JP6311983B2 - Method for producing siloxane compound - Google Patents
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- JP6311983B2 JP6311983B2 JP2014127715A JP2014127715A JP6311983B2 JP 6311983 B2 JP6311983 B2 JP 6311983B2 JP 2014127715 A JP2014127715 A JP 2014127715A JP 2014127715 A JP2014127715 A JP 2014127715A JP 6311983 B2 JP6311983 B2 JP 6311983B2
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- -1 siloxane compound Chemical class 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 21
- 238000009833 condensation Methods 0.000 claims description 17
- 230000005494 condensation Effects 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 150000002816 nickel compounds Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 230000001548 androgenic effect Effects 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 125000004430 oxygen atom Chemical group O* 0.000 description 15
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 125000005843 halogen group Chemical group 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 description 7
- 125000004437 phosphorous atom Chemical group 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 125000004434 sulfur atom Chemical group 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910020175 SiOH Inorganic materials 0.000 description 6
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 0 CCC(*)(CC(*1=CC1)OC)O*1OC(CC=C)(*C)CC(*)O1 Chemical compound CCC(*)(CC(*1=CC1)OC)O*1OC(CC=C)(*C)CC(*)O1 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YBMAWNCLJNNCMV-BUOKYLHBSA-L (e)-1,1,1,5,5,5-hexafluoro-4-oxopent-2-en-2-olate;nickel(2+) Chemical compound [Ni+2].FC(F)(F)C(/[O-])=C\C(=O)C(F)(F)F.FC(F)(F)C(/[O-])=C\C(=O)C(F)(F)F YBMAWNCLJNNCMV-BUOKYLHBSA-L 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Description
本発明は、シロキサン化合物の製造方法に関し、より詳しくは所定のニッケル化合物を触媒として用いるシロキサン化合物の製造方法に関する。 The present invention relates to a method for producing a siloxane compound, and more particularly to a method for producing a siloxane compound using a predetermined nickel compound as a catalyst.
シロキサン結合（Ｓｉ−Ｏ−Ｓｉ）は、有機化合物の基本骨格である炭素−炭素結合（Ｃ−Ｃ）や炭素−酸素結合（Ｃ−Ｏ）よりも結合エネルギーが大きく、耐熱性、耐擦傷性、耐候性に優れており、シロキサン結合を有するオルガノポリシロキサンは、シリコーンオイル、シリコーンゴム、コーティング材、シーリング材等の様々な用途に利用されている。 Siloxane bonds (Si-O-Si) have higher bond energy than carbon-carbon bonds (C-C) and carbon-oxygen bonds (C-O), which are the basic skeletons of organic compounds, and have heat resistance and scratch resistance. Organopolysiloxane, which is excellent in weather resistance and has a siloxane bond, is used in various applications such as silicone oil, silicone rubber, coating material and sealing material.
シロキサン結合を形成するための代表的な前駆体としては、シラノール化合物（ＳｉＯＨ）が広く知られており、ハロゲン化シラン（ＳｉＸ）、アルコキシシラン（ＳｉＯＲ）、シラノール（ＳｉＯＨ）等との縮合反応によって、シロキサン結合を有するシロキサン化合物を容易に形成できることが知られている。
・ ＳｉＯＨ ＋ ＳｉＸ → ＳｉＯＳｉ ＋ＨＸ
・ ＳｉＯＨ ＋ ＳｉＯＲ → ＳｉＯＳｉ ＋ＲＯＨ
・ ＳｉＯＨ ＋ ＳｉＯＨ → ＳｉＯＳｉ ＋Ｈ２Ｏ
また、触媒としては、ロジウム、白金、パラジウム錯体等の高価で希少な貴金属触媒が知られている（非特許文献１-４参照）。これに対し、比較的安価な塩基を触媒とする反
応についても知られてはいるものの、９０℃の加熱が必要であり、エネルギーコストがかかってしまう（非特許文献５参照）。
As a typical precursor for forming a siloxane bond, a silanol compound (SiOH) is widely known, and by a condensation reaction with a halogenated silane (SiX), an alkoxysilane (SiOR), a silanol (SiOH), or the like. It is known that a siloxane compound having a siloxane bond can be easily formed.
