JP6550626B2 - Process for producing periodic polysiloxanes by polycondensation of symmetrical oligosiloxanes - Google Patents
Process for producing periodic polysiloxanes by polycondensation of symmetrical oligosiloxanes Download PDFInfo
- Publication number
- JP6550626B2 JP6550626B2 JP2017539946A JP2017539946A JP6550626B2 JP 6550626 B2 JP6550626 B2 JP 6550626B2 JP 2017539946 A JP2017539946 A JP 2017539946A JP 2017539946 A JP2017539946 A JP 2017539946A JP 6550626 B2 JP6550626 B2 JP 6550626B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrocarbon group
- formula
- group
- iii
- following formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 polysiloxanes Polymers 0.000 title claims description 56
- 229920001296 polysiloxane Polymers 0.000 title claims description 50
- 238000000034 method Methods 0.000 title description 7
- 238000006068 polycondensation reaction Methods 0.000 title description 4
- 230000000737 periodic effect Effects 0.000 title description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 125000005843 halogen group Chemical group 0.000 claims description 27
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 125000000962 organic group Chemical group 0.000 claims description 21
- 125000004429 atom Chemical group 0.000 claims description 20
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 239000002841 Lewis acid Substances 0.000 claims description 11
- 150000007517 lewis acids Chemical class 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 26
- 150000002430 hydrocarbons Chemical group 0.000 description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000001254 matrix assisted laser desorption--ionisation time-of-flight mass spectrum Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011345 viscous material Substances 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- VPCNLBSZKIATCM-UHFFFAOYSA-N dimethylsilyloxy-[dimethylsilyloxy(diphenyl)silyl]oxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O[SiH](C)C)O[Si](O[SiH](C)C)(C=1C=CC=CC=1)C1=CC=CC=C1 VPCNLBSZKIATCM-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 230000002463 transducing effect Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Description
本発明は、ポリシロキサンの製造方法に関し、より詳しくは側鎖の有機基が周期的に配列されたポリシロキサンを製造することができるポリシロキサンの製造方法に関する。 The present invention relates to a method for producing a polysiloxane, and more particularly to a method for producing a polysiloxane capable of producing a polysiloxane in which side chain organic groups are periodically arranged.
「ポリシロキサン」は、無機化合物と有機化合物の特性を兼ね備えた高分子材料であり、その利用は、電子機器、化学品、化粧品等の多岐にわたる。ポリシロキサンは、シロキサン結合（Ｓｉ−Ｏ−Ｓｉ）を主骨格として、側鎖にメチル基やフェニル基等の有機基を有した構造であり、耐久性、消泡性、離型性、疎水性等の特性を奏することが知られている。これらの特性は、側鎖の有機基に由来しており、例えばポリジメチルシロキサンのメチル基の一部をフェニル基に置き換えることによって、耐熱性や粘度を高めることができる一方、ハロゲン化フェニル等の有機基を導入することで潤滑性等を付与することもできる。 The “polysiloxane” is a polymer material having the characteristics of an inorganic compound and an organic compound, and the use thereof is diverse in electronic devices, chemicals, cosmetics and the like. Polysiloxane has a structure having a siloxane bond (Si-O-Si) as a main skeleton and an organic group such as a methyl group or a phenyl group in a side chain, and has durability, antifoaming property, releasability, hydrophobicity. It is known to exhibit the following characteristics. These properties are derived from the side chain organic group, and for example, the heat resistance and the viscosity can be enhanced by replacing a part of the methyl group of polydimethylsiloxane with a phenyl group, while the halogenated phenyl etc. Lubricity etc. can also be provided by introduce | transducing an organic group.
ポリシロキサンの合成法としては、環状シロキサンを開環重合する方法や２種以上の有機シランモノマーを共重合する方法等が知られている。近年、これらの方法を応用して、周期的な構造を有するポリシロキサンを合成する試みがなされている。例えば２種の有機官能基を含む環状トリシロキサンを原料とし、反応開始剤として２級ブチルリチウムを用いて重合する方法（非特許文献１参照）、トリフルオロメタンスルホン酸を用いる方法（非特許文献２参照）、（Ｍｅ）４Ｎ［Ｓｉ（Ｍｅ）２Ｏ］ｎＮ（Ｍｅ）４を用いる方法（非特許文献３参照）等が報告されている。As a synthesis method of polysiloxane, a method of ring-opening polymerization of cyclic siloxane, a method of copolymerizing two or more kinds of organosilane monomers, and the like are known. In recent years, attempts have been made to synthesize polysiloxanes having a periodic structure by applying these methods. For example, a method of using a cyclic trisiloxane containing two organic functional groups as a raw material and polymerizing using secondary butyllithium as a reaction initiator (see Non-Patent Document 1), a method using trifluoromethanesulfonic acid (Non-Patent Document 2) And a method using (Me) 4 N [Si (Me) 2 O] n N (Me) 4 (see Non-Patent Document 3) and the like have been reported.
前述のようにポリシロキサンは、側鎖の有機基によって様々な特性を奏することが知られているが、例えば２種類以上の有機基がランダムに配列されてしまうと、目的とする特性が低下してしまうことも指摘されている（特許文献１参照）。
本発明は、側鎖の有機基が周期的に配列したポリシロキサンを効率良く製造することができるポリシロキサンの製造方法を提供することを目的とする。As described above, polysiloxanes are known to exhibit various properties depending on the side chain organic group, but when, for example, two or more types of organic groups are randomly arranged, the target properties are degraded. It has also been pointed out that the problem may occur (see Patent Document 1).
An object of this invention is to provide the manufacturing method of polysiloxane which can manufacture efficiently the polysiloxane which the organic group of the side chain arranged periodically.
本発明者らは、前記課題を解決すべく鋭意検討を重ねた結果、有機基の配列が同一であり、かつ対称性のオリゴシロキサン同士を、ルイス酸の存在下で重縮合させることにより、側鎖の有機基が周期的に配列されたポリシロキサンを効率良く製造することができることを見出し、本発明を完成させた。
即ち、本発明は以下の通りである。As a result of intensive studies to solve the above problems, the inventors of the present invention have found that oligosiloxanes having identical organic group sequences and symmetry are polycondensed in the presence of a Lewis acid. The present inventors have found that a polysiloxane in which chain organic groups are periodically arranged can be efficiently produced, and the present invention has been completed.
