JP6562318B2 - Siloxane compound and method for producing siloxane compound - Google Patents

Description

  The present invention relates to a siloxane compound and a method for producing the siloxane compound, and more particularly to a siloxane compound that can be used in a wide range of fields such as automobiles, architecture, electronics, medicine, and the like.

  Siloxane compounds (silicones) play an important role in a wide range of fields such as automobile materials, building materials, electronic materials, and pharmaceuticals because of their unique properties. In recent years, it is indispensable in the environment and energy fields, such as LED sealing materials and eco-tire silane coupling agents, and it is no exaggeration to say that there are no fields that do not use siloxane compounds (2009 market scale: 115 (Billion dollars, production: 1.23 million tons per year).

Most of the siloxane compounds are generally synthesized via silanol by hydrolysis such as sol-gel method using chlorosilane or alkoxysilane as a raw material. This silanol (including silane diol, silane triol, and silane tetraol), except for some silane diols and silane triols having bulky substituents such as phenyl groups, condenses simultaneously with hydrolysis in the presence of water. However, it is difficult to synthesize with good yield. In addition, it is known that the stability is very low and polymerization occurs quickly (Non-Patent Documents 2 and 3). Therefore, there are still many problems and limitations such as 1) many reaction by-products, 2) difficult structure control of the product, and 3) inability to adapt to the reaction with water-weak substrates.
Therefore, there is a demand for an anhydrous condition silanol synthesis method or synthesis of siloxane not via silanol.

  As a method capable of synthesizing silanol under anhydrous conditions, a method is known in which n-BuLi is allowed to act on silyl ether of pyrrolidine to obtain a silanol compound (Non-patent Document 1). However, this method is not a reaction intended to synthesize siloxane in the first place. Even if siloxane is synthesized, a siloxane compound is synthesized because siloxane bonds are cleaved nucleophilically by n-BuLi. It ’s difficult.

On the other hand, several examples of the synthesis of siloxane not via silanol have been reported on the synthesis of siloxane by cross-coupling using a catalyst.
As one of them, Piers and Rubinsztajn et al. Reported that a siloxane bond can be formed with the elimination of methane by reacting alkoxysilane with hydrosilane in the presence of B (C ₆ F ₅ ) ₃ catalyst. (Non-Patent Documents 4 and 5). However, in this reaction, B (C ₆ F ₅ ) ₃ which is a Lewis acid catalyst has problems such as disproportionation between raw material substrates and the reaction cannot be controlled. It's hard to say.

Recently, Bae et al. Have reported that a siloxane bond can be formed with the elimination of methanol by reacting the following silanol and methoxysilane in the presence of a Ba (OH) ₂ catalyst (Non-patent Document 6). ). However, in this reaction, only a small portion of stable silanol can be applied, and it is difficult to say that this method is suitable for industrialization.

Moreover, Kuroda et al. Have reported that a siloxane bond can be formed with the elimination of alkyl chloride by reacting the following alkoxysilane and chlorosilane in the presence of a bismuth chloride catalyst (Non-patent Document 7). However, in this reaction, since the substrate is limited to a small part, it is difficult to say that the method is suitable for industrialization.

  Furthermore, since the methods described in Non-Patent Documents 4 to 7 all use a homogeneous catalyst, there is a problem that it is not easy to remove from the reaction system after the reaction and remains in the obtained product. is there.

J. Am. Chem. Soc. 2000, 122, 408-409. Fyfe, C. A .; Aroca, P. P. J. Phys. Chem. B 1997, 101, 9504. Kim, Y .; Jung, E. Chem. Lett. 2002, 992. Parks, D. J .; Blackwell, J. M .; Piers, W. E. J. Org. Chem. 2000, 65, 3090. Rubinsztajn. S .; Cella, J. A. Macromolecules 2005, 38, 1061. Synthetic Metals 2009, 159, 1288-1290. Angew. Chem. Int. Ed. 2010, 49, 5273-5277.

As described above, the siloxane compound can be synthesized via the silanol compound, but the silanol group (Si—OH) is rapidly condensed in the presence of water. It is difficult to selectively synthesize these siloxane compounds with high yield, and it is difficult to obtain a composition in which these siloxane compounds are stably blended at a high concentration.
The present invention provides a useful low molecular weight siloxane compound having a silanol group, that is, a hydroxyl group, and a composition thereof, and further provides a method for producing a siloxane compound capable of efficiently producing such a siloxane compound. The purpose is to do.

As a result of intensive studies to solve the above-mentioned problems, the present inventors can actually prepare a composition containing a specific amount of a specific siloxane compound having a hydroxyl group. Was found to be very useful as a raw material for silicone resins, and the present invention was completed.
That is, the present invention is as follows.

（式（Ａ−２）〜（Ａ−６）中、Ｒはそれぞれ独立して水素原子、又は炭素数１〜２０の炭化水素基を表す。）
＜２＞ 前記式（Ａ−１）〜（Ａ−６）で表されるシロキサン化合物の少なくとも１種の含有量が、５〜９０質量％である、＜１＞に記載の組成物。
＜３＞ 下記式（Ｂ）で表されるシロキサン化合物。

＜４＞ ＜３＞に記載の式（Ｂ）で表されるシロキサン化合物を０．１質量％以上１００質量％未満含む組成物。
＜５＞ 水の含有量が２５質量％以下である、＜１＞、＜２＞、＜４＞の何れかに記載の組成物。
＜６＞ アミド化合物を０質量％より多く９９質量％以下含む、＜１＞、＜２＞、＜４＞、＜５＞の何れかに記載の組成物。
＜７＞ 前記アミド化合物の前記式（Ａ−１）〜（Ａ−６）で表されるシロキサン化合物又は式（Ｂ）で表されるシロキサン化合物に対する比率（アミド結合の総物質量／シロキサン化合物の総物質量）が０よりも大きく９００以下である、＜６＞に記載の組成物。
＜８＞ 前記アミド化合物が、テトラメチル尿素である、＜６＞又は＜７＞に記載の組成物。
＜９＞ アンモニウム塩を含み、前記アンモニウム塩の前記式（Ａ−１）〜（Ａ−６）で表されるシロキサン化合物又は式（Ｂ）で表されるシロキサン化合物に対する比率（アンモニウム塩の総物質量／シロキサン化合物の総物質量）が０より大きく１０以下である、＜１＞、＜２＞、＜４＞〜＜８＞の何れかに記載の組成物。
＜１０＞ パラジウム（Ｐｄ）元素と、白金（Ｐｔ）、ルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、イリジウム（Ｉｒ）、及び金（Ａｕ）からなる群より選択される少なくとも１種の元素とを含有する固体触媒の存在下、下記式（１）で表される構造を有するシロキサン化合物と水素を反応させて下記式（２）で表される構造を有するシロキサン化合物を生成する水素添加工程を含むことを特徴とするシロキサン化合物の製造方法。

（式（１）中、Ａｒは窒素原子、酸素原子、及びハロゲン原子からなる群より選択される少なくとも１種の原子を含んでいてもよい炭素数４〜２０の芳香族炭化水素基を表す。）
＜１１＞ 前記反応工程が、アミド化合物を含む溶媒中で行われる、＜１０＞に記載のシロキサン化合物の製造方法。
＜１２＞ 前記反応工程で得られた生成物にアンモニウム塩を添加するアンモニウム塩添加工程を含む、＜１０＞又は＜１１＞に記載のシロキサン化合物の製造方法。
＜１３＞ 前記反応工程で得られた生成物にアミド化合物を添加するアミド化合物添加工程を含む、＜１０＞〜＜１２＞の何れかに記載のシロキサン化合物の製造方法。
＜１４＞ 前記反応工程で得られた生成物、前記アンモニウム塩添加工程で得られた生成物、又は前記アミド化合物添加工程で得られた生成物を凍結させて、減圧下にさらす凍結乾燥工程を含む、＜１０＞〜＜１３＞の何れかに記載のシロキサン化合物の製造方法。
＜１５＞ 前記反応工程で得られた生成物、前記アンモニウム塩添加工程で得られた生成物、又は前記アミド化合物添加工程で得られた生成物から貧溶媒法により結晶を析出させる結晶化工程を含む、＜１０＞〜＜１３＞の何れかに記載のシロキサン化合物の製造方法。
＜１６＞ アミド化合物の存在下、下記式（３）で表されるシロキサン化合物から下記式（４）で表されるシロキサン化合物を生成する環化工程を含むことを特徴とするシロキサン化合物の製造方法。

（式（３）及び（４）中、Ｒ’’’はそれぞれ独立して水素原子、ヒドロキシル基、又は炭素数１〜２０の炭化水素基を、ｎは１〜１０の整数を表す。）
＜１７＞ 前記環化工程が、前記式（３）で表されるシロキサン化合物を含む組成物に前記アミド化合物を添加することによって行う工程である、＜１６＞に記載のシロキサン化合物の製造方法。
＜１８＞ 前記アミド化合物が、下記式（ｉ）又は（ｉｉ）で表される化合物の少なくとも１種である、＜１６＞又は＜１７＞に記載のシロキサン化合物の製造方法。

（式（ｉ）及び（ｉｉ）中、Ｒ’及びＲ”はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基を表す。但し、Ｒ’及び／又はＲ”として、２以上の炭化水素基を分子内に有する場合、炭化水素基同士が連結して環状構造を形成していてもよい。）
＜１９＞ 前記アミド化合物が、下記式（ｉｉｉ）〜（ｖ）で表される繰り返し構造の少なくとも１種を有する高分子化合物である、＜１６＞〜＜１８＞の何れかに記載のシロキサン化合物の製造方法。

（式（ｉｉｉ）〜（ｖ）中、Ｒ’及びＲ’’はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基を表す。但し、Ｒ’及び／又はＲ’’として、２以上の炭化水素基を分子内に有する場合、炭化水素基同士が連結して環状構造を形成していてもよい。）
＜２０＞ 前記環化工程で得られた生成物を凍結させて、減圧下にさらす凍結乾燥工程を含む、＜１６＞〜＜１９＞の何れかに記載のシロキサン化合物の製造方法。<1> A composition containing 1% by mass or more and less than 100% by mass of at least one siloxane compound represented by the following formulas (A-1) to (A-6).

(In formulas (A-2) to (A-6), R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
<2> The composition according to <1>, wherein the content of at least one of the siloxane compounds represented by the formulas (A-1) to (A-6) is 5 to 90% by mass.
<3> A siloxane compound represented by the following formula (B).

<4> A composition containing 0.1% by mass or more and less than 100% by mass of the siloxane compound represented by the formula (B) according to <3>.
<5> The composition according to any one of <1>, <2>, and <4>, wherein the water content is 25% by mass or less.
<6> The composition according to any one of <1>, <2>, <4>, and <5>, containing an amide compound in an amount of more than 0% by mass and 99% by mass or less.
<7> Ratio of the amide compound to the siloxane compound represented by the formulas (A-1) to (A-6) or the siloxane compound represented by the formula (B) (total amount of amide bond / siloxane compound <6> The composition according to <6>, wherein the total amount of substances is greater than 0 and 900 or less.
<8> The composition according to <6> or <7>, wherein the amide compound is tetramethylurea.
<9> Ammonium salt-containing ratio of the ammonium salt to the siloxane compound represented by the formulas (A-1) to (A-6) or the siloxane compound represented by the formula (B) (total substance of ammonium salt) The composition according to any one of <1>, <2>, and <4> to <8>, wherein (amount / total amount of siloxane compound) is greater than 0 and 10 or less.
<10> Contains a palladium (Pd) element and at least one element selected from the group consisting of platinum (Pt), ruthenium (Ru), rhodium (Rh), iridium (Ir), and gold (Au) A hydrogenation step of reacting a siloxane compound having a structure represented by the following formula (1) with hydrogen in the presence of a solid catalyst to produce a siloxane compound having a structure represented by the following formula (2). A process for producing a siloxane compound characterized by the above.

(In the formula (1), Ar represents an aromatic hydrocarbon group having 4 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a halogen atom. )
<11> The method for producing a siloxane compound according to <10>, wherein the reaction step is performed in a solvent containing an amide compound.
<12> The method for producing a siloxane compound according to <10> or <11>, including an ammonium salt addition step of adding an ammonium salt to the product obtained in the reaction step.
<13> The method for producing a siloxane compound according to any one of <10> to <12>, including an amide compound addition step of adding an amide compound to the product obtained in the reaction step.
<14> A freeze-drying step in which the product obtained in the reaction step, the product obtained in the ammonium salt addition step, or the product obtained in the amide compound addition step is frozen and exposed to reduced pressure. The manufacturing method of the siloxane compound in any one of <10>-<13> containing.
<15> A crystallization step for precipitating crystals by a poor solvent method from the product obtained in the reaction step, the product obtained in the ammonium salt addition step, or the product obtained in the amide compound addition step. The manufacturing method of the siloxane compound in any one of <10>-<13> containing.
<16> A method for producing a siloxane compound, comprising a cyclization step of producing a siloxane compound represented by the following formula (4) from a siloxane compound represented by the following formula (3) in the presence of an amide compound: .

(In formulas (3) and (4), R ′ ″ each independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 1 to 10)
<17> The method for producing a siloxane compound according to <16>, wherein the cyclization step is a step performed by adding the amide compound to a composition containing the siloxane compound represented by the formula (3).
<18> The method for producing a siloxane compound according to <16> or <17>, wherein the amide compound is at least one compound represented by the following formula (i) or (ii).

(In the formulas (i) and (ii), R ′ and R ″ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are two or more. (When it has a hydrocarbon group in a molecule | numerator, hydrocarbon groups may connect and it may form the cyclic structure.)
<19> The siloxane compound according to any one of <16> to <18>, wherein the amide compound is a polymer compound having at least one repeating structure represented by the following formulas (iii) to (v): Manufacturing method.

