JP7023511B2 - Method for producing cyclic siloxane compound and cyclic siloxane compound - Google Patents

Description

The present invention relates to a method for producing a cyclic siloxane compound and a cyclic siloxane compound.

Siloxane compounds typified by polysiloxane are functional chemicals and materials used in various industrial fields such as construction, electricity, automobiles, medical treatment, and daily necessities in the form of oil, rubber, resin, and the like. .. In order to improve the functionality and performance of such a siloxane compound, a method for efficiently producing a compound having a cyclic siloxane structure having excellent thermal stability and the like, and a method for efficiently producing a cyclic compound having higher functionality and performance. The development of siloxane compounds is also an important issue.

As a general method for producing cyclic siloxane, (A) a method for hydrolyzing chlorosilanes (for example, Patent Documents 1 and 2 and Non-Patent Documents 1 and 2) and (B) chlorosilanes and silanols are present as bases. Methods for reacting below (eg, Patent Document 3 and Non-Patent Documents 3 and 4) and the like have been known.

On the other hand, a compound having a structure in which silicon atoms at diagonal positions of cyclotetrasiloxane are bonded to each other with an oxycilylene oxy group is a bicyclic pentamer having five silicon atoms (bicyclo [3.3.3] pentasiloxane). ), And has two cyclotetrasiloxane skeletons in the molecule. Therefore, the bicyclic pentamer compound is expected to have physical properties such as thermal stability superior to that of a simple cyclotetrasiloxane compound. As such a bicyclic pentamer compound, a compound having a substituent such as a phenyl group or a methyl group is known. Examples of the method for producing them include (C) a method of reacting chlorosilanes and silanols in the presence of a base (for example, Patent Document 4 and Non-Patent Documents 4 and 5), and (D) bicyclo [1] of a bicyclic oligosilane. .1.1] A method of reacting pentasilane with an oxidizing agent (m-chloroperbenzoic acid) (Non-Patent Document 6) and the like have been reported.

As a method for producing the cyclic siloxane, (E) 1,1,3,3,5,5-hexamethyltrisiloxane and diphenylsilanediol are reacted in the presence of a tris (pentafluorophenyl) borate catalyst. A method for obtaining a cyclic tetramer by allowing the mixture to be obtained is known (for example, Patent Document 5 and Non-Patent Document 7).

Special Publication No. 63-28893 Japanese Unexamined Patent Publication No. 07-285974 Japanese Unexamined Patent Publication No. 08-157487 U.S. Pat. No. 3,145,225 US 2013/79539

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) Angewandte Chemie International Edition, 56, 8706 (2017)

However, the above-mentioned conventional manufacturing method has problems in the following points.
(1) When chlorosilanes are used as raw materials, it is not easy to handle the raw material compounds because hydrogen chloride having a corrosive action is likely to be generated by their hydrolysis. Since corrosive hydrogen chloride and its salts are also produced when silanediol is reacted, special care must be taken in the storage of raw materials, the reaction container, the treatment of waste, etc. (Methods A, B, and). C).
(2) When a bicyclic oligosilane is used as a raw material, it is not easy to produce the raw material compound, and an expensive oxidizing agent is required even in the oxidation reaction (method D). Further, the polymer compound containing a cyclic siloxane skeleton is expected to be applied to a functional material having excellent thermal stability and mechanical properties, but has not been produced so far.
(3) In the methods of Patent Document 5 and Non-Patent Document 7, hydrogen chloride is not generated and an expensive oxidizing agent is not required, but the yield of the target siloxane compound is low.
For these reasons, there has been a demand for an industrially more advantageous method that can solve the problems of the prior art.

An object of the present invention is to provide an efficient and selective method for producing a siloxane compound having a cyclic skeleton.

As a result of diligent research to solve the above problems, the present inventors have found that a cyclic siloxane compound can be efficiently produced by reacting a predetermined compound in the presence of a predetermined catalyst, and complete the present invention. I came to let you.

（式（１）中、Ｒ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
Ｒ^B1及びＲ^B2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかである。
ただし、Ｒ^A1及びＲ^A2の組み合わせ並びにＲ^C1及びＲ^C2の組み合わせとＲ^B1及びＲ^B2の組み合わせとは、互いに同一でない。）
［２］
Ｒ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2が、それぞれ独立して、水素原子、アルキル基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
Ｒ^B1及びＲ^B2が、それぞれ独立して、アリール基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかである、［１］に記載の製造方法。
［３］
前記環状シロキサン化合物が、前記環骨格を１つ有する化合物である、［１］に記載の製造方法。
［４］
前記環骨格を１つ有する化合物が、下記式（３）で表される化合物である、［３］に記載の製造方法。

（式（３）中、Ｒ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
Ｒ^B1及びＲ^B2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
Ｒ^D1及びＲ^D2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、アルコキシ基、及びシロキシ基からなる群より選ばれるいずれかであり、
ｐ’は、０以上の整数である。
ただし、Ｒ^A1及びＲ^A2の組み合わせ並びにＲ^C1及びＲ^C2の組み合わせとＲ^B1及びＲ^B2の組み合わせとは、互いに同一でない。）
［５］
下記式（１）で表される化合物と、少なくとも２個のヒドロキシ基を有するケイ素化合物とを、遷移金属ヒドリド錯体触媒の存在下で反応させ、－Ｓｉ－Ｏ－結合により環骨格を形成する工程を含む、前記環骨格を少なくとも１つ有する環状シロキサン化合物の製造方法。

（式（１）中、Ｒ ^A1 、Ｒ ^A2 、Ｒ ^C1 及びＲ ^C2 は、それぞれ独立して、アルコキシ基であり、
Ｒ ^B1 及びＲ ^B2 は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ ^X1 )(Ｒ ^X2 )Ｈ基（Ｒ ^X1 及びＲ ^X2 は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかである。）
［６］
下記式（１）で表される化合物と、アルコール化合物又は少なくとも２個のヒドロキシ基若しくはアルコキシ基を有するケイ素化合物とを、ホウ素触媒及び／又は遷移金属ヒドリド錯体触媒の存在下で反応させ、－Ｓｉ－Ｏ－結合により環骨格を形成する工程を含む、前記環骨格を少なくとも１つ有する環状シロキサン化合物の製造方法であって、

（式（１）中、Ｒ ^A1 、Ｒ ^A2 、Ｒ ^C1 及びＲ ^C2 は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
Ｒ ^B1 及びＲ ^B2 は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ ^X1 )(Ｒ ^X2 )Ｈ基（Ｒ ^X1 及びＲ ^X2 は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかである。
ただし、Ｒ ^A1 及びＲ ^A2 の組み合わせ並びにＲ ^C1 及びＲ ^C2 の組み合わせとＲ ^B1 及びＲ ^B2 の組み合わせとは、互いに同一でない。）
前記環状シロキサン化合物が、前記環骨格内のケイ素原子間で形成される架橋環を少なくとも１つ含む、２以上の環から構成される化合物であり、
前記環骨格を形成する工程において、前記式（１）で表される化合物（式（１）中、Ｒ^B1及びＲ^B2の少なくとも一方は、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基である。）と、少なくとも３個のヒドロキシ基若しくはアルコキシ基を有するケイ素化合物とを反応させる、製造方法。
［７］
前記環骨格内のケイ素原子間で形成される架橋環を少なくとも１つ含む、２以上の環から構成される化合物が、下記式（４）で表される化合物であり、
少なくとも３個のヒドロキシ基若しくはアルコキシ基を有するケイ素化合物が、式（Ａ１－１）で表される化合物である、［６］に記載の製造方法。

（式（４）中、Ｒ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
Ｒ^B2は、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
Ｒ^D2は、アルキル基、アリール基、アルケニル基、アルコキシ基、及びシロキシ基からなる群より選ばれるいずれかであり、

（式（Ａ１－１）中、Ｒ^D1は、アルコキシ基であり、
Ｒ^D2は、アルキル基、アリール基、アルケニル基、アルコキシ基、及びシロキシ基からなる群より選ばれるいずれかであり、
Ｒ^E1及びＲ^E2は、アルキル基である。）
［８］
下記式（１）で表される化合物と、アルコール化合物又は少なくとも２個のヒドロキシ基若しくはアルコキシ基を有するケイ素化合物とを、ホウ素触媒及び／又は遷移金属ヒドリド錯体触媒の存在下で反応させ、－Ｓｉ－Ｏ－結合により環骨格を形成する工程を含む、前記環骨格を少なくとも１つ有する環状シロキサン化合物の製造方法であって、

（式（１）中、Ｒ ^A1 、Ｒ ^A2 、Ｒ ^C1 及びＲ ^C2 は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
Ｒ ^B1 及びＲ ^B2 は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ ^X1 )(Ｒ ^X2 )Ｈ基（Ｒ ^X1 及びＲ ^X2 は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかである。
ただし、Ｒ ^A1 及びＲ ^A2 の組み合わせ並びにＲ ^C1 及びＲ ^C2 の組み合わせとＲ ^B1 及びＲ ^B2 の組み合わせとは、互いに同一でない。）
前記環状シロキサン化合物が、前記環骨格内のケイ素原子間で形成される架橋環を少なくとも１つ含む、２以上の環から構成される化合物であり、
前記環骨格を形成する工程において、前記式（１）で表される化合物（式（１）中、Ｒ^B1及びＲ^B2は、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基である。）と、少なくとも４個のヒドロキシ基若しくはアルコキシ基を有するケイ素化合物とを反応させる、製造方法。
［９］
前記環骨格内のケイ素原子間で形成される架橋環を少なくとも１つ含む、２以上の環から構成される化合物が、下記式（５）で表される構造を有する化合物であり、
少なくとも４個のヒドロキシ基若しくはアルコキシ基を有するケイ素化合物が、式（Ａ１－２）で表される化合物である、［８］に記載の製造方法。