That is, the present invention is as follows.
＜１＞ ルイス酸の存在下、下記式（Ｉ−１）で表されるオリゴシロキサンと下記式（ＩＩ−１）で表されるオリゴシロキサン、下記式（Ｉ−２）で表されるオリゴシロキサンと下記式（ＩＩ−２）で表されるオリゴシロキサン、又は下記式（Ｉ−３）で表されるオリゴシロキサンと下記式（ＩＩ−３）で表されるオリゴシロキサンを重縮合させる反応工程を含むことを特徴とするポリシロキサンの製造方法。
（式（Ｉ−１）〜（Ｉ−３）中、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１同士、Ｒ２同士、・・、Ｒ８同士はそれぞれ同一の炭化水素基であることを、Ｒ１〜Ｒ８間はそれぞれ同一又は異なる炭化水素基であることを表す。但し、Ｒ１、Ｒ３、Ｒ５、Ｒ７が全て同一の炭化水素基であり、かつＲ２、Ｒ４、Ｒ６、Ｒ８が全て同一の炭化水素基である場合を除く。）
（式（ＩＩ−１）〜（ＩＩ−３）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１〜Ｒ８は式（Ｉ−１）〜（Ｉ−３）のＲ１〜Ｒ８とそれぞれ同一の炭化水素基であることを表す。）
＜２＞ ルイス酸の存在下、下記式（ＩＩＩ−１）で表されるオリゴシロキサンと下記式（ＩＶ−１）で表されるオリゴシロキサン、下記式（ＩＩＩ−２）で表されるオリゴシロキサンと下記式（ＩＶ−２）で表されるオリゴシロキサン、又は下記式（ＩＩＩ−３）で表されるオリゴシロキサンと下記式（ＩＶ−３）で表されるオリゴシロキサンを重縮合させる反応工程を含むことを特徴とするポリシロキサンの製造方法。
（式（ＩＩＩ−１）〜（ＩＩＩ−３）中、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１同士、Ｒ２同士、・・、Ｒ８同士はそれぞれ同一の炭化水素基であることを、Ｒ１〜Ｒ８間はそれぞれ同一又は異なる炭化水素基であることを表す。但し、Ｒ１、Ｒ３、Ｒ５、Ｒ７が全て同一の炭化水素基であり、かつＲ２、Ｒ４、Ｒ６、Ｒ８が全て同一の炭化水素基である場合を除く。）
（式（ＩＶ−１）〜（ＩＶ−３）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１〜Ｒ８は式（ＩＩＩ−１）〜（ＩＩＩ−３）のＲ１〜Ｒ８とそれぞれ同一の炭化水素基であることを表す。）
＜３＞ 前記式（Ｉ−１）で表されるオリゴシロキサンが、下記式（Ｉ−１−１）で表されるオリゴシロキサンであり、かつ前記式（ＩＩ−１）で表されるオリゴシロキサンが、下記式（ＩＩ−１−１）で表されるオリゴシロキサンである、＜１＞に記載のポリシロキサンの製造方法。
（式（Ｉ−１−１）中、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１同士及びＲ３同士はそれぞれ同一の炭化水素基であることを、Ｒ１とＲ３間はそれぞれ異なる炭化水素基であることを表す。）
（式（ＩＩ−１−１）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１及びＲ３は式（Ｉ−１−１）のＲ１及びＲ３とそれぞれ同一の炭化水素基であることを表す。）
＜４＞ 前記式（ＩＩＩ−１）で表されるオリゴシロキサンが、下記式（ＩＩＩ−１−１）で表されるオリゴシロキサンであり、かつ前記式（ＩＶ−１）で表されるオリゴシロキサンが、下記式（ＩＶ−１−１）で表されるオリゴシロキサンである、＜２＞に記載のポリシロキサンの製造方法。
（式（ＩＩＩ−１−１）中、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１同士及びＲ３同士はそれぞれ同一の炭化水素基であることを、Ｒ１とＲ３間はそれぞれ異なる炭化水素基であることを表す。）
（式（ＩＶ−１−１）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１及びＲ３は式（ＩＩＩ−１−１）のＲ１及びＲ３とそれぞれ同一の炭化水素基であることを表す。）
＜５＞ 前記ルイス酸が、トリス（ペンタフルオロフェニル）ボラン（Ｂ（Ｃ６Ｆ５）３）、三フッ化ホウ素（ＢＦ３）、塩化鉄（ＩＩＩ）（ＦｅＣｌ３）、塩化アルミニウム（ＩＩＩ）（ＡｌＣｌ３）、及び塩化亜鉛（ＩＩ）（ＺｎＣｌ２）からなる群より選択される少なくとも１種である、＜１＞〜＜４＞の何れかに記載のポリシロキサンの製造方法。＜６＞ 製造されるポリシロキサンが、有機基が周期的に配列した直鎖状のポリシロキサンである、＜１＞〜＜５＞の何れかに記載のポリシロキサンの製造方法。<1> In the presence of a Lewis acid, an oligosiloxane represented by the following formula (I-1), an oligosiloxane represented by the following formula (II-1), and an oligosiloxane represented by the following formula (I-2) And an oligosiloxane represented by the following formula (II-2), or a reaction step of polycondensing an oligosiloxane represented by the following formula (I-3) and an oligosiloxane represented by the following formula (II-3): A method for producing polysiloxane, comprising:
(In formulas (I-1) to (I-3), R 1 to R 8 may have at least one atom selected from the group consisting of an oxygen atom and a halogen atom, and may have 1 to 20 carbon atoms. Representing a hydrocarbon group, R 1 each, R 2 each, ···, R 8 each being the same hydrocarbon group, and R 1 to R 8 each being the same or a different hydrocarbon group However, the case where R 1 , R 3 , R 5 and R 7 are all the same hydrocarbon group, and R 2 , R 4 , R 6 and R 8 are all the same hydrocarbon group is excluded. )
(In formulas (II-1) to (II-3), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 to R 8 are selected from the group consisting of an oxygen atom and a halogen atom. It represents at least one contains the atoms carbon atoms which may 1 to 20 hydrocarbon group, each
<2> In the presence of a Lewis acid, an oligosiloxane represented by the following formula (III-1), an oligosiloxane represented by the following formula (IV-1), and an oligosiloxane represented by the following formula (III-2) And an oligosiloxane represented by the following formula (IV-2), or a reaction step of polycondensing an oligosiloxane represented by the following formula (III-3) and an oligosiloxane represented by the following formula (IV-3): A method for producing polysiloxane, comprising:
(In the formulas (III-1) to (III-3), R 1 to R 8 have 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. Representing a hydrocarbon group, R 1 each, R 2 each, ···, R 8 each being the same hydrocarbon group, and R 1 to R 8 each being the same or a different hydrocarbon group However, the case where R 1 , R 3 , R 5 and R 7 are all the same hydrocarbon group, and R 2 , R 4 , R 6 and R 8 are all the same hydrocarbon group is excluded. )
(In formulas (IV-1) to (IV-3), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 to R 8 are selected from the group consisting of an oxygen atom and a halogen atom. It represents at least one contains the atoms carbon atoms which may 1 to 20 hydrocarbon group, each
<3> The oligosiloxane represented by the formula (I-1) is an oligosiloxane represented by the following formula (I-1-1) and the oligosiloxane represented by the formula (II-1) The manufacturing method of the polysiloxane as described in <1> which is an oligo siloxane represented by following formula (II-1-1).