(In the formulas (iii) to (v), R ′ and R ″ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are 2 When the above hydrocarbon groups are contained in the molecule, the hydrocarbon groups may be linked to form a cyclic structure.)
<20> The method for producing a siloxane compound according to any one of <16> to <19>, comprising a freeze-drying step in which the product obtained in the cyclization step is frozen and exposed to reduced pressure.

  ADVANTAGE OF THE INVENTION According to this invention, the siloxane compound which has a hydroxyl group which can be utilized as a raw material etc. of a silicone resin, and its composition can be provided.

4 is a measurement result of IR of the composition obtained in Example 16. 4 is a measurement result of IR of the composition obtained in Example 17. 2 is a measurement result of IR of the composition obtained in Example 18. FIG. 2 is a measurement result of IR of the composition obtained in Example 19. FIG. It is a measurement result of IR of the composition obtained in Example 20. 2 is a measurement result of IR of the composition obtained in Example 21. FIG. 4 is a measurement result of IR of the composition obtained in Example 22. 4 is a measurement result of IR of the composition obtained in Example 23. 4 is a measurement result of IR of the composition obtained in Example 24. 4 is a measurement result of IR of the composition obtained in Example 25. 2 is a measurement result of IR of the composition obtained in Example 26. FIG. 4 is a measurement result of IR of the composition obtained in Example 27. 4 is a measurement result of IR of the composition obtained in Example 28. 4 is a measurement result of IR of the composition obtained in Example 29. 4 is a measurement result of IR of the composition obtained in Example 30. 2 is a measurement result of IR of the composition obtained in Example 31. FIG. 3 is a measurement result of IR of the composition obtained in Example 32. FIG.

  The details of the present invention will be described with specific examples. However, the present invention is not limited to the following contents without departing from the gist of the present invention, and can be implemented with appropriate modifications.

（式（Ａ−２）〜（Ａ−６）中、Ｒはそれぞれ独立して水素原子、又は炭素数１〜２０の炭化水素基を表す。）
式（Ａ−１）〜（Ａ−６）で表されるシロキサン化合物は、ジシロキサン化合物であり、ヒドロキシル基が残存した化合物である。
前述のようにシロキサン化合物は、シラノール化合物を経由して合成することができるが、シラノール基（Ｓｉ−ＯＨ）が水の存在下で速やかに縮合してしまうため、シラノール基が残存した低分子量のシロキサン化合物を選択的に収率良く合成することは困難であり、またこれらのシロキサン化合物を高濃度で安定的に配合した組成物を得ることも難しいのが現状である。
本発明者らは、無水条件でシロキサン化合物を製造したり、シラノール基の縮合を抑える作用がある溶媒中でシロキサン化合物を製造したりする等の工夫を行うことにより、式（Ａ−１）〜（Ａ−６）で表されるシロキサン化合物を１質量％以上１００質量％未満含んだ組成物を調製することに成功するとともに、得られた組成物においてシロキサン化合物が安定的に存在できるため、この組成物がシリコーン樹脂の原料等として非常に有用であること見出したのである。<Composition>
The composition which is one embodiment of the present invention (hereinafter sometimes abbreviated as “the composition of the present invention”) is at least one of the siloxane compounds represented by the following formulas (A-1) to (A-6). It contains 1% by mass or more and less than 100% by mass of seeds.

(In formulas (A-2) to (A-6), R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
The siloxane compounds represented by formulas (A-1) to (A-6) are disiloxane compounds and are compounds in which hydroxyl groups remain.
As described above, the siloxane compound can be synthesized via a silanol compound, but since the silanol group (Si-OH) is rapidly condensed in the presence of water, the low molecular weight of the silanol group remaining is low. It is difficult to selectively synthesize siloxane compounds with high yield, and it is difficult to obtain a composition in which these siloxane compounds are stably blended at a high concentration.
The inventors of the present invention can produce a siloxane compound under anhydrous conditions or produce a siloxane compound in a solvent having an action of suppressing the condensation of silanol groups. While successfully preparing a composition containing 1% by mass or more and less than 100% by mass of the siloxane compound represented by (A-6), the siloxane compound can be stably present in the obtained composition. The present inventors have found that the composition is very useful as a raw material for silicone resins.

（式（Ａ−２）〜（Ａ−６）中、Ｒはそれぞれ独立して水素原子、又は炭素数１〜２０の炭化水素基を表す。）
Ｒはそれぞれ水素原子、又は炭素数１〜２０の炭化水素基を表しているが、「炭化水素基」は、直鎖状の飽和炭化水素基に限られず、炭素−炭素不飽和結合、分岐構造、環状構造のそれぞれを有していてもよいことを意味する。
Ｒが炭化水素基である場合の炭素数は、好ましくは８以下、より好ましくは７以下、さらに好ましくは６以下、特に好ましくは４以下である。
Ｒとしては、水素原子（−Ｈ）、メチル基（−Ｍｅ）、エチル基（−Ｅｔ）、ｎ−プロピル基（−^ｎＰｒ）、ｉ−プロピル基（−^ｉＰｒ）、ｎ−ブチル基（−^ｎＢｕ）、ｔ−ブチル基（−^ｔＢｕ）、ｎ−ヘキシル基（−^ｎＨｅｘ）、シクロへキシル基（−^ｃＨｅｘ）、フェニル基（−Ｐｈ）、ナフチル基、アントリル基、フルオレニル基等が挙げられるが、メチル基が特に好ましい。
式（Ａ−２）〜（Ａ−６）で表されるシロキサン化合物としては、下記式で表される化合物が挙げられる。

Although the composition of this invention contains at least 1 sort (s) of the siloxane compound represented by Formula (A-1)-(A-6), it is represented by following formula (A-2)-(A-6) The specific type of the siloxane compound represented by) is not particularly limited, and can be appropriately selected depending on the purpose.

(In formulas (A-2) to (A-6), R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, but the “hydrocarbon group” is not limited to a straight-chain saturated hydrocarbon group, and includes a carbon-carbon unsaturated bond and a branched structure. , Meaning that each of the ring structures may have.
The carbon number when R is a hydrocarbon group is preferably 8 or less, more preferably 7 or less, still more preferably 6 or less, and particularly preferably 4 or less.
R includes a hydrogen atom (—H), a methyl group (—Me), an ethyl group (—Et), an n-propyl group ( ^—n Pr), an i-propyl group ( ^—i Pr), an n-butyl group ( - ⁿ Bu), t-butyl group ^(- t Bu), n- hexyl group ^(- n Hex), cyclohexyl group ^(- c Hex), phenyl group (-Ph), naphthyl group, anthryl group, fluorenyl group Among them, a methyl group is particularly preferable.
Examples of the siloxane compounds represented by the formulas (A-2) to (A-6) include compounds represented by the following formulas.

  The composition of the present invention is characterized by containing at least one siloxane compound represented by the formulas (A-1) to (A-6) in an amount of 1% by mass or more and less than 100% by mass. When two or more types are included, the total content) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 19% by mass or more, and most preferably 23% by mass or more. Preferably, it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less. Within the above range, the composition of the present invention can be easily used for various applications, and the stability of the composition of the present invention can be kept good.

  If the composition of this invention contains the siloxane compound (henceforth a "siloxane compound" may be abbreviated as a siloxane compound) represented by Formula (A-1)-(A-6), other compounds are included. Specific compounds may include water, amine compounds, amide compounds, ammonium salts, and the like. Hereinafter, these compounds will be described in detail.

Water is a preferable compound because it promotes the condensation of silanol groups and reduces the stability of the composition of the present invention. In addition, water can be mixed from the air or can be generated by condensation of silanol groups, and is also used for hydrolysis of halogenated silanes and alkoxysilanes. It is a compound that is easily contained in the composition obtained by the method.
The water content in the composition of the present invention is usually 25% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. Most preferably, it is 0.01 mass% or less. Within the above range, the composition of the present invention can be easily used for various applications, and the stability of the composition of the present invention can be kept good.

An amine compound is a compound that may be used in the process of producing a siloxane compound, and is a compound that has the effect of suppressing the condensation of silanol groups and stabilizing the composition of the present invention.
The amine compound is not particularly limited as long as it has an amino group (which may be any of primary amine, secondary amine, and tertiary amine) (amino group and Compounds having both amide bonds shall be classified as “amide compounds”.), Aniline (NH ₂ Ph), diphenylamine (NHPh ₂ ), dimethylpyridine (Me ₂ Pyr), di-tert-butylpyridine ( ^t Bu ₂ Pyr), pyrazine (Pyraz), triphenylamine _(NPh 3), triethylamine _(Et 3 N), di - isopropylethylamine ⁽ⁱ _Pr 2 EtN), and the like. Of the amine compounds, aniline (NH ₂ Ph) is particularly preferable. In addition, the amine compound contained in a composition is not restricted to one type, You may contain 2 or more types.
The content of the amine compound in the composition of the present invention (when two or more types are included, the total content) is preferably more than 0% by mass, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass. Above, particularly preferably 0.10% by mass or more, usually less than 95% by mass, preferably 50% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, particularly preferably 2.5% by mass. % Or less. Within the above range, the composition of the present invention can be easily used for various applications, and the stability of the composition of the present invention can be kept good.

（式（ｉ）及び（ｉｉ）中、Ｒ’及びＲ’’はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基を表す。但し、Ｒ’及び／又はＲ’’として、２以上の炭化水素基を分子内に有する場合、炭化水素基同士が連結して環状構造を形成していてもよい。）

（式（ｉｉｉ）〜（ｖ）中、Ｒ’及びＲ’’はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基を表す。但し、Ｒ’及び／又はＲ’’として、２以上の炭化水素基を分子内に有する場合、炭化水素基同士が連結して環状構造を形成していてもよい。）
Ｒ’はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基を表しているが、水素原子、メチル基（−Ｍｅ）、エチル基（−Ｅｔ）、ｎ−プロピル基（−^ｎＰｒ）、ｉ−プロピル基（−^ｉＰｒ）、ｎ−ブチル基（−^ｎＢｕ）、ｔ−ブチル基（−^ｔＢｕ）、ｎ−ヘキシル基（−^ｎＨｅｘ）、シクロへキシル基（−^ｃＨｅｘ）、フェニル基（−Ｐｈ）が挙げられる。
Ｒ’’はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基を表しているが、水素原子、メチル基（−Ｍｅ）、エチル基（−Ｅｔ）、ｎ−プロピル基（−^ｎＰｒ）、ｉ−プロピル基（−^ｉＰｒ）、ｎ−ブチル基（−^ｎＢｕ）、ｔ−ブチル基（−^ｔＢｕ）、ｎ−ヘキシル基（−^ｎＨｅｘ）、シクロへキシル基（−^ｃＨｅｘ）、フェニル基（−Ｐｈ）が挙げられる。
なお、Ｒ’及び／又はＲ’’として、２以上の炭化水素基を分子内に有する場合、炭化水素基同士が連結して環状構造を形成していてもよいが、「環状構造を形成」しているとは、例えば下記式で表されるアミド化合物のような構造を意味する。

式（ｉｉｉ）〜（ｖ）で表される繰り返し構造の少なくとも１種を有する高分子化合物の数平均分子量（Ｍ_ｎ）は、通常１，０００以上、好ましくは５，０００以上、より好ましくは１０，０００以上であり、通常１，０００，０００以下、好ましくは５００，０００以下、より好ましくは２００，０００以下である。
式（ｉｉｉ）〜（ｖ）で表される繰り返し構造の少なくとも１種を有する高分子化合物の重量平均分子量（Ｍ_ｗ）は、通常１，０００以上、好ましくは５，０００以上、より好ましくは１０，０００以上であり、通常１，０００，０００以下、好ましくは５００，０００以下、より好ましくは２００，０００以下である。
式（ｉｉｉ）〜（ｖ）で表される繰り返し構造の少なくとも１種を有する高分子化合物のアミド結合の数は、通常１０以上、好ましくは５０以上、より好ましくは１００以上であり、通常１０，０００以下、好ましくは５，０００以下、より好ましくは２，０００以下である。
式（ｉ）で表される化合物としては、ホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、アセトアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、２−ピロリドン、Ｎ−メチルピロリドン、２−ピペリドン、ε−カプロラクタム等が挙げられる。
式（ｉｉ）で表される化合物としては、尿素、テトラメチル尿素（Ｍｅ_４Ｕｒｅａ）、テトラフェニル尿素等が挙げられる。
式（ｉｉｉ）で表される繰り返し構造のみからなる高分子化合物としては、ポリビニルピロリドン、ポリビニルポリピロリドン、ポリビニルピペリドン、ポリビニルカプロラクタム等が挙げられる。
式（ｉｖ）で表される繰り返し構造のみからなる高分子化合物としては、ポリアクリルアミド、ポリ−Ｎ−メチルアクリルアミド、ポリ−Ｎ−エチルアクリルアミド、ポリ−Ｎ−エチルメタクリルアミド、ポリ−Ｎ−プロピルアクリルアミド、ポリ−Ｎ−プロピルメタクリルアミド、ポリ−Ｎ−イソプロピルアクリルアミド、ポリ−Ｎ−イソプロピルメタクリルアミド、ポリ−Ｎ−エチルメチルアクリルアミド、ポリ−Ｎ−ジエチルアクリルアミド、ポリ−Ｎ−イソプロピルメチルアクリルアミド、ポリ−Ｎ−メチルプロピルアクリルアミド、ポリ−Ｎ−シクロプロピルアクリルアミド、ポリ−Ｎ−シクロペンチニルアクリルアミド等が挙げられる。
式（ｖ）で表される繰り返し構造のみからなる高分子化合物としては、ポリ−２−メチルオキサゾリン、ポリ−２−エチルオキサゾリン、ポリ−２−プロピルオキサゾリン等が挙げられる。
なお、組成物に含まれるアミド化合物は、１種類に限られず、２種類以上を含むものであってもよい。
本発明の組成物におけるアミド化合物の含有量（２種類以上含む場合は総含有量）は、好ましくは０質量％より多く、より好ましくは０．２質量％以上、さらに好ましくは１質量％以上であり、通常９９質量％以下、好ましくは９５質量％以下、より好ましくは９０質量％以下、さらに好ましくは８０質量％以下である。上記範囲内であると、本発明の組成物を様々な用途に利用し易くなるとともに、本発明の組成物の安定性を良好に保つことができる。
また、本発明の組成物におけるアミド化合物のシロキサン化合物に対する比率（アミド結合の総物質量／シロキサン化合物の総物質量）は、好ましくは０より大きく、より好ましくは１以上であり、通常９００以下、好ましくは４５０以下、より好ましくは１５０以下、さらに好ましくは１０以下である。なお、「アミド化合物のシロキサン化合物に対する比率」は、括弧書きで「アミド結合の総物質量／シロキサン化合物の総物質量」と記載されているように、アミド結合の物質量換算で計算するものとする。即ち、分子内にアミド結合を２つ有するアミド化合物１ｍｏｌ／シロキサン化合物１ｍｏｌは「２」となる。An amide compound is a compound that may be used in the production process of a siloxane compound, and is a compound that has an effect of suppressing the condensation of silanol groups and stabilizing the composition of the present invention.
The specific type of the amide compound is not particularly limited as long as it has at least one amide bond (a compound having both an amino group and an amide bond is classified as an “amide compound”). In addition to the compound represented by the following formula (i) or (ii), a polymer compound having at least one of repeating structures represented by the following formulas (iii) to (v) can be given. Hereinafter, the “compound represented by the formula (i) or (ii)”, the “polymer compound having at least one repeating structure represented by the formulas (iii) to (v)” and the like will be described in detail.