（式（５）中、Ｒ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかであり、
ｎは、２以上の整数である。）

（式（Ａ１－２）中、Ｒ^D1及びＲ^D2は、アルコキシ基であり、Ｒ^E1及びＲ^E2は、アルキル基である。）
［１０］
下記式（１）で表される化合物と、アルコール化合物又は少なくとも２個のヒドロキシ基若しくはアルコキシ基を有するケイ素化合物とを、ホウ素触媒及び／又は遷移金属ヒドリド錯体触媒の存在下で反応させ、－Ｓｉ－Ｏ－結合により環骨格を形成する工程を含む、前記環骨格を少なくとも１つ有する環状シロキサン化合物の製造方法であって、

（式（１）中、Ｒ ^A1 、Ｒ ^A2 、Ｒ ^C1 及びＲ ^C2 は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
Ｒ ^B1 及びＲ ^B2 は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ ^X1 )(Ｒ ^X2 )Ｈ基（Ｒ ^X1 及びＲ ^X2 は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかである。
ただし、Ｒ ^A1 及びＲ ^A2 の組み合わせ並びにＲ ^C1 及びＲ ^C2 の組み合わせとＲ ^B1 及びＲ ^B2 の組み合わせとは、互いに同一でない。）
前記環状シロキサン化合物が、少なくとも１つのスピロ環を含む、２以上の環から構成される化合物であり、
前記式（１）におけるＲ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2は、それぞれ独立して、アルコキシ基であり、Ｒ^B1及びＲ^B2は、それぞれ独立して、アルキル基、アリール基、及び、アルケニル基からなる群より選ばれるいずれかであり、
前記式（１）で表される化合物と、少なくとも２個のヒドロキシ基を有するシラン化合物とを、遷移金属ヒドリド錯体触媒の存在下で反応させ、さらに下記式（２）で表される化合物をホウ素触媒の存在下で反応させる工程を含む、製造方法。

（式（２）中、Ｒ^A1'、Ｒ^A2'、Ｒ^C1'及びＲ^C2'は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
Ｒ^B1'及びＲ^B2'は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1')(Ｒ^X2')Ｈ基（Ｒ^X1'及びＲ^X2'は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
ｎは、１以上の整数である。
ただし、Ｒ^A1'及びＲ^A2'の組み合わせ並びにＲ^C1'及びＲ^C2'の組み合わせとＲ^B1'及びＲ^B2'の組み合わせとは、互いに同一でない。）
［１１］
前記少なくとも１つのスピロ環を含む、２以上の環から構成される化合物が、下記式（６）で表される構造を有する化合物である、［１０］に記載の製造方法。

（式（６）中、Ｑ¹及びＱ²は、それぞれ独立して以下の構造：

（Ｒ^B1'、Ｒ^B2'は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1')(Ｒ^X2')Ｈ基（Ｒ^X1'及びＲ^X2'は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、Ｒ^C1'、Ｒ^C2'は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、ｎは１以上の整数である。）で表され、
Ｒ^B1及びＲ^B2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
Ｒ^D1及びＲ^D2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、アルコキシ基、及びシロキシ基からなる群より選ばれるいずれかであり、
Ｒ^A1'及びＲ^A2'は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
ｐ及びＮは、１以上の整数である。）
［１２］
前記少なくとも１つのスピロ環を含む、２以上の環から構成される化合物が、下記式（６－１）で表される化合物である、［１０］に記載の製造方法。

（式（６－１）中、Ｑ¹及びＱ²は、それぞれ独立して以下の構造：

で表され、
Ｒ^B1及びＲ^B2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
Ｒ^D1及びＲ^D2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、アルコキシ基、及びシロキシ基からなる群より選ばれるいずれかであり、
Ｒ^A1'及びＲ^A2'は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
Ｒ^B1'及びＲ^B2'は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1')(Ｒ^X2')Ｈ基（Ｒ^X1'及びＲ^X2'は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
Ｒ^C1'及びＲ^C2'は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
ｐ及びｎは、１以上の整数である。）
［１３］
下記式（II）で表される、環状シロキサン化合物。

（式（II）中、Ｒ^eは、シロキシ基であり、
Ｒ^f、Ｒ^g1、Ｒ^g2、Ｒ^h1、Ｒ^h2、Ｒⁱ¹、及びＲⁱ²は、それぞれ独立して、アルキル基、アリール基、及び、アルケニル基からなる群より選ばれるいずれかである。）
［１４］
下記式（III）で表される構造を有する、環状シロキサン化合物。

（式（III）中、Ｒ^j1、Ｒ^j2、Ｒ^k1、Ｒ^k2、Ｒ^l1、Ｒ^l2、Ｒ^m1、及びＲ^m2は、それぞれ独立して、アルキル基、アリール基、及び、アルケニル基からなる群より選ばれるいずれかであり、
ｎは、２以上の整数である。）
［１５］
下記式（IV）で表される構造を有する、環状シロキサン化合物。

（式（IV）中、Ｒⁿ¹、Ｒⁿ²、Ｒ^o1、Ｒ^o2、Ｒ^p1、Ｒ^p2、Ｒ^q1、Ｒ^q2、Ｒ^r1、Ｒ^r2、Ｒ^s1、及びＲ^s2は、それぞれ独立して、アルキル基、アリール基、及び、アルケニル基からなる群より選ばれるいずれかであり、
ｍ１、ｍ２、ｍ３は、それぞれ独立して、１又は２の整数であり、
ｎは、１以上の整数である。
ただし、Ｒⁿ¹及びＲⁿ²の組み合わせ並びにＲ^r1及びＲ^r2の組み合わせと、Ｒ^p1及びＲ^p2の組み合わせとは、互いに同一でない。） That is, this application provides the following inventions.
[1]
It comprises a step of reacting a compound represented by the following formula (1) with an alcohol compound in the presence of a boron catalyst and / or a transition metal hydride complex catalyst to form a ring skeleton by an —Si—O— bond. , A method for producing a cyclic siloxane compound having at least one ring skeleton.

(In the formula (1), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Any of the group consisting of an aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2 , the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. )
[2]
^RA1 , ^RA2 , ^RC1 and ^RC2 are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group.
R ^B1 and R ^B2 are independent aryl groups and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independently alkyl groups, aryl groups, and alkenyl groups, respectively. The production method according to [1], which is one selected from the group consisting of groups.).
[3]
The production method according to [1], wherein the cyclic siloxane compound is a compound having one ring skeleton.
[4]
The production method according to [3], wherein the compound having one ring skeleton is a compound represented by the following formula (3).

In formula (3), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Whichever is selected from the group consisting of an aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group.
p'is an integer greater than or equal to 0.
However, the combination of R ^A1 and R ^A2 , the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. )
[5]
A step of reacting a compound represented by the following formula (1) with a silicon compound having at least two hydroxy groups in the presence of a transition metal hydride complex catalyst to form a ring skeleton by an —Si—O— bond. A method for producing a cyclic siloxane compound having at least one ring skeleton, comprising the above.

(In the formula (1), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently alkoxy groups, respectively.
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Any of the group consisting of an aryl group, and an alkenyl group.). )
[6]
The compound represented by the following formula (1) is reacted with an alcohol compound or a silicon compound having at least two hydroxy groups or an alkoxy group in the presence of a boron catalyst and / or a transition metal hydride complex catalyst, and −Si. A method for producing a cyclic siloxane compound having at least one ring skeleton, which comprises a step of forming a ring skeleton by an —O— bond.

(In the formula (1), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Any of the group consisting of an aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2 , the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. )
The cyclic siloxane compound is a compound composed of two or more rings containing at least one crosslinked ring formed between silicon atoms in the ring skeleton.
In the step of forming the ring skeleton, at least one of RB1 and ^RB2 in the compound represented by the formula (1) is an ^-OSi (R ^X1 ) (R ^X2 ) H group. ) And a silicon compound having at least 3 hydroxy groups or alkoxy groups.
[ 7 ]
A compound composed of two or more rings containing at least one crosslinked ring formed between silicon atoms in the ring skeleton is a compound represented by the following formula (4).
The production method according to [ 6 ], wherein the silicon compound having at least three hydroxy groups or alkoxy groups is a compound represented by the formula (A1-1).

(In formula (4), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B2 is an alkyl group, an aryl group, an alkenyl group, and -OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 are independently composed of an alkyl group, an aryl group, and an alkenyl group, respectively. It is one of the groups selected from the group consisting of.)
R ^D2 is one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group.

(In the formula (A1-1), R ^D1 is an alkoxy group, and
R ^D2 is one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group.
R ^E1 and R ^E2 are alkyl groups. )
[ 8 ]
The compound represented by the following formula (1) is reacted with an alcohol compound or a silicon compound having at least two hydroxy groups or an alkoxy group in the presence of a boron catalyst and / or a transition metal hydride complex catalyst, and −Si. A method for producing a cyclic siloxane compound having at least one ring skeleton, which comprises a step of forming a ring skeleton by an —O— bond.