(In Formula (I-1-1), R 1 and R 3 represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. And R 1 and R 3 are the same hydrocarbon group, and R 1 and R 3 are different hydrocarbon groups.)
(In formula (II-1-1), R is each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 and R 3 are at least one selected from the group consisting of an oxygen atom and a halogen atom Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain an atom, and R 1 and R 3 are the same hydrocarbon groups as R 1 and R 3 in formula (I-1-1), respectively. Represents.)
<4> The oligosiloxane represented by the formula (III-1) is an oligosiloxane represented by the following formula (III-1-1) and the oligosiloxane represented by the formula (IV-1) The manufacturing method of the polysiloxane as described in <2> which is oligosiloxane represented by following formula (IV-1-1).
(In Formula (III-1-1), R 1 and R 3 represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. And R 1 and R 3 are the same hydrocarbon group, and R 1 and R 3 are different hydrocarbon groups.)
(In formula (IV-1-1), R is each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 and R 3 are at least one selected from the group consisting of an oxygen atom and a halogen atom Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain an atom, and R 1 and R 3 are the same hydrocarbon groups as R 1 and R 3 in formula (III-1-1), respectively. Represents.)
<5> The Lewis acid is tris (pentafluorophenyl) borane (B (C 6 F 5 ) 3 ), boron trifluoride (BF 3 ), iron chloride (III) (FeCl 3 ), aluminum chloride (III) The method for producing a polysiloxane according to any one of <1> to <4>, which is at least one selected from the group consisting of (AlCl 3 ) and zinc chloride (II) (ZnCl 2 ). <6> The method for producing a polysiloxane according to any one of <1> to <5>, wherein the produced polysiloxane is a linear polysiloxane in which organic groups are periodically arranged.
本発明によれば、側鎖の有機基が周期的に配列したポリシロキサンを効率良く製造することができる。 According to the present invention, polysiloxane in which side chain organic groups are periodically arranged can be efficiently produced.
本発明の詳細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 details of the present invention, specific examples will be given and described, but the present invention is not limited to the following contents without departing from the spirit of the present invention, and can be implemented with appropriate modifications.
＜ポリシロキサンの製造方法＞
本発明の一態様であるポリシロキサンの製造方法は、ルイス酸の存在下、下記式（Ｉ−１）で表されるオリゴシロキサンと下記式（ＩＩ−１）で表されるオリゴシロキサン、下記式（Ｉ−２）で表されるオリゴシロキサンと下記式（ＩＩ−２）で表されるオリゴシロキサン、又は下記式（Ｉ−３）で表されるオリゴシロキサンと下記式（ＩＩ−３）で表されるオリゴシロキサンを重縮合させる反応工程を含むことを特徴とする。
（式（Ｉ−１）〜（Ｉ−３）中、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１同士、Ｒ２同士、・・、Ｒ８同士はそれぞれ同一の炭化水素基であることを、Ｒ１〜Ｒ８間はそれぞれ同一又は異なる炭化水素基であることを表す。但し、Ｒ１、Ｒ３、Ｒ５、Ｒ７が全て同一の炭化水素基であり、かつＲ２、Ｒ４、Ｒ６、Ｒ８が全て同一の炭化水素基である場合を除く。）
（式（ＩＩ−１）〜（ＩＩ−３）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１〜Ｒ８は式（Ｉ−１）〜（Ｉ−３）のＲ１〜Ｒ８とそれぞれ同一の炭化水素基であることを表す。）
本発明の別の態様であるポリシロキサンの製造方法は、ルイス酸の存在下、下記式（ＩＩＩ−１）で表されるオリゴシロキサンと下記式（ＩＶ−１）で表されるオリゴシロキサン、下記式（ＩＩＩ−２）で表されるオリゴシロキサンと下記式（ＩＶ−２）で表されるオリゴシロキサン、又は下記式（ＩＩＩ−３）で表されるオリゴシロキサンと下記式（ＩＶ−３）で表されるオリゴシロキサンを重縮合させる反応工程を含むことを特徴とする。
（式（ＩＩＩ−１）〜（ＩＩＩ−３）中、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１同士、Ｒ２同士、・・、Ｒ８同士はそれぞれ同一の炭化水素基であることを、Ｒ１〜Ｒ８間はそれぞれ同一又は異なる炭化水素基であることを表す。但し、Ｒ１、Ｒ３、Ｒ５、Ｒ７が全て同一の炭化水素基であり、かつＲ２、Ｒ４、Ｒ６、Ｒ８が全て同一の炭化水素基である場合を除く。）
（式（ＩＶ−１）〜（ＩＶ−３）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１〜Ｒ８は式（ＩＩＩ−１）〜（ＩＩＩ−３）のＲ１〜Ｒ８とそれぞれ同一の炭化水素基であることを表す。）<Method for producing polysiloxane>
In the method for producing a polysiloxane which is one embodiment of the present invention, an oligosiloxane represented by the following formula (I-1), an oligosiloxane represented by the following formula (II-1), The oligosiloxane represented by (I-2) and the oligosiloxane represented by the following formula (II-2), or the oligosiloxane represented by the following formula (I-3) and the following formula (II-3). Reaction step of polycondensing the oligosiloxane.