・ SiOH + SiX → SiOSi + HX
・ SiOH + SiOR → SiOSi + ROH
・ SiOH + SiOH → SiOSi + H 2 O
Further, as the catalyst, expensive and rare noble metal catalysts such as rhodium, platinum, and palladium complexes are known (see Non-Patent Documents 1-4). On the other hand, although a reaction using a relatively inexpensive base as a catalyst is known, heating at 90 ° C. is necessary, and energy cost is increased (see Non-Patent Document 5).
前述のようにシロキサン結合を有するオルガノポリシロキサンは様々な分野に応用でき有用であるため、シロキサン結合を形成する反応をより安価に実施することができれば、有機ケイ素化合物を利用した材料等のコスト低減に繋がる優れた技術になり得る。
本発明は、ロジウム、白金、パラジウム錯体等の代わりとなる触媒を見出し、シロキサン化合物の新規な製造方法を提供することを課題とする。
As mentioned above, organopolysiloxanes with siloxane bonds can be applied to various fields and are useful, so if the reaction to form siloxane bonds can be carried out at a lower cost, the cost of materials using organosilicon compounds can be reduced. It can be an excellent technology that leads to
An object of the present invention is to find a catalyst that can replace rhodium, platinum, palladium complex, and the like, and to provide a novel method for producing a siloxane compound.
本発明者らは、上記の課題を解決すべく鋭意検討を重ねた結果、ヒドロシランとシラノールの縮合反応において二配座のアルカンジオナート配位子を有するニッケル錯体化合物が触媒として作用することを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that a nickel complex compound having a bidentate alkanedionate ligand acts as a catalyst in the condensation reaction of hydrosilane and silanol. The present invention has been completed.
即ち、本発明は以下の通りである。
＜１＞ 下記式（Ａ−１）、（Ａ−２）、又は（Ａ−３）で表されるヒドロシラン化合物
と下記式（Ｂ−１）、（Ｂ−２）、又は（Ｂ−３）で表されるシラノール化合物とを反応させてシロキサン結合を形成する縮合工程を含むシロキサン化合物の製造方法であって、前記縮合工程が、下記式（Ｃ）で表されるニッケル化合物を触媒として用いる工程である、シロキサン化合物の製造方法。
＜２＞前記縮合工程が、１５０℃以下の条件で行われる工程である、＜１＞に記載のシロキサン化合物の製造方法。
＜３＞ 前記縮合工程が、ハロゲン系有機溶媒を溶媒として用いる工程である、＜１＞ま
たは＜２＞に記載のシロキサン化合物の製造方法。
That is, the present invention is as follows.
<1> A hydrosilane compound represented by the following formula (A-1), (A-2), or (A-3) and the following formula (B-1), (B-2), or (B-3) A process for producing a siloxane compound comprising a condensation step of forming a siloxane bond by reacting with a silanol compound represented by the formula, wherein the condensation step uses a nickel compound represented by the following formula (C) as a catalyst: A method for producing a siloxane compound.
<2> The method for producing a siloxane compound according to <1>, wherein the condensation step is a step performed under conditions of 150 ° C. or lower.
<3> The method for producing a siloxane compound according to <1> or <2>, wherein the condensation step is a step using a halogen-based organic solvent as a solvent.
本発明によれば、シロキサン化合物を効率よく製造することができる。 According to the present invention, a siloxane compound can be produced efficiently.
本発明を説明するに当たり、具体例を挙げて説明するが、本発明の趣旨を逸脱しない限
り以下の内容に限定されるものではなく、適宜変更して実施することができる。
In describing the present invention, specific examples will be described. 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.
