substituted with groups that do not participate in the reaction. The number of substituents may be one or more, and all hydrogen atoms bonded to carbon atoms may be substituted. Groups that do not participate in the reaction include, for example, chlorine atoms, fluorine atoms, and alkoxy groups.
e is an integer of 1-1000, preferably 1-500, more preferably 1-100, still more preferably 1-10.

Specific examples of the silanol represented by formula (IIA5) include those listed as specific examples of formula (IIA1), formula (IIA2), and formula (IIA3), and dodecamethyl-1,3,5,7 ,9,11-hexasiloxane-1,11-diol, hexadecamethyl-1,3,5,7,9,11,13,15-octasiloxane-1,15-diol, polydimethylsiloxane-α,ω - Diol (average degree of polymerization = 10 to 1000).

In formula (VA1), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹³ , R ¹⁴ , b, c, d, and e are are synonymous with R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹³ , R ¹⁴ , b, c, d, and e in ). v is an integer of 1 to 10,000, preferably 1 to 8,000, more preferably 1 to 6,000. The group attached to the terminal silyl group is an acyloxy group, a hydroxy group, or an alkoxy group.

Furthermore, the cyclic siloxane compound represented by the formula (IVA1) (where a is 0) is reacted with a silanol represented by the formula (IIA6) to obtain the formula (VA2). cyclic siloxane compounds can be produced.

In formula (IIA6), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently have a carbon number selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group. 1 to 12 hydrocarbon groups. Preferred numbers of carbon atoms and specific examples of R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same as those shown for R ¹ in Formula (IA). Also, the hydrogen atoms bonded to the carbon atoms of R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ may be substituted with groups that do not participate in the reaction. The number of substituents may be one or more, and all hydrogen atoms bonded to carbon atoms may be substituted. Examples of groups that do not participate in the reaction include groups such as chlorine atoms, fluorine atoms, and alkoxy groups.
f, g, and h are each independently an integer of 1-6.

In formula (VA2), ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R15 , ^R16 , ^R17 , ^R18 , ^R19 , ^R20 , b, c, d, f, g and h are R ³ , R ⁴ , R 5 , R ⁶ , R ⁷ , R ⁸ , R ¹⁵ , R 16 , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ¹⁸ , R ¹⁹ , Synonymous with R ²⁰ , b, c, d, f, g, and h. w is an integer of 1 to 10,000, preferably 1 to 8,000, more preferably 1 to 6,000. The group attached to the terminal silyl group is an acyloxy group, a hydroxy group, or an alkoxy group.

In the production of the cyclic siloxane compounds represented by formulas (VA1) and (VA2), the molar ratio of silanol to acyloxysilane can be arbitrarily selected depending on the structure, molecular weight, etc. of the target product. Considering the yield of the product relative to the acyloxysilane, it is usually 0.4 to 20, preferably 0.5 to 10, more preferably 0.5 to 5.
In the production of the cyclic siloxane compounds represented by the formulas (VA1) and (VA2), the molar ratio of acyloxysilane and silanol is adjusted to 1:1 when producing higher molecular weight products. However, there may be an error in the molar ratio, and the error is preferably within 30%, more preferably within 20%, and even more preferably within 10%.

In the production of the cyclic siloxane compound represented by formula (VA2), the reaction can be carried out by adding a silanol having one hydroxy group or an acyloxysilane having one acyloxy group.
For example, a cyclic siloxane compound represented by formula (IVA1) (where a is 0), a silanol represented by formula (IIA6), and a silanol represented by formula (IIA4) or formula (IA2 ):
^{R21R22R23SiOCOR24 ( IA2 )}
A cyclic siloxane compound represented by the formula (VA3) or (VA4) can be produced by reacting the acyloxysilane represented by the formula (VA3) or (VA4).

In formula (IA2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group. , R ²⁴ is an alkyl group having 1 to 3 carbon atoms.
Preferred numbers of carbon atoms and specific examples of R ²¹ , R ²² , R ²³ and R ²⁴ are the same as those shown for R ¹ or R ² in formula (IA). Also, the hydrogen atoms bonded to the carbon atoms of R ²¹ , R ²² , R ²³ and R ²⁴ may be substituted with groups that do not participate in the reaction. The number of substituents may be one or more, and all hydrogen atoms bonded to carbon atoms may be substituted. Examples of groups that do not participate in the reaction include groups such as chlorine atoms, fluorine atoms, and alkoxy groups.

Acyloxysilanes represented by formula (IA2) specifically include acetoxytrimethylsilane, acetoxytriethylsilane, acetoxydimethylphenylsilane, acetoxymethyldiphenylsilane, and the like.

In formulas (VA3) and (VA4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R 8 , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁵ , R ¹⁶ , ^{R 17 ,} R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , b, c, d, f, g, and h are represented by formula (IVA1), formula (IIA6), formula (IIA4), formula (IA2) ^In , ^R3 , ^R4 , R5, ^{R6 , R7} , ^R8 , ^R10 , R11, R12, ^R15 , ^R16 , ^R17 , ^R18 , ^R19 , ^R20 , ^{R21 ,} Same as R ²² , R ²³ , b, c, d, f, g, and h. w1 and w2 are each independently an integer of 1 to 10,000, preferably 1 to 8,000, more preferably 1 to 6,000.

A preferred method for producing the cyclic siloxane compound represented by the formula (VA3) is, for example, to the cyclic siloxane compound represented by the formula (IVA1) (when a is 0 in the formula), z1 equivalent A method of reacting a silanol represented by the formula (IIA4) (0 < z1 ≤ 1) and then reacting a silanol represented by the formula (IIA6) in an amount of (2-z1)/2 equivalents may be mentioned. (Scheme 2).

Further, as a preferred method for producing the cyclic siloxane compound represented by the formula (VA4), for example, the formula ( A method of reacting an acyloxysilane represented by IA2), followed by reaction with (2-z2)/2 equivalents of a cyclic siloxane compound represented by the formula (IVA1) (where a is 0) (Scheme 3).

Furthermore, in the production of the cyclic siloxane compound represented by formula (VA2), both a silanol having one hydroxy group and an acyloxysilane having one acyloxy group can be added to carry out the reaction.
For example, a cyclic siloxane compound represented by the formula (IVA1) (where a is 0), a silanol represented by the formula (IIA6), a silanol represented by the formula (IIA4), and a silanol represented by the formula (IA2) At least one selected from the group consisting of cyclic siloxane compounds represented by formula (VA5), formula (VA3), and/or formula (VA4) can be produced by reacting the represented acyloxysilane.

In formula ( ^VA5 ) ^{, R3 , R4} , R5, ^R6 , ^R7 , ^R8 , R10, R11, ^{R12, R15 , R16} , ^R17 , ^R18 , ^R19 , ^R20 , R ²¹ , R ²² , R ²³ , b, c, d, f, g, and h are R ³ , R in Formula (IVA1), Formula (IIA6), Formula (IIA4), and Formula (IA2) respectively. ⁴ , R5 ^{, R6} , ^{R7 , R8} , R10, R11, ^R12 , ^R15 , ^R16 , ^{R17 , R18} , R19, ^R20 , ^R21 , ^R22 , ^{R23 ,} Synonymous with b, c, d, f, g, and h. w3 is an integer of 0 or more and 10,000 or less, preferably 1 to 8,000, more preferably 1 to 6,000.

A preferred method for producing the cyclic siloxane compound represented by the formula (VA5) is, for example, a z3 equivalent (0< The intermediate mixture (A) is produced by reacting the silanol represented by the formula (IIA4) of z3 ≤ 1), and z3 equivalent (z3 is the above A method of reacting an acyloxysilane represented by the formula (IA2) of (synonymous definition) to produce an intermediate mixture (B), and then mixing and reacting the intermediate mixture (A) and the intermediate mixture (B) (Scheme 4).

Although the above-described reaction between acetoxysilane and silanol proceeds without a catalyst, a base or the like may be added to facilitate the reaction.
As the base, organic and inorganic bases can be used, and specific examples of organic bases include triethylamine, tripropylamine, diisopropylethylamine, dicyclohexylmethylamine, pyridine, and dimethylaniline. Specific examples of inorganic bases include sodium carbonate, potassium carbonate, cesium carbonate, and potassium phosphate.
Basic ion-exchange resins having functional groups such as amino groups, basic inorganic solid compounds such as silica having amino groups and the like can also be used.