(In the formulas (i) and (ii), R ′ and R ″ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are 2 When the above hydrocarbon groups are contained in the molecule, the hydrocarbon groups may be linked to form a cyclic structure.)

(In the formulas (iii) to (v), R ′ and R ″ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are 2 When the above hydrocarbon groups are contained in the molecule, the hydrocarbon groups may be linked to form a cyclic structure.)
R ′ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, but a hydrogen atom, a methyl group (—Me), an ethyl group (—Et), an n-propyl group ( ^—n Pr). ), I-propyl group ( ^-i Pr), n-butyl group ( ^-n Bu), t-butyl group ( ^-t Bu), n-hexyl group ( ^-n Hex), cyclohexyl group ( ^-c Hex) ), A phenyl group (-Ph).
R ″ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, but a hydrogen atom, a methyl group (—Me), an ethyl group (—Et), an n-propyl group ( ^—n Pr), i-propyl group ( ^-i Pr), n-butyl group ( ^-n Bu), t-butyl group ( ^-t Bu), n-hexyl group ( ^-n Hex), cyclohexyl group ( ^-c Hex) and phenyl group (-Ph).
When R ′ and / or R ″ have two or more hydrocarbon groups in the molecule, the hydrocarbon groups may be linked to form a cyclic structure, but “form a cyclic structure”. The term “has” means a structure such as an amide compound represented by the following formula.

The number average molecular weight (M _n ) of the polymer compound having at least one of the repeating structures represented by formulas (iii) to (v) is usually 1,000 or more, preferably 5,000 or more, more preferably 10 Is 1,000,000 or less, usually 1,000,000 or less, preferably 500,000 or less, more preferably 200,000 or less.
The weight average molecular weight (M _w ) of the polymer compound having at least one of the repeating structures represented by formulas (iii) to (v) is usually 1,000 or more, preferably 5,000 or more, more preferably 10 Is 1,000,000 or less, usually 1,000,000 or less, preferably 500,000 or less, more preferably 200,000 or less.
The number of amide bonds of the polymer compound having at least one of the repeating structures represented by formulas (iii) to (v) is usually 10 or more, preferably 50 or more, more preferably 100 or more. 000 or less, preferably 5,000 or less, more preferably 2,000 or less.
Examples of the compound represented by the formula (i) include formamide, N, N-dimethylformamide (DMF), acetamide, N-methylacetamide, N, N-dimethylacetamide (DMAc), 2-pyrrolidone, N-methylpyrrolidone, Examples include 2-piperidone and ε-caprolactam.
Examples of the compound represented by the formula (ii) include urea, tetramethylurea (Me ₄ Urea), and tetraphenylurea.
Examples of the polymer compound having only the repeating structure represented by the formula (iii) include polyvinyl pyrrolidone, polyvinyl polypyrrolidone, polyvinyl piperidone, and polyvinyl caprolactam.
Examples of the polymer compound having only a repeating structure represented by the formula (iv) include polyacrylamide, poly-N-methylacrylamide, poly-N-ethylacrylamide, poly-N-ethylmethacrylamide, and poly-N-propylacrylamide. , Poly-N-propylmethacrylamide, poly-N-isopropylacrylamide, poly-N-isopropylmethacrylamide, poly-N-ethylmethylacrylamide, poly-N-diethylacrylamide, poly-N-isopropylmethylacrylamide, poly-N -Methylpropylacrylamide, poly-N-cyclopropylacrylamide, poly-N-cyclopentynylacrylamide and the like.
Examples of the polymer compound consisting only of the repeating structure represented by the formula (v) include poly-2-methyloxazoline, poly-2-ethyloxazoline, poly-2-propyloxazoline and the like.
In addition, the amide compound contained in the composition is not limited to one type, and may include two or more types.
The content of the amide compound in the composition of the present invention (when two or more types are included, the total content) is preferably more than 0% by mass, more preferably 0.2% by mass or more, and even more preferably 1% by mass or more. It is usually 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less. Within the above range, the composition of the present invention can be easily used for various applications, and the stability of the composition of the present invention can be kept good.
The ratio of the amide compound to the siloxane compound in the composition of the present invention (total amount of amide bond / total amount of siloxane compound) is preferably greater than 0, more preferably 1 or more, and usually 900 or less. Preferably it is 450 or less, More preferably, it is 150 or less, More preferably, it is 10 or less. Note that the “ratio of amide compound to siloxane compound” is calculated in terms of the amount of amide bond as calculated in parentheses, as “total amount of amide bond / total amount of siloxane compound”. To do. That is, 1 mol of amide compound having 2 amide bonds in the molecule / 1 mol of siloxane compound is “2”.

  The total content in the case of containing both the amine compound and the amide compound is preferably more than 0% by mass, more preferably 0.2% by mass or more, further preferably 1% by mass or more, and usually 99% by mass or less. Preferably it is 95 mass% or less, More preferably, it is 90 mass% or less, More preferably, it is 80 mass% or less. Within the above range, the composition of the present invention can be easily used for various applications, and the stability of the composition of the present invention can be kept good.

An ammonium salt is a compound that has the effect of suppressing the condensation of silanol groups and stabilizing the composition of the present invention, and can be used as an additive (stabilizer).
The ammonium salt is not particularly limited as long as it is a compound comprising an ammonium ion and a counter anion. Examples of the ammonium ion include tetrahydroammonium ion (NH ₄ ⁺ ), tetramethylammonium ion (NMe ₄ ⁺ ), Tetraethylammonium ion (NEt ₄ ⁺ ), tetrapropylammonium ion (NPr ₄ ⁺ ), tetrabutylammonium ion (NBu ₄ ⁺ ), benzyltributylammonium ion (NBnBu ₃ ⁺ ), tributyl (methyl) ammonium (NBu ₃ Me ⁺ ) Ion, tetrapentylammonium ion (NPen ₄ ⁺ ), tetrahexylammonium ion (NHex ₄ ⁺ ), tetraheptylammonium ion (NHep ₄ ⁺ ), 1-butyl-1-methylpi Examples include rhodium ion (BuMePyr ⁺ ), methyltrioctylammonium ion (NMeOct ₃ ⁺ ), and dimethyldioctadecylammonium ion. As counter anions, fluoride ions (F ⁻ ), chloride ions (Cl ⁻ ), bromide ions (Br ⁻ ), iodide ions (I ⁻ ), acetoxy ions (AcO ⁻ ), nitrate ions (NO ₃ ). ^- ), Azide ion (N ₃ ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), perchlorate ion (ClO ₄ ⁻ ), sulfate ion (HSO ₄ ⁻ ) and the like.
As the ammonium salt, tetrabutylammonium chloride (NBu ₄ Cl) and tetrabutylammonium bromide (NBu ₄ Br) are particularly preferable. In addition, the ammonium salt contained in a composition is not restricted to one type, You may contain 2 or more types.
The content of ammonium salt in the composition of the present invention (when two or more types are included, the total content) is preferably more than 0% by mass, more preferably 50% by mass or more, and usually less than 95% by mass, preferably 80% by mass or less.
The ratio of ammonium salt to siloxane compound in the composition of the present invention (total amount of ammonium salt / total amount of siloxane compound) is preferably greater than 0, more preferably 1 or more, and usually 10 or less. Preferably it is 4 or less, More preferably, it is 2 or less.
Within the above range, the composition of the present invention can be easily used for various applications, and the stability of the composition of the present invention can be kept good.

  The state of the composition of the present invention may be either liquid or solid, but is preferably solid. When it is solid, the composition of the present invention can be easily used for various applications, and the stability of the composition of the present invention can be kept good.

  The use of the composition of the present invention is not particularly limited, but raw materials (reactants) such as silicone resins, coating agents, resins, insulating films, gas barrier films, zeolites, mesoporous silica, fertilizers, agricultural chemicals, pharmaceuticals, health foods, etc. Can be mentioned.

  If the composition of this invention contains 1 mass% or more and less than 100 mass% of at least 1 sort (s) of the siloxane compound represented by the above-mentioned formula (A-1)-(A-6), the manufacturing method will be Although not particularly limited, details will be described later in <Manufacturing Method of Siloxane Compound> as a preferable manufacturing method.

式（Ｂ）で表されるシロキサン化合物は、シランテトラオールの四量体又はジシロキサンヘキサオールの二量体が環化した環状テトラシロキサン化合物であるが、従来法において、この化合物が得られたことは報告されていなかった。
本発明者らは、無水条件でシロキサン化合物を生成する反応において、テトラメチル尿素（Ｍｅ_４Ｕｒｅａ）等のアミド化合物のみを利用すること、また鎖状のシロキサン化合物にアミド化合物を添加することによって、環化したシロキサン化合物、即ち式（Ｂ）で表されるシロキサン化合物を調製することが可能であることを見出したのである。式（Ｂ）で表されるシラノール化合物が得られる詳細なメカニズムは十分に明らかとなっていないが、以下の理由によるものと考えられる。
前述のようにアミノ化合物、アミド化合物、アンモニウム塩は、それぞれシラノール基の縮合を抑える作用があるが、この中でもアミノ化合物やアンモニウム塩はその作用が強い一方、アミド化合物のみでは弱いものと考えられる。そのため、例えばアミド化合物を溶媒とし、アミン化合物等を含まない条件でシラノール化合物を生成させることにより、生成したシラノール化合物が適度に縮合して直鎖状や環状の四量体が形成し、それ以上の縮合が抑制されて、生成物として得られるものと考えられる。<Siloxane compound>
A siloxane compound which is another embodiment of the present invention (hereinafter sometimes abbreviated as “siloxane compound of the present invention”) is a compound represented by the following formula (B).

The siloxane compound represented by the formula (B) is a cyclic tetrasiloxane compound obtained by cyclization of a tetramer of silanetetraol or a dimer of disiloxanehexaol. In the conventional method, this compound was obtained. That was not reported.
The present inventors use only an amide compound such as tetramethylurea (Me ₄ Urea) in a reaction for producing a siloxane compound under anhydrous conditions, or by adding an amide compound to a chain siloxane compound, It was found that a cyclized siloxane compound, that is, a siloxane compound represented by the formula (B) can be prepared. Although the detailed mechanism by which the silanol compound represented by Formula (B) is obtained is not fully clarified, it is considered to be due to the following reason.
As described above, amino compounds, amide compounds, and ammonium salts have the effect of suppressing the condensation of silanol groups, but among them, amino compounds and ammonium salts have strong effects, but only amide compounds are considered to be weak. Therefore, for example, by using a amide compound as a solvent and generating a silanol compound under conditions that do not contain an amine compound, etc., the generated silanol compound is appropriately condensed to form a linear or cyclic tetramer. It is considered that the condensation of is suppressed and obtained as a product.

As described above, the siloxane compound of the present invention is suitable as a raw material for a silicone resin, but it may be used in the state of a composition containing a compound other than a silanol compound. The content of the siloxane compound represented by the formula (B) in this composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 5% by mass or more, and particularly preferably 10%. % By mass or more, most preferably 21% by mass or more, and preferably less than 100% by mass. When it is within the above range, it can be easily used as a raw material for the silicone resin and the stability of the composition can be kept good.
Moreover, water, an amine compound, an amide compound, an ammonium salt etc. are mentioned as a compound contained in this composition. Since these details are the same as those described in the above <Composition>, they will be omitted.