(In formulas (I-1) to (I-3), R 1 to R 8 may have at least one atom selected from the group consisting of an oxygen atom and a halogen atom, and may have 1 to 20 carbon atoms. Representing a hydrocarbon group, R 1 each, R 2 each, ···, R 8 each being the same hydrocarbon group, and R 1 to R 8 each being the same or a different hydrocarbon group However, the case where R 1 , R 3 , R 5 and R 7 are all the same hydrocarbon group, and R 2 , R 4 , R 6 and R 8 are all the same hydrocarbon group is excluded. )
(In formulas (II-1) to (II-3), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 to R 8 are selected from the group consisting of an oxygen atom and a halogen atom. It represents at least one contains the atoms carbon atoms which may 1 to 20 hydrocarbon group, each
According to another embodiment of the present invention, there is provided a method for producing a polysiloxane in the presence of a Lewis acid, an oligosiloxane represented by the following formula (III-1), an oligosiloxane represented by the following formula (IV-1), An oligosiloxane represented by the formula (III-2) and an oligosiloxane represented by the following formula (IV-2), or an oligosiloxane represented by the following formula (III-3) and the following formula (IV-3) It is characterized by including a reaction step of polycondensation of the represented oligosiloxane.
(In the formulas (III-1) to (III-3), R 1 to R 8 have 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. Representing a hydrocarbon group, R 1 each, R 2 each, ···, R 8 each being the same hydrocarbon group, and R 1 to R 8 each being the same or a different hydrocarbon group However, the case where R 1 , R 3 , R 5 and R 7 are all the same hydrocarbon group, and R 2 , R 4 , R 6 and R 8 are all the same hydrocarbon group is excluded. )
(In formulas (IV-1) to (IV-3), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 to R 8 are selected from the group consisting of an oxygen atom and a halogen atom. It represents at least one contains the atoms carbon atoms which may 1 to 20 hydrocarbon group, each
前述のようにポリシロキサンは、側鎖の有機基によって様々な特性を奏することが知られているが、例えば２種類以上の有機基がランダムに配列されてしまうと、目的とする特性が低下してしまうことも指摘されている。
特にポリシロキサンを得るための重縮合反応は、副反応として「環化反応」や「官能基交換反応」が進行してしまうことがあり、これらが側鎖の有機基が周期的に配列したポリシロキサンを効率良く得ることを困難にしているのである。
「環化反応」は、例えば下記式に示されるように２つのヒドロシリル基（Ｓｉ−Ｈ）を有したジシロキサンと２つのアルコキシシリル基（Ｓｉ−ＯＲ）を有したシランを縮合させる場合に生じることがあり、ポリシロキサンが効率良く得られないこととなる。
一方、「官能基交換反応」は、図１に示されるようにヒドロシリル基とアルコキシシリル基が交換してしまう反応であり、これによって、得られるポリシロキサンの有機基の配列が乱れてしまうこととなるのである。
本発明者らは、「環化反応」が６員環のシロキサンが特に生成し易いことに基づき、ケイ素原子の数が増えるほどシロキサンの環化反応が生じ難くなることに着目するとともに、有機基の配列が同一であり、かつ対称性のオリゴシロキサン同士を重縮合させることによって、たとえ「官能基交換反応」が生じた場合であっても、有機基の配列を乱れないようにすることができることを見出したのである。
以下、「式（Ｉ−１）で表されるオリゴシロキサン」等におけるＲ１〜Ｒ８、Ｒ等について、並びに「ルイス酸」、反応条件等について詳細に説明する。As described above, polysiloxanes are known to exhibit various properties depending on the side chain organic group, but when, for example, two or more types of organic groups are randomly arranged, the target properties are degraded. It has also been pointed out.
In particular, in the polycondensation reaction for obtaining polysiloxane, a “cyclization reaction” or a “functional group exchange reaction” may proceed as a side reaction, and these are polys in which organic groups of side chains are periodically arranged. This makes it difficult to obtain siloxane efficiently.
The "cyclization reaction" occurs, for example, when condensing a disiloxane having two hydrosilyl groups (Si-H) with a silane having two alkoxysilyl groups (Si-OR) as shown in the following formula In some cases, the polysiloxane can not be obtained efficiently.
On the other hand, “functional group exchange reaction” is a reaction in which a hydrosilyl group and an alkoxysilyl group are exchanged as shown in FIG. 1, whereby the arrangement of the organic groups of the obtained polysiloxane is disturbed and It becomes.
The present inventors pay attention to the fact that the cyclization reaction of siloxane becomes more difficult to occur as the number of silicon atoms increases, since the “cyclization reaction” particularly easily generates a six-membered ring siloxane, and an organic group The arrangement of organic groups can be prevented from being disturbed even if a "functional group exchange reaction" occurs, by polycondensing the symmetrical oligosiloxanes which are identical in the arrangement of Was found.
Hereinafter, R 1 to R 8 , R, etc. in “oligosiloxane represented by the formula (I-1)”, etc., “Lewis acid”, reaction conditions, etc. will be described in detail.