＜シロキサン化合物の製造方法＞
本発明の一態様であるシロキサン化合物の製造方法（以下、「本発明の製造方法」と略す場合がある。）は、下記式（Ａ−１）、（Ａ−２）、又は（Ａ−３）で表されるヒドロシラン化合物と下記式（Ｂ−１）、（Ｂ−２）、又は（Ｂ−３）で表されるシラノール化合物とを反応させてシロキサン結合を形成する縮合工程（以下、「本発明に係る縮合工程」と略す場合がある。）を含むシロキサン化合物の製造方法であり、縮合工程において、下記式（Ｃ）で表されるニッケル化合物を触媒として用いることを特徴とする。
なお、「反応させてシロキサン結合を形成する」とは、下記反応式に示される反応のように、式（Ａ−１）、（Ａ−２）、又は（Ａ−３）で表されるヒドロシラン化合物と式（Ｂ−１）、（Ｂ−２）、又は（Ｂ−３）で表されるシラノール化合物の縮合反応によって、Ｓｉ−Ｏ−Ｓｉ構造が少なくとも１つ形成することを意味する。
The method for producing a siloxane compound which is one embodiment of the present invention (hereinafter sometimes abbreviated as “the production method of the present invention”) is represented by the following formula (A-1), (A-2), or (A-3). ) And a silanol compound represented by the following formula (B-1), (B-2), or (B-3) to form a siloxane bond (hereinafter, “ And a nickel compound represented by the following formula (C) is used as a catalyst in the condensation step.
In addition, “react to form a siloxane bond” means a hydrosilane represented by the formula (A-1), (A-2), or (A-3) as in the reaction shown in the following reaction formula. It means that at least one Si—O—Si structure is formed by a condensation reaction between the compound and the silanol compound represented by the formula (B-1), (B-2), or (B-3).
本発明に係る縮合工程は、下記式（Ａ−１）、（Ａ−２）、又は（Ａ−３）で表されるヒドロシラン化合物を反応物とする工程であるが、ヒドロシラン化合物の具体的種類は特に限定されず、目的に応じて適宜選択することができる。また、使用するヒドロシラン化合物は、１種類に限られず、２種類以上を使用してもよい。
Ｒ１は、それぞれ独立して酸素原子及びケイ素原子からなる群より選択される少なくとも１種を含んでもよい炭素数１〜２０の炭化水素基を表しているが、Ｒ１の炭素数は、好ましくは１以上であり、好ましくは１０以下、より好ましくは６以下、さらに好ましくは
３以下である。
また、Ｒ１は、直鎖状の飽和炭化水素基に限られず、分岐構造、環状構造、炭素−炭素不飽和結合のそれぞれを有していてもよい（分岐構造、環状構造、及び炭素−炭素不飽和結合からなる群より選択される少なくとも１種を有していてもよい。）。
Ｒ１としては、メチル基（−Ｍｅ）、エチル基（−Ｅｔ）、フェニル基（−Ｐｈ）、ナフチル基等が挙げられる。
The condensation step according to the present invention is a step in which a hydrosilane compound represented by the following formula (A-1), (A-2), or (A-3) is used as a reaction product. Is not particularly limited, and can be appropriately selected depending on the purpose. Moreover, the hydrosilane compound to be used is not limited to one type, and two or more types may be used.
R 1 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one selected from the group consisting of an oxygen atom and a silicon atom, and the carbon number of R 1 is preferably Is 1 or more, preferably 10 or less, more preferably 6 or less, and even more preferably 3 or less.
R 1 is not limited to a linear saturated hydrocarbon group, and may have a branched structure, a cyclic structure, or a carbon-carbon unsaturated bond (branched structure, cyclic structure, and carbon-carbon). It may have at least one selected from the group consisting of unsaturated bonds).
Examples of R 1 include a methyl group (—Me), an ethyl group (—Et), a phenyl group (—Ph), and a naphthyl group.