The reaction in the production method of the present invention can be carried out in a liquid phase or gas phase depending on the reaction temperature and reaction pressure. In addition, as the form of the reaction device, various conventionally known forms such as a batch type and a flow type can be used.
The reaction temperature is generally -30°C or higher, preferably -20 to 300°C, more preferably -10 to 200°C, and still more preferably -10 to 150°C.
The reaction pressure is generally 0.1 to 100 atmospheres, preferably 0.1 to 50 atmospheres, more preferably 0.1 to 20 atmospheres, still more preferably 0.1 to 10 atmospheres.
The reaction time may be appropriately adjusted according to the amount of raw materials and catalyst, the reaction temperature, the form of the reaction apparatus, etc., and is usually 0.1 to 1000 hours, preferably 0.1 to 800 hours, more preferably 0.1. ~500 hours.

When the reaction in the production method of the present invention is carried out in a liquid phase system, it can be carried out with or without a solvent. When a solvent is used, nitrile solvents such as acetonitrile, propionitrile, and benzonitrile; Ether solvents such as tetrahydrofuran, diethyl ether, tert-butyl methyl ether, and dibutyl ether; Hydrocarbon solvents such as toluene and xylene; Chlorobenzene, 1,2- or 1,3-dichlorobenzene, 1,2 , 3- or 1,2,4-trichlorobenzene and other halogenated hydrocarbon solvents; They can also be mixed and used.
When the reaction in the production method of the present invention is carried out in the gas phase, the reaction can be carried out by mixing an inert gas such as nitrogen.

When the reaction is carried out using a solvent, it is preferable to appropriately select the solvent from the viewpoint of the solubility of the raw materials and the product, the selectivity of the reaction, etc., depending on the type of the target product.
For example, in the production of compounds represented by formula (IIIA), formula (IVA1), and formula (IVA2), a tetraacyloxysilane such as tetraacetoxysilane and a silanol such as diphenylsilanediol are reacted as raw materials. Nitrile-based solvents and ketone-based solvents, which have high solubility in these raw materials, are preferred when the solvent is used.
In the production of high-molecular-weight cyclic siloxane compounds such as the cyclic siloxane compounds represented by the formulas (VA1) and (VA2), ether-based solvents that have high solubility in the product and can suppress side reactions, Hydrocarbon solvents are preferred.

The reaction in the production method of the present invention can also be performed under microwave irradiation. In the reaction system in the production method of the present invention, the raw materials such as acetoxysilane and silanol have relatively large dielectric loss coefficients and absorb microwaves efficiently. and the reaction can be carried out more efficiently.

Various commercially available devices equipped with contact or non-contact temperature sensors can be used in the microwave irradiation reaction. Moreover, the power of microwave irradiation, the type of cavity (multimode, single mode), the mode of irradiation (continuous, intermittent), etc. can be arbitrarily determined according to the scale and type of reaction. The frequency of microwaves is usually 0.3 to 30 GHz, preferably the IMS frequency band allocated for use in industrial, scientific and medical fields, more preferably 2.45 GHz band and 5.8 GHz band. be.

In the microwave irradiation reaction, a heating material (susceptor) that generates heat by absorbing microwaves can be added to the reaction system in order to heat the reaction system more efficiently. As the type of heating material, for example, activated carbon, graphite, silicon carbide, titanium carbide, and various conventionally known materials can be used. Also, a molded catalyst obtained by mixing the above-described catalyst and heating material powder and firing the mixture using an appropriate binder such as sepiolite or formite can also be used.

The reaction in the production method of the present invention proceeds even in a closed system reactor, but by making the reactor an open system and continuously removing the reaction product out of the reaction system, the reaction proceeds more efficiently. You can also let

The cyclic siloxane compound produced by the production method of the present invention can be isolated by performing appropriate purification, and the purification is carried out by means commonly used in organic chemistry such as distillation, recrystallization, reprecipitation, and chromatography. easily reached.

[Cyclic siloxane compound]
A cyclic siloxane compound can be provided by the production method of the present invention.
Examples of the cyclic siloxane compound of the present invention include a compound represented by Formula (IIIB), which is a monocyclic cyclotetrasiloxane compound.

In formula (IIIB), R ^a1 , R ^a2 , R ^a3 , R ^a4 , and R ^a5 each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 2 carbon atoms. is an alkenyl group of ~3,
X ¹ is an acetoxy group, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or a siloxy group having 3 to 20 carbon atoms;
i is 0 or 1,
j1 and j2 are each independently an integer of 1-6.

Examples of the alkyl group having 1 to 6 carbon atoms in the compound of the present invention include methyl group, ethyl group, propyl group, butyl group and hexyl group.
Examples of the aryl group having 6 to 10 carbon atoms in the compound of the present invention include phenyl group, tolyl group, xylyl group and naphthyl group.
Examples of alkenyl groups having 2 to 3 carbon atoms in the compounds of the present invention include vinyl groups and propenyl groups.
The alkoxy group having 1 to 6 carbon atoms in the compound of the present invention includes, for example, methoxy group, ethoxy group, propoxy group, butoxy group and hexyloxy group.
Examples of the siloxy group having 3 to 20 carbon atoms in the compound of the present invention include trimethylsiloxy group, triethylsiloxy group, tert-butyldimethylsiloxy group, dimethylphenylsiloxy group, methyldiphenylsiloxy group and triphenylsiloxy group. .

Preferred examples of combinations of (R ^a1 , R ^a2 , R ^a3 , R ^a4 , R ^a5 , X ¹ , i, j1, j2) in the compound of formula (IIIB) include (-, phenyl group, phenyl group, phenyl group, phenyl group, acetoxy group, 0, 1, 1), (-, methyl group, phenyl group, methyl group, phenyl group, acetoxy group, 0, 1, 1), (-, methyl group, methyl group, methyl group, methyl group, acetoxy group, 0, 1, 1), (-, phenyl group, phenyl group, methyl group, methyl group, acetoxy group, 0, 1, 1), (-, phenyl group, phenyl group, methyl group, phenyl group, acetoxy group, 0, 1, 1), (-, methyl group, methyl group, methyl group, phenyl group, acetoxy group, 0, 1, 1), (methyl group, phenyl group, phenyl group , phenyl group, phenyl group, acetoxy group, 1, 1, 1), (ethyl group, phenyl group, phenyl group, phenyl group, phenyl group, acetoxy group, 1, 1, 1), (vinyl group, phenyl group, phenyl group, phenyl group, phenyl group, acetoxy group, 1, 1, 1), (-, phenyl group, phenyl group, phenyl group, phenyl group, acetoxy group, 0, 2, 2), (-, methyl group, methyl group, methyl group, methyl group, acetoxy group, 0, 2, 2).
A hyphen "-" in parentheses means absent.

Bicyclic or tricyclic compounds include those represented by formula (IVB1) or formula (IVB2).

In formula (IVB1) and formula (IVB2), R ^a6 , R ^a7 , R ^a8 , R ^a9 , R ^a10 and R ^a11 each independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group,
X ² is an acetoxy group, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or a siloxy group having 3 to 20 carbon atoms;
k1, k2, and k3 are each independently an integer of 1-6.

Preferred examples of the combination of (R ^a6 , R ^a7 , R ^a8 , R ^a9 , R ^a10 , R ^a11 , X ² , k1, k2, k3) in the compound of formula (IVB1) or (IVB2) include (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, acetoxy group, 1, 1, 1), (methyl group, phenyl group, methyl group, phenyl group, methyl group, phenyl group, acetoxy group, 1 , 1, 1), (methyl group, methyl group, phenyl group, phenyl group, phenyl group, phenyl group, acetoxy group, 1, 1, 1), (methyl group, methyl group, methyl group, methyl group, phenyl group , phenyl group, acetoxy group, 1, 1, 1), (methyl group, methyl group, methyl group, methyl group, methyl group, methyl group, acetoxy group, 1, 1, 1), (methyl group, methyl group, methyl group, methyl group, methyl group, methyl group, acetoxy group, 2, 2, 2).