（式（１）中、Ａｒは窒素原子、酸素原子、及びハロゲン原子からなる群より選択される少なくとも１種の原子を含んでいてもよい炭素数４〜２０の芳香族炭化水素基を表す。）
式（１）で表される構造は、アリールメチルオキシ基（−ＯＣＨ_２Ａｒ）がシロキサン化合物のケイ素原子に結合した構造であるが、水素との反応によってこの構造からヒドロキシル基（−ＯＨ）が形成し、式（２）で表される構造を有したシロキサン化合物を製造することができるのである。前述のようにシロキサン化合物は、シラノール化合物を経由して合成することができるが、シラノール基が水の存在下で速やかに縮合してしまうため、シラノール基が残存した低分子量のシロキサン化合物を選択的に収率良く合成することは困難であった。
本発明者らは、式（１）で表される構造を有するシロキサン化合物と水素を反応させることによって、高収率で式（２）で表される構造を有したシロキサン化合物を製造できることを見出すとともに、無水条件でシロキサン化合物を製造できるため、得られた組成物においてシロキサン化合物が安定的に存在でき、シリコーン樹脂の原料等として活用できることを明らかとしたのである。
なお、式（１）で表される構造及び式（２）で表される構造の波線は、その先の構造が任意であることを意味しており、例えば式（１）で表される構造においてケイ素原子に結合しているアリールメチルオキシ基（−ＯＣＨ_２Ａｒ）が２つ以上存在していてもよいことを意味する。
また「固体触媒」は、構成元素としてパラジウム（Ｐｄ）と白金（Ｐｔ）等を含有し、室温下において固体であるものであれば、パラジウム（Ｐｄ）等の状態は特に限定されないことを意味する。即ち、「固体触媒」においてパラジウム（Ｐｄ）は、酸化パラジウム（ＩＩ）の状態にあっても、表面が酸化され、内部が金属パラジウムの状態にあっても、或いは白金等と合金を形成していてもよい。<Manufacturing method 1 of a siloxane compound>
A method for producing a siloxane compound according to another embodiment of the present invention includes a palladium (Pd) element, platinum (Pt), ruthenium (Ru), rhodium (Rh), iridium (Ir), and gold (Au). A structure represented by the following formula (2) by reacting a siloxane compound having a structure represented by the following formula (1) with hydrogen in the presence of a solid catalyst containing at least one element selected from the group It includes a hydrogenation step (hereinafter sometimes abbreviated as a “hydrogenation step”) for producing a siloxane compound having the following.

(In the formula (1), Ar represents an aromatic hydrocarbon group having 4 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a halogen atom. )
The structure represented by the formula (1) is a structure in which an arylmethyloxy group (—OCH ₂ Ar) is bonded to a silicon atom of a siloxane compound, and a hydroxyl group (—OH) is formed from this structure by reaction with hydrogen. Thus, a siloxane compound having a structure represented by the formula (2) can be produced. As described above, the siloxane compound can be synthesized via the silanol compound. However, since the silanol group rapidly condenses in the presence of water, the low molecular weight siloxane compound in which the silanol group remains is selectively used. It was difficult to synthesize with good yield.
The present inventors have found that a siloxane compound having a structure represented by formula (2) can be produced in a high yield by reacting a siloxane compound having a structure represented by formula (1) with hydrogen. At the same time, since the siloxane compound can be produced under anhydrous conditions, it has been clarified that the siloxane compound can be stably present in the obtained composition and can be used as a raw material for the silicone resin.
In addition, the wavy line of the structure represented by Formula (1) and the structure represented by Formula (2) means that the structure ahead is arbitrary, for example, the structure represented by Formula (1) It means that two or more arylmethyloxy groups (—OCH ₂ Ar) bonded to a silicon atom may be present.
Further, the “solid catalyst” means that palladium (Pd) and the like are not particularly limited as long as they contain palladium (Pd) and platinum (Pt) as constituent elements and are solid at room temperature. . That is, in the “solid catalyst”, palladium (Pd) is in the form of palladium (II) oxide, the surface is oxidized, and the inside is in the form of metallic palladium, or forms an alloy with platinum or the like. May be.

（式（１）中、Ａｒは窒素原子、酸素原子、及びハロゲン原子からなる群より選択される少なくとも１種の原子を含んでいてもよい炭素数４〜２０の芳香族炭化水素基を表す。）
式（１）中のＡｒは、窒素原子、酸素原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数４〜２０の芳香族炭化水素基を表しているが、「芳香族炭化水素基」とは、フェニル基のような芳香族性を有する単環の芳香族炭化水素基が含まれるほか、ナフチル基のような芳香族性を有する多環の芳香族炭化水素基も含まれることを意味する。また、「窒素原子、酸素原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい」とは、アミノ基（−ＮＨ_２）、ニトロ基（−ＮＯ_２）、フルオロ基（−Ｆ）等の窒素原子、酸素原子、又はハロゲン原子を含む官能基を含んでいてもよいことを意味するほか、エーテル基（−Ｏ−）、イミノ基（−ＮＨ−）等の窒素原子、酸素原子、又はハロゲン原子を含む連結基を炭素骨格の内部又は末端に含んでいてもよいことを意味する。従って、「窒素原子、酸素原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい」芳香族炭化水素基としては、例えばニトロフェニル基のようなニトロ基を含む炭素数６の芳香族炭化水素基や、ピリジル基のように炭化骨格の内部に窒素原子を含む炭素数５の複素環構造等が含まれる。
芳香族炭化水素基の炭素数は、好ましくは６以上であり、通常１８以下、好ましくは１４以下である。
芳香族炭化水素基が官能基を含む場合、官能基としては、アミノ基（−ＮＨ_２）、ニトロ基（−ＮＯ_２）、メトキシ基（−ＯＭｅ）、エトキシ基（−ＯＥｔ）、フルオロ基（−Ｆ）、クロロ基（−Ｃｌ）、ブロモ基（−Ｂｒ）、ヨード基（−Ｉ）、トリフルオロメチル基（−ＣＦ_３）等が挙げられる。
具体的な芳香族炭化水素基としては、フェニル基（−Ｐｈ）、ナフチル基（−Ｃ_１０Ｈ_７）、アミノフェニル基（−ＰｈＮＨ_２）、ニトロフェニル基（−ＰｈＮＯ_２）、メトキシフェニル基（−ＰｈＯＭｅ）、エトキシフェニル基（−ＰｈＯＥｔ）、フルオロフェニル基（−ＰｈＦ）、ジフルオロフェニル基（−ＰｈＦ_２）等が挙げられる。The hydrogenation step is a step of reacting a siloxane compound having a structure represented by formula (1) with hydrogen to produce a siloxane compound having a structure represented by formula (2). It does not specifically limit to the compound represented, It can select suitably according to the objective.

(In the formula (1), Ar represents an aromatic hydrocarbon group having 4 to 20 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a halogen atom. )
Ar in the formula (1) represents an aromatic hydrocarbon group having 4 to 20 carbon atoms that may contain at least one selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom. The "aromatic hydrocarbon group" includes a monocyclic aromatic hydrocarbon group having aromaticity such as a phenyl group and a polycyclic aromatic carbon group having aromaticity such as a naphthyl group. It means that a hydrogen group is also included. In addition, “may contain at least one selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom” means an amino group (—NH ₂ ), a nitro group (—NO ₂ ), a fluoro group This means that it may contain a functional group containing a nitrogen atom, oxygen atom or halogen atom such as (—F), or a nitrogen atom such as an ether group (—O—) or imino group (—NH—). , An oxygen atom, or a linking group containing a halogen atom may be contained in the carbon skeleton or at the terminal. Accordingly, the aromatic hydrocarbon group “which may contain at least one selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom” includes, for example, the number of carbons containing a nitro group such as a nitrophenyl group. 6 aromatic hydrocarbon groups, and heterocyclic structures having 5 carbon atoms containing a nitrogen atom inside the carbonized skeleton, such as a pyridyl group, are included.
The carbon number of the aromatic hydrocarbon group is preferably 6 or more, and is usually 18 or less, preferably 14 or less.
When the aromatic hydrocarbon group includes a functional group, examples of the functional group include an amino group (—NH ₂ ), a nitro group (—NO ₂ ), a methoxy group (—OMe), an ethoxy group (—OEt), a fluoro group ( -F), chloro group (-Cl), bromo group (-Br), iodo group (-I), trifluoromethyl group (-CF _3), and the like.
Specific examples of the aromatic hydrocarbon group include a phenyl group (—Ph), a naphthyl group (—C ₁₀ H ₇ ), an aminophenyl group (—PhNH ₂ ), a nitrophenyl group (—PhNO ₂ ), a methoxyphenyl group ( -PhOMe), ethoxyphenyl group (-PhOEt), fluorophenyl group (-PhF), difluorophenyl group (-PhF _2), and the like.

  The number of silicon atoms in the siloxane compound having the structure represented by the formula (1) and the siloxane compound having the structure represented by the formula (2) is usually 12 or less, preferably 6 or less, more preferably 4 or less. Usually, it is 1 or more.

（式中、Ｒはそれぞれ独立して水素原子、又は炭素数１〜２０の炭化水素基を表す。）Examples of the siloxane compound having a structure represented by the formula (1) include disiloxane compounds represented by the following formula.

(In the formula, each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

（式中、Ｒはそれぞれ独立して水素原子、又は炭素数１〜２０の炭化水素基を表す。）Moreover, the trisiloxane compound represented by a following formula is also mentioned as a siloxane compound which has a structure represented by Formula (1).

(In the formula, each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

（式中、Ｒはそれぞれ独立して水素原子、又は炭素数１〜２０の炭化水素基を表す。）Moreover, the tetrasiloxane compound represented by a following formula is also mentioned as a siloxane compound which has a structure represented by Formula (1).

(In the formula, each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

In the hydrogenation step, the catalyst is at least one selected from the group consisting of palladium (Pd) element, platinum (Pt), ruthenium (Ru), rhodium (Rh), iridium (Ir), and gold (Au). Although it is characterized by being a solid catalyst containing an element, the specific material form of a solid catalyst is not specifically limited. For example, it may be in any form such as one in which palladium and platinum are supported on a catalyst carrier, one in which palladium is supported on metal platinum particles, and a mixture of metal palladium particles and metal platinum particles. Among these, those supported on a catalyst carrier are preferable because of their high specific surface area.
As the catalyst carrier, known materials used as the catalyst carrier can be appropriately adopted. Specifically, carbon materials such as activated carbon, graphite carbon, and acetylene black, silicon oxide, aluminum oxide, silica alumina, and chromium oxide are used. And metal oxides such as cerium oxide, titanium oxide, and zirconium oxide. Since the specific surface area is high, it is preferable to use a carbon material such as activated carbon as the catalyst carrier. The catalyst carrier is more preferably a porous material.

The combination of elements such as palladium (Pd) element and platinum (Pt) in the solid catalyst is not particularly limited and can be appropriately selected according to the purpose, but palladium (Pd) element, platinum (Pt) element, palladium (Pd) element and ruthenium (Ru) element, palladium (Pd) element and rhodium (Rh), palladium (Pd) element and iridium (Ir), palladium (Pd) element and gold (Au), palladium (Pd) element Examples include a combination of platinum (Pt) element and ruthenium (Ru), palladium (Pd) element, platinum (Pt) element, rhodium (Rh), and the like. Among these, a combination of a palladium (Pd) element and a platinum (Pt) element is particularly preferable because a siloxane compound can be produced with a good yield.
When the solid catalyst contains a platinum (Pt) element, the ratio (mass ratio) of the platinum (Pt) element to the palladium (Pd) element is usually 0.0001 or more, preferably 0.001 or more, more preferably 0.00. It is 01 or more, and is usually 1 or less, preferably 0.25 or less, more preferably 0.15 or less.
When the solid catalyst contains a ruthenium (Ru) element, the ratio (mass ratio) of the ruthenium (Ru) element to the palladium (Pd) element is usually 0.0001 or more, preferably 0.001 or more, more preferably 0.8. It is 01 or more, and is usually 1 or less, preferably 0.25 or less, more preferably 0.15 or less.
When the solid catalyst contains a rhodium (Rh) element, the ratio (mass ratio) of the rhodium (Rh) element to the palladium (Pd) element is usually 0.0001 or more, preferably 0.001 or more, more preferably 0.8. It is 01 or more, and is usually 1 or less, preferably 0.25 or less, more preferably 0.15 or less.
When the solid catalyst contains an iridium (Ir) element, the ratio (mass ratio) of the iridium (Ir) element to the palladium (Pd) element is usually 0.0001 or more, preferably 0.001 or more, more preferably 0.8. It is 01 or more, and is usually 1 or less, preferably 0.25 or less, more preferably 0.15 or less.
When the solid catalyst contains a gold (Au) element, the ratio (mass ratio) of the gold (Au) element to the palladium (Pd) element is usually 0.0001 or more, preferably 0.001 or more, more preferably 0.00. It is 01 or more, and is usually 1 or less, preferably 0.25 or less, more preferably 0.15 or less.
Within the above range, a siloxane compound can be produced with a good yield.

The content of palladium (Pd) element and the like in the solid catalyst is not particularly limited and can be appropriately selected according to the purpose. However, when the solid catalyst is supported on a carbon material (catalyst support), The content of the palladium (Pd) element is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less. More preferably, it is 20 mass% or less.
When the solid catalyst contains a platinum (Pt) element and is supported on a carbon material (catalyst support), the content of the platinum (Pt) element is usually 0.01% by mass or more, preferably 0.8%. 1% by mass or more, more preferably 1% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less.
When the solid catalyst contains a ruthenium (Ru) element and is supported on a carbon material (catalyst support), the content of the ruthenium (Ru) element is usually 0.01% by mass or more, preferably 0.8%. 1% by mass or more, more preferably 1% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less.
When the solid catalyst contains a rhodium (Rh) element and is supported on a carbon material (catalyst support), the content of the rhodium (Rh) element is usually 0.01% by mass or more, preferably 0.8%. 1% by mass or more, more preferably 1% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less.
When the solid catalyst contains an iridium (Ir) element and is supported on a carbon material (catalyst support), the content of the iridium (Ir) element is usually 0.01% by mass or more, preferably 0.8%. 1% by mass or more, more preferably 1% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less.
When the solid catalyst contains a gold (Au) element and is supported on a carbon material (catalyst support), the content of the gold (Au) element is usually 0.01% by mass or more, preferably 0.8%. 1% by mass or more, more preferably 1% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less.