式（Ａ−１）、（Ａ−２）、又は（Ａ−３）で表されるヒドロシラン化合物としては、以下のヒドロシラン化合物が挙げられる。
本発明に係る縮合工程は、下記式（Ｂ−１）、（Ｂ−２）、又は（Ｂ−３）で表されるシラノール化合物を反応物とする工程であるが、シラノール化合物の具体的種類は特に限定されず、目的に応じて適宜選択することができる。また、使用するシラノール化合物は、１種類に限られず、２種類以上を使用してもよい。
Ｒ２が酸素原子及びケイ素原子からなる群より選択される少なくとも１種を含んでもよい炭素数１〜２０の炭化水素基である場合、Ｒ２の炭素数は、好ましくは１以上であり、
好ましくは１０以下、より好ましくは６以下、さらに好ましくは３以下である。
また、Ｒ２の炭化水素基は、直鎖状の飽和炭化水素基に限られず、分岐構造、環状構造、炭素−炭素不飽和結合のそれぞれを有していてもよい（分岐構造、環状構造、及び炭素−炭素不飽和結合からなる群より選択される少なくとも１種を有していてもよい。）。
Ｒ２の炭化水素基としては、メチル基（−Ｍｅ）、エチル基（−Ｅｔ）、ｎ−プロピル基（−ｎＰｒ）、イソプロピル基（−ｉＰｒ）、フェニル基（−Ｐｈ）等が挙げられる。これらの中でも、エチル基が特に好ましい。
The condensation step according to the present invention is a step in which a silanol compound represented by the following formula (B-1), (B-2), or (B-3) is used as a reaction product. Is not particularly limited, and can be appropriately selected depending on the purpose. Moreover, the silanol compound to be used is not limited to one type, and two or more types may be used.
When R 2 is a hydrocarbon group having 1 to 20 carbon atoms that may include at least one selected from the group consisting of an oxygen atom and a silicon atom, the carbon number of R 2 is preferably 1 or more,
Preferably it is 10 or less, More preferably, it is 6 or less, More preferably, it is 3 or less.
The hydrocarbon group for R 2 is not limited to a linear saturated hydrocarbon group, and may have a branched structure, a cyclic structure, or a carbon-carbon unsaturated bond (branched structure, cyclic structure, And at least one selected from the group consisting of carbon-carbon unsaturated bonds.
Examples of the hydrocarbon group for R 2 include a methyl group (—Me), an ethyl group (—Et), an n-propyl group ( —n Pr), an isopropyl group ( —i Pr), and a phenyl group (—Ph). It is done. Among these, an ethyl group is particularly preferable.
式（Ｂ−１）、（Ｂ−２）、又は（Ｂ−３）で表されるシラノール化合物としては、以下のシラノール化合物が挙げられる。
本発明に係る縮合工程における式（Ａ−１）、（Ａ−２）、又は（Ａ−３）で表されるヒドロシラン化合物と式（Ｂ−１）、（Ｂ−２）、又は（Ｂ−３）で表されるシラノール化合物の使用量は、特に限定されず、目的に応じて適宜選択することができる。 The hydrosilane compound represented by formula (A-1), (A-2), or (A-3) and the formula (B-1), (B-2), or (B-) in the condensation step according to the present invention. The usage-amount of the silanol compound represented by 3) is not specifically limited, It can select suitably according to the objective.