式（Ｉ−１）〜（Ｉ〜３）、（ＩＩ−１）〜（ＩＩ〜３）、（ＩＩＩ−１）〜（ＩＩＩ〜３）、（ＩＶ−１）〜（ＩＶ〜３）中、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表しているが、「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」とは、クロロ基（−Ｃｌ）、フルオロ基（−Ｆ）等の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−）等の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。また、「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。
なお、Ｒ１同士、Ｒ２同士、・・、Ｒ８同士はそれぞれ同一の炭化水素基であることを、Ｒ１〜Ｒ８間はそれぞれ同一又は異なる炭化水素基であることを表す。また、Ｒ１、Ｒ３、Ｒ５、Ｒ７が全て同一の炭化水素基であり、かつＲ２、Ｒ４、Ｒ６、Ｒ８が全て同一の炭化水素基であるオリゴシロキサンは、「式（Ｉ−１）で表されるオリゴシロキサン」等から除かれる。これは、「式（Ｉ−１）で表されるオリゴシロキサン」等が、それぞれ異なる有機基を有した対称性のオリゴシロキサンであることを表している。
また、式（ＩＩ−１）〜（ＩＩ−３）のＲ１〜Ｒ８は、式（Ｉ−１）〜（Ｉ−３）のＲ１〜Ｒ８とそれぞれ同一の炭化水素基であり、式（ＩＶ−１）〜（ＩＶ−３）のＲ１〜Ｒ８は、式（ＩＩＩ−１）〜（ＩＩＩ−３）のＲ１〜Ｒ８とそれぞれ同一の炭化水素基であることを表している。これは例えば「式（Ｉ−１）で表されるオリゴシロキサン」と「式（ＩＩ−１）で表されるオリゴシロキサン」の有機基の配列が同一であり、「式（ＩＩＩ−１）で表されるオリゴシロキサン」と「式（ＩＶ−１）で表されるオリゴシロキサン」の有機基の配列が同一であることを表しているのである。
Ｒ１〜Ｒ８の炭化水素基の炭素数は、好ましくは１２以下、より好ましくは６以下である。
Ｒ１〜Ｒ８の炭化水素基に含まれる官能基としては、エーテル基（−Ｏ−）、フルオロ基（−Ｆ）、クロロ基（−Ｃｌ）等が挙げられる。
Ｒ１〜Ｒ８としては、メチル基（−Ｍｅ）、エチル基（−Ｅｔ）、ビニル基（−ＣＨ＝ＣＨ２）、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）、フェニル基（−Ｐｈ）等が挙げられる。In formulas (I-1) to (I-3), (II-1) to (II-3), (III-1) to (III-3), (IV-1) to (IV-3), R 1 to R 8 represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. "May contain at least one atom selected from the group consisting of" includes a functional group containing an oxygen atom or a halogen atom such as a chloro group (-Cl) or a fluoro group (-F). In addition, it means that a linking group containing an oxygen atom or a halogen atom such as an ether group (—O—) may be contained inside or at the end of the carbon skeleton. In addition, “hydrocarbon group” means that it is not limited to a linear saturated hydrocarbon group, and may have a carbon-carbon unsaturated bond, a branched structure, or a cyclic structure.
Incidentally, indicating that R 1 together, R 2 to each other, ..., that together R 8 are the same hydrocarbon groups, respectively, while
Further, R 1 to R 8 of formula (II-1) ~ (II -3) are each the R 1 to R 8 identical hydrocarbon radical of the formula (I-1) ~ (I -3), It indicates that R 1 to R 8 of formula (IV-1) ~ (IV -3) are each the R 1 to R 8 identical hydrocarbon radical of the formula (III-1) ~ (III -3) ing. For example, the organic groups of “oligosiloxane represented by formula (I-1)” and “oligosiloxane represented by formula (II-1)” have the same sequence, This means that the arrangement of the organic groups of the “oligosiloxane represented” and the “oligosiloxane represented by the formula (IV-1)” is the same.
The carbon number of the hydrocarbon group of R 1 to R 8 is preferably 12 or less, more preferably 6 or less.
Examples of the functional group contained in the hydrocarbon group of R 1 to R 8 include an ether group (—O—), a fluoro group (—F), a chloro group (—Cl), and the like.
The R 1 to R 8, methyl group (-Me), ethyl (-Et), a vinyl group (-CH = CH 2), n- propyl (- n Pr), i- propyl (- i Pr ), n-butyl group (- n Bu), t- butyl (- t Bu), and the like phenyl group (-Ph) is.
式（ＩＩ）、（ＩＶ）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を表しているが、「炭化水素基」については、Ｒ１〜Ｒ８と同義である。
Ｒの炭化水素基の炭素数は、好ましくは３以下、より好ましくは２以下である。
Ｒとしては、メチル基（−Ｍｅ）、エチル基（−Ｅｔ）、ビニル基（−ＣＨ＝ＣＨ２）、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）、フェニル基（−Ｐｈ）等が挙げられる。In formulas (II) and (IV), each R independently represents a hydrocarbon group having 1 to 6 carbon atoms, and the “hydrocarbon group” has the same meaning as R 1 to R 8 .
The carbon number of the hydrocarbon group of R is preferably 3 or less, more preferably 2 or less.
As R, a methyl group (-Me), ethyl (-Et), a vinyl group (-CH = CH 2), n- propyl (- n Pr), i- propyl (- i Pr), n- butyl (- n Bu), t- butyl (- t Bu), and the like phenyl group (-Ph) is.
式（Ｉ）で表されるオリゴシロキサンとしては、下記式（Ｉ−１−１）で表されるオリゴシロキサンが好ましい。
（式（Ｉ−１−１）中、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１同士及びＲ３同士はそれぞれ同一の炭化水素基であることを、Ｒ１とＲ３間はそれぞれ異なる炭化水素基であることを表す。）
また、具体的な式（Ｉ−１）で表されるオリゴシロキサンとしては、下記式で表されるものが挙げられる。
(In Formula (I-1-1), R 1 and R 3 represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. And R 1 and R 3 are the same hydrocarbon group, and R 1 and R 3 are different hydrocarbon groups.)
Moreover, as oligosiloxane represented by specific Formula (I-1), what is represented by a following formula is mentioned.