(In the formula (1), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Any of the group consisting of an aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2 , the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. )
The cyclic siloxane compound is a compound composed of two or more rings containing at least one crosslinked ring formed between silicon atoms in the ring skeleton.
In the step of forming the ring skeleton, the compound represented by the formula (1) (in the formula (1), RB1 and ^RB2 are ^—OSI (R ^X1 ) (R ^X2 ) H groups). , A production method for reacting with a silicon compound having at least 4 hydroxy groups or alkoxy groups.
[ 9 ]
A compound composed of two or more rings containing at least one crosslinked ring formed between silicon atoms in the ring skeleton is a compound having a structure represented by the following formula (5).
The production method according to [ 8 ], wherein the silicon compound having at least four hydroxy groups or alkoxy groups is a compound represented by the formula (A1-2).

(In formula (5), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^X1 and R ^X2 are each independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.
n is an integer of 2 or more. )

(In the formula (A1-2), R ^D1 and R ^D2 are alkoxy groups, and R ^E1 and RE ² are alkyl groups.)
[ 10 ]
The compound represented by the following formula (1) is reacted with an alcohol compound or a silicon compound having at least two hydroxy groups or an alkoxy group in the presence of a boron catalyst and / or a transition metal hydride complex catalyst, and −Si. A method for producing a cyclic siloxane compound having at least one ring skeleton, which comprises a step of forming a ring skeleton by an —O— bond.

(In the formula (1), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Any of the group consisting of an aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2 , the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. )
The cyclic siloxane compound is a compound composed of two or more rings containing at least one spiro ring.
^RA1 , ^RA2 , ^RC1 and ^RC2 in the above formula (1) are independently alkoxy groups, and ^RB1 and ^RB2 are independently alkyl groups, aryl groups and alkenyl groups, respectively. It is one of the groups selected from the group consisting of groups.
The compound represented by the formula (1) is reacted with a silane compound having at least two hydroxy groups in the presence of a transition metal hydride complex catalyst, and the compound represented by the following formula (2) is further subjected to boron. A production method comprising a step of reacting in the presence of a catalyst.

(In the formula (2), RA1', ^{RA2' , RC1'and RC2'are} independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Is either
R ^B1'and R ^B2'are independent of each other, and the alkyl group, aryl group, alkenyl group, and -OSi (R ^X1' ) (R ^X2' ) H group (R ^X1'and R ^X2' are respectively. Independently, any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.)
n is an integer of 1 or more.
However, the combination of R A1'and R ^{A2' ,} the combination of R C1'and R ^{C2' ,} and the combination of R ^B1'and R ^B2'are not the same as each other. )
[ 11 ]
The production method according to [ 10 ], wherein the compound composed of two or more rings containing at least one spiro ring is a compound having a structure represented by the following formula (6).

(In equation (6), ^Q1 and ^Q2 have the following structures independently of each other:

(R ^B1'and R ^B2'are independent of each other, and the alkyl group, aryl group, alkenyl group, and -OSi (R ^X1' ) (R ^X2' ) H group (R ^X1'and R ^X2' are Each is independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group), and ^{RC1'and RC2'are independent} of each other. , Which is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group, and n is an integer of 1 or more.)
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Whichever is selected from the group consisting of an aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group.
^{RA1'and RA2'are} independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group.
p and N are integers of 1 or more. )
[ 12 ]
The production method according to [10], wherein the compound composed of two or more rings containing at least one spiro ring is a compound represented by the following formula (6-1).

(In equation (6-1), ^Q1 and ^Q2 have the following structures independently:

Represented by
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Whichever is selected from the group consisting of an aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group.
^{RA1'and RA2'are} independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group.
R ^B1'and R ^B2'are independent of each other, and the alkyl group, aryl group, alkenyl group, and -OSi (R ^X1' ) (R ^X2' ) H group (R ^X1'and R ^X2' are respectively. Independently, any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.)
R ^C1'and R ^C2'are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group.
p and n are integers of 1 or more. )
[ 13]
A cyclic siloxane compound represented by the following formula (II).

(In formula (II), Re is a siroxy ^group ,
R ^f , R ^g1 , R ^g2 , R ^h1 , R ^h2 , R ⁱ¹ , and R ⁱ² are each independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group. )
[14]
A cyclic siloxane compound having a structure represented by the following formula (III).

In formula (III), R ^j1 , R ^j2 , R ^k1 , R ^k2 , R ^l1 , R ^l2 , R ^m1 , and R ^m2 are independently composed of an alkyl group, an aryl group, and an alkenyl group, respectively. One of the choices from the group,
n is an integer of 2 or more. )
[15]
A cyclic siloxane compound having a structure represented by the following formula (IV).

(In equation (IV), R ⁿ¹ , R ⁿ² , R ^o1 , R ^o2 , R ^p1 , R ^p2 , R ^q1 , R ^q2 , R ^r1 , R ^r2 , R ^s1 , and R ^s2 are independent of each other. It is one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.
m1, m2, and m3 are independently integers of 1 or 2, respectively.
n is an integer of 1 or more.
However, the combination of R ⁿ¹ and R ⁿ² , the combination of R ^r1 and R ^r2 , and the combination of R ^p1 and R ^p2 are not the same as each other. )

According to the present invention, it is possible to provide an efficient method for producing a cyclic siloxane compound, a novel cyclic siloxane compound obtained by the production method, a composition containing the compound, and a heat-resistant material containing the composition. ..

It is a figure which shows the spectral data of ¹ H NMR, ¹³ C NMR, ²⁹ Si NMR of compound 12. It is a figure which shows the spectral data of ¹ H NMR, ¹³ C NMR, ²⁹ Si NMR of compound 16. It is a figure which shows the result of having measured the thermophysical property of compound 16 by the differential scanning calorimetry under the nitrogen atmosphere. It is a figure which shows the result of having measured the thermal property of compound 16 by the differential scanning calorimetry under the air atmosphere.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist thereof.

[Method for producing cyclic siloxane compound]
In the production method of the present invention, a compound represented by the following formula (1) and an alcohol compound or a silicon compound having at least two hydroxy groups or an alkoxy group are used in the presence of a boron catalyst and / or a transition metal hydride complex catalyst. A method for producing a cyclic siloxane compound having at least one ring skeleton, which comprises a step of reacting underneath to form a ring skeleton by an —Si—O— bond.

(Compound represented by the formula (1))
The compound represented by the formula (1) in the production method of the present invention is represented below.

In formula (1), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. ,
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Any of the group consisting of an aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2 , the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other.

R ^A1 , R ^A2 , R ^C1 and R ^C2 in the formula (1) are independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group, and are R ^B1 . And R ^B2 are independently from an aryl group and an -OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 are independently from an alkyl group, an aryl group, and an alkoxy group, respectively. It is one selected from the group consisting of.) It is preferable to be one selected from the group consisting of.

Examples of the alkyl group in the formula (1) include a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a group of a combination thereof, and specifically, methyl. Group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, cyclopropylmethyl group, pentyl group, isopentyl group, sec-pentyl group, Examples thereof include neopentyl group, tert-pentyl group, cyclopentyl group, hexyl group, and cyclohexyl group. Among these, preferably, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, and a tert-pentyl group. , Neopentyl group, and hexyl group, more preferably a methyl group, an ethyl group, and a propyl group, and further preferably a methyl group and an ethyl group.

Examples of the alkenyl group in the formula (1) include a linear or branched alkenyl group having 1 to 10 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, and a butenyl group. Be done. Among these, a vinyl group is preferable.

Examples of the alkoxy group in the formula (1) include an alkoxy group having 1 to 10 carbon atoms, and specifically, a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, and an n-butyloxy group. Group, sec-butyloxy group, tert-butyloxy group, isobutyloxy group, n-pentyloxy group, 2,2-dimethylpropyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, 2-methylpentyloxy Groups and 2-ethylhexyloxy groups are included. Among these, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, sec-butyloxy group, tert-butyloxy group, and isobutyloxy group are preferable, and methoxy is more preferable. Groups, ethoxy groups, n-propyloxy groups, and isopropyloxy groups, more preferably methoxy groups and ethoxy groups.

Examples of the aryl group in the formula (1) include an aryl group having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. Among these, a phenyl group is preferable.

The compound represented by the formula (1) can be obtained by synthesizing it by using an organic synthesis method, and for example, Patent Document 4: US Pat. No. 3,145,225, Non-Patent Document 4: J.Gen.Chem. It can be manufactured with reference to .USSR, 54,306 (1984), Non-Patent Document 5: Z.Anorg.Allg.Chem., 636,1212 (2010), ACS Catal., 7, 1836 (2017).
Specifically, it can be obtained by reacting silanediol and chlorosilane in the presence of a base as shown below.

（シランジオールにおけるＲ^B1及びＲ^B2は、式（１）におけるＲ^B1及びＲ^B2と同義である。クロロシランにおけるＲ¹及びＲ²は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかである。）

( ^RB1 and RB2 in silanediol are synonymous with ^RB1 and ^RB2 in formula (1). ^R1 and ^R2 in chlorosilane are independently hydrogen atoms, alkyl groups, aryl groups and ^alkoxys , respectively. It is one selected from the group consisting of a group and an alkoxy group.)