Furthermore, the present invention provides a polymeric cyclic siloxane compound. Examples of high-molecular cyclic siloxane compounds include compounds represented by formula (VB1), which are compounds composed of a bicyclic siloxane unit and a mono- or oligo-siloxane unit.

Formula (VB1) wherein R ^a12 , R ^a13 , R ^a14 , R ^a15 , R ^a16 , R ^a17 , R ^a18 and R ^a19 are each independently an alkyl or aryl group having 1 to 6 carbon atoms; ,
l1, l2, l3, and l4 are each independently an integer of 1 to 6, x is an integer of 1 or more and 10000 or less, and the group bonded to the terminal silyl group is an acetoxy group, a hydroxy or an alkoxy group.

^{[ _ _ _ _ _ _ _} phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, methyl group, methyl group, 1, 1, 1, 1), (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, methyl group, phenyl group, 1, 1, 1, 1), (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, 1, 1, 1, 1) , (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, methyl group, methyl group, 1, 1, 1, 2), (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group , phenyl group, methyl group, methyl group, 1, 1, 1, 3).
x is preferably 2 or more and 5000 or less, more preferably 2 or more and 3000 or less.
The group bonded to the terminal silyl group is preferably a hydroxy group or an alkoxy group, more preferably a hydroxy group or a methoxy group.

The present invention can also provide a cyclic siloxane compound represented by formula (VB2), which is a compound whose main chain is composed only of bicyclic siloxane units.

In formula (VB2), ^Ra20 , ^Ra21 , ^Ra22 , ^Ra23 , ^Ra24 , ^Ra25 , ^Ra26 , ^Ra27 , ^Ra28 , ^Ra29 , ^Ra30 , and ^Ra31 each independently have a carbon number an alkyl group of 1 to 6 or an aryl group of 6 to 10 carbon atoms, m1, m2, m3, m4, m5, and m6 are each independently an integer of 1 to 6, and y is 1 or more and 10,000 The group that is an integer below and is bonded to the terminal silyl group is an acetoxy group, a hydroxy group, or an alkoxy group.

In the compound of formula (VB2), (R ^a20 , R ^a21 , R ^a22 , R ^a23 , R ^a24 , R ^a25 , R a26 , R ^a27 , R ^a28 , R ^a29 , R ^a30 , R ^a31 , ^m1 , m2, m3 , m4, m5, and m6), (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, 1, 1, 1, 1, 1, 1), (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, methyl group, methyl group, methyl group, methyl group, methyl group, methyl groups, 1, 1, 1, 1, 1, 1).
y is preferably 2 or more and 5000 or less, more preferably 2 or more and 3000 or less.
The group bonded to the terminal silyl group is preferably a hydroxy group or an alkoxy group, more preferably a hydroxy group or a methoxy group.

A cyclic siloxane compound represented by the formula (VB3) can be provided by a reaction system or the like using three types of silicon compounds as raw materials.

In formula (VB3) ^{, Ra32} , ^Ra33 , ^Ra34 , ^Ra35 , Ra36, ^Ra37 , ^Ra38 , ^Ra39 , ^Ra40 , ^Ra41 , ^Ra42 , ^Ra43 , ^Ra44 , ^Ra45 , and R ^a46 is each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, m7, m8, m9, m10, m11, and m12 are each independently an integer of 1 to 6 and y1 is an integer of 0 or more and 10000 or less.

In the compound of formula (VB3), (R ^a32 , R ^a33 , R ^a34 , R ^a35 , R ^a36 , R ^a37 , R a38 , R ^a39 , R ^a40 , R ^a41 , R ^a42 , R ^a43 , R ^a44 , ^{R a45} , R ^a46 , m7, m8, m9, m10, m11, m12) include (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, 1, 1, 1, 1, 1, 1), (ethyl group, ethyl group, ethyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, 1, 1, 1, 1, 1, 1), (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, methyl group, methyl group, methyl group, methyl group, methyl group, methyl group, 1, 1, 1, 1, 1, 1) are mentioned.
y1 is preferably 0 or more and 5000 or less, more preferably 0 or more and 3000 or less.

Furthermore, a cyclic siloxane compound represented by the formula (VB4) can also be provided by a reaction system using four types of silicon compounds.

In formula (VB4), ^Ra47 , ^Ra48 , ^Ra49 , ^Ra50 , ^Ra51 , ^Ra52 , ^{Ra53 , Ra54} , ^{Ra55, Ra56} , ^Ra57 , ^Ra58 , ^Ra59 , ^Ra60 , ^Ra61 , R ^a62 , R ^a63 , and R ^a64 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m13, m14, m15, m16, m17, and m18 are Each is independently an integer of 1 to 6, and y2 is an integer of 0 or more and 10,000 or less.

In the compound of formula (VB4), (R ^a47 , R ^a48 , R ^a49 , R ^a50 , R ^a51 , R ^a52 , R a53 , R ^a54 , R ^a55 , R ^a56 , R ^a57 , R ^a58 , ^{R a59 ,} R ^a60 , R ^a61 , R ^a62 , R ^a63 , R ^a64 , m13, m14, m15, m16, m17, m18) include (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, 1, 1, 1, 1, 1, 1) , (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, ethyl group, ethyl group, ethyl group, 1, 1, 1, 1, 1, 1), (phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, phenyl group, methyl group, methyl group, methyl group, methyl group, methyl group, methyl group, phenyl group, phenyl group, phenyl group, 1, 1, 1, 1, 1, 1).
y2 is preferably 0 or more and 5000 or less, more preferably 0 or more and 3000 or less.

The cyclic siloxane compounds of formula (VA1), formula (VA2), formula (VA3), formula (VA4), formula (VA5), formula (VB1), formula (VB2), formula (VB3) and formula (VB4) are Since they have thermally stable cyclic skeletons, materials containing these compounds as compositions can be used as heat-resistant materials and the like. As the cyclic siloxane composition, not only one kind but also two or more kinds of cyclic siloxane compounds can be used at the same time.
In addition, since the cyclic siloxane compounds represented by formulas (IIIB) and (IVB) have highly reactive acyloxy groups, hydroxy groups, and/or alkoxy groups, they are used as synthetic intermediates and surface modifiers. , raw materials for sol-gel materials, etc., and have high utility value as functional chemicals.

According to the present invention, a cyclic siloxane compound having a cyclotetrasiloxane skeleton, a bicyclo[3.3.3]cyclopentasiloxane skeleton, or the like can be efficiently produced. Moreover, novel cyclic siloxane compounds and polymer compounds can be obtained by the production method of the present invention, and the polymer compounds are materials excellent in thermal stability and mechanical properties.

Specifically, the present invention has the following effects.
(1) Acyloxysilane as a raw material does not generate corrosive compounds such as hydrogen chloride even when hydrolyzed, so it is highly safe and readily available.
(2) The co-product of the reaction is a carboxylic acid and does not produce strongly corrosive compounds such as hydrogen chloride.
(3) The reaction proceeds even under mild conditions such as room temperature.
(4) A novel cyclic siloxane compound having a reactive substituent (such as an acyloxy group) can be produced.
(5) Using reactive substituents, not only low-molecular-weight compounds but also novel high-molecular-weight compounds can be produced.
(6) Polymeric cyclic siloxane compounds have high thermal stability, and compositions containing such cyclic siloxane compounds can be used as novel heat-resistant materials.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
An acetonitrile solution of 0.55 mmol of diphenylsilanediol (IIAa) was added to an acetonitrile solution of 1.11 mmol of tetraacetoxysilane (IAa) and stirred at about 25° C. (room temperature) for 1 hour (total volume of acetonitrile was 2.5 mmol). 8 mL). After that, an acetonitrile solution of 0.55 mmol of IIAa was added (the volume of acetonitrile was 2.8 mL) and stirred at about 25° C. for 1 day. The product was analyzed by a nuclear magnetic resonance apparatus (hereinafter referred to as NMR), and the yield of the product was measured. It was found that 3,5,7-cyclotetrasiloxane (IIIAa) was produced in >95% yield (see Table 1).
Deuterated acetonitrile was used as the heavy solvent in the NMR measurement. As a method for calculating the yield of the product, in ²⁹ Si NMR, trimethylphenylsilane was added as an internal standard, and the peak (-4.0 ppm) thereof was used as a reference, and the yield was calculated from the integration ratio of the peak of the product.