The solid catalyst may be commercially available or may be prepared by itself. For example, ASCA-2 (Pd4.5 mass%, Pt 0.5 mass%) manufactured by N.E.
In addition, as a method for preparing a solid catalyst, a known method can be appropriately employed. For example, in the case where palladium and platinum are supported on a catalyst carrier, the catalyst carrier is impregnated with a palladium salt, and further impregnated with a platinum salt. And a method of coprecipitation of a palladium salt and a platinum salt on a catalyst support. Examples of the raw material used for the preparation of the solid catalyst include chlorides such as palladium (Pd), hydrochlorides, nitrates, sulfates, organic acid salts, ammine salts, alkali salts, and organic complexes. For example, as the palladium (Pd) source, divalent palladium chloride, sodium chloropalladate, potassium chloropalladate, palladium nitrate, palladium acetate, etc., and as the platinum (Pt) source, chloroplatinic acid, potassium chloroplatinate, etc. The ruthenium (Ru) source is ruthenium chloride, ruthenium nitrate, the rhodium (Rh) source is rhodium chloride, rhodium sulfate, the iridium (Ir) source is iridium sulfate, iridium chloride, and the like (Au Sources include chloroauric acid, sodium gold sulfite, gold acetate and the like.

  The amount of the solid catalyst used in the hydrogenation step is not particularly limited and can be appropriately selected according to the purpose. However, when expressed as the total amount (substance amount) of palladium (Pd) element, it is converted into an arylmethyloxy group. , Usually 0.1 mol% or more, preferably 0.5 mol% or more, more preferably 1.0 mol% or more, usually 15.0 mol% or less, preferably 10.0 mol% or less, more preferably 5.0 mol% or less. It is. Within the above range, a siloxane compound can be produced with a good yield.

The hydrogenation step is not particularly limited, but a siloxane compound having a structure represented by the following formula (2) is obtained by reacting a siloxane compound having a structure represented by the formula (1) with hydrogen under anhydrous conditions. It is preferable that it is the process to produce | generate.
“Anhydrous conditions” means that the reaction system does not contain water as much as possible, such as not using water or a compound containing water as a raw material, or proceeding the reaction so that moisture in the atmosphere does not mix. It means to control the raw materials and reaction. Therefore, for example, the generated siloxane compound may condense and water may be generated. However, the “anhydrous condition” does not mean a completely anhydrous condition that does not include such water. It means that the specific concentration of water contained therein is not particularly limited.

（式（ｉ）及び（ｉｉ）中、Ｒ’及びＲ’’はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基を表す。但し、Ｒ’及び／又はＲ’’として、２以上の炭化水素基を分子内に有する場合、炭化水素基同士が連結して環状構造を形成していてもよい。）
なお、Ｒ’とＲ’’については、前述のものと同様である。The hydrogenation step is preferably a step using a solvent.
Examples of the solvent include aliphatic hydrocarbon compounds such as n-hexane, n-heptane and n-octane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, alicyclic hydrocarbon compounds such as cyclohexane and decalin, Alcohol compounds such as methanol, ethanol, n-propanol and i-propanol, tetrahydrofuran (THF), tetrahydropyran, dioxane, diethyl ether, dimethyl ether, diisopropyl ether, diphenyl ether, methyl ethyl ether and other ether compounds, ethyl acetate, n-acetate Ester compounds such as amyl and ethyl lactate, halogenated hydrocarbon compounds such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane and hexachloroethane, N, N-dimethylformamide (DMF), N-me Ruasetoamido, N, N-dimethylacetamide (DMAc), acetamide, amide compounds such as tetramethylurea, acetone, methyl ethyl ketone, phenyl methyl ketone, aprotic polar solvents such as dimethyl sulfoxide (DMSO). These reaction solvents may be a mixture of two or more.
Among these, amide compounds represented by the following formula (i) or (ii) are mentioned. As described above, it is possible to prepare a cyclized siloxane compound by using only an amide compound such as tetramethylurea (Me ₄ Urea) in a reaction for generating a siloxane compound under anhydrous conditions. The cyclic siloxane compound can be selectively produced by selecting a solvent.

(In the formulas (i) and (ii), R ′ and R ″ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are 2 When the above hydrocarbon groups are contained in the molecule, the hydrocarbon groups may be linked to form a cyclic structure.)
Note that R ′ and R ″ are the same as those described above.

The hydrogenation step is preferably a step performed in the presence of an amine compound. “In the presence of an amine compound” means, for example, that an amine compound is added to a solution containing a siloxane compound having a structure represented by the formula (1) and a solvent. Producing a siloxane compound in good yield to react with hydrogen in the presence of an amine compound to neutralize the acid produced when hydrogen is allowed to act on the solid catalyst and suppress condensation of silanol groups. Can do. The “amine compound” is not particularly limited as long as it has an amino group (which may be any of primary amine, secondary amine, and tertiary amine). (Compounds having both amino groups and amide bonds shall be classified as “amide compounds”.), Aniline (NH ₂ Ph), diphenylamine (NHPh ₂ ), dimethylpyridine (Me ₂ Pyr), di-tert - butylpyridine ^(t _Bu 2 Pyr), pyrazine (Pyraz), triphenylamine _(NPh 3), triethylamine _(Et 3 N), di - isopropylethylamine ⁽ⁱ _Pr 2 EtN), and the like. Of the amine compounds, aniline (NH ₂ Ph) is particularly preferable. In addition, the amine compound contained in a composition is not restricted to one type, You may contain 2 or more types.
The addition amount (substance amount) of the amine compound is not particularly limited and can be appropriately selected depending on the purpose, but is usually 0.0001 times or more, preferably 0.001 times or more in terms of benzyloxy group. Preferably it is 0.01 times or more, usually 10.0 times or less, preferably 2.0 times or less, more preferably 1.0 times or less.

The temperature condition of the hydrogenation step is usually −80 ° C. or higher, preferably −20 ° C. or higher, more preferably 0 ° C. or higher, and usually 250 ° C. or lower, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
Hydrogen in the hydrogenation step is usually present in the gas phase as hydrogen gas, but the hydrogen pressure (hydrogen partial pressure) is usually 0.01 atm or higher, preferably 0.1 atm or higher, more preferably 1 It is at least atmospheric pressure and is usually at most 100 atm, preferably at most 10 atm, more preferably at most 5 atm.
The reaction time of the hydrogenation step is usually 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1.0 hour or longer, usually 24 hours or shorter, preferably 12 hours or shorter, more preferably 6 hours. It is as follows.
Within the above range, a siloxane compound can be produced with a good yield.

  The specific operation procedure for reacting the siloxane compound having the structure represented by the formula (1) with hydrogen in the hydrogenation step is not particularly limited, and a known procedure can be appropriately employed. Usually, a solid catalyst and a siloxane compound having a structure represented by the formula (1) are charged into a reaction vessel and mixed (may contain a solvent and an amine compound), and the reaction vessel is further filled with hydrogen gas. Replace and react. After completion of the reaction, the solid catalyst can be separated by centrifugation or a filter, or filtered through Celite or Hyflo Supercell, and the silanol compound is taken out.

  The production method of the present invention is not particularly limited as long as it includes the above-described hydrogenation step. For example, an ammonium salt addition step of adding an ammonium salt to the product obtained in the hydrogenation step (hereinafter referred to as “ammonium salt addition step”) , May be abbreviated as “ammonium salt addition step”.), An amide compound addition step of adding an amide compound to the product obtained in the hydrogenation step (hereinafter, abbreviated as “amide compound addition step”). The product obtained in the hydrogenation step, the product obtained in the ammonium salt addition step, or the product obtained in the amide compound addition step is frozen and subjected to a lyophilization step (hereinafter referred to as “freezing”). From the product obtained in the hydrogenation step, the product obtained in the ammonium salt addition step, or the product obtained in the amide compound addition step. Solvent method by crystallization step of precipitating crystals (hereinafter, may be abbreviated as "crystallization step".) And the like may include a. Hereinafter, the ammonium salt addition step, the amide compound addition step, the freeze-drying step, and the crystallization step will be described in detail.

(Ammonium salt addition process)
The ammonium salt addition step is a step of adding an ammonium salt to the product obtained in the hydrogenation step, but the specific kind of ammonium salt, the amount of ammonium salt used, etc. are not particularly limited, and are appropriately determined according to the purpose. You can choose. The “ammonium salt” means a compound comprising an ammonium ion and a counter anion, and the structure of the ammonium ion and the counter anion is not particularly limited. The ammonium salt is considered to suppress the condensation of silanol groups. Hereinafter, a specific example will be described.
As ammonium ions, tetrahydroammonium ions (NH ₄ ⁺ ), tetramethylammonium ions (NMe ₄ ⁺ ), tetrapropylammonium ions (NPr ₄ ⁺ ), tetrabutylammonium ions (NBu ₄ ⁺ ), benzyltributylammonium ions (NBnBu) ₃ ^+), tributyl (methyl) ammonium _(NBu 3 Me ⁺⁾ ions, tetrapentylammonium ion (NPen ₄ ^+), the tetra-hexyl ammonium ion (nhex ₄ ^+), tetra heptyl ammonium ion (NHep ₄ ^+), 1- butyl -1-methyl pyrrolidium ion (BuMePyr ^+), methyl trioctyl ammonium ion (NMeOct ₃ ^+), dimethyl dioctadecyl ammonium ion and the like can be mentioned, et al That.
Counter anions include fluoride ion (F ⁻ ), chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodide ion (I ⁻ ), acetoxy ion (AcO ⁻ ), nitrate ion (NO ₃ ⁻ ). , Azide ion (N ₃ ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), perchlorate ion (ClO ₄ ⁻ ), sulfate ion (HSO ₄ ⁻ ) and the like.
As the ammonium salt, tetrabutylammonium chloride (NBu ₄ Cl), tetrabutylammonium bromide (NBu ₄ Br), and tetrapentylammonium chloride (NPen ₄ Cl) are particularly preferable. In addition, the ammonium salt contained in a composition is not restricted to one type, You may contain 2 or more types.

  The amount of the ammonium salt used is usually greater than 0 times, preferably 1 times or more, usually 10 times or less, preferably 3 times or less, more preferably 2 times or less in terms of the amount of the siloxane compound. .

（式（ｉ）及び（ｉｉ）中、Ｒ’及びＲ’’はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基を表す。但し、Ｒ’及び／又はＲ’’として、２以上の炭化水素基を分子内に有する場合、炭化水素基同士が連結して環状構造を形成していてもよい。）

（式（ｉｉｉ）〜（ｖ）中、Ｒ’及びＲ’’はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基を表す。但し、Ｒ’及び／又はＲ’’として、２以上の炭化水素基を分子内に有する場合、炭化水素基同士が連結して環状構造を形成していてもよい。）
なお、式（ｉ）で表される化合物としては、ホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、アセトアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、２−ピロリドン、Ｎ−メチルピロリドン、２−ピペリドン、ε−カプロラクタム等が挙げられる。
式（ｉｉ）で表される化合物としては、尿素、テトラメチル尿素（Ｍｅ_４Ｕｒｅａ）、テトラフェニル尿素等が挙げられる。
式（ｉｉｉ）で表される繰り返し構造のみからなる高分子化合物としては、ポリビニルピロリドン、ポリビニルポリピロリドン、ポリビニルピペリドン、ポリビニルカプロラクタム等が挙げられる。
式（ｉｖ）で表される繰り返し構造のみからなる高分子化合物としては、ポリアクリルアミド、ポリ−Ｎ−メチルアクリルアミド、ポリ−Ｎ−エチルアクリルアミド、ポリ−Ｎ−エチルメタクリルアミド、ポリ−Ｎ−プロピルアクリルアミド、ポリ−Ｎ−プロピルメタクリルアミド、ポリ−Ｎ−イソプロピルアクリルアミド、ポリ−Ｎ−イソプロピルメタクリルアミド、ポリ−Ｎ−エチルメチルアクリルアミド、ポリ−Ｎ−ジエチルアクリルアミド、ポリ−Ｎ−イソプロピルメチルアクリルアミド、ポリ−Ｎ−メチルプロピルアクリルアミド、ポリ−Ｎ−シクロプロピルアクリルアミド、ポリ−Ｎ−シクロペンチニルアクリルアミド等が挙げられる。
式（ｖ）で表される繰り返し構造のみからなる高分子化合物としては、ポリ−２−メチルオキサゾリン、ポリ−２−エチルオキサゾリン、ポリ−２−プロピルオキサゾリン等が挙げられる。
アミド化合物としては、尿素、テトラメチル尿素、ポリビニルピロリドン、ポリ−Ｎ−イソプロピルアクリルアミドが特に好ましい。なお、組成物に含まれるアミド化合物は、１種類に限られず、２種類以上を含むものであっても良い。(Amide compound addition process)
The amide compound addition step is a step of adding an amide compound to the product obtained in the hydrogenation step, but the specific type of the amide compound, the amount of the amide compound used, etc. are not particularly limited, and are appropriately determined according to the purpose. You can choose. As described above, it is possible to prepare a cyclized siloxane compound by adding an amide compound to a chain siloxane compound, but the amide compound addition step is used to produce a cyclic siloxane compound. can do.
Examples of the amide compound include the compound represented by the formula (i) or (ii) described above, and a polymer compound having at least one repeating structure represented by the formulas (iii) to (v).