Specifically, when at ^least one of ^RA1 and ^RA2 and at least one of RC1 and ^RC2 are hydrogen atoms, silanediol and silane are required as transition metals as shown below. It can also be obtained by reacting in the presence of a ligand accordingly.

（シランジオールにおけるＲ^B1及びＲ^B2は、式（１）におけるＲ^B1及びＲ^B2と同義である。シランにおけるＲ¹及びＲ²の少なくとも一方は、水素原子であり、もう一方は、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかである。）

(RB1 and RB2 in ^{silanediol are synonymous with RB1 and RB2} in formula (1). At least ^one of ^R1 and ^R2 in silane is a hydrogen atom and the other is an alkyl group. It is one selected from the group consisting of an aryl group, an alkenyl group, and an alkoxy group.)

(Alcohol compound)
The alcohol compound in the production method of the present invention may be any alcohol having at least one hydroxy group, and may be a divalent alcohol or a trihydric alcohol in addition to the monohydric alcohol. Examples of the alcohol compound include methanol, ethanol, n-propanol, n-butanol, methylcyclohexanol, cyclohexanol, benzyl alcohol and the like. Among these, benzyl alcohol is preferable.

(Silicon compound having at least two hydroxy groups or alkoxy groups)
The silicon compound having at least two hydroxy groups or alkoxy groups in the production method of the present invention is a silicon compound containing at least two silicon atoms and a hydroxy group bond (Si—OH), or at least two silicon compounds. , A silicon compound having a bond (Si-OR) between a silicon atom and an alkoxy group.

A silicon compound having at least two hydroxy groups or an alkoxy group is preferably represented by the following formula (A1).

In the formula (A1), R ^D1 and R ^D2 are independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a syroxy group, and R ^E1 and R ^E2 are R E1 and R E2. , They are identical to each other, are hydrogen atoms or alkyl groups, and p is an integer of 1 or more.

The siloxy group is a chain or branched monovalent group containing at least one —O—Si— bond. Here, at least one —O—Si— contained in the siloxy group is bonded to the silicon atom in the formula (A1) via the oxygen atom in the —O—Si—.
Specifically, as the syroxy group, the syroxy group (S) shown below (hereinafter, referred to as "syroxy group (S)") is preferably mentioned.

Among the syroxy groups ( ^S ), RS1 and ^RS2 are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a syroxy group (S), and Z. ¹ is an arbitrary divalent organic group and ^RS3 is an arbitrary monovalent organic group. f is 0 or 1, and F is an integer of 1 or more. The upper limit of F is not particularly limited, but is usually 1000, preferably 100, and more preferably 50.
Examples of the arbitrary divalent organic group of Z ¹ include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group and a butylene group; and a phenylene group and a naphthylene group having 6 to 10 carbon atoms. 10 arylene groups; -Si ( ^RS1' ) ( ^RS2' )-( ^{RS1'and RS2' are} independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. ); And a group combining these;
Any monovalent organic group of ^RS3 includes, for example, a hydroxy group, an alkyl group, an aryl group, and an alkenyl group.

When both R ^E1 and R ^E2 in the formula (A1) are hydrogen atoms, the R ^D1 and R ^D2 are preferably an alkyl group, an aryl group or an alkenyl group, and more preferably an alkyl group or an aryl group. It is the basis.

p is preferably an integer of 1 to 2.

As the alkyl group, aryl group, alkenyl group, and alkoxy group in the formula (A1) and the siloxy group (S), the same groups as the alkyl group, the aryl group, the alkenyl group, and the alkoxy group in the formula (1) are used. Examples can be given and similar preferred groups can be mentioned.

(Boron catalyst)
The boron catalyst used in the production method of the present invention is not particularly limited as long as it contains boron, and is, for example, triphenylborane, tris (pentafluorophenyl) borane, tris (2,3,4,5). -Tetrafluorophenyl) borane, tris (2,4,6-trifluorophenyl) borane, tris (2,3-difluorophenyl) borane, tris (2-fluorophenyl) borane, tris [3,5-bis (tri) Included are fluoromethyl) phenyl] borane, tris [4- (trifluoromethyl) phenyl] borane, trimethylborane, triethylborane, tris (trifluoromethyl) borane, diphenylfluoroborane, and bis (pentafluorophenyl) chloroborane. Among these, tris (pentafluorophenyl) borane is preferable.

(Transition metal hydride complex catalyst)
The transition metal hydride complex catalyst used in the production method of the present invention is not particularly limited as long as it is a complex having a bond between a transition metal atom and a hydrogen atom.
Examples of transition metals include copper, iron, rhodium, iridium, rhenium, tungsten, platinum, palladium, manganese, cobalt, nickel, chromium, molybdenum, and ruthenium. Of these, copper and ruthenium are preferred.
A ligand other than hydride may be coordinated to the transition metal hydride complex, and the ligand may be, for example, 2,2'-bipyridine, 1,10-phenanthroline, N, N, N'. , N'-tetramethylethylenediamine, triphenylphosphine, and 2- (dicyclohexylphosphino) biphenyl, carbon monoxide, cyclopentadiene.

Further, in the production method of the present invention, a ligand may be separately added to the system in which the transition metal hydride complex is present. Examples of the ligand to be added separately include xantphos, 1,3-bisdiphenylphosphinopropane, 1,1,1-tris (diphenylphosphinomethylethane) and the like, in addition to the above-mentioned ligand.

The amount of the boron catalyst or the transition metal hydride complex catalyst used in the production method of the present invention is not particularly limited, but is usually 0.001 to 1.0 equivalent with respect to the amount of substance of the compound represented by the formula (1). Yes, preferably 0.005 to 0.50 equivalents, more preferably 0.01 to 0.10 equivalents.

The production method of the present invention can be carried out with or without a solvent. When a solvent is used, a nitrile solvent such as acetonitrile, propionitrile and benzonitrile; a ketone solvent such as acetone and methyl ethyl ketone; an ether solvent such as tetrahydrofuran, diethyl ether, tert-butyl methyl ether and dibutyl ether; benzene. , Aromatic hydrocarbon solvents such as toluene and xylene; and various other solvents except those that react with the raw materials can be used. The solvent may be used alone or in combination of two or more.
When the reaction in the production method of the present invention is carried out in the gas phase, the reaction can also be carried out by mixing an inert gas such as nitrogen with the raw material and the solvent.

When the reaction is carried out using a solvent, it is preferable to appropriately select the solvent from the viewpoints of the type of catalyst, the solubility of the raw material and the product, the selectivity of the reaction, and the like, depending on the type of the target product.
In the production method of the present invention, it is preferable to carry out the reaction using a solvent from the viewpoint of smoothly proceeding the reaction of forming a ring skeleton by the —Si—O— bond.
When a boron catalyst is used as the catalyst, the solvent in the production method of the present invention is preferably a ketone solvent, an ether solvent, and an aromatic hydrocarbon solvent.
Further, the solvent in the production method of the present invention is preferably an aromatic hydrocarbon solvent, and more preferably toluene, from the viewpoint of smoothly proceeding the reaction.

The amount of the solvent used is such that the total of the compound represented by the formula (1) and the alcohol compound or the silicon compound having at least two hydroxy groups or alkoxy groups is 0.01 to 5 mol / L. It is preferably 0.05 to 1 mol / L, more preferably 0.05 to 0.5 mol / L, and even more preferably 0.05 to 0.5 mol / L.

In the production method of the present invention, the substance amount ratio of the compound represented by the formula (1) to the alcohol compound or the silicon compound having at least two hydroxy groups or alkoxy groups is the compound represented by the formula (1). The amount of the alcohol compound or the silicon compound having at least two hydroxy groups or alkoxy groups is preferably 0.1 to 10 equivalents, more preferably 0.5 to 3 equivalents, and 0. It is even more preferably 7 to 1.5 equivalents, even more preferably 0.8 to 1.2 equivalents, and even more preferably 0.9 to 1.1 equivalents.

The reaction in the production method of the present invention can be carried out in a liquid phase or a gas phase state depending on the reaction temperature and the reaction pressure. Further, 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 usually −30 ° C. or higher, preferably −20 to 300 ° C., more preferably −10 to 200 ° C., still more preferably −10 to 150 ° C.
The reaction pressure is usually 0.1 to 100 atm, preferably 0.1 to 50 atm, more preferably 0.1 to 20 atm, and even more preferably 0.1 to 10 atm.
The reaction time may be appropriately adjusted according to the amount of the raw material and the 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. It takes about 500 hours.

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

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. Easy to reach.

In the production method of the present invention, the step of forming a ring skeleton by an —Si—O— bond specifically refers to the step of forming the following ring skeleton.

The cyclic siloxane compound obtained by the production method of the present invention has at least one ring skeleton formed by an —Si—O— bond. The cyclic siloxane compound may contain two or more ring skeletons by further forming an —Si—O— bond at the bond position indicated by the wavy line of the ring skeleton shown above.
Here, when the cyclic siloxane compound contains two or more ring skeletons, the cyclic siloxane compound is a compound having a crosslinked ring formed between silicon atoms in the ring skeleton, or at least one of the silicon atoms in the ring skeleton. It is a compound that becomes a spiro atom and has a spiro ring.
That is, the cyclic siloxane compound obtained by the production method of the present invention is a compound having one ring skeleton formed by 1) -Si—O— bond (hereinafter, also referred to as cyclic siloxane compound A), and 2) ring skeleton. A compound composed of two or more rings (hereinafter, also referred to as cyclic siloxane compound B) containing at least one bridge formed by an —Si—O— bond between silicon atoms in the compound (hereinafter, also referred to as cyclic siloxane compound B), and 3) -Si. It is a compound composed of two or more rings (hereinafter, also referred to as cyclic siloxane compound C) containing at least one spiro ring formed by an -O- bond.