式（ＩＩ−１）で表されるオリゴシロキサンとしては、下記式（ＩＩ−１−１）で表されるオリゴシロキサンが好ましい。
（式（ＩＩ−１−１）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１同士及びＲ３同士はそれぞれ同一の炭化水素基であることを、Ｒ１とＲ３間はそれぞれ異なる炭化水素基であることを表す。）
また、具体的な式（ＩＩ−１）で表されるオリゴシロキサンとしては、下記式で表されるものが挙げられる。
(In formula (II-1-1), R is each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 and R 3 are at least one selected from the group consisting of an oxygen atom and a halogen atom Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain an atom, R 1 and R 3 are the same hydrocarbon group, and R 1 and R 3 are different hydrocarbon groups. Represents that.)
Moreover, as oligosiloxane represented by specific Formula (II-1), what is represented by a following formula is mentioned.
式（ＩＩＩ−１）で表されるオリゴシロキサンとしては、下記式（ＩＩＩ−１−１）で表されるオリゴシロキサンが好ましい。
（式（ＩＩＩ−１−１）中、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１同士及びＲ３同士はそれぞれ同一の炭化水素基であることを、Ｒ１とＲ３間はそれぞれ異なる炭化水素基であることを表す。）
また、具体的な式（ＩＩＩ−１）で表されるオリゴシロキサンとしては、下記式で表されるものが挙げられる。
(In Formula (III-1-1), R 1 and R 3 represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. And R 1 and R 3 are the same hydrocarbon group, and R 1 and R 3 are different hydrocarbon groups.)
Moreover, as oligosiloxane represented by specific Formula (III-1), what is represented by a following formula is mentioned.
式（ＩＶ−１−１）で表されるオリゴシロキサンとしては、下記式（ＩＶ−１−１）で表されるオリゴシロキサンが好ましい。
（式（ＩＶ−１−１）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１同士及びＲ３同士はそれぞれ同一の炭化水素基であることを、Ｒ１とＲ３間はそれぞれ異なる炭化水素基であることを表す。）
式（ＩＶ−１）で表されるオリゴシロキサンとしては、下記式で表されるものが挙げられる。
(In formula (IV-1-1), R is each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 and R 3 are at least one selected from the group consisting of an oxygen atom and a halogen atom Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain an atom, R 1 and R 3 are the same hydrocarbon group, and R 1 and R 3 are different hydrocarbon groups. Represents that.)
As oligosiloxane represented by Formula (IV-1), what is represented by a following formula is mentioned.
反応工程における式（Ｉ−１）で表されるオリゴシロキサンと式（ＩＩ−１）で表されるオリゴシロキサンの使用量等は、目的のポリシロキサン等に応じて適宜選択することができるが、式（ＩＩ−１）で表されるオリゴシロキサンの使用量は、式（Ｉ−１）で表されるオリゴシロキサンの使用量に対して、同じ物質量（［ｍｏｌ］）あることが好ましい。同じ物質量であると、ポリシロキサンをより効率良く製造することができる。 The amount of the oligosiloxane represented by the formula (I-1) and the oligosiloxane represented by the formula (II-1) in the reaction step can be appropriately selected according to the target polysiloxane, etc. The amount of the oligosiloxane represented by the formula (II-1) is preferably the same amount ([mol]) as the amount of the oligosiloxane represented by the formula (I-1). Polysiloxane can be more efficiently produced when the same amount of material is used.
ルイス酸は、ルイス酸性を有する公知の化合物であれば、その種類は特に限定されないが、トリス（ペンタフルオロフェニル）ボラン（Ｂ（Ｃ６Ｆ５）３）、三フッ化ホウ素（ＢＦ３）、塩化鉄（ＩＩＩ）（ＦｅＣｌ３）、塩化アルミニウム（ＩＩＩ）（ＡｌＣｌ３）、塩化亜鉛（ＩＩ）（ＺｎＣｌ２）等が挙げられる。The type of Lewis acid is not particularly limited as long as it is a known compound having Lewis acidity, but tris (pentafluorophenyl) borane (B (C 6 F 5 ) 3 ), boron trifluoride (BF 3 ), Examples thereof include iron (III) chloride (FeCl 3 ), aluminum (III) chloride (AlCl 3 ), and zinc (II) chloride (ZnCl 2 ).
反応工程におけるルイス酸の使用量は、目的に応じて適宜選択することができるが、式（Ｉ−１）で表されるオリゴシロキサンの使用量に対して、物質量（［ｍｏｌ］）で、通常０．００１倍以上であり、通常０．０５倍以下である。上記範囲内であると、ポリシロキサンをより効率良く製造することができる。 The amount of Lewis acid used in the reaction step can be appropriately selected according to the purpose, but the amount of substance ([mol]) with respect to the amount of oligosiloxane represented by formula (I-1) Usually it is 0.001 times or more and usually 0.05 times or less. Within the above range, polysiloxane can be produced more efficiently.
反応工程は、溶媒を使用しても、使用しなくてもよいが、溶媒を使用しない方が好ましい。また、溶媒を使用する場合、その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、具体的にはヘキサン、ベンゼン、トルエン等の炭化水素系溶媒、塩化メチレン、クロロホルム等のハロゲン系溶媒等が挙げられる。 The reaction step may or may not use a solvent, but it is preferable not to use a solvent. When a solvent is used, the type of the solvent is not particularly limited and may be appropriately selected according to the purpose. Specifically, hydrocarbon solvents such as hexane, benzene, toluene, methylene chloride, chloroform Etc., and the like.
反応工程の反応温度は、通常１０℃以上、好ましくは２５℃以上であり、通常６０℃以下、好ましくは３０℃以下である。上記範囲内であると、ポリシロキサンをより効率良く製造することができる。
反応工程の反応時間は、通常３０分以上、好ましくは１時間以上であり、通常２時間以下、好ましくは１時間以下である。
反応工程は、通常窒素、アルゴン等の不活性雰囲気下で行う。The reaction temperature in the reaction step is usually 10 ° C. or more, preferably 25 ° C. or more, and usually 60 ° C. or less, preferably 30 ° C. or less. A polysiloxane can be more efficiently manufactured as it is in the said range.