本発明に係る縮合工程は、下記式（Ｃ）で表されるニッケル化合物を触媒として用いることを特徴とするが、触媒の具体的種類は特に限定されず、目的に応じて適宜選択することができる。また、使用する触媒は、１種類に限られず、２種類以上を使用してもよい。
なお、「窒素原子、酸素原子、硫黄原子、ケイ素原子、リン原子、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（−ＮＨ２）、ヒドロキシル基（−ＯＨ）、メルカプト基（−ＳＨ）、フルオロ基（−Ｆ）等の窒素原子、酸素原子、硫黄原子、ケイ素原子、リン原子、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−）、チオエーテル基（−Ｓ−）等の窒素原子、酸素原子、硫黄原子、ケイ素原子、又はリン原子を含む連結基を炭素骨格の内部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、硫黄原子、ケイ素原子、リン原子、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」炭化水素基には、例えば−ＣＨ２−ＣＨ２−ＯＨのようにヒドロキシル基を含んでいる炭素数２の炭化水素基、−ＣＨ２−Ｏ−ＣＨ３のようにエーテル基を炭素骨格の内部に含んでいる炭素数２の炭化水素基等が含まれる。
The condensation step according to the present invention is characterized by using a nickel compound represented by the following formula (C) as a catalyst, but the specific type of the catalyst is not particularly limited and may be appropriately selected according to the purpose. it can. Moreover, the catalyst to be used is not restricted to 1 type, You may use 2 or more types.
In addition, “it may contain at least one selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a halogen atom” means an amino group (—NH 2 ), a hydroxyl group It may contain a functional group containing a nitrogen atom, oxygen atom, sulfur atom, silicon atom, phosphorus atom, or halogen atom such as a group (—OH), mercapto group (—SH), or fluoro group (—F). in addition to mean an ether group (-O-), include a nitrogen atom, an oxygen atom, such as a thioether group (-S-), a sulfur atom, a silicon atom, or a linking group containing a phosphorus atom in the inner portion of the carbon skeleton It means that you may go out. Accordingly, the hydrocarbon group “which may contain at least one selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a halogen atom” includes, for example, —CH 2 —CH A hydrocarbon group having 2 carbon atoms containing a hydroxyl group such as 2- OH, a hydrocarbon group having 2 carbon atoms containing an ether group in the carbon skeleton such as —CH 2 —O—CH 3 , etc. Is included.
なお、Ｒ３中のハロゲン原子は、具体的にはフッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。好ましくはフッ素原子である。
式（Ｃ）で表されるニッケル化合物としては、以下のものが挙げられる。例えば式（Ｃ−２）の化合物は、ニッケル（ＩＩ）アセチルアセトナートという名称でシグマアルドリッチ社等から市販されており、購入して用いることができる。また、式（Ｃ−３）の化合物も、ニッケル（ＩＩ）ヘキサフルオロアセチルアセトナート水和物等の名称で東京化成工業株式会社等から市販されており、購入して用いることができる。
Specific examples of the halogen atom in R 3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred is a fluorine atom.
The following are mentioned as a nickel compound represented by Formula (C). For example, the compound of the formula (C-2) is commercially available from Sigma-Aldrich Corporation under the name of nickel (II) acetylacetonate, and can be purchased and used. The compound of formula (C-3) is also commercially available from Tokyo Kasei Kogyo Co., Ltd. under the name of nickel (II) hexafluoroacetylacetonate hydrate and can be purchased and used.
２．０ｍｏｌ％以下である。上記範囲内であると、シロキサン化合物を収率良く製造し易くなる。
本発明に係る縮合工程における溶媒の種類は、特に限定されず、目的に応じて適宜選択することができるが、アセトニトリル（ＣＨ３ＣＮ）等のニトリル系有機溶媒；クロロホルム（ＣＨＣｌ３）、塩化メチレン（ＣＨ２Ｃｌ２）等のハロゲン系有機溶媒；ジエチルエーテル（ＥｔＯＥｔ）、テトラヒドロフラン（ＴＨＦ）等のエーテル系有機溶媒；トルエン、キシレン等の芳香族炭化水素系溶媒等が挙げられる。これらの中でも、塩化メチレンが特に好ましい。 The type of the solvent in the condensation step according to the present invention is not particularly limited and may be appropriately selected according to the purpose. Nitrile organic solvents such as acetonitrile (CH 3 CN); chloroform (CHCl 3 ) and methylene chloride Halogenous organic solvents such as (CH 2 Cl 2 ); Ether organic solvents such as diethyl ether (EtOEt) and tetrahydrofuran (THF); Aromatic hydrocarbon solvents such as toluene and xylene. Among these, methylene chloride is particularly preferable.