<1) A compound having one ring skeleton formed by a -Si-O- bond>
The cyclic siloxane compound A is preferably represented by the following formula (3).

R ^A1 , R ^A2 , R ^B1 , R ^B2 , R ^C1 , R ^C2 , R ^D1 and R ^D2 in the formula (3) are R ^A1 , R ^A2 , R ^B1 in the formula (1) and the formula (A1). , R ^B2 , R ^C1 , R ^C2 , R ^{D 1} and R ^{D 2} . p'is an integer greater than or equal to 0. The upper limit of p'is 10, preferably 5, and more preferably 2.

The compound in which p'is 0 in the formula (3) can be obtained by reacting the compound represented by the formula (1) with an alcohol compound.
The compound in which p'is 1 or more in the formula (3) is a compound represented by the formula (1) and a silicon compound having at least two hydroxy groups or an alkoxy group, preferably represented by the formula (A1). It can be obtained by reacting with a compound.
At this time, it is preferable that R ^B1 and R ^B2 in the formula (1) are independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.

<2) A compound composed of two or more rings containing at least one crosslink formed by an —Si—O— bond between silicon atoms in the ring skeleton>
When producing the cyclic siloxane compound ^B , at least one of RB1 and ^RB2 in the compound represented by the formula (1) is -OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 are Each is independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group). The compound to be reacted with the compound represented by the formula (1) is a silicon compound having at least three hydroxy groups or alkoxy groups.

The cyclic siloxane compound B is preferably a compound represented by the following formula (4) or a compound having a structure represented by the formula (5).

In the formula (4), R ^A1 , R ^A2 , R ^B2 , R ^C1 , R ^C2 , R ^D2 , R ^X 1 and R ^{X 2} are R ^A1 , R ^A2 , R ^B2 in the formula (1) and the formula (A1). , R ^C1 , R ^C2 , R ^D2 , R ^X 1 and R ^{X 2} .
When producing the compound represented by the formula (4), the R ^B1 in the formula (1) is an —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 are each independently alkylated. It is one selected from the group consisting of a group, an aryl group, and an alkenyl group), and in the formula (A1), ^RD1 is an alkoxy group, ^RE1 and ^RE2 are alkyl groups, and p. Is preferably 1.

In the formula (5), R ^A1 , R ^A2 , R ^C1 , R ^C2 , R ^X 1 and R ^{X 2} are R ^A1 , R ^A2 , R ^C1 , R ^C2 , R ^X 1 in the formula (1) and the formula (A1). And R ^X2 , where n is an integer greater than or equal to 2. The upper limit of n is not particularly limited, but is usually 10000, preferably 5000, and more preferably 1000.
When producing a compound having a structure represented by the formula (5), RB1 and RB2 in the formula (1) are ^−OSi (R ^X1 ) (R ^X2 ) H groups, and are in the formula ( ^A1 ). Of the above, R ^D1 and R ^D2 are preferably alkoxy groups, R ^E1 and R ^E2 are alkyl groups, and p is preferably 1.

The compound having the structure represented by the formula (5) is preferably a cyclic polymer having both ends bonded to each other and having the structure represented by the formula (5) as a constituent unit.
Further, the terminal of the compound having the structure represented by the formula (5) is hydrogen or R ^{E '} (RE'is an alkyl group) as represented by the following formula (5'). May be good.

Further, the terminal in the formula (5'), that is, Si—H and ^—ORE'in −OSi (R ^X1 ) (R ^X2 ) H is modified, and an alkyl group, an aryl group, an alkenyl group, an alkoxy group, Alternatively, it may be modified with a siloxy group or the like.
Here, the alkyl group, the aryl group, the alkenyl group, the alkoxy group, and the syroxy group are the same groups as the alkyl group, the aryl group, the alkenyl group, the alkoxy group, and the syroxy group in the formulas (1) and (A1). Can be exemplified, and similar preferable groups can be mentioned.

<3) A compound composed of two or more rings, including at least one spiro ring formed by a -Si—O— bond>
When producing the ^cyclic siloxane compound ^C , ^RA1 , RA2, RC1 and ^RC2 in the formula (1) are independently alkoxy groups, and ^RB1 and ^RB2 are independent, respectively. It is one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.
Further, when the cyclic siloxane compound C is produced, the compound represented by the above formula (1) and a silane compound having at least two hydroxy groups are reacted in the presence of a transition metal hydride complex catalyst, and further described below. The step of reacting the compound represented by the formula (2) in the presence of a boron catalyst is included.

In formula (2), ^RA1' , ^RA2' , ^RC1' , and ^RC2'are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Either,
R ^B1'and R ^B2'are independent of each other, and the alkyl group, aryl group, alkenyl group, and -OSi (R ^X1' ) (R ^X2' ) H group (R ^X1'and R ^X2' are respectively. Independently, any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.)
n is an integer of 1 or more. The upper limit of n is 10, preferably 5, and more preferably 2.
However, the combination of R A1'and R ^{A2' ,} the combination of R C1'and R ^{C2' ,} and the combination of R ^B1'and R ^B2'are not the same as each other.

As the alkyl group, aryl group, alkenyl group, and alkoxy group in the formula (2), the same groups as the alkyl group, the aryl group, the alkenyl group, and the alkoxy group in the formula (1) can be exemplified. Similar preferred groups can be mentioned.

The cyclic siloxane compound C preferably has a structure represented by the following formula (6).

In equation (6), N is an integer of 1 or more, and Q ¹ and Q ² are independently represented by the following structures.

In formula (6), R ^B1 , R ^B2 , R ^D1 , R ^D2 , R ^A1' , R ^A2' , R ^B1' , R ^B2' , R ^C1' , R ^C2' , p and n are the formulas (1). ), R ^B1 , R ^B2 , R ^D1 , R ^D2 , R ^A1' , R ^A2' , R ^B1' , R ^B2' , R ^C1' , R ^C2' , p. And n are synonymous with n.

When producing the compound represented by the formula (6), R ^E1 and R ^E2 in the formula (A1) are hydrogen atoms.

When N in the formula (6) is 1, the compound having the structure represented by the formula (6) is preferably represented by the formula (6-1).

In Eq. (6-1), R ^B1 , R ^B2 , R ^D1 , R ^D2 , R ^A1' , R ^A2' , R ^B1' , R ^B2' , Q ¹ and Q ² are Eq. (1), Eq. (1). Synonymous with R ^B1 , R ^B2 , R ^D1 , R ^D2 , R ^A1' , R ^A2' , R ^B1' , R ^B2' , Q ¹ and Q ² in A1), formula (2) and formula (6). be.

When N in the formula (6) is 2 or more, R B1'and R ^{B2' in} the formula (2) (where, when n is 2 or more, R ^B1'and R in the formula (2) (At least one combination of ^B2' ) are both -OSi (R ^X1' ) (R ^X2' ) H groups.

When N is 2 or more in the structure represented by the formula (6), both ends are represented by> Si ( ^RB1' ) ( ^RB2 ') as shown by the formula (6-1). However, both ends may be combined to form a spiro ring. That is, when both ends are put together to form a spiro ring, a macro ring composed of a plurality of spiro rings is formed.

[Cyclic siloxane compound]
The 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 compounds represented by the following formula (I).

In formula (I), R ^a1 , R ^a2 , R ^c1 and R ^c2 are independently alkoxy groups.
R ^b1 , R ^b2 , R ^d1 and R ^d2 are each independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.
m is an integer of 0 to 2.

As the alkoxy group, the alkyl group, the aryl group, and the alkenyl group in the formula (I), the same groups as the alkoxy group, the alkyl group, the aryl group, and the alkenyl group in the formula (1) can be exemplified. Similar preferred groups can be mentioned.

Specific examples of the compound represented by the formula (I) include compounds having a combination of substituents shown in Table 1 below.

Examples of the cyclic siloxane compound of the present invention include compounds represented by the following formula (II).

In formula (II), Re is one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a ^syroxy group.
R ^f , R ^g1 , R ^g2 , R ^h1 , R ^h2 , R ⁱ¹ , and R ⁱ² are each independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.

The siloxy group is a chain or branched group containing at least one —O—Si— bond. Here, at least one —O—Si— contained in the siloxy group is bonded to the silicon atom in the formula (A1) via the oxygen atom in the —O—Si—.
Specifically, the syroxy group (S) shown below is preferably mentioned as the syroxy group.

Among the syroxy groups ( ^S ), RS1 and ^RS2 are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a syroxy group (S), and Z. ¹ is any divalent organic group, and ^RS3 is any monovalent organic group. f is 0 or 1, and F is an integer of 1 or more. The upper limit of F is not particularly limited, but is usually 1000, preferably 100, and more preferably 50.
Examples of the arbitrary divalent organic group of Z ¹ include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group and a butylene group; and a phenylene group and a naphthylene group having 6 to 10 carbon atoms. 10 arylene groups; -Si ( ^RS1' ) ( ^RS2' )-( ^{RS1'and RS2' are} independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Any of these; as well as a combination of these;
Any monovalent organic group of ^RS3 includes, for example, a hydroxy group, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group.