The reaction time of the reaction step is usually 30 minutes or more, preferably 1 hour or more, and usually 2 hours or less, preferably 1 hour or less.
The reaction step is usually carried out under an inert atmosphere such as nitrogen, argon or the like.
本発明の製造方法によって製造されるポリシロキサンは、目的に応じて適宜選択することができ、その種類は特に限定されないが、直鎖状のポリシロキサンであることが好ましい。直鎖状のポリシロキサンであると、幅広い用途に利用することができる。
本発明の製造方法によって製造されるポリシロキサンの重合度は、通常ｎ＝２以上であり、通常ｎ＝１４０以下である。Although the polysiloxane manufactured by the manufacturing method of this invention can be suitably selected according to the objective, The kind is not specifically limited, It is preferable that it is linear polysiloxane. Linear polysiloxanes can be used in a wide variety of applications.
The polymerization degree of the polysiloxane produced by the production method of the present invention is usually n = 2 or more, and usually n = 140 or less.
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.
＜実施例１：（−ＳｉＭｅ２ＯＳｉＰｈ２ＯＳｉＭｅ２Ｏ−）からなるポリシロキサンの製造＞
５０ｍＬシュレンクフラスコ内部を窒素置換した。このフラスコに１，１，３，３−テトラメチル−２，２−ジフェニルトリシロキサン３３２ｍｇ（１ｍｍｏｌ）及び１，３−ジエトキシ−１，１，３，３−テトラメチル−２，２−ジフェニルトリシロキサン４２０ｍｇ（１ｍｍｏｌ）を加えた。フラスコ内に空気が入らないよう、窒素を流しながらトリス(ペンタフルオロフェニル)ボラン２６ｍｇ（０．０５ｍｍｏｌ）を加え、常温で1時間撹拌し反応させた。反応初期にガス発生を伴う発熱を観測した。
得られた透明粘性体の１Ｈ，１３Ｃ，２９ＳｉＮＭＲを測定したところ、ＡＢＡ周期に帰属可能なシグナルを観測した。また、ＭＡＬＤＩ−ＴＯＦＭＳによって繰り返し構造分の質量増加を観測できたことから、−ＳｉＭｅ２ＯＳｉＰｈ２ＯＳｉＭｅ２Ｏ−の構造が周期的に配列したポリシロキサンが生成していることが確認された。<Example 1: (- SiMe 2 OSiPh 2 OSiMe 2 O-) preparation of a polysiloxane consisting of>
The inside of the 50 mL Schlenk flask was purged with nitrogen. To this flask, 332 mg (1 mmol) of 1,1,3,3-tetramethyl-2,2-diphenyltrisiloxane and 1,3-diethoxy-1,1,3,3-tetramethyl-2,2-diphenyltrisiloxane were added. 420 mg (1 mmol) was added. 26 mg (0.05 mmol) of tris (pentafluorophenyl) borane was added while flowing nitrogen so as to prevent air from entering the flask, and the mixture was reacted by stirring at room temperature for 1 hour. An exotherm with gas evolution was observed at the beginning of the reaction.
When 1 H, 13 C, 29 Si NMR of the obtained transparent viscous material was measured, a signal that could be assigned to the ABA period was observed. Also, since that can be observed mass increase of the repeating structural component by MALDI-TOFMS, the -SiMe 2 OSiPh 2 OSiMe 2 O- structure polysiloxane is generated that periodically sequence was confirmed.
＜実施例２：（−ＳｉＭｅ２ＯＳｉＰｈ２ＯＳｉＰｈ２ＯＳｉＭｅ２Ｏ−）からなるポリシロキサンの製造＞
３０ｍＬシュレンクフラスコ内部を窒素置換した。このフラスコに１，１，７，７−テトラメチル−３，３，５，５−テトラフェニルテトラシロキサン５３１ｍｇ（１ｍｍｏｌ）及び１，７−ジエトキシ−１，１，７，７−テトラメチル−３，３，５，５−テトラフェニルテトラシロキサン６１８ｍｇ（１ｍｍｏｌ）及び２００μＬの脱水トルエンを加え、フラスコ内に空気が入らないよう、窒素を流しながらトリス(ペンタフルオロフェニル)ボラン５ｍｇ（０．０１ｍｍｏｌ）を加え、常温で１時間撹拌し反応させた。反応初期にガス発生を伴う発熱を観測した。
得られた透明粘性体の１Ｈ，１３Ｃ，２９ＳｉＮＭＲを測定したところ、ＡＢＡ周期に帰属可能なシグナルを観測した。また、ＭＡＬＤＩ−ＴＯＦＭＳによって繰り返し構造分の質量増加を観測できたことから、−ＳｉＭｅ２ＯＳｉＰｈ２ＯＳｉＰｈ２ＯＳｉＭｅ２Ｏ−の構造が周期的に配列したポリシロキサンが生成していることが確認された。<Example 2: (- SiMe 2 OSiPh 2 OSiPh 2 OSiMe 2 O-) preparation of a polysiloxane consisting of>
The inside of the 30 mL Schlenk flask was purged with nitrogen. The flask was charged with 531 mg (1 mmol) of 1,1,7,7-tetramethyl-3,3,5,5-tetraphenyltetrasiloxane and 1,7-diethoxy-1,1,7,7-tetramethyl-3, Add 618 mg (1 mmol) of 3,5,5-tetraphenyl tetrasiloxane and 200 μL of dehydrated toluene, add 5 mg (0.01 mmol) of tris (pentafluorophenyl) borane while flushing with nitrogen so that air does not enter the flask. The reaction was stirred for 1 hour at room temperature. An exotherm with gas evolution was observed at the beginning of the reaction.
When 1 H, 13 C, 29 Si NMR of the obtained transparent viscous material was measured, a signal that could be assigned to the ABA period was observed. In addition, it was confirmed that the polysiloxane in which the structure of -SiMe 2 OSiPh 2 OSiPh 2 OSiMe 2 O was periodically formed was formed because the mass increase of the structural component could be observed repeatedly by MALDI-TOF MS. .