本発明に係る縮合工程における反応温度、反応時間等の反応条件は、特に限定されず、目的に応じて適宜選択することができる。
反応温度は、通常０℃以上、好ましくは１０℃以上であり、通常１５０℃以下、好ましくは８０℃以下である。上記範囲内であれば、有機ケイ素化合物をより収率良く製造することができる。
反応時間は、通常１時間以上、好ましくは３時間以上であり、通常１００時間以下、好ましくは５０時間以下である。
雰囲気ガスは、空気であっても、或いは窒素（Ｎ２）、アルゴン（Ａｒ）等の不活性ガスであってもよい。
Reaction conditions such as reaction temperature and reaction time in the condensation step according to the present invention are not particularly limited, and can be appropriately selected according to the purpose.
The reaction temperature is usually 0 ° C. or higher, preferably 10 ° C. or higher, and is usually 150 ° C. or lower, preferably 80 ° C. or lower. If it is in the said range, an organosilicon compound can be manufactured with a sufficient yield.
The reaction time is usually 1 hour or longer, preferably 3 hours or longer, usually 100 hours or shorter, preferably 50 hours or shorter.
The atmospheric gas may be air or an inert gas such as nitrogen (N 2 ) or argon (Ar).
以下に実施例及び比較例を挙げて本発明をさらに具体的に説明するが、本発明の趣旨を逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.
＜トリエチルシラノールとフェニルシランの縮合反応＞
（実施例１）
反応容器に触媒Ｃ−１（２１．４ｍｇ、０.０５０ｍｍｏｌ）、トリエチルシラノール
（１３４．２ｍｇ、１．０ ｍｍｏｌ）及び塩化メチレン（ＣＨ２Ｃｌ２、５ｍＬ）を投
入した。次にフェニルシラン（１０９．０ｍｇ、１．０ｍｍｏｌ）を加えて、室温で２０時間撹拌した。下記生成物（１）の収率は５４％、生成物（２）の収率は１２％であった。
生成物の収率はメシチレン（８５．２ｍｇ、 ０．７７ｍｍｏｌ）を内部標準として用
いたガスクロマトグラフィーで決定した。
全ての操作は真空ライン、Schlenk操作、または窒素雰囲気下に保たれたMBraunドライ
ボックスを用いて実施された。溶媒は、脱水脱酸素化して用いた。
Example 1
Catalyst C-1 (21.4 mg, 0.050 mmol), triethylsilanol (134.2 mg, 1.0 mmol) and methylene chloride (CH 2 Cl 2 , 5 mL) were added to the reaction vessel. Next, phenylsilane (109.0 mg, 1.0 mmol) was added, and the mixture was stirred at room temperature for 20 hours. The yield of the following product (1) was 54%, and the yield of the product (2) was 12%.
The product yield was determined by gas chromatography using mesitylene (85.2 mg, 0.77 mmol) as an internal standard.
All operations were performed using a vacuum line, a Schlenk operation, or an MBraun dry box kept under a nitrogen atmosphere. The solvent was used after dehydration and deoxygenation.
（実施例２）
反応条件を０℃で９５時間の撹拌に変更した以外、実施例１と同様の方法で反応を行った。生成物（１）の収率は９％、生成物（２）の収率は５９％であった。
(Example 2)
The reaction was carried out in the same manner as in Example 1 except that the reaction conditions were changed to stirring at 0 ° C. for 95 hours. The yield of product (1) was 9% and the yield of product (2) was 59%.