As the alkyl group, aryl group, alkenyl group, and alkoxy group in the formula (II), the same groups as the alkyl group, the aryl group, the alkenyl group, and the alkoxy group in the formula (1) can be exemplified. Similar preferred groups can be mentioned.

Specific examples of the compound represented by the formula (II) include compounds having a combination of substituents shown in Table 2 below.

In the table, S-1, S-2, and S-3 are represented by the following formulas, respectively.

R ^{S3 and F in S-1, S-2, and S-3 are synonymous with R S3 and} F in the syroxy group (S).
The wavy line in S-3 represents a bond to a group represented by another formula S-3.

Examples of the cyclic siloxane compound of the present invention include compounds having a structure represented by the following formula (III).

In formula (III), R ^j1 , R ^j2 , R ^k1 , R ^k2 , R ^l1 , R ^l2 , R ^m1 , and R ^m2 independently consist of an alkyl group, an aryl group, and an alkenyl group, respectively. Is one of the choices
n is an integer of 2 or more.

As the alkyl group, aryl group, and alkenyl group in the formula (III), the same groups as the alkyl group, the aryl group, and the alkenyl group in the formula (1) can be exemplified, and the same preferable group is mentioned. be able to.

The compound having the structure represented by the formula (III) is preferably a cyclic polymer having both ends bonded to each other and having the structure represented by the formula (III) as a constituent unit.
Further, the terminal of the compound having the structure represented by the formula (III) is hydrogen or R ^{E '} (RE'is an alkyl group) as represented by the following formula (III'). May be good.

Further, the terminal in the formula (III'), that is, Si—H and ^—ORE'in −OSi (R ^m1 ) (R ^m2 ) H is modified, and an alkyl group, an aryl group, an alkenyl group, an alkoxy group, Alternatively, it may be modified with a siloxy group or the like.
Here, the alkyl group, the aryl group, the alkenyl group, the alkoxy group, and the syroxy group are the same groups as the alkyl group, the aryl group, the alkenyl group, the alkoxy group, and the syroxy group in the formulas (1) and (A1). Can be exemplified, and similar preferable groups can be mentioned.

Specific examples of the compound having the structure represented by the formula (III) include compounds having a combination of substituents shown in Table 3 below.

Examples of the cyclic siloxane compound of the present invention include compounds having a structure represented by the following formula (IV).

In equation (IV), R ⁿ¹ , R ⁿ² , R ^o1 , R ^o2 , R ^p1 , R ^p2 , R ^q1 , R ^q2 , R ^r1 , R ^r2 , R ^s1 , and R ^s2 are independently alkylated. It is one selected from the group consisting of a group, an aryl group, and an alkenyl group.
m1, m2, and m3 are independently integers of 1 or 2, respectively.
n is an integer of 1 or more.
However, the combination of R ⁿ¹ and R ⁿ² , the combination of R ^r1 and R ^r2 , and the combination of R ^p1 and R ^p2 are not the same as each other.

When n in the formula (IV) is 1, the compound having the structure represented by the formula (IV) is preferably represented by the formula (IV-1).

In equation (IV-1), R ⁿ¹ , R ⁿ² , R ^o1 , R ^o2 , R ^p1 , R ^p2 , R ^q1 , R ^q2 , R ^r1 , R ^r2 , R ^s1 , R ^s2 , R ^t1 , R ^t2 , R ^u1 and R ^u2 are each independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.
m1, m2, and m3 are independently integers of 1 or 2, respectively.
n is an integer of 1 or more.
However, the combination of R ⁿ¹ and R ⁿ² , the combination of R ^r1 and R ^r2 , and the combination of R ^p1 and R ^p2 are not the same as each other.
R ^t1 , R ^t2 , R ^u1 and R ^u2 are preferably aryl groups, more preferably phenyl groups.

As the alkyl group, aryl group, and alkenyl group in the formula (IV) and the formula (IV-1), the same group as the alkyl group, the aryl group, and the alkenyl group in the formula (1) can be exemplified. , Similar preferred groups can be mentioned.

When n is 2 or more in the compound having the structure represented by the formula (IV), both ends are> Si (R ^t1 ) (R ^t2 ) or> Si (as shown by the formula (IV-1). The structure may be represented by R ^u1 ) (R ^u2 ), or both ends may be combined to form a spiro ring. That is, when both ends are put together to form a spiro ring, a macro ring composed of a plurality of spiro rings is formed.

Specific examples of the compound having the structure represented by the formula (IV) include compounds having a combination of substituents shown in Tables 4 to 6 below.

A novel cyclic siloxane compound or polymer compound can be obtained by the production method of the present invention, and the polymer compound is a material having excellent thermal stability and mechanical properties.
Since the cyclic siloxane compound of the present invention has a thermally stable cyclic skeleton, a material containing these compounds as a composition can be used as a heat-resistant material or the like. As the composition of the cyclic siloxane, not only one kind but also two or more kinds of cyclic siloxane compounds can be used at the same time.

In detail, the present invention exhibits the following effects of the invention.
(1) The raw materials alkoxysilane, silanol, and hydrosilane do not generate corrosive compounds such as hydrogen chloride even when hydrolyzed, so that they are highly safe and easily available.
(2) The co-products of the reaction are hydrogen and hydrocarbons, and strong corrosive compounds such as hydrogen chloride are not produced.
(3) The reaction proceeds under mild conditions of about room temperature, and a cyclic siloxane compound can be obtained in high yield.
(4) A novel cyclic siloxane compound can be produced.
(5) Not only low molecular weight compounds but also high molecular weight compounds can be produced.
(6) The polymer-based cyclic siloxane compound has high thermal stability, and the composition containing the cyclic siloxane compound can be used as a novel heat-resistant material.

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

The trisiloxane compound as a raw material is described in Patent Document 4: US Pat. No. 3,145,225, Non-Patent Document 4: J.Gen.Chem.USSR, 54,306 (1984), Non-Patent Document 5: Z.Anorg.Allg.Chem. Manufactured with reference to ., 636, 1212 (2010), ACS Catal., 7, 1836 (2017).
Commercially available reagents were used for other reagents.

[Example 1] Synthesis of compound 1

Add bis (dimethylsiloxy) diphenylsilane (166 mg, 0.5 mmol), benzyl alcohol (54 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), toluene (5 mL) to the test tube. The reaction was carried out at 25 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the solvent was removed with an evaporator, and compound 1 was purified using a recycling device. Compound 1 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolated yield of compound 1 was 82%.

[Example 2] Examination of reaction conditions for the synthesis of compound 1

Alcohol R ¹ The same procedure as in Example 1 was carried out except that the types of OH and the types of solvents shown in Table 1 were used. The results are shown in Table 7. The yield is the yield obtained from NMR, and compounds 2 and 3 other than compound 1 are as shown above.

[Example 3]

Add bis (diethylsiloxy) diphenylsilane (194 mg, 0.5 mmol), benzyl alcohol (54 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), toluene (5 mL) to the test tube. The reaction was carried out at 25 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the solvent was removed with an evaporator, and the target compound 4 was purified using a recycling device. Compound 4 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolated yield of compound 4 was 77%.

[Example 4] Synthesis of compound 5

In vitro bis (diethylsiloxy) diphenylsilane (194 mg, 0.5 mmol), dimethoxydiphenylsilane (122 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), toluene (5 mL) In addition, the reaction was carried out at 25 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the solvent was removed by an evaporator, and the target compound 5 was purified by silica gel column chromatography. Compound 5 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolated yield of compound 5 was 89%.

The peak positions of Compound 5 in the ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, benzene-d ₆ ): δ: 7.20-7.84, 0.96, 0.68.
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ: 136.5, 134.9, 130.8, 128.5, 7.9, 7.1.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -15.4, -45.0.

[Example 5] Synthesis of compound 6

In vitro bis (diethylsiloxy) diphenylsilane (194 mg, 0.5 mmol), dimethoxymethylphenylsilane (91 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), toluene (5 mL). In addition, the reaction was carried out at 25 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the solvent was removed by an evaporator, and the target compound 6 was purified by silica gel column chromatography. Compound 6 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolated yield of compound 6 was 89%.

[Example 6] Synthesis of compound 7

In vitro bis (diethylsiloxy) diphenylsilane (194 mg, 0.5 mmol), dimethoxydicyclopentylsilane (114 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), toluene (2.5 mL). In addition, the reaction was carried out at 25 ° C. for 12 hours under an argon atmosphere. After completion of the reaction, the solvent was removed by an evaporator, the target compound 7 was purified by silica gel column chromatography, and the compound was identified by ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolated yield of compound 7 was 93%.

The peak positions of compound 7 in the ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, benzene-d ₆ ): δ: 7.84-7.86 (m), 7.18-7.24 (m), 1.79-1.83 (m), 1.56-1.65 (m), 1.48-1.53 (m), 1.25 (t), 0.70 (q).
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ: 137.0, 134.9, 130.6, 128.7, 28.4, 27.8, 26.2, 8.1, 7.3.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -18.8, -22.6, -46.6.