(In the formulas (i) and (ii), R ′ and R ″ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are 2 When the above hydrocarbon groups are contained in the molecule, the hydrocarbon groups may be linked to form a cyclic structure.)

(In the formulas (iii) to (v), R ′ and R ″ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are 2 When the above hydrocarbon groups are contained in the molecule, the hydrocarbon groups may be linked to form a cyclic structure.)
The compounds represented by formula (i) include formamide, N, N-dimethylformamide (DMF), acetamide, N-methylacetamide, N, N-dimethylacetamide (DMAc), 2-pyrrolidone, N-methyl. Examples include pyrrolidone, 2-piperidone, and ε-caprolactam.
Examples of the compound represented by the formula (ii) include urea, tetramethylurea (Me ₄ Urea), and tetraphenylurea.
Examples of the polymer compound having only the repeating structure represented by the formula (iii) include polyvinyl pyrrolidone, polyvinyl polypyrrolidone, polyvinyl piperidone, and polyvinyl caprolactam.
Examples of the polymer compound having only a repeating structure represented by the formula (iv) include polyacrylamide, poly-N-methylacrylamide, poly-N-ethylacrylamide, poly-N-ethylmethacrylamide, and poly-N-propylacrylamide. , Poly-N-propylmethacrylamide, poly-N-isopropylacrylamide, poly-N-isopropylmethacrylamide, poly-N-ethylmethylacrylamide, poly-N-diethylacrylamide, poly-N-isopropylmethylacrylamide, poly-N -Methylpropylacrylamide, poly-N-cyclopropylacrylamide, poly-N-cyclopentynylacrylamide and the like.
Examples of the polymer compound consisting only of the repeating structure represented by the formula (v) include poly-2-methyloxazoline, poly-2-ethyloxazoline, poly-2-propyloxazoline and the like.
As the amide compound, urea, tetramethylurea, polyvinylpyrrolidone, and poly-N-isopropylacrylamide are particularly preferable. In addition, the amide compound contained in the composition is not limited to one type, and may include two or more types.

  The amount of the amide compound used is usually greater than 0 times, preferably 1 time or more, usually 900 times or less, preferably 450 times or less, more preferably, in terms of the total amount of amide bonds relative to the siloxane compound. Is 150 times or less, more preferably 10 times or less, and particularly preferably 6 times or less.

(Freeze drying process)
The freeze-drying step is a step in which the product obtained in the hydrogenation step, the product obtained in the ammonium salt addition step, or the product obtained in the amide compound addition step is frozen and exposed to reduced pressure. The freezing temperature, drying temperature, drying pressure, drying time and the like are not particularly limited and can be appropriately selected according to the purpose. Hereinafter, a specific example will be described.
The freezing temperature is not particularly limited as long as the product obtained in the ammonium salt addition step or the amide addition step is frozen. It is usually −196 ° C. or higher, preferably −150 ° C. or higher, more preferably −100 ° C. or higher.
The drying temperature is usually 10 ° C. or lower, preferably 0 ° C. or lower, more preferably −20 ° C. or lower, and usually −196 ° C. or higher, preferably −150 ° C. or higher, more preferably −100 ° C. or higher.
The drying pressure is usually 100 Pa or less, preferably 20 Pa or less, more preferably 3 Pa or less, and usually 10 ⁻⁵ Pa or more, preferably 0.01 Pa or more, more preferably 1 Pa or more.
The drying time is usually 200 hours or less, preferably 100 hours or less, more preferably 50 hours or less, and usually 1 hour or more, preferably 5 hours or more, more preferably 10 hours or more.

(Crystallization process)
The crystallization step is a step of precipitating crystals by a poor solvent method from the product obtained in the hydrogenation step, the product obtained in the ammonium salt addition step, or the product obtained in the amide compound addition step. The solvent to be used, the crystallization time (standing time), etc. are not particularly limited and can be appropriately selected according to the purpose. Hereinafter, a specific example will be described.
The boiling point of the solvent used is usually 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and usually 300 ° C. or lower, preferably 200 ° C. or lower, more preferably 100 ° C. or lower.
Examples of the solvent to be used include diethyl ether (Et ₂ O), N, N-dimethylacetamide, N, N-dimethylformamide, N-methylacetamide, dimethyl sulfoxide (DMSO), tetramethylurea and the like.
The crystallization time (standing time) is usually 720 hours or less, preferably 240 hours or less, more preferably 50 hours or less, usually 1 hour or more, preferably 5 hours or more, more preferably 10 hours or more.

（式（３）及び（４）中、Ｒ’’’はそれぞれ独立して水素原子、ヒドロキシル基、又は炭素数１〜２０の炭化水素基を、ｎは１〜１０の整数を表す。）
前述のように、本発明者らは鎖状のシロキサン化合物にアミド化合物を添加することによって、環化したシロキサン化合物を調製することが可能であることを見出しており、環化工程を含むシロキサン化合物の製造方法も本発明の一態様である。なお、環化工程を含むシロキサン化合物の製造方法も、環化工程で得られた生成物を凍結させて、減圧下にさらす凍結乾燥工程を含むことが好ましい。凍結乾燥工程については、前述のものと同様である。<Method 2 for producing siloxane compound>
The method for producing a siloxane compound according to another embodiment of the present invention includes a cyclization in which a siloxane compound represented by the following formula (4) is produced from a siloxane compound represented by the following formula (3) in the presence of an amide compound. Including a step (hereinafter sometimes abbreviated as “cyclization step”).

(In formulas (3) and (4), R ′ ″ each independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 1 to 10)
As described above, the present inventors have found that a cyclized siloxane compound can be prepared by adding an amide compound to a chain siloxane compound, and the siloxane compound includes a cyclization step. The manufacturing method is also an embodiment of the present invention. In addition, it is preferable that the manufacturing method of the siloxane compound including a cyclization process also includes the freeze-drying process which freezes the product obtained by the cyclization process and exposes it under reduced pressure. The freeze-drying process is the same as that described above.

（式（３）及び（４）中、Ｒ’’’はそれぞれ独立して水素原子、ヒドロキシル基、又は炭素数１〜２０の炭化水素基を、ｎは１〜１０の整数を表す。）
Ｒ’’’はそれぞれ独立して水素原子、ヒドロキシル基、又は炭素数１〜２０の炭化水素基を表しているが、「炭化水素基」は前述のものと同義である。
Ｒ’’’が炭化水素基である場合の炭素数は、好ましくは８以下、より好ましくは７以下、さらに好ましくは６以下、特に好ましくは４以下である。
Ｒ’’’としては、水素原子（−Ｈ）、ヒドロキシル基（−ＯＨ）、メチル基（−Ｍｅ）、エチル基（−Ｅｔ）、ｎ−プロピル基（−^ｎＰｒ）、ｉ−プロピル基（−^ｉＰｒ）、ｎ−ブチル基（−^ｎＢｕ）、ｔ−ブチル基（−^ｔＢｕ）、ｎ−ヘキシル基（−^ｎＨｅｘ）、シクロへキシル基（−^ｃＨｅｘ）、フェニル基（−Ｐｈ）、ナフチル基、アントリル基、フルオレニル基等が挙げられるが、水素原子、ヒドロキシル基、メチル基が特に好ましい。
ｎは１〜１０の整数であるが、好ましくは４以下、より好ましくは２以下である。The cyclization step is a step of producing the siloxane compound represented by the formula (4) from the siloxane compound represented by the formula (3) in the presence of the amide compound. It is not specifically limited, It can select suitably according to the objective.

(In formulas (3) and (4), R ′ ″ each independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 1 to 10)
R ′ ″ each independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 20 carbon atoms, and the “hydrocarbon group” has the same meaning as described above.
When R ′ ″ is a hydrocarbon group, the carbon number is preferably 8 or less, more preferably 7 or less, still more preferably 6 or less, and particularly preferably 4 or less.
R ′ ″ includes a hydrogen atom (—H), a hydroxyl group (—OH), a methyl group (—Me), an ethyl group (—Et), an n-propyl group ( ^—n Pr), an i-propyl group ( - ⁱ Pr), n- butyl ^(- n Bu), t- butyl ^(- t Bu), n- hexyl group ^(- n Hex), cyclohexyl group ^(- c Hex), phenyl group (-Ph ), A naphthyl group, an anthryl group, a fluorenyl group, and the like, and a hydrogen atom, a hydroxyl group, and a methyl group are particularly preferable.
n is an integer of 1 to 10, preferably 4 or less, more preferably 2 or less.

Examples of the siloxane compound represented by the formula (3) include a trisiloxane compound represented by the following formula.

  Although the specific operation procedure which produces | generates the siloxane compound represented by Formula (4) from the siloxane compound represented by Formula (3) in a cyclization process is not specifically limited, The siloxane compound represented by Formula (3) It may be performed by adding an amide compound to the composition containing.

（式（ｉ）及び（ｉｉ）中、Ｒ’及びＲ’’はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基を表す。但し、Ｒ’及び／又はＲ’’として、２以上の炭化水素基を分子内に有する場合、炭化水素基同士が連結して環状構造を形成していてもよい。）

（式（ｉｉｉ）〜（ｖ）中、Ｒ’及びＲ’’はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基を表す。但し、Ｒ’及び／又はＲ’’として、２以上の炭化水素基を分子内に有する場合、炭化水素基同士が連結して環状構造を形成していてもよい。）
なお、式（ｉ）で表される化合物としては、ホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、アセトアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、２−ピロリドン、Ｎ−メチルピロリドン、２−ピペリドン、ε−カプロラクタム等が挙げられる。
式（ｉｉ）で表される化合物としては、尿素、テトラメチル尿素（Ｍｅ_４Ｕｒｅａ）、テトラフェニル尿素等が挙げられる。
式（ｉｉｉ）で表される繰り返し構造のみからなる高分子化合物としては、ポリビニルピロリドン、ポリビニルポリピロリドン、ポリビニルピペリドン、ポリビニルカプロラクタム等が挙げられる。
式（ｉｖ）で表される繰り返し構造のみからなる高分子化合物としては、ポリアクリルアミド、ポリ−Ｎ−メチルアクリルアミド、ポリ−Ｎ−エチルアクリルアミド、ポリ−Ｎ−エチルメタクリルアミド、ポリ−Ｎ−プロピルアクリルアミド、ポリ−Ｎ−プロピルメタクリルアミド、ポリ−Ｎ−イソプロピルアクリルアミド、ポリ−Ｎ−イソプロピルメタクリルアミド、ポリ−Ｎ−エチルメチルアクリルアミド、ポリ−Ｎ−ジエチルアクリルアミド、ポリ−Ｎ−イソプロピルメチルアクリルアミド、ポリ−Ｎ−メチルプロピルアクリルアミド、ポリ−Ｎ−シクロプロピルアクリルアミド、ポリ−Ｎ−シクロペンチニルアクリルアミド等が挙げられる。
式（ｖ）で表される繰り返し構造のみからなる高分子化合物としては、ポリ−２−メチルオキサゾリン、ポリ−２−エチルオキサゾリン、ポリ−２−プロピルオキサゾリン等が挙げられる。
アミド化合物としては、尿素、テトラメチル尿素、ポリビニルピロリドン、ポリ−Ｎ−イソプロピルアクリルアミドが特に好ましい。なお、組成物に含まれるアミド化合物は、１種類に限られず、２種類以上を含むものであっても良い。The cyclization step is a step of producing the siloxane compound represented by the formula (4) from the siloxane compound represented by the formula (3) in the presence of the amide compound. Or the high molecular compound which has at least 1 sort (s) of the repeating structure represented by following formula (iii)-(v) other than the compound represented by (ii) is mentioned.

(In the formulas (i) and (ii), R ′ and R ″ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are 2 When the above hydrocarbon groups are contained in the molecule, the hydrocarbon groups may be linked to form a cyclic structure.)

(In the formulas (iii) to (v), R ′ and R ″ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, provided that R ′ and / or R ″ are 2 When the above hydrocarbon groups are contained in the molecule, the hydrocarbon groups may be linked to form a cyclic structure.)
The compounds represented by formula (i) include formamide, N, N-dimethylformamide (DMF), acetamide, N-methylacetamide, N, N-dimethylacetamide (DMAc), 2-pyrrolidone, N-methyl. Examples include pyrrolidone, 2-piperidone, and ε-caprolactam.
Examples of the compound represented by the formula (ii) include urea, tetramethylurea (Me ₄ Urea), and tetraphenylurea.
Examples of the polymer compound having only the repeating structure represented by the formula (iii) include polyvinyl pyrrolidone, polyvinyl polypyrrolidone, polyvinyl piperidone, and polyvinyl caprolactam.
Examples of the polymer compound having only a repeating structure represented by the formula (iv) include polyacrylamide, poly-N-methylacrylamide, poly-N-ethylacrylamide, poly-N-ethylmethacrylamide, and poly-N-propylacrylamide. , Poly-N-propylmethacrylamide, poly-N-isopropylacrylamide, poly-N-isopropylmethacrylamide, poly-N-ethylmethylacrylamide, poly-N-diethylacrylamide, poly-N-isopropylmethylacrylamide, poly-N -Methylpropylacrylamide, poly-N-cyclopropylacrylamide, poly-N-cyclopentynylacrylamide and the like.
Examples of the polymer compound consisting only of the repeating structure represented by the formula (v) include poly-2-methyloxazoline, poly-2-ethyloxazoline, poly-2-propyloxazoline and the like.
As the amide compound, urea, tetramethylurea, polyvinylpyrrolidone, and poly-N-isopropylacrylamide are particularly preferable. In addition, the amide compound contained in the composition is not limited to one type, and may include two or more types.