（実施例３）
触媒をＣ−２に変更し、反応条件を室温で５２時間の撹拌に変更した以外、実施例１と同様の方法で反応を行った。生成物（１）の収率は３２％、生成物（２）の収率は１２％であった。
The reaction was carried out in the same manner as in Example 1 except that the catalyst was changed to C-2 and the reaction conditions were changed to stirring for 52 hours at room temperature. The yield of product (1) was 32% and the yield of product (2) was 12%.
（実施例４）
フェニルシランをジフェニルシラン（１６８ｍｇ、１．０ｍｍｏｌ）に変更し、反応条件を５０℃で１６時間の撹拌に変更した以外、実施例１と同様の方法で反応を行った。下記生成物（３）の収量は０．５７ｍｍｏｌ、収率は６３％であった。
The reaction was carried out in the same manner as in Example 1 except that phenylsilane was changed to diphenylsilane (168 mg, 1.0 mmol) and the reaction conditions were changed to stirring at 50 ° C. for 16 hours. The yield of the following product (3) was 0.57 mmol, and the yield was 63%.
（実施例５）
触媒Ｃ−１の添加量を０.０１０ｍｍｏｌに変更し、トリエチルシラノールをトリメチ
ルシラノール（９０．０ｍｇ、１．０ｍｍｏｌ）に変更し、反応条件を室温で６．５時間の撹拌に変更した以外、実施例１と同様の方法で反応を行った。生成物（４）の収量は０．５ｍｍｏｌ、収率は５０％、生成物（５）の収量は０．２５ｍｍｏｌ、収率は２５％であった。
Implementation was performed except that the amount of catalyst C-1 added was changed to 0.010 mmol, triethylsilanol was changed to trimethylsilanol (90.0 mg, 1.0 mmol), and the reaction conditions were changed to 6.5 hours of stirring at room temperature. The reaction was carried out in the same manner as in Example 1. The yield of the product (4) was 0.5 mmol, the yield was 50%, the yield of the product (5) was 0.25 mmol, and the yield was 25%.
（実施例６）
トリメチルシラノールをフェニルシランの２倍量（１８０ｍｇ、２．０ｍｍｏｌ）に変更し、反応条件を室温で１９時間の撹拌に変更した以外、実施例５と同様の方法で反応を行った。下記生成物（５）の収量は０．７５ｍｍｏｌ、収率は７４％、生成物（６）の収量は０．１５ｍｍｏｌであった。
The reaction was performed in the same manner as in Example 5 except that trimethylsilanol was changed to twice the amount of phenylsilane (180 mg, 2.0 mmol), and the reaction conditions were changed to stirring at room temperature for 19 hours. The yield of the following product (5) was 0.75 mmol, the yield was 74%, and the yield of the product (6) was 0.15 mmol.
（実施例７）
トリメチルシラノールをフェニルシランの３倍量（２７３ｍｇ、３．０ｍｍｏｌ）に変更した以外、実施例６と同様の方法で反応を行った。生成物（５）の収量は０．４９ｍｍｏｌ、収率は４９％、生成物（６）の収量は０．５５ｍｍｏｌ、収率は５５％であった。
(Example 7)
The reaction was performed in the same manner as in Example 6 except that trimethylsilanol was changed to 3 times the amount of phenylsilane (273 mg, 3.0 mmol). The yield of the product (5) was 0.49 mmol, the yield was 49%, the yield of the product (6) was 0.55 mmol, and the yield was 55%.
本発明の製造方法によって得られたシロキサン化合物は、シリコーンオイル、シリコーンゴム、コーティング材等の原料として利用することができる。 The siloxane compound obtained by the production method of the present invention can be used as a raw material for silicone oil, silicone rubber, coating material and the like.
Claims (3)
前記縮合工程が、下記式（Ｃ）で表されるニッケル化合物を触媒として用いる工程である、シロキサン化合物の製造方法。
The method for producing a siloxane compound, wherein the condensation step is a step using a nickel compound represented by the following formula (C) as a catalyst.
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