(Examples 2 to 11)
The reaction and analysis were carried out in the same manner as in Example 1 by changing the reaction conditions (types of raw materials, etc.), and the yield of the product was measured by NMR. Table 1 shows the results.

(Example 12)
An acetonitrile solution of 0.92 mmol of tetraacetoxysilane (IAa) was added with an acetonitrile solution of 0.46 mmol of diphenylsilanediol (IIAa) and stirred at about 25° C. (room temperature) for 1 hour (total volume of acetonitrile was 2.5 mmol). 3 mL). After that, an acetonitrile solution of 0.46 mmol of IIAa was added (the volume of acetonitrile was 2.3 mL) and stirred at about 25° C. for 1 day. Further, an acetonitrile solution of 0.46 mmol of IIAa was added (the volume of acetonitrile was 4.6 mL) and stirred at about 25° C. for 1 day. The product was analyzed by NMR, and the yield of the product was determined. It was found that 3,5,7,9-pentasiloxane (IVA1a) was produced in 40% yield (see Table 1).

(Examples 13-26)
The reaction and analysis were carried out in the same manner as in Example 12 by changing the reaction conditions (type of raw material, presence or absence of base, etc.). Table 1 shows the reaction conditions and the yield of the product determined by NMR measurement.

Notes in Table 1 are shown below.
1) The reaction was carried out at about 25°C (room temperature).
2) IAa: tetraacetoxysilane, IAb: methyltriacetoxysilane, IAc: ethyltriacetoxysilane, IAd: vinyltriacetoxysilane.
3) IIAa: diphenylsilanediol, IIAb: methylphenylsilanediol, IIAc: dimethylsilanediol, IIAd, tetraphenyl-1,3-disiloxane-1,3-diol, IIAe: tetramethyl-1,3-disiloxane -1,3-diol, IIAf: Hexamethyl-1,3,5-trisiloxane-1,5-diol.
4) Py: pyridine.
5) MeCN: acetonitrile, _Me2CO : acetone.
6) The notation of x+y+z is x for the stirring time after addition of silanol IIA1, y for the stirring time after the addition of silanol IIA2, and z for the stirring time after the addition of silanol IIA3. indicates that Here, h indicates hour, d indicates day, and w indicates week.
7) In the structural formula of the product, Me is a methyl group, Ph is a phenyl group, Et is an ethyl group, and Vi is a vinyl group.
8) The yield was calculated by nuclear magnetic resonance spectroscopy.
9) A mixture of two stereoisomers (approximately 1:1).
10) A mixture of two stereoisomers (about 2:1).

(Example 27)
0.54 mmol of methanol and 0.72 mmol of triethylamine were added to an acetonitrile solution containing 0.06 mmol of IIIAa (the amount of acetonitrile in the reaction solution obtained in Example 1 was about 0.5 mL), and the mixture was kept at about 25°C for 1 day. Stirred. The product was analyzed by NMR, gas chromatograph (hereinafter GC), and gas chromatograph mass spectrometer (hereinafter GC-MS), and the yield of the product was measured by NMR. -tetramethoxy-3,3,7,7-tetraphenyl-1,3,5,7-cyclotetrasiloxane (IIIAa-(OMe) ₄ ) was found to be produced in >95% yield (Table 2).

(Examples 28-55)
The reaction and analysis were carried out in the same manner as in Example 27 by changing the reaction conditions (type of raw material, type of reactant, presence/absence of base, etc.). Table 2 shows the reaction conditions and the yield of the product determined by NMR measurement.

Notes in Table 2 are shown below.
1) The reaction was carried out at about 25°C (room temperature).
2) Acyloxysilanes obtained in Table 1.
3) MeOH: Methanol, Ph ₃ SiOH: Triphenylsilanol, Me ₃ SiOH: Trimethylsilanol, Et ₃ SiOH: Triethylsilanol.
4) _Et3N : triethylamine, Py: pyridine.
5) MeCN: acetonitrile, PhMe: toluene, _CD3CN : deuterated acetonitrile, THF- _d8 : deuterated tetrahydrofuran.
6) h indicates hour, d indicates day.
7) In the structural formula of the product, Me is a methyl group, Ph is a phenyl group, Et is an ethyl group, and Vi is a vinyl group.
8) The yield was calculated by nuclear magnetic resonance spectroscopy.
9) A mixture of two stereoisomers (about 1:1).
10) Leave powdery acyloxysilane in an atmosphere of saturated steam (25°C).
11) A mixture of two stereoisomers (about 2:1).

Table 3 shows the nuclear magnetic resonance spectrum and/or mass spectrometry data of the cyclic siloxane compounds obtained in Examples.

Notes in Table 3 are shown below.
1) Cyclic siloxane compounds obtained in Tables 1, 2 and Examples 75-77.
2) ²⁹ Si NMR chemical shift values. _CD3CN , _C6D6 , or _CDCl3 was used as _the NMR solvent (in parentheses if a solvent other than _CD3CN was used), and the relaxation reagent Cr(acac) ₃ (chromium(III) Acetylacetonate) was added and measured. The numbers in parentheses indicate the number of silicon atoms based on the integral ratio of peak areas.
3) GC-MS: gas chromatograph mass spectrometer, EI method: electron impact ionization method (70 eV).
4) TOF-MS: time-of-flight mass spectrometer, ESI method: electrospray ionization method, MALDI method: matrix-assisted laser desorption ionization method.
5) A mixture of two stereoisomers.

A modification step of converting the cyclic siloxane compounds represented by formula (IIIA), formula (IVA1), and formula (IVA2) and the remaining acyloxy groups to other groups (hydroxy groups, alkoxy groups, or siloxy groups). The cyclic siloxane compound thus prepared can be easily isolated by operations such as reprecipitation, recrystallization, and chromatography.
Moreover, since the cyclic siloxane compound represented by the formula (IIIA) is generally produced in high yield, it can be isolated simply by distilling off the volatile components under reduced pressure, as shown in the following examples.
Furthermore, since the reaction for converting the remaining acyloxy group in formula (IVA1) and the like to a hydroxyl group generally proceeds under mild conditions, for example, the acyloxy compound is allowed to stand in an atmosphere of saturated steam and then dried under reduced pressure. It can be easily produced and isolated by a simple method such as

(Example 56)
An acetonitrile solution of 0.30 mmol of diphenylsilanediol (IIAa) was added to an acetonitrile solution of 0.30 mmol of tetraacetoxysilane (IAa) and stirred at about 25° C. (room temperature) for 1 hour (total volume of acetonitrile was 0.30 mmol). 75 mL). After that, an acetonitrile solution of 0.15 mmol of IIAa was added (volume of acetonitrile was 0.75 mL) and stirred at about 25° C. for 1 day. The reaction solution was concentrated under reduced pressure and the volatile components were distilled off to give 0.143 mmol of IIIAa as a white solid (yield ≧95%).

(Example 57)
An acetonitrile solution of 0.60 mmol of tetraacetoxysilane (IAa) was added with an acetonitrile solution of 0.30 mmol of dimethylsilanediol (IIAc) and stirred at about 25° C. (room temperature) for 1 hour (the total volume of acetonitrile was 1.5 mmol). 5 mL). After that, an acetonitrile solution of 0.30 mmol of IIAc was added (the volume of acetonitrile was 1.5 mL) and stirred at about 25° C. for 1 day. The reaction solution was concentrated under reduced pressure to evaporate the volatile components to obtain 0.29 mmol of IIIAc as a colorless viscous liquid (yield ≧95%).

(Example 58)
An acetonitrile solution of 0.60 mmol of tetraacetoxysilane (IAa) was added with an acetonitrile solution of 0.30 mmol of diphenylsilanediol (IIAa) and stirred at about 25° C. (room temperature) for 1 hour (the total volume of acetonitrile was 1.5 mmol). 5 mL). After that, an acetonitrile solution of 0.30 mmol of dimethylsilanediol (IIAc) was added (the volume of acetonitrile was 1.5 mL) and stirred at about 25° C. for 1 day. The reaction solution was concentrated under reduced pressure to evaporate the volatile components to obtain 0.29 mmol of IIIAd as a colorless viscous liquid (yield ≧95%).