  The amount of the amide compound used is usually greater than 0 times, preferably 1 time or more, usually 900 times or less, preferably 450 times or less, more preferably, in terms of the total amount of amide bonds relative to the siloxane compound. Is 150 times or less, more preferably 10 times or less, and particularly preferably 6 times or less.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Synthesis Example 1: Synthesis of hexabenzyloxydisiloxane (Si (OBn) ₃ ) ₂ O>
Benzyl alcohol (23.8 g, 220.1 mmol), triethylamine (22.3 g, 220.4 mmol), dimethylaminopyridine (42.8 mg, 0.35 mmol) were placed in a two-necked flask equipped with a magnetic stir bar, and 300 ml of dichloromethane was added. Diluted with This was cooled to 0 ° C., and hexachlorodisiloxane (9.9 g, 34.8 mmol) was added dropwise over 2 hours. After the dropwise addition, the mixture was stirred at room temperature for 20 hours, dichloromethane was distilled off, and liquid separation was performed as a hexane solution to obtain a precursor hexabenzyloxydisiloxane in a yield of 57% (14.1 g).

<Synthesis Example 2: Synthesis of tetrabenzyloxysilane (Si (OBn) ₄ )>
Benzyl alcohol (64.3 g, 594.6 mmol), triethylamine (60.2 g, 594.9 mmol), and dimethylaminopyridine (177.2 mg, 1.45 mmol) were placed in a two-necked flask equipped with a magnetic stir bar with 500 mL of dichloromethane. Diluted. This was cooled to 0 ° C., and tetrachlorosilane (24.6 g, 145 mmol) was added dropwise over 4 hours. After dropwise addition, the mixture was stirred at room temperature for 12 hours, dichloromethane was distilled off, and liquid separation was carried out as a hexane solution to obtain a precursor tetrabenzyloxysilane in a yield of 87% (57.7 g).

<Synthesis Example 3: Synthesis of octabenzyloxytrisiloxane ((BnO) ₃ SiOSi (OBn) ₂ OSi (OBn) ₃ )>
Benzyl alcohol (22.0 g, 203.4 mmol), triethylamine (20.6 g, 203.6 mmol), dimethylaminopyridine (29.9 mg, 0.24 mmol) were placed in a two-necked flask equipped with a magnetic stir bar, and dichloromethane 300 Dilute with ml. This was cooled to 0 ° C., and octachlorotrisiloxane (9.8 g, 24.5 mmol) was added dropwise over 2 hours. After the dropwise addition, the mixture was stirred at room temperature for 24 hours, and dichloromethane was distilled off, followed by liquid separation as a hexane solution, whereby the precursor octabenzyloxytrisiloxane was obtained in a yield of 26% (6.3 g).

<Example 1>
In a two-necked flask equipped with a magnetic stir bar, 42.6 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. The hexabenzyloxydisiloxane obtained in Example 1 (107.2 mg, 0.150 mmol) was added, and 1.6 ml of N, N-dimethylacetamide (DMAc) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter.
^When analyzed by ¹ H, ¹³ C, ²⁹ Si-NMR (DMAc / THF-d ₈ : -80.5 ppm), it was confirmed that disiloxane hexaol and the like were produced. Table 1 shows the yield results of the products and the like.

<Example 2>
The reaction was performed in the same manner as in Example 1 except that N, N-dimethylacetamide (DMAc) was changed to N, N-dimethylformamide (DMF). Table 1 shows the yield results of the products and the like.

<Example 3>
The reaction was performed in the same manner as in Example 1 except that N, N-dimethylacetamide (DMAc) was changed to tetramethylurea (Me ₄ Urea). Table 1 shows the yield results of the products and the like.

<Example 4>
The reaction was performed in the same manner as in Example 1 except that dimethylacetamide (DMAc) was changed to a mixed solution of 1.44 ml of N-methylacetamide (MMAc) and 0.16 ml of N, N-dimethylacetamide (DMAc). . ^When analyzed by ¹ H, ¹³ C, ²⁹ Si-NMR (MMAc + DMAc / THF-d ₈ : -80.8 ppm), it was confirmed that disiloxane hexaol and the like were produced. Table 1 shows the yield results of the products and the like.

<Example 5>
In a two-necked flask equipped with a magnetic stir bar, 74.6 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Hexabenzyloxydisiloxane (107.2 mg, 0.150 mmol) obtained in Example 1 was added, 1.6 ml of N, N-dimethylacetamide (DMAc) and aniline having a substance amount of 0.035 times in terms of benzyloxy group (NH2Ph, 2.9 mg) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter.
^When analyzed by ¹ H (DMAc / THF-d ₈ : 5.8 ppm), ¹³ C, ²⁹ Si-NMR (DMAc / THF-d ₈ : −80.5 ppm), disiloxane hexaol and the like are produced. It was confirmed. Table 2 shows the yield results of the products and the like.

<Example 6>
The reaction was carried out in the same manner as in Example 5, except that aniline (NH ₂ Ph) was changed to 0.052 times the substance amount in terms of benzyloxy group. Table 2 shows the yield results of the products and the like.

<Example 7>
The reaction was performed in the same manner as in Example 5 except that aniline (NH ₂ Ph) was changed to a substance amount of 0.070 times in terms of benzyloxy group. Table 2 shows the yield results of the products and the like.

<Example 8>
In a two-necked flask equipped with a magnetic stir bar, 74.5 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Hexabenzyloxydisiloxane (107.2 mg, 0.150 mmol) obtained in Example 1 was added, and 1.6 ml of tetramethylurea (Me ₄ Urea) and an aniline having a substance amount of 0.026 times in terms of benzyloxy group ( NH ₂ Ph, 2.2 mg) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter.
^When analyzed by ¹ H, ¹³ C, ²⁹ Si-NMR (Me ₄ Urea / THF-d ₈ : -80.0 ppm), it was confirmed that disiloxane hexaol and the like were produced. Table 3 shows the yield results of the products and the like.

<Example 9>
The reaction was carried out in the same manner as in Example 8, except that aniline (NH ₂ Ph) was changed to a substance amount 0.035 times in terms of benzyloxy group. ^When analyzed by ¹ H (Me ₄ Urea / THF-d ₈ : 5.4 ppm), ¹³ C, ²⁹ Si-NMR (Me ₄ Urea / THF-d ₈ : −79.9 ppm), disiloxane hexaol and the like were analyzed. It was confirmed that it was generated. Table 3 shows the yield results of the products and the like.

<Example 10>
The reaction was carried out in the same manner as in Example 8, except that aniline (NH ₂ Ph) was changed to a 0.043-fold substance amount in terms of benzyloxy group. Table 3 shows the yield results of the products and the like.

<Example 11>
In a two-necked flask equipped with a magnetic stir bar, 99.4 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Octylbenzyloxytrisiloxane (146.0 mg, 0.150 mmol) obtained in Example 3 was added, 1.6 ml of N, N-dimethylacetamide (DMAc) and aniline having a substance amount of 0.026 times in terms of benzyloxy group (NH ₂ Ph, 2.9 mg) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter.
^When analyzed by ¹ H (DMAc / THF-d ₈ : 6.6 ppm), ¹³ C, ²⁹ Si-NMR (DMAc / THF-d ₈ : −83.0 ppm), cyclic trisiloxane hexaol and the like were produced. It was confirmed that Table 4 shows the yield results of the products.

<Example 12>
The reaction was performed in the same manner as in Example 11 except that aniline (NH ₂ Ph) was changed to a substance amount of 0.035 times in terms of benzyloxy group. Table 4 shows the yield results of the products.

<Example 13>
The reaction was performed in the same manner as in Example 11 except that aniline (NH ₂ Ph) was changed to a substance amount 0.053 times in terms of benzyloxy group. Table 4 shows the yield results of the products.

<Example 14>
The reaction was performed in the same manner as in Example 11 except that aniline (NH ₂ Ph) was changed to a substance amount of 0.070 times in terms of benzyloxy group. Table 4 shows the yield results of the products.

<Example 15>
In a two-necked flask equipped with a magnetic stir bar, 99.4 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Octabenzyloxytrisiloxane (146.0 mg, 0.150 mmol) obtained in Example 3 was added, 1.6 ml of tetramethylurea (Me ₄ Urea) and aniline having a substance amount of 0.018 times in terms of benzyloxy group ( NH ₂ Ph, 2.0 mg) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter.
^When analyzed by ¹ H, ¹³ C, ²⁹ Si-NMR (Me ₄ Urea / THF-d ₈ : -82.7 ppm), it was confirmed that cyclic trisiloxane hexaol and the like were produced. Table 5 shows the yield results of the products and the like.

<Example 16>
In a two-necked flask equipped with a magnetic stir bar, 74.5 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Hexabenzyloxydisiloxane (107.2 mg, 0.150 mmol) obtained in Example 1 was added, and 1.6 ml of tetramethylurea (Me ₄ Urea) and aniline having a substance amount of 0.035 times in terms of benzyloxy group ( NH ₂ Ph (2.9 mg) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst could be filtered through a filter. To this, tetrabutylammonium chloride (Bu ₄ NCl, 125.1 mg) and 14.4 ml of tetramethylurea (Me ₄ Urea) having a substance amount of 3.0 times in terms of hexabenzyloxydisiloxane were added, and disiloxane hexaol was added. A composition (solution) containing the above was obtained.
This composition was frozen using liquid nitrogen (−196 ° C.) and vacuum freeze-dried to sublime tetramethylurea and the like under reduced pressure (freeze-drying step (1) degree of vacuum 1 to 3 Pa, shelf temperature. −40 ° C., holding time 12 hours, freeze-drying step (2) Decompression degree 1 to 3 Pa, shelf temperature from −40 ° C. to −15 ° C. over 12 hours, freeze-drying step (3) Decompression degree 1 to 3 Pa, −15 ° C., holding time 18 hours). After completion of drying, the inside of the glass vial was replaced with an inert gas and sealed with a rubber stopper to obtain 161.8 mg of a composition containing powdered disiloxane hexaol and the like.
The composition ^{_{1 H-NMR (DMF-d}} 7 /THF-d8:6.1ppm), 13 C, 29 Si-NMR (DMF-d 7 / THF-d 8: -80.1ppm) and analyzed by IR As a result, it was confirmed that disiloxane hexaol was contained. This composition is shown in Table 6, and the results of IR analysis of the composition are shown in FIG.

<Example 17>
Composition 211 containing powdered disiloxane hexaol and the like in the same manner as in Example 16 except that the amount of tetrabutylammonium chloride added was changed to 4.0 times the amount of substance in terms of hexabenzyloxydisiloxane. .5 mg was obtained.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d8: 6.1 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ /THF-d8:-80.0 ppm) and IR. However, it was confirmed that disiloxane hexaol was contained. This composition is shown in Table 7, and the results of IR analysis of the composition are shown in FIG.

<Example 18>
Powdered disiloxane was prepared in the same manner as in Example 16, except that tetrabutylammonium chloride was changed to polyvinylpyrrolidone and the amount of polyvinylpyrrolidone was changed to 3.0 times the amount of hexabenzyloxydisiloxane. 186.2 mg of a composition containing hexaol and the like was obtained.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.0 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -80.6 ppm) and IR. As a result of analysis, it was confirmed that disiloxane hexaol and the like were contained. The result of IR analysis of this composition is shown in FIG.

<Example 19>
In a two-necked flask equipped with a magnetic stir bar, 74.5 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Hexabenzyloxydisiloxane (107.2 mg, 0.150 mmol) obtained in Example 1 was added, and 1.6 ml of tetramethylurea (Me ₄ Urea) and aniline having a substance amount of 0.035 times in terms of benzyloxy group ( NH ₂ Ph (2.9 mg) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter. As a structure stabilizer, tetrabutylammonium chloride (Bu ₄ NCl, 83.4 mg) having a substance amount of 2.0 times in terms of hexabenzyloxydisiloxane and 0.8 ml of tetramethylurea (Me ₄ Urea) were added. Then, a composition (solution) containing disiloxane hexaol and the like was obtained.
To this composition, 3.7 g of diethyl ether (Et ₂ O) was added and mixed, and allowed to stand at −40 ° C. for 90 hours to precipitate crystals. The crystals were washed with diethyl ether to obtain 90.0 mg of a composition (crystals) containing disiloxane hexaol.
The composition ^{_{1 H-NMR (DMF-d}} 7 /THF-d8:6.1ppm), 13 C, 29 Si-NMR (DMF-d 7 / THF-d 8: -80.1ppm), IR and X Analysis by linear crystal structure analysis confirmed that disiloxane hexaol and the like were contained. This composition is shown in Table 8, and the results of IR analysis of the composition are shown in FIG.

<Example 20>
Crystals were precipitated by the same method as in Example 19 except that the standing at −40 ° C. for 90 hours was changed to standing at room temperature for 90 hours. This crystal was washed with diethyl ether to obtain 51.7 mg of a composition (crystal) containing disiloxane hexaol.
This composition was subjected to ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.1 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -80.1 ppm), IR and Analysis by X-ray crystal structure analysis confirmed that disiloxane hexaol and the like were contained. This composition is shown in Table 9, and the results of IR analysis of the composition are shown in FIG.