[Example 7] Synthesis of compound 8

In vitro bis (dimethylsiloxy) diphenylsilane (166 mg, 0.5 mmol), dimethylsilanediol (46 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), toluene (2.5 mL) In addition, the reaction was carried out at 25 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the solvent was removed by an evaporator, and the target compound 8 was purified by silica gel column chromatography. Compound 8 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolated yield of compound 8 was 77%.

The peak positions of Compound 8 in the ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, benzene-d ₆ ): δ: 7.83-7.84 (m), 7.19-7.23 (m), 0.21 (s), 0.17 (s).
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ: 136.6, 134.9, 130.7, 128.5, 1.31, 1.28.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -17.5, -18.5, -45.7.

[Example 8] Synthesis of compound 9

Test tubes of bis (dimethylsiloxy) diphenylsilane (166 mg, 0.5 mmol), diethoxymethylvinylsilane (80 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), toluene (2.5 mL). In addition, the reaction was carried out at 25 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the solvent was removed by an evaporator, and the target compound 9 was purified by silica gel column chromatography. Compound 9 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolated yield of compound 9 was 78%.

The peak positions of compound 9 in the ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR spectra were as follows.
^{1 1} H NMR (600 MHz, benzene-d ₆ ): δ: 7.81-7.84 (m), 7.16-7.23 (m), 6.08-6.14 (m), 5.86-5.91 (m), 0.25 (s), 0.21 ( d).
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ: 137.0, 136.5 (d), 134.9 (d), 134.0, 130.7 (d), 128.5 (d), 1.3, -0.3.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ-16.9, -32.9, -45.6.

[Example 9] Synthesis of compound 10

In vitro bis (hexylsiloxy) diphenylsilane (222 mg, 0.5 mmol), dimethoxydiphenylsilane (122 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), toluene (2.5 mL) In addition, the reaction was carried out at 40 ° C. for 48 hours under an argon atmosphere. After completion of the reaction, hexane (10 mL) and acettril (15 mL) were added to the reaction solution, the hexane layer was extracted, the solvent was removed by an evaporator, and the target compound 10 was purified by ODS silica gel column chromatography. Compound 10 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolated yield of compound 10 was 66%.

The peak positions of Compound 10 in the ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, benzene-d ₆ ): δ: 7.81-7.83 (m), 7.17-7.21 (m), 5.29 (d), 1.36-1.45 (m), 1.07-1.24 (m), 0.82- 0.90 (m), 0.68-0.75 (m).
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ: 135.6, 135.5, 135.3, 135.0, 134.99, 134.95, 130.9, 128.6, 33.1 (d), 32.2 (d), 23.2 (d), 22.4 (d), 17.4 (d), 14.7 (d).
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -30.8 (d), -42.8 (d).

[Example 10] Synthesis of compound 11

Triphenylsiloxytriethoxysilane (219 mg, 0.5 mmol), tris (dimethylsiloki) phenylsilane (165 mg, 0.5 mmol), tris (pentafluorophenyl) borane (26 mg, 0.05 mmol), toluene (15 mL) In addition to the test tube, the reaction was carried out at 60 ° C. for 24 hours under an argon atmosphere. After completion of the reaction, the solvent was removed by an evaporator, and the target compound 11 was purified by silica gel column chromatography. Compound 11 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolated yield of compound 11 was 30%.

¹ H NMR (600 MHz, benzene-d ₆ ): δ 7.86-7.88, 7.82-8.84, 7.18-7.20, 0.22.
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ 136.0, 135.98, 134.8, 132.4, 131.2, 130.6, 128.5, 128.4, 0.8.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -12.0, -17.5, -72.4, -101.3.

[Example 11] Synthesis of compound 12

In vitro tetraisopropoxysilane (264 mg, 1 mmol), tetrakis (dimethylsiloxy) silane (329 mg, 1 mmol), tris (pentafluorophenyl) borane (51 mg, 0.1 mmol), toluene (20 mL) In addition, the reaction was carried out at room temperature for 48 hours under an argon atmosphere. After completion of the reaction, the solvent was removed with an evaporator, and the target compound 12 was purified using alumina. Compound 12 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. Further, as a result of GPC measurement of the obtained compound 12, it was a polymer having a number average molecular weight (M _n ) of 8810 or more, and as a result of measuring the thermophysical properties by differential scanning calorific value analysis, the degree of weight loss of 5% was 436. It turned out to be ℃.
FIG. 1 shows spectral data of ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR.

[Example 12] Synthesis of compound 13

Bis (diethoxysiloxy) diphenylsilane (45 mg, 0.1 mmol), diphenylsilanediol (22 mg, 0.1 mmol), hydrogenated (triphenylphosphine) copper hexamer (2.5 mg, 0.00125 mmol), xantphos (xantphos, 4.3 mg) , 0.0075 mmol) and toluene (2 mL) were added to the test tube and reacted at 25 ° C. for 36 hours under an argon atmosphere. The yield of compound 13 was 86%.
The yield of compound 13 was determined by ²⁹ Si NMR using phenyltrimethylsilane (30 mg, 0.2 mmol) as an internal standard.
The peak positions in the ²⁹ Si NMR spectrum were as follows.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -44.2, -93.8.

[Example 13] Synthesis of compound 14

Bis (diethoxysiloxy) diphenylsilane (226.4 mg, 0.5 mmol), diphenylsilanediol (108.2 mg, 0.5 mmol), hydrogenated (triphenylphosphine) copper hexamer (12.3 mg, 0.00625 mmol), xantphos (xantphos, 21.7 mg) , 0.0375 mmol) and toluene (10 mL) were added to the test tube and reacted at 25 ° C. for 24 hours under an argon atmosphere. After the reaction, bis (dimethylsiloxy) diphenylsilane (332.6 mg, 1.0 mmol) and tris (pentafluorophenyl) borane (52 mg, 0.1 mmol) were added to a test tube and reacted at 25 ° C. for 24 hours under an argon atmosphere. rice field. After completion of the reaction, the solvent was removed by an evaporator, and the target compound 14 was purified by silica gel column chromatography. Compound 14 was identified using ¹ H NMR, ¹³ C NMR, ²⁹ Si NMR. The isolated yield of compound 14 was 73%.

The peak positions of compound 14 in the ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, THF-d ₈ ): δ 7.39-7.42, 7.16-7.20, 7.06-7.11, -0.20.
¹³ C [ ¹ H] NMR (151 MHz, THF-d ₈ ): δ 136.98, 136.97, 135.8, 135.5, 131.5, 131.3, 129.1, 129.0, 1.0.
²⁹ Si [ ¹ H] NMR (119 MHz, THF-d ₈ ): δ -17.7, -46.4, -47.5, -108.8.

[Example 14] Synthesis of compound 15

Bis (diethoxysiloxy) diphenylsilane (226.4 mg, 0.5 mmol), tetramethyldisiloxanediol (83.2 mg, 0.5 mmol), hydrogenated (triphenylphosphine) copper hexamer (12.3 mg, 0.00625 mmol), xantphos, 21.7 mg, 0.0375 mmol) and toluene (10 mL) were added to the test tube, and the mixture was reacted at 25 ° C. for 16 hours under an argon atmosphere. After the reaction, bis (dimethylsiloxy) diphenylsilane (332.6 mg, 1.0 mmol) and tris (pentafluorophenyl) borane (52 mg, 0.1 mmol) were added to a test tube, and the mixture was reacted at 25 ° C. for 24 hours under an argon atmosphere. .. After completion of the reaction, the solvent was removed by an evaporator, and the target compound 15 was purified by silica gel column chromatography. Compound 15 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolated yield of compound 15 was 55%.

The peak positions of compound 15 in the ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, THF-d ₈ ): δ 7.92-7.94 (m), 7.78-7.82 (m), 7.16-7.22 (m), 0.21 (d), 0.13 (s).
¹³ C [ ¹ H] NMR (151 MHz, THF-d ₈ ): δ 136.98, 136.97, 135.8, 135.5, 131.5, 131.3, 129.1, 129.0, 1.1 (d), 0.9.
²⁹ Si [ ¹ H] NMR (119 MHz, THF-d ₈ ): δ -15.7, -19.1, -44.9, -46.0, -107.2.

[Example 15] Synthesis of compound 16

Bis (diethoxysiloxy) diphenylsilane (452.8 mg, 1 mmol), diphenylsilanediol (216.3 mg, 1 mmol), hydrogenated (triphenylphosphine) copper hexamer (24.6 mg, 0.0125 mmol), xantphos (xantphos, 43.4 mg) , 0.075 mmol) and toluene (20 mL) were added to the test tube and reacted at 25 ° C. for 16 hours under an argon atmosphere. After the reaction, tetrakis (dimethylsiloxy) silane (328.7 mg, 1.0 mmol) and tris (pentafluorophenyl) borane (52 mg, 0.1 mmol) were added to a test tube, and the mixture was reacted at 25 ° C. for 24 hours under an argon atmosphere. After completion of the reaction, hexane (10 mL) was added to the reaction solution, and the mixture was filtered using a syringe filter. After concentrating the filtrate, the diluted solution containing toluene (10 mL) was filtered using alumina (2 g). The filtrate was concentrated to give compound 16 (875 mg). Compound 16 was analyzed using ¹ H NMR, ¹³ _C NMR, ²⁹ Si NMR, GPC, and DSC. It was suggested that the spirosiloxane polymer.
Figure 2 shows the spectral data of ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR.
In addition, Fig. 3 shows the results of measuring the thermal properties by differential scanning calorimetry under a nitrogen atmosphere. Figure 4 shows the results of measuring the thermal properties by differential scanning calorimetry under an air atmosphere.