(Example 59)
An acetonitrile solution of 0.60 mmol of tetraacetoxysilane (IAa) was added with an acetonitrile solution of 0.30 mmol of diphenylsilanediol (IIAa), and the mixture was stirred at about 25° C. (room temperature) for 1 hour (the total volume of acetonitrile was 1.0 mmol). 5 mL). After that, an acetonitrile solution of 0.30 mmol of methylphenylsilanediol (IIAb) was added (the volume of acetonitrile was 1.5 mL) and stirred at about 25° C. for 1 day. The reaction solution was concentrated under reduced pressure to evaporate volatile components to give 0.29 mmol of IIIAe as a colorless viscous liquid (yield ≧95%).

(Example 60)
An acetonitrile solution of 0.60 mmol of tetraacetoxysilane (IAa) was added with an acetonitrile solution of 0.3015 mmol of dimethylsilanediol (IIAc) and stirred at about 25° C. (room temperature) for 1 hour (total volume of acetonitrile was 1.5 mmol). 5 mL). After that, an acetonitrile solution of 0.30 mmol of methylphenylsilanediol (IIAb) was added (the volume of acetonitrile was 1.5 mL) and stirred at about 25° C. for 1 day. The reaction solution was concentrated under reduced pressure to evaporate the volatile components to obtain 0.29 mmol of IIIAf as a colorless viscous liquid (yield ≧95%).

(Example 61)
An acetonitrile solution of 0.70 mmol of tetraacetoxysilane (IAa) was added with an acetonitrile solution of 0.35 mmol of diphenylsilanediol (IIAa) and stirred at about 25° C. (room temperature) for 1 hour (the total volume of acetonitrile was 1.5 mmol). 74 mL). A solution of (IIAa) 0.35 mmol in acetonitrile was then added (volume of acetonitrile was 1.74 mL) and stirred at about 25° C. for 1 hour. After 66 mL of acetonitrile was added to the reaction solution, an acetonitrile solution of 0.35 mmol of IIAa (the volume of acetonitrile was 70 mL) was gradually added, and the mixture was stirred at about 25° C. for 24 hours. The reaction solution was concentrated, the precipitated solid was filtered, the solid was washed with acetonitrile and dried to give 0.198 mmol of IVA1a as a white solid (57% yield). IVA1a was obtained as a colorless crystalline solid by recrystallization using acetonitrile.

(Example 62)
0.15 mmol of white solid IVA1a was allowed to stand at 25° C. for 2 days in an atmosphere of saturated steam and then dried under reduced pressure to obtain 0.145 mmol of white solid IVA1a-(OH) ₂ ( Yield ≧95%).

(Example 63)
To a toluene solution of 0.1 mmol of diacyloxycyclic siloxane (IVA1a), a toluene solution of 0.2 mmol of triphenylsilanol (IIA4a) and 0.4 mmol of pyridine were added, and the mixture was stirred at about 25°C for 1 day (total volume of toluene is approximately 0.44 mL). By adding acetonitrile to the reaction solution, 1,5-bis(triphenylsiloxy)-3,3,7,7,10,10-hexaphenyl-bicyclo[3.3.3]-1,3,5, 7,9-Pentasiloxane (IVA1a-(OSiPh ₃ ) ₂ ) was obtained as a colorless crystalline solid.

(Example 64)
A toluene solution of 0.1 mmol of triethylsilanol (IIA4c) and 0.4 mmol of pyridine were added to a toluene solution of 0.1 mmol of diacyloxycyclic siloxane (IVA1a), and the mixture was stirred at about 25° C. for one day (the total volume of toluene was about 0.44 mL). By adding acetonitrile to the reaction solution, 1,5-bis(triethylsiloxy)-3,3,7,7,10,10-hexaphenyl-bicyclo[3.3.3]-1,3,5,7 ,9-pentasiloxane (IVA1a-(OSiEt ₃ ) ₂ ) was obtained as a colorless crystalline solid.

Furthermore, as shown in the following examples, a polymeric cyclic siloxane compound can be produced by reacting a cyclic siloxane compound having two acyloxy groups with silanediol.

(Example 65)
A tetrahydrofuran solution of 0.2 mmol of dimethylsilanediol (IIAc) and 0.8 mmol of pyridine were added to a solution of 0.2 mmol of diacyloxycyclic siloxane (IVA1a) in tetrahydrofuran and stirred at about 25°C (total volume of tetrahydrofuran was 2 .0 mL). In order to confirm the progress of the reaction, after 1 day, 3 days, 7 days, 10 days, and 14 days, the reaction solution was analyzed by gel permeation chromatography (hereinafter referred to as GPC), resulting in the following structure VA1a-a ( In the following structural formulas, Ph represents a phenyl group and Me represents a methyl group.) was measured for molecular weight (see Table 4). In order to purify the product, after 7 days and 14 days, half of the reaction solution was added to 50 mL of methanol, and the formed precipitate was filtered, washed with methanol and dried. As a result, VA1a-a was obtained as a white powdery solid, respectively (VA1a-a1 obtained after treatment after 7 days was 0.070 mmol per repeating structural unit, yield 35%, after treatment after 14 days. VA1a-a2 thus obtained was 0.072 mmol per repeating structural unit, yield 36%, total yield 71%). The molecular weights of VA1a-a after purification were Mw38200 (Mw/Mn=2.3) for VA1a-a1 and Mw59800 (Mw/Mn=2.2) for VA1a-a2 (see Table 4). ).

(Examples 66-74)
Table 4 shows the results of reaction, analysis, and purification of the product in the same manner as in Example 65 by changing the reaction conditions (type of raw material, type of solvent, etc.).

Notes in Table 4 are shown below.
1) The reaction was carried out at about 25°C (room temperature).
2) IVA1a: 1,1,5,5-tetraacetoxy-3,3,7,7,10,10-hexaphenylbicyclo[3.3.3]-1,3,5,7,10-pentasiloxane.
3) IIAa: diphenylsilanediol, IIAb: methylphenylsilanediol, IIAc: dimethylsilanediol, IIAe: tetramethyl-1,3-disiloxane-1,3-diol, IIAf: hexamethyl-1,3,5-tri Siloxane-1,5-diol.
4) Py: pyridine.
5) THF: tetrahydrofuran, PhMe: toluene.
6) d indicates the day.
7) In the structural formula of the product, Me represents a methyl group, Ph represents a phenyl group, and n represents a structure in which multiple repeating structural units in parentheses are linked.
8) Molecular weight of product estimated by gel permeation chromatography (toluene eluent, polystyrene standard). Mw is the weight average molecular weight, Mn is the number average molecular weight, and Mw/Mn is the dispersity.
9) Yield numbers indicate the yield of the polymer product after purification obtained by pouring the reaction mixture into methanol. In one example, when there are two numbers, the yield obtained by processing half of the reaction solution after a certain period of time, and the yield obtained by processing the other half after a certain period of time. Yields are indicated, and the numbers in [] indicate their total yields.
10) Molecular weight of product after purification.

Alternatively, as shown in the following examples, a cyclic siloxane compound having two acyloxy groups may be reacted with a cyclic siloxane compound having two hydroxy groups to produce a polymeric cyclic siloxane compound. can.

(Example 75)
A tetrahydrofuran solution of 0.12 mmol of cyclic siloxane diol (IIA6a) (the same compound as IVA1a-(OH) ₂ ) and 0.48 mmol of pyridine were added to a solution of 0.12 mmol of diacyloxy cyclic siloxane (IVA1a) in tetrahydrofuran. Stir at 25° C. (total volume of tetrahydrofuran is 2.46 mL). After one day, the reaction solution was analyzed by GPC, and it was found that VA2a having the following structure was produced with a molecular weight of Mw=4300 (Mw/Mn=2.3). Two days later, the reaction solution was added to 50 mL of methanol, and the precipitate formed was filtered, washed with methanol, and dried. As a result, VA2a was obtained as a white powdery solid (0.19 mmol per repeating structural unit, yield 79%, molecular weight of tetrahydrofuran solubles Mw=15300, Mw/Mn=2.5).