<Example 21>
In a two-necked flask equipped with a magnetic stir bar, 74.5 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Hexabenzyloxydisiloxane (107.2 mg, 0.150 mmol) obtained in Example 1 was added, and 1.6 ml of tetramethylurea (Me ₄ Urea) and aniline having a substance amount of 0.035 times in terms of benzyloxy group ( NH ₂ Ph (2.9 mg) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter. To this, tetrabutylammonium bromide (Bu ₄ NBr, 96.7 mg) having a substance amount of 2.0 times in terms of hexabenzyloxydisiloxane was added as a structure stabilizer, and a composition containing disiloxane hexaol or the like ( Solution).
To this composition, 2.7 g of diethyl ether (Et ₂ O) was added and mixed, and allowed to stand at −40 ° C. for 570 hours to precipitate crystals. The crystals were washed with diethyl ether to obtain 82.6 mg of a composition (crystals) containing disiloxane hexaol.
This composition was subjected to ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.1 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -80.5 ppm), IR and Analysis by X-ray crystal structure analysis confirmed that disiloxane hexaol and the like were contained. This composition is shown in Table 10, and the results of IR analysis of the composition are shown in FIG.

<Example 22>
In a two-necked flask equipped with a magnetic stir bar, 28.6 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. The tetrabenzyloxysilane (69.0 mg, 0.151 mmol) obtained in Example 2 was added, and 1.6 ml of tetramethylurea (Me ₄ Urea) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter. A composition containing a cyclic tetrasiloxane octaol and the like, in which tetrabutylammonium chloride (Bu ₄ NCl, 41.7 mg) having a substance amount of 1.0 times in terms of tetrabenzyloxysilane is added as a structure stabilizer. Solution).
To this composition, 2.9 g of diethyl ether (Et ₂ O) was added and mixed, and allowed to stand at room temperature for 120 hours to precipitate crystals. The crystals were washed with diethyl ether to obtain 10.5 mg of a composition (crystals) containing cyclic tetrasiloxane octaol.
The composition ^{_{1 H-NMR (DMF-d}} 7 /THF-d8:6.4ppm), 13 C, 29 Si-NMR (DMF-d 7 / THF-d 8: -88.9ppm), IR and X Analysis by line crystal structure analysis confirmed that cyclic tetrasiloxane octaol and the like were contained. This composition is shown in Table 11, and the results of IR analysis of the composition are shown in FIG.

<Example 23>
In a two-necked flask equipped with a magnetic stirrer, 28.8 mg of ASCA-2 (Pd4.5% by mass, Pt0.5% by mass) manufactured by N.E. The tetrabenzyloxysilane (103.1 mg, 0.226 mmol) obtained in Example 2 was added, and 1.6 ml of tetramethylurea (Me ₄ Urea) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter. A composition containing a cyclic tetrasiloxane octaol and the like as a structure stabilizer is added as a structure stabilizer tetrabutylammonium chloride (Bu ₄ NCl, 63.0 mg) having a substance amount of 1.0 times in terms of tetrabenzyloxysilane. Solution).
To this composition, 2.5 g of diethyl ether (Et ₂ O) was added, mixed, and allowed to stand at −40 ° C. for 90 hours to precipitate crystals. The crystals were washed with diethyl ether to obtain 4.9 mg of a composition (crystals) containing cyclic tetrasiloxane octaol.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.4 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -88.9 ppm), IR. Analysis revealed that cyclic tetrasiloxane octaol and the like were included. This composition is shown in Table 12, and the results of IR analysis of the composition are shown in FIG.

<Example 24>
In a two-necked flask equipped with a magnetic stirring bar, 43.0 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Hexabenzyloxydisiloxane (107.2 mg, 0.150 mmol) obtained in Example 1 was added, and 1.6 ml of tetramethylurea (Me ₄ Urea) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter. In this composition, tetrabutylammonium chloride (Bu ₄ NCl, 83.4 mg) having a substance amount of 2.0 times in terms of hexabenzyloxydisiloxane was added as a structure stabilizer, and a composition containing cyclic tetrasiloxane octaol and the like (Solution) was obtained.
To this composition, 2.3 g of diethyl ether (Et ₂ O) was added and mixed, and allowed to stand at room temperature for 90 hours to precipitate crystals. This crystal was washed with diethyl ether to obtain 51.9 mg of a composition (crystal) containing cyclic tetrasiloxane octaol.
This composition was subjected to ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.4 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -88.9 ppm), IR and Analysis by X-ray crystal structure analysis confirmed that cyclic tetrasiloxane octaol and the like were contained. This composition is shown in Table 13, and the results of IR analysis of the composition are shown in FIG.

<Example 25>
In a two-necked flask equipped with a magnetic stir bar, 99.4 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Octabenzyloxytrisiloxane (146.0 mg, 0.150 mmol) obtained in Example 3 was added, 1.6 ml of tetramethylurea (Me ₄ Urea) and aniline having a substance amount of 0.018 times in terms of benzyloxy group ( NH ₂ Ph, 2.0 mg) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter. To this, tetrabutylammonium chloride (Bu ₄ NCl, 250.2 mg) and tetramethylurea (Me ₄ Urea) 23.4 ml, which are 6.0 times the amount of octabenzyloxytrisiloxane, were added, and cyclic trisiloxane hexasiloxane was added. A composition (solution) containing oar and the like was obtained.
This composition was frozen using liquid nitrogen (−196 ° C.) and vacuum freeze-dried to sublime tetramethylurea and the like under reduced pressure (freeze-drying step (1) degree of vacuum 1 to 3 Pa, shelf temperature. −40 ° C., holding time 24 hours, freeze-drying step (2) Decompression degree 1 to 3 Pa, shelf temperature from −40 ° C. to −15 ° C. over 72 hours, freeze-drying step (3) Decompression degree 1 to 3 Pa, −15 ° C., holding time 12 hours). After completion of drying, the inside of the glass vial was replaced with an inert gas and sealed with a rubber stopper to obtain 344.2 mg of a composition containing powdered cyclic trisiloxane hexaol and the like.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.7 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : −81.2 ppm) and IR. As a result of analysis, it was confirmed that cyclic trisiloxane hexaol and the like were contained. This composition is shown in Table 14, and the results of IR analysis of the composition are shown in FIG.

<Example 26>
Powder was obtained in the same manner as in Example 25 except that tetrabutylammonium chloride was changed to tetrahexylammonium chloride and the amount of tetrahexylammonium chloride was changed to 2.0 times the amount of substance in terms of octabenzyloxytrisiloxane. 189.5 mg of a composition containing a cyclic trisiloxane hexaol or the like was obtained.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.6 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -81.4 ppm) and IR. As a result of analysis, it was confirmed that cyclic trisiloxane hexaol and the like were contained. This composition is shown in Table 15, and the results of IR analysis of the composition are shown in FIG.

<Example 27>
In a two-necked flask equipped with a magnetic stir bar, 99.4 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Octylbenzyloxytrisiloxane (146.0 mg, 0.150 mmol) obtained in Example 3 was added, 1.6 ml of N, N-dimethylacetamide (DMAc) and aniline having a substance amount of 0.035 times in terms of benzyloxy group (NH ₂ Ph, 3.9 mg) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter. In this composition, tetrabutylammonium chloride (Bu ₄ NCl, 41.7 mg) having a substance amount of 1.0-fold in terms of octabenzyloxytrisiloxane is added as a structure stabilizer, and the composition contains cyclic trisiloxane hexaol and the like. (Solution) was obtained.
To this composition, 3.3 g of diethyl ether (Et ₂ O) was added and mixed, and allowed to stand at −40 ° C. for 72 hours to precipitate a liquid substance. This liquid substance was washed with diethyl ether to obtain 40.1 mg of a composition (liquid) containing cyclic trisiloxane hexaol.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.7 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -81.9 ppm), IR. As a result of analysis, it was confirmed that cyclic trisiloxane hexaol and the like were contained. This composition is shown in Table 16, and the results of IR analysis of the composition are shown in FIG.

<Example 28>
In a two-necked flask equipped with a magnetic stir bar, 99.4 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Octabenzyloxytrisiloxane (146.0 mg, 0.150 mmol) obtained in Example 3 was added, 1.6 ml of tetramethylurea (Me ₄ Urea) and aniline having a substance amount of 0.018 times in terms of benzyloxy group ( NH ₂ Ph, 2.0 mg) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter. To this, 14.4 ml of tetramethylurea (Me ₄ Urea) was added to obtain a composition (solution) containing cyclic trisiloxane hexaol and the like.
This composition was frozen using liquid nitrogen (−196 ° C.) and vacuum freeze-dried to sublime tetramethylurea and the like under reduced pressure (freeze-drying step (1) degree of vacuum 1 to 3 Pa, shelf temperature. −40 ° C., holding time 168 hours). After completion of drying, the inside of the glass vial was replaced with an inert gas and sealed with a rubber stopper to obtain 75.0 mg of a composition containing a solid (containing microcrystals) cyclic trisiloxane hexaol and the like.
This composition was subjected to ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.8 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -82.9 ppm) and IR and Analysis by X-ray crystal structure analysis confirmed that cyclic trisiloxane hexaol and the like were contained. This composition is shown in Table 17, and the results of IR analysis of the composition are shown in FIG.

<Example 29>
In a two-necked flask equipped with a magnetic stir bar, 99.4 mg of ASCA-2 (Pd 4.5 mass%, Pt 0.5 mass%) manufactured by N.E. Octabenzyloxytrisiloxane (146.0 mg, 0.150 mmol) obtained in Example 3 was added, 1.6 ml of tetramethylurea (Me ₄ Urea) and aniline having a substance amount of 0.018 times in terms of benzyloxy group ( NH ₂ Ph, 2.0 mg) was added. The gas was replaced with hydrogen gas and reacted at room temperature for 2.0 hours. Thereafter, the catalyst was filtered through a filter. To this, urea (Urea, 18.0 mg) and 14.4 ml of tetramethylurea (Me ₄ Urea) were added in an amount of 2.0 times the amount of octabenzyloxytrisiloxane, and cyclic trisiloxane hexaol and the like were contained. A composition (solution) was obtained.
This composition was frozen using liquid nitrogen (−196 ° C.) and vacuum freeze-dried to sublime tetramethylurea and the like under reduced pressure (freeze-drying step (1) degree of vacuum 1 to 3 Pa, shelf temperature. −40 ° C., holding time 168 hours). After completion of drying, the inside of the glass vial was replaced with an inert gas and sealed with a rubber stopper to obtain 107.6 mg of a composition containing a solid cyclic trisiloxane hexaol and the like.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.9 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : −82.9 ppm) and IR. As a result of analysis, it was confirmed that cyclic trisiloxane hexaol and the like were contained. This composition is shown in Table 18, and the results of IR analysis of the composition are shown in FIG.

<Example 30>
The same method as in Example 29 except that urea was changed to polyvinyl pyrrolidone (polyvinyl pyrrolidone 25 manufactured by Nacalai Tesque) and the amount of polyvinyl pyrrolidone was changed to 3.0 times the amount of substance in terms of octabenzyloxytrisiloxane. As a result, 123.9 mg of a composition containing solid cyclic trisiloxane hexaol and the like was obtained.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.8 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -82.9 ppm) and IR. As a result of analysis, it was confirmed that cyclic trisiloxane hexaol and the like were contained. This composition is shown in Table 19, and the results of IR analysis of the composition are shown in FIG.

<Example 31>
Urea was changed to poly-N-isopropylacrylamide (poly (N-isopropylacrylamide) manufactured by Sigma-Aldrich, Mn: 20000 to 40000), and the amount of poly-N-isopropylacrylamide added was the amount of substance in terms of octabenzyloxytrisiloxane Was changed to 3.0 times, and 118.5 mg of a composition containing a solid cyclic trisiloxane hexaol or the like was obtained in the same manner as in Example 29.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.8 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -82.9 ppm) and IR. As a result of analysis, it was confirmed that cyclic trisiloxane hexaol and the like were contained. This composition is shown in Table 20, and the results of IR analysis of the composition are shown in FIG.

<Example 32>
Urea was changed to poly-2-ethyloxazoline (poly (2-ethyl-2-oxazoline) manufactured by Sigma-Aldrich, M _w 50,000), and the addition amount of poly-2-ethyloxazoline was converted to octabenzyloxytrisiloxane 129.8 mg of a composition containing solid (paste-like) cyclic trisiloxane hexaol and the like was obtained in the same manner as in Example 29 except that the amount of the substance was changed to 3.0 times.
This composition was analyzed by ¹ H-NMR (DMF-d ₇ / THF-d ₈ : 6.8 ppm), ¹³ C, ²⁹ Si-NMR (DMF-d ₇ / THF-d ₈ : -82.9 ppm) and IR. As a result of analysis, it was confirmed that cyclic trisiloxane hexaol and the like were contained. The result of IR analysis of this composition is shown in FIG.

  The composition of the present invention can be used as a raw material for silicone resins used in a wide range of fields such as automobiles, architecture, and electronics.

Claims (5)

A siloxane compound represented by the following formula (A-1) unrealized less than 1 wt% to 100 wt%, acetamide, N- methylacetamide, N, N- dimethylacetamide, urea, from tetramethyl urea and tetraphenyl urea at least one amide compound 0 wt% more 99 wt% or less including the composition selected from the group consisting of.

The composition according to claim 1, wherein the content of the siloxane compound represented by the formula (A-1 ) is 5 to 90 mass%. The composition according to claim 1 or 2, wherein the water content is 25% by mass or less. Formula ratio against the (A-1) a siloxane compound represented by (total material amount of the total substance amount / siloxane compound of the amide bond) is 900 or less greater than 0 of the amide compound according to claim 1 4. The composition according to any one of 3 . Include ammonium salts, (total material amount of the total substance amount / siloxane compound of the ammonium salt) Ratio against the siloxane compound represented by the formula of the ammonium salt (A-1) is 10 or less larger than 0, The composition according to any one of claims 1 to 4 .

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