According to the production method of the present invention, a cyclic siloxane compound useful as a functional chemical or a material can be produced more efficiently and safely, and a novel cyclic siloxane compound and its use can be provided, so that the utility value of the present invention is high. , Its industrial significance is enormous.

Claims (15)

It comprises a step of reacting a compound represented by the following formula (1) with an alcohol compound in the presence of a boron catalyst and / or a transition metal hydride complex catalyst to form a ring skeleton by an —Si—O— bond. , A method for producing a cyclic siloxane compound having at least one ring skeleton.

(In the formula (1), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Any of the group consisting of an aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2 , the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. ) ^RA1 , ^RA2 , ^RC1 and ^RC2 are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group.
R ^B1 and R ^B2 are independently aryl groups and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independently alkyl groups, aryl groups, and alkenyl groups, respectively. The production method according to claim 1, which is any one selected from the group consisting of groups.). The production method according to claim 1, wherein the cyclic siloxane compound is a compound having one ring skeleton. The production method according to claim 3, wherein the compound having one ring skeleton is a compound represented by the following formula (3).

In formula (3), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Whichever is selected from the group consisting of an aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group.
p'is an integer greater than or equal to 0.
However, the combination of R ^A1 and R ^A2 , the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. ) A step of reacting a compound represented by the following formula (1) with a silicon compound having at least two hydroxy groups in the presence of a transition metal hydride complex catalyst to form a ring skeleton by an —Si—O— bond. A method for producing a cyclic siloxane compound having at least one ring skeleton, comprising the above.

(In equation (1), R ^A1 , R ^A2 , R ^C1 And R ^C2 Are independently alkoxy groups,
R ^B1 And R ^B2 Are independently an alkyl group, an aryl group, an alkenyl group, and -OSi (R). ^X1 ) (R ^X2 ) H group (R ^X1 And R ^X2 Is independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group. ) Is selected from the group consisting of. ) The compound represented by the following formula (1) is reacted with an alcohol compound or a silicon compound having at least two hydroxy groups or an alkoxy group in the presence of a boron catalyst and / or a transition metal hydride complex catalyst, and −Si. A method for producing a cyclic siloxane compound having at least one ring skeleton, which comprises a step of forming a ring skeleton by an —O— bond.

(In the formula (1), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Any of the group consisting of an aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2 , the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. )
The cyclic siloxane compound is a compound composed of two or more rings containing at least one crosslinked ring formed between silicon atoms in the ring skeleton.
In the step of forming the ring skeleton, at least one of RB1 and ^RB2 in the compound represented by the formula (1) is an ^-OSi (R ^X1 ) (R ^X2 ) H group. ) And a silicon compound having at least 3 hydroxy groups or alkoxy groups. A compound composed of two or more rings containing at least one crosslinked ring formed between silicon atoms in the ring skeleton is a compound represented by the following formula (4).
The production method according to claim 6 , wherein the silicon compound having at least three hydroxy groups or alkoxy groups is a compound represented by the formula (A1-1).

In formula (4), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B2 is an alkyl group, an aryl group, an alkenyl group, and -OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 are independently composed of an alkyl group, an aryl group, and an alkenyl group, respectively. It is one of the groups selected from the group consisting of.)
R ^D2 is one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group.

(In the formula (A1-1), R ^D1 is an alkoxy group, and
R ^D2 is one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group.
R ^E1 and R ^E2 are alkyl groups. ) The compound represented by the following formula (1) is reacted with an alcohol compound or a silicon compound having at least two hydroxy groups or an alkoxy group in the presence of a boron catalyst and / or a transition metal hydride complex catalyst, and −Si. A method for producing a cyclic siloxane compound having at least one ring skeleton, which comprises a step of forming a ring skeleton by an —O— bond.

(In the formula (1), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Any of the group consisting of an aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2 , the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. )
The cyclic siloxane compound is a compound composed of two or more rings containing at least one crosslinked ring formed between silicon atoms in the ring skeleton.
In the step of forming the ring skeleton, the compound represented by the formula (1) (in the formula (1), RB1 and ^RB2 are ^—OSI (R ^X1 ) (R ^X2 ) H groups). , A production method for reacting with a silicon compound having at least 4 hydroxy groups or alkoxy groups. A compound composed of two or more rings containing at least one crosslinked ring formed between silicon atoms in the ring skeleton is a compound having a structure represented by the following formula (5).
The production method according to claim 8 , wherein the silicon compound having at least four hydroxy groups or alkoxy groups is a compound represented by the formula (A1-2).

In formula (5), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^X1 and R ^X2 are each independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.
n is an integer of 2 or more. )

(In the formula (A1-2), R ^D1 and R ^D2 are alkoxy groups, and R ^E1 and RE ² are alkyl groups.) The compound represented by the following formula (1) is reacted with an alcohol compound or a silicon compound having at least two hydroxy groups or an alkoxy group in the presence of a boron catalyst and / or a transition metal hydride complex catalyst, and −Si. A method for producing a cyclic siloxane compound having at least one ring skeleton, which comprises a step of forming a ring skeleton by an —O— bond.

(In the formula (1), ^RA1 , ^RA2 , ^RC1 and ^RC2 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. can be,
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Any of the group consisting of an aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2 , the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. )
The cyclic siloxane compound is a compound composed of two or more rings containing at least one spiro ring.
^RA1 , ^RA2 , ^RC1 and ^RC2 in the above formula (1) are independently alkoxy groups, and ^RB1 and ^RB2 are independently alkyl groups, aryl groups and alkenyl groups, respectively. It is one of the groups selected from the group consisting of groups.
The compound represented by the formula (1) is reacted with a silane compound having at least two hydroxy groups in the presence of a transition metal hydride complex catalyst, and the compound represented by the following formula (2) is further subjected to boron. A production method comprising a step of reacting in the presence of a catalyst.

(In the formula (2), RA1', ^{RA2' , RC1'and RC2'are} independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Is either
R ^B1'and R ^B2'are independent of each other, and the alkyl group, aryl group, alkenyl group, and -OSi (R ^X1' ) (R ^X2' ) H group (R ^X1'and R ^X2' are respectively. Independently, any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.)
n is an integer of 1 or more.
However, the combination of R A1'and R ^{A2' ,} the combination of R C1'and R ^{C2' ,} and the combination of R ^B1'and R ^B2'are not the same as each other. ) The production method according to claim 10 , wherein the compound composed of two or more rings containing at least one spiro ring is a compound having a structure represented by the following formula (6).

(In equation (6), ^Q1 and ^Q2 have the following structures independently of each other:

(R ^B1'and R ^B2'are independent of each other, and the alkyl group, aryl group, alkenyl group, and -OSi (R ^X1' ) (R ^X2' ) H group (R ^X1'and R ^X2' are Each is independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group), and ^{RC1'and RC2' are} independent of each other. , Which is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group, and n is an integer of 1 or more.)
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Whichever is selected from the group consisting of an aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group.
^{RA1'and RA2'are} independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group.
p and N are integers of 1 or more. ) The production method according to claim 10, wherein the compound composed of two or more rings containing at least one spiro ring is a compound represented by the following formula (6-1).

(In equation (6-1), ^Q1 and ^Q2 have the following structures independently:

Represented by
R ^B1 and R ^B2 are independent alkyl groups, aryl groups, alkenyl groups, and -OSi (R ^X1 ) (R ^X2 ) H groups (R ^X1 and R ^X2 are independent alkyl groups, respectively. , Whichever is selected from the group consisting of an aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group.
^{RA1'and RA2'are} independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group.
R ^B1'and R ^B2'are independent of each other, and the alkyl group, aryl group, alkenyl group, and -OSi (R ^X1' ) (R ^X2' ) H group (R ^X1'and R ^X2' are respectively. Independently, any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.)
R ^C1'and R ^C2'are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group.
p and n are integers of 1 or more. ) A cyclic siloxane compound represented by the following formula (II).

(In formula (II), Re is a siroxy ^group ,
R ^f , R ^g1 , R ^g2 , R ^h1 , R ^h2 , R ⁱ¹ , and R ⁱ² are each independently selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group. ) A cyclic siloxane compound having a structure represented by the following formula (III).

In formula (III), R ^j1 , R ^j2 , R ^k1 , R ^k2 , R ^l1 , R ^l2 , R ^m1 , and R ^m2 are independently composed of an alkyl group, an aryl group, and an alkenyl group, respectively. One of the choices from the group,
n is an integer of 2 or more. ) A cyclic siloxane compound having a structure represented by the following formula (IV).

(In equation (IV), R ⁿ¹ , R ⁿ² , R ^o1 , R ^o2 , R ^p1 , R ^p2 , R ^q1 , R ^q2 , R ^r1 , R ^r2 , R ^s1 , and R ^s2 are independent of each other. It is one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.
m1, m2, and m3 are independently integers of 1 or 2, respectively.
n is an integer of 1 or more.
However, the combination of R ⁿ¹ and R ⁿ² , the combination of R ^r1 and R ^r2 , and the combination of R ^p1 and R ^p2 are not the same as each other. )

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