Additionally, the reaction could also be run with three or four starting materials, as shown in the following examples.

(Example 76)
A toluene solution of 0.106 mmol of triphenylsilanol (IIA4a) and 0.212 mmol of pyridine were added to a toluene solution of 0.106 mmol of diacyloxycyclic siloxane (IVA1a) and stirred at about 25° C. for one day (total volume of toluene is 2.4 mL). As a result of measuring the reaction solution by NMR, unreacted IVA1a and compounds IVA1a-(OSiPh ₃ ) (OCOMe) in which one or two of the acyloxy groups of IVA1a were converted to siloxy groups and (OSiPh ₃ ) ₂ was found to be present in a ratio of approximately 1:2:1. A toluene solution of 0.053 mmol of cyclic siloxane diol (IIA6a) (the same compound as IVA1a-(OH) ₂ ) was added to the reaction solution (volume of toluene was 0.5 mL), and the mixture was stirred at about 25° C. for 1 day. . As a result of measuring the obtained reaction solution by NMR, it was found that IVA1a-(OSiPh ₃ ) ₂ , VA3a-1 and VA3a-2, which are cyclic siloxane compounds having the following structures, were present. Each product was separated and purified using preparative GPC ( _{tetrahydrofuran eluent} ). and 0.0125 mmol (46%, 27%, and 21%, respectively, for IIA4a). Table 3 shows the nuclear magnetic resonance spectrum and/or mass spectrometry data of the obtained cyclic siloxane compounds VA3a-1 and VA3a-2.

(Example 77)
A toluene solution of 0.10 mmol of triphenylsilanol (IIA4a) and 0.20 mmol of pyridine were added to a toluene solution of 0.10 mmol of diacyloxycyclic siloxane (IVA1a) and stirred at about 25°C for 1 day to form an intermediate mixture. (A) was obtained (2 mL total volume of toluene). The obtained intermediate mixture (A) was measured by NMR, and as a result, unreacted IVA1a and IVA1a-(OSiPh ₃ )(OCOMe) and IVA1a-(OSiPh ₃ ) ₂ were found to be present in a ratio of about 1:2:1.
Also, 0.10 mmol of acetoxytrimethylsilane (IA2a) and 0.20 mmol of pyridine were added to a toluene solution of 0.10 mmol of cyclic siloxane diol (IIA6a) (the same compound as IVA1a-(OH) ₂ ), resulting in about 25 After stirring at ℃ for 1 day, an intermediate mixture (B) was obtained (volume of toluene was 2 mL). The obtained intermediate mixture (B) was measured by NMR, and as a result, unreacted IIA6a and IVA1a-(OSiMe ₃ )(OH) and IVA1a-(OSiMe ₃ ) ₂ were found to be present in a ratio of about 1:2:1.
Subsequently, the intermediate mixture (A) and the intermediate mixture (B) were mixed and stirred at about 25° C. for one day to obtain a reaction solution (C). The resulting reaction solution (C) was measured by NMR, and the presence of cyclic siloxane compounds IVA1a-(OSiPh ₃ ) ₂ , IVA1a-(OSiMe ₃ ) ₂ , VA5a-1, and VA3a-1 having the following structures was confirmed. I found out. As a result of separating and purifying each product using preparative GPC (tetrahydrofuran eluent), IVA1a-(OSiPh ₃ ) ₂ , IVA1a-(OSiMe ₃ ) ₂ , VA5a-1, and VA3a-1 were respectively 0.022mmol, 0.011mmol, 0.024mmol and 0.010mmol were obtained (44%, 22%, 24% and 20% yields for (IIA4a) or (IA2a) respectively). Table 3 shows the nuclear magnetic resonance spectrum and mass spectrometry data of the obtained cyclic siloxane compound (VA5a-1).

Since the polymer compound containing a cyclic siloxane skeleton has a thermally stable cyclic skeleton, it showed high thermal stability in nitrogen and air by thermogravimetric analysis, as shown in the following examples.

(Example 78)
In order to investigate the thermal stability of the polymeric cyclic siloxane (VA1a-a1) obtained in Example 65, a thermogravimetric analyzer was used in nitrogen or air at a heating rate of 10°C/min. The temperature was raised from room temperature to 1000° C., and the weight change was measured. As a result, the 5% weight loss temperature (hereinafter referred to as Td ₅ ) was 506°C in nitrogen and 494°C in air, indicating high thermal stability in both atmospheres (see Table 5). .

(Examples 79-94)
Thermogravimetric analysis was performed in the same manner for other polymeric cyclic siloxane compounds (Table 5). As a result, it was found that all the compounds had a Td ₅ of 430° C. or more and had high thermal stability.

Notes in Table 5 are shown below.
1) Cyclic siloxane compounds obtained in Table 4 and Example 75.
2) Molecular weight estimated by gel permeation chromatography (toluene eluent, polystyrene standard). Mw is the weight average molecular weight, Mn is the number average molecular weight, and Mw/Mn is the dispersity.
3) Measured in nitrogen or air (atmospheric gas flow rate is 200 mL/min). The temperature range for measurement was 30 to 1000°C, the temperature increase rate was 10°C/min, Td ₅ was 5% weight loss, and the residue was the remaining weight % after heating to 980°C.

Comparing Td ₅ in air, Td ₅ (532° C.) of VA1c-a1 having a diphenylsiloxane moiety is about 40° C. higher than Td ₅ (494° C.) of VA1a-a1 having a dimethylsiloxane moiety, Phenyl groups were more advantageous than methyl groups as silicon-bonded substituents for obtaining high thermal stability (Examples 78 and 86). In addition, among compounds having the same repeating structural unit, Td ₅ (513° C.) of the compound having a large molecular weight is about 20° C. higher than Td ₅ (494° C.) of the compound having a small molecular weight. A trend towards higher thermal stability was observed for the compounds (Examples 78 and 79).

The high-molecular-weight cyclic siloxane compound can be used in various forms such as coating films, films, additives, fillers, and the like. In particular, a compound having an oligosiloxane moiety with an appropriate molecular weight in its main chain is advantageous for forming a coating film or film. gave a more transparent coating film.

Compounds having a cyclic siloxane structure can be used not only singly, but also as a mixture of multiple types, or as a mixture with other materials.

The production method of the present invention can more efficiently and safely produce cyclic siloxane compounds that are useful as functional chemicals and materials, and can provide novel cyclic siloxane compounds and their uses, so the utility value of the present invention is high. , its industrial significance is enormous.

Claims (11)

Each - -Si-O- bonds are formed between the OH group and each Si of two molecules of acyloxysilane, and the product is reacted with at least one molecule of silanol having two -OH groups. A method for producing a cyclic siloxane compound having a cyclic siloxane with a ring skeleton formed by -Si-O- bonds, comprising a step of performing a stepwise reaction as follows,
The acyloxysilane is an acyloxysilane represented by formula (IA),
The silanol is a silanol represented by formula (IIA1) (silanol added in step 1 below) and a silanol represented by formula (IIA2) (silanol added in step 2 below),
The cyclic siloxane compound is a compound represented by formula (IIIA),
The step of continuously reacting comprises step 1 of adding a silanol represented by formula (IIA1); and step 2 of adding a silanol represented by formula (IIA2) after step 1 ; A method for producing a cyclic siloxane compound.
^{R1aSi (} _OCOR2 ) _4-a (IA)
(In formula (IA), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; R ² is a and a is 0 or 1. The hydrogen atoms bonded to the carbon atoms of R ¹ and R ² may be substituted with groups that do not participate in the reaction.);
HO ^{( SiR3R4O} ) _bH (IIA1)
(In formula (IIA1), R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and b is , an integer of 1 to 6. The hydrogen atoms bonded to the carbon atoms of R ³ and R ⁴ may be substituted with groups that do not participate in the reaction.);
HO ^{( SiR5R6O} ) _cH (IIA2)
(In formula (IIA2), R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and c is , an integer of 1 to 6. The hydrogen atoms bonded to the carbon atoms of R ⁵ and R ⁶ may be substituted with groups that do not participate in the reaction.);

(In formula (IIIA), a, b, c, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are a , b, c, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ .) Each - -Si-O- bonds are formed between the OH group and each Si of two molecules of acyloxysilane, and the product is reacted with at least one molecule of silanol having two -OH groups. A method for producing a cyclic siloxane compound having a cyclic siloxane with a ring skeleton formed by -Si-O- bonds, comprising a step of performing a stepwise reaction as follows,
The acyloxysilane is an acyloxysilane represented by formula (IA),
The silanol is a silanol represented by formula (IIA1) (silanol added in step 1 below), a silanol represented by formula (IIA2) (silanol added in step 2 below), and a formula (IIA3). is a silanol (silanol added in step 3 below),
The cyclic siloxane compound is a compound represented by formula (IVA1) and/or (IVA2),
The step of reacting continuously includes step 1 of adding a silanol represented by formula (IIA1); step 2 of adding a silanol represented by formula (IIA2) after step 1; and step 2. followed by step 3 of adding a silanol represented by formula (IIA3); a method for producing a cyclic siloxane compound.
^{R1aSi (} _OCOR2 ) _4-a (IA)
(In formula (IA), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; R ² is a and a is 0 or 1. The hydrogen atoms bonded to the carbon atoms of R ¹ and R ² may be substituted with groups that do not participate in the reaction.);
HO ^{( SiR3R4O} ) _bH (IIA1)
(In formula (IIA1), R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and b is , an integer of 1 to 6. The hydrogen atoms bonded to the carbon atoms of R ³ and R ⁴ may be substituted with groups that do not participate in the reaction.);
HO ^{( SiR5R6O} ) _cH (IIA2)
(In formula (IIA2), R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and c is , an integer of 1 to 6. The hydrogen atoms bonded to the carbon atoms of R ⁵ and R ⁶ may be substituted with groups that do not participate in the reaction.);
HO ^{( SiR7R8O} ) _dH (IIA3)
(In formula (IIA3), R ⁷ and R ⁸ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and d is , an integer of 1 to 6. The hydrogen atoms bonded to the carbon atoms of R ⁷ and R ⁸ may be substituted with groups that do not participate in the reaction.);

(In formula (IVA1) and formula (IVA2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , a, b, c, and d are represented by formula (IA) , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , a, b, c, and d in formula (IIA1), formula (IIA2), and formula (IIA3) synonymous.) When an acyloxy group remains in the cyclic siloxane compound, the cyclic siloxane compound is reacted with water or an alcohol represented by the formula (VIA) to replace at least one of the remaining acyloxy groups with a hydroxy group or an alkoxy group. further comprising a modification step of converting to
3. The method for producing a cyclic siloxane compound according to claim 1 or 2, wherein the alkoxy group is represented by -OR ⁹ group (R ⁹ has the same definition as R ⁹ in formula (VIA)).
^R9OH (VIA)
(In formula (VIA), R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, and an aralkyl group. The hydrogen atom bonded to the carbon atom of R ⁹ is It may be substituted with a group that does not participate in the reaction.) A modification step of reacting the cyclic siloxane compound with a silanol represented by the formula (IIA4) to convert at least one of the remaining acyloxy groups into siloxy groups when the cyclic siloxane compound has residual acyloxy groups. further comprising
the siloxy group is represented by a —OSiR ¹⁰ R ¹¹ R ¹² group (R ¹⁰ , R ¹¹ and R ¹² have the same meanings as R ¹⁰ , R ¹¹ and R ¹² in formula (IIA4)); The method for producing a cyclic siloxane compound according to claim 1 or 2 .
^{R10R11R12SiOH ( IIA4} )
(In formula (IIA4), R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; The hydrogen atoms bonded to the carbon atoms of R ¹⁰ , R ¹¹ and R ¹² may be substituted with groups that do not participate in the reaction.) A method for producing a cyclic siloxane compound represented by formula (VA1), comprising reacting a cyclic siloxane compound represented by formula (IVA1) with a silanol represented by formula (IIA5).

(In formula (IVA1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group. a selected hydrocarbon group having 1 to 12 carbon atoms, R ² is an alkyl group having 1 to 3 carbon atoms, a is 0, b, c, and d are each independently 1 to is an integer of 6. The hydrogen atoms bonded to the carbon atoms of ^{R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are substituted with groups that do not participate in the reaction. is also good.);
HO ^{( SiR13R14O} ) _eH (IIA5)
(In formula (IIA5), R ¹³ and R ¹⁴ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and e is , an integer of 1 to 1000. The hydrogen atoms bonded to the carbon atoms of R ¹³ and R ¹⁴ may be substituted with groups that do not participate in the reaction.);

(In formula (VA1), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹³ , R ¹⁴ , b, c, d, and e represent formula (IVA1) and formula (IIA5), respectively. ) is synonymous with R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹³ , R ¹⁴ , b, c, d and e in v is an integer of 1 or more and 10000 or less , the group attached to the terminal silyl group is an acyloxy group, a hydroxy group, or an alkoxy group.) A method for producing a cyclic siloxane compound represented by formula (VA2), comprising reacting a cyclic siloxane compound represented by formula (IVA1) with a silanol represented by formula (IIA6).

(In formula (IVA1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group. a selected hydrocarbon group having 1 to 12 carbon atoms, R ² is an alkyl group having 1 to 3 carbon atoms, a is 0, b, c, and d are each independently 1 to is an integer of 6. The hydrogen atoms bonded to the carbon atoms of ^{R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are substituted with groups that do not participate in the reaction. is also good.);

(In formula (IIA6), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a carbon selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group. a hydrocarbon group of numbers 1 to 12, f, g and h are each independently an integer of 1 to 6. R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ A hydrogen atom attached to a carbon atom may be substituted with a group that does not participate in the reaction.);

⁽ in formula (VA2), R ³ , R ⁴ , R 5 , R ⁶ , R ⁷ , R ⁸ , R ^{15 , R 16 ,} R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , b, c, d, f , g, and h are respectively R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R 15 , R ¹⁶ , R ¹⁷ , R ¹⁸ , ^{R 19 in} formula (IVA1) and formula (IIA6) , R ²⁰ , b, c, d, f, g, and h, w is an integer of 1 or more and 10000 or less, and the group bonded to the terminal silyl group is an acyloxy group or a hydroxy group. , or an alkoxy group.) In the step of reacting the cyclic siloxane compound represented by the formula (IVA1) with the silanol represented by the formula (IIA6), the silanol represented by the formula (IIA4) and/or the silanol represented by the formula (IA2) 7. The production method according to claim 6 , wherein acyloxysilane is added to obtain at least one cyclic siloxane compound selected from the group consisting of formula (VA3), formula (VA4), and formula (VA5).
^{R10R11R12SiOH ( IIA4} )
(In formula (IIA4), R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; The hydrogen atoms bonded to the carbon atoms of R ¹⁰ , R ¹¹ and R ¹² may be substituted with groups that do not participate in the reaction.);
^{R21R22R23SiOCOR24 ( IA2 )}
(in formula (IA2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; and R ²⁴ is an alkyl group having 1 to 3 carbon atoms.The hydrogen atoms bonded to the carbon atoms of ^{R 21} , R ²² and R ²³ may be substituted with groups that do not participate in the reaction.) ;

(In formula (VA3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 10 , R 11 , R 12 , R 15 , R 16 , R 17 , R 18} , ^{R 19 ,} R ²⁰ , b, c, d, f, g, and h are R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , b, c, d, f, g, and h w1 is 1 or more and 10,000 is an integer below.);

(In formula (VA4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 15 , R 16 , R 17} , R ¹⁸ , R 19 , R ²⁰ , R ²¹ , ^{R 22 ,} R ²³ , b, c, d, f, g, and h are R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , b, c, d, f, g, and h w2 is 1 or more and 10,000 is an integer below.);

(In formula (VA5), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 10 , R 11 , R 12 , R 15 , R 16 , R 17 , R 18} , ^{R 19 ,} R ²⁰ , R ²¹ , R ²² , R ²³ , b, c, d, f, g, and h are R ³ , R in formula (IVA1), formula (IIA6), formula (IIA4), and formula (IA2) ⁴ , R5 ^{, R6} , ^{R7 , R8} , R10, R11, ^R12 , ^R15 , ^R16 , ^{R17 , R18} , R19, ^R20 , ^R21 , ^R22 , ^{R23 ,} (synonymous with b, c, d, f, g, and h. w3 is an integer of 0 or more and 10,000 or less.) A cyclic siloxane compound represented by formula (IIIB), formula (IVB1), formula (IVB2), formula (VB1), formula (VB2), formula (VB3), or formula (VB4).

(In formula (IIIB), R ^a1 is an alkenyl group having 2 to 3 carbon atoms, and R ^a2 , R ^a3 , R ^a4 , and R ^a5 are each independently an alkyl group having 1 to 6 carbon atoms or a carbon an aryl group having a number of 6 to 10, X ¹ is an acetoxy group, i is 0 or 1, j1 and j2 are each independently an integer of 1 to 6.);

(in formula (IVB1), R ^a6 , R ^a7 , R ^a8 , R ^a9 , R ^a10 and R ^a11 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; , X ² is an acetoxy group, a hydroxy group, k1, k2, and k3 are each independently an integer of 1 to 6,
In formula (IVB2), R ^a6 , R ^a7 , R ^a8 , R ^a9 , R ^a10 and R ^a11 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; X ² is an acetoxy group, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or a siloxy group having 3 to 20 carbon atoms, and k1, k2, and k3 are each independently an integer of 1 to 6. . );

(in formula (VB1), R ^a12 , R ^a13 , R ^a14 , R ^a15 , R ^a16 , R ^a17 , R ^a18 , and R ^a19 are each independently an alkyl group or an aryl group having 1 to 6 carbon atoms; , l1, l2, l3, and l4 are each independently an integer of 1 to 6, x is an integer of 1 or more and 10000 or less, and the group bonded to the terminal silyl group is an acetoxy group, a hydroxy group or an alkoxy group);

(In formula (VB2), ^Ra20 , ^Ra21 , ^Ra22 , Ra23, ^Ra24 , ^Ra25 , ^Ra26 , ^Ra27 , ^Ra28 , ^{Ra29 , Ra30} , and ^Ra31 are each independently a carbon an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, m1, m2, m3, m4, m5, and m6 are each independently an integer of 1 to 6, and y is 1 or more It is an integer of 10000 or less, and the group bonded to the terminal silyl group is an acetoxy group, a hydroxy group, or an alkoxy group.);

(in formula (VB3), ^Ra32 , ^Ra33 , ^Ra34 , ^Ra35 , Ra36, ^Ra37 , ^Ra38 , ^Ra39 , ^Ra40 , ^Ra41 , ^Ra42 , ^Ra43 , ^Ra44 , ^Ra45 , ^and R ^a46 is each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m7, m8, m9, m10, m11, and m12 are each independently is an integer, and y1 is an integer of 0 or more and 10000 or less.);

(In formula (VB4), ^Ra47 , ^Ra48 , ^Ra49 , ^Ra50 , ^Ra51 , ^Ra52 , ^Ra53 , ^Ra54 , ^{Ra55, Ra56} , ^{Ra57 , Ra58} , ^Ra59 , ^Ra60 , R ^a61 , R ^a62 , R ^a63 , and R ^a64 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m13, m14, m15, m16, m17, and m18 are , are each independently an integer of 1 to 6, and y2 is an integer of 0 or more and 10000 or less.) A composition comprising at least one cyclic siloxane compound selected from the group consisting of formula (VA1), formula (VA2), formula (VA3), formula (VA4), and formula (VA5).

(In formula (VA1), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹³ , and R ¹⁴ are each independently selected from an alkyl group, an aryl group, an alkenyl group, and an aralkyl group. a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of b, c, and d each independently being an integer of 1 to 6, and e being an integer of 1 to 1,000 ^. , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹³ and R ¹⁴ may be substituted with groups that do not participate in the reaction, and v is 1 or more. It is an integer of 10000 or less, and the group bonded to the terminal silyl group is an acyloxy group, a hydroxy group, or an alkoxy group.);

(In formula (VA2), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent an alkyl a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of groups, aryl groups, alkenyl groups, and aralkyl groups, and b, c, d, f, g, and h each independently represent 1 to 6 The hydrogen atoms bonded to the carbon atoms of ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R15 , ^R16 , ^R17 , ^R18 , ^R19 , and ^R20 are , may be substituted with a group that does not participate in the reaction, w is an integer of 1 or more and 10000 or less, and the group bonded to the terminal silyl group is an acyloxy group, a hydroxy group, or an alkoxy group. );

(in formula (VA3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 10 , R 11 , R 12 , R 15 , R 16 , R 17 , R 18 ,} R ¹⁹ , and Each R ²⁰ is independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and b, c, d, f, g and h each independently represents an integer of 1 to 6. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R 10 , R ¹¹ , R ¹² , R ¹⁵ , R ¹⁶ , R ^{17 ,} Hydrogen atoms bonded to carbon atoms of R ¹⁸ , R ¹⁹ and R ²⁰ may be substituted with groups that do not participate in the reaction, w1 is an integer of 1 or more and 10000 or less);

(in formula (VA4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 15 , R 16 , R 17 , R 18} , R ¹⁹ , R ²⁰ , ^{R 21 ,} R ²² , and R ²³ is each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group, and b, c, d, f, g and h each independently represents an integer of 1 to 6. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R 15 , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ^{20 ,} hydrogen atoms bonded to carbon atoms of R ²¹ , R ²² and R ²³ may be substituted with groups that do not participate in the reaction, w2 is an integer of 1 or more and 10000 or less);

(In formula (VA5), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 , R 10 , R 11 , R 12 , R 15 , R 16 , R 17 , R 18} , ^{R 19 ,} R ²⁰ , R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an aralkyl group; , d, f, g, and h are each independently an integer of 1 to 6. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² , Hydrogen atoms bonded to carbon atoms of R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ may be substituted with groups that do not participate in the reaction. w3 is an integer from 0 to 10000.) A composition comprising at least one cyclic siloxane compound selected from the group consisting of formula (VB1), formula (VB2), formula (VB3), and formula (VB4).

(in formula (VB1), R ^a12 , R ^a13 , R ^a14 , R ^a15 , R ^a16 , R ^a17 , R ^a18 , and R ^a19 are each independently an alkyl group or an aryl group having 1 to 6 carbon atoms; , l1, l2, l3, and l4 are each independently an integer of 1 to 6, x is an integer of 1 or more and 10000 or less, and the group bonded to the terminal silyl group is an acetoxy group, a hydroxy group or an alkoxy group);

(In formula (VB2), ^Ra20 , ^Ra21 , ^Ra22 , Ra23, ^Ra24 , ^Ra25 , ^Ra26 , ^Ra27 , ^Ra28 , ^{Ra29 , Ra30} , and ^Ra31 are each independently a carbon an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, m1, m2, m3, m4, m5, and m6 are each independently an integer of 1 to 6, and y is 1 or more It is an integer of 10000 or less, and the group bonded to the terminal silyl group is an acetoxy group, a hydroxy group, or an alkoxy group.);

(in formula (VB3), ^Ra32 , ^Ra33 , ^Ra34 , ^Ra35 , Ra36, ^Ra37 , ^Ra38 , ^Ra39 , ^Ra40 , ^Ra41 , ^Ra42 , ^Ra43 , ^Ra44 , ^Ra45 , ^and R ^a46 is each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m7, m8, m9, m10, m11, and m12 are each independently is an integer, and y1 is an integer of 0 or more and 10000 or less.);

(In formula (VB4) ^{, Ra47} , ^Ra48 , ^Ra49 , ^Ra50 , ^Ra51 , ^Ra52 , ^Ra53 , ^Ra54 , ^{Ra55, Ra56} , ^Ra57 , ^Ra58 , ^Ra59 , ^Ra60 , R ^a61 , R ^a62 , R ^a63 , and R ^a64 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and m13, m14, m15, m16, m17, and m18 are , are each independently an integer of 1 to 6, and y2 is an integer of 0 or more and 10000 or less.) A heat resistant material comprising the composition according to claim 9 or 10 .