＜比較例：ポリシロキサンの製造＞
５０ｍｌフラスコに１０ｇの乾燥トルエン及び５．０×１０−３ｍｍｏｌのＢ（Ｃ６Ｆ５）３を入れた。得られた混合物を５０℃に加熱し、そこに２．６８ｇ（２０ｍｍｏｌ）の１，１，３，３−テトラメチルジシロキサンと４．８８ｇ（２０ｍｍｏｌ）のジフェニルジメトキシシランの混合物を３０分間にわたり滴下した。最初の数滴後、ガス発生を伴う発熱を観測した。滴下完了後、得られた混合物を５０℃でさらに６０分間加熱した。得られた白色固体を含む粘性液体の１Ｈ，１３Ｃ，２９Ｓｉ ＮＭＲを測定した結果、周期構造に帰属できないシグナルを観測した。
A 50 ml flask was charged with 10 g of dry toluene and 5.0 × 10 −3 mmol of B (C 6 F 5 ) 3 . The resulting mixture is heated to 50 ° C., and a mixture of 2.68 g (20 mmol) of 1,1,3,3-tetramethyldisiloxane and 4.88 g (20 mmol) of diphenyldimethoxysilane is added dropwise over 30 minutes. did. After the first few drops, an exotherm with gas evolution was observed. After the addition was complete, the resulting mixture was heated at 50 ° C. for an additional 60 minutes. As a result of measuring 1 H, 13 C, 29 Si NMR of the obtained viscous liquid containing a white solid, a signal that could not be assigned to the periodic structure was observed.
本発明の製造方法によって製造されたポリシロキサンは、電子機器、電気機械、自動車、化粧品等に利用されるシリコーンオイル、シリコーンゴム等として有用である。 The polysiloxane produced by the production method of the present invention is useful as silicone oil, silicone rubber, etc. used in electronic equipment, electric machines, automobiles, cosmetics and the like.
Claims (6)
（式（Ｉ−１）〜（Ｉ−３）中、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１同士、Ｒ２同士、・・、Ｒ８同士はそれぞれ同一の炭化水素基であることを、Ｒ１〜Ｒ８間はそれぞれ同一又は異なる炭化水素基であることを表す。但し、Ｒ１、Ｒ３、Ｒ５、Ｒ７が全て同一の炭化水素基であり、かつＲ２、Ｒ４、Ｒ６、Ｒ８が全て同一の炭化水素基である場合を除く。）
（式（ＩＩ−１）〜（ＩＩ−３）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１〜Ｒ８は式（Ｉ−１）〜（Ｉ−３）のＲ１〜Ｒ８とそれぞれ同一の炭化水素基であることを表す。）In the presence of a Lewis acid, an oligosiloxane represented by the following formula (I-1) and an oligosiloxane represented by the following formula (II-1), an oligosiloxane represented by the following formula (I-2) and the following formula Including a reaction step of polycondensing the oligosiloxane represented by (II-2) or the oligosiloxane represented by the following formula (I-3) and the oligosiloxane represented by the following formula (II-3). A method for producing a polysiloxane.
(In formulas (I-1) to (I-3), R 1 to R 8 may have at least one atom selected from the group consisting of an oxygen atom and a halogen atom, and may have 1 to 20 carbon atoms. Representing a hydrocarbon group, R 1 each, R 2 each, ···, R 8 each being the same hydrocarbon group, and R 1 to R 8 each being the same or a different hydrocarbon group However, the case where R 1 , R 3 , R 5 and R 7 are all the same hydrocarbon group, and R 2 , R 4 , R 6 and R 8 are all the same hydrocarbon group is excluded. )
(In formulas (II-1) to (II-3), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 to R 8 are selected from the group consisting of an oxygen atom and a halogen atom. It represents at least one contains the atoms carbon atoms which may 1 to 20 hydrocarbon group, each identical R 1 to R 8 and R 1 to R 8 of formula (I-1) ~ (I -3) Represents a hydrocarbon group of
（式（ＩＩＩ−１）〜（ＩＩＩ−３）中、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１同士、Ｒ２同士、・・、Ｒ８同士はそれぞれ同一の炭化水素基であることを、Ｒ１〜Ｒ８間はそれぞれ同一又は異なる炭化水素基であることを表す。但し、Ｒ１、Ｒ３、Ｒ５、Ｒ７が全て同一の炭化水素基であり、かつＲ２、Ｒ４、Ｒ６、Ｒ８が全て同一の炭化水素基である場合を除く。）
（式（ＩＶ−１）〜（ＩＶ−３）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１〜Ｒ８は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１〜２０の炭化水素基を表し、Ｒ１〜Ｒ８は式（ＩＩＩ−１）〜（ＩＩＩ−３）のＲ１〜Ｒ８とそれぞれ同一の炭化水素基であることを表す。）In the presence of a Lewis acid, an oligosiloxane represented by the following formula (III-1) and an oligosiloxane represented by the following formula (IV-1), an oligosiloxane represented by the following formula (III-2) and the following formula Including a reaction step of polycondensing the oligosiloxane represented by (IV-2) or the oligosiloxane represented by the following formula (III-3) and the oligosiloxane represented by the following formula (IV-3). A method for producing a polysiloxane.
(In the formulas (III-1) to (III-3), R 1 to R 8 have 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. Representing a hydrocarbon group, R 1 each, R 2 each, ···, R 8 each being the same hydrocarbon group, and R 1 to R 8 each being the same or a different hydrocarbon group However, the case where R 1 , R 3 , R 5 and R 7 are all the same hydrocarbon group, and R 2 , R 4 , R 6 and R 8 are all the same hydrocarbon group is excluded. )
(In formulas (IV-1) to (IV-3), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 to R 8 are selected from the group consisting of an oxygen atom and a halogen atom. It represents at least one contains the atoms carbon atoms which may 1 to 20 hydrocarbon group, each identical R 1 to R 8 and R 1 to R 8 of formula (III-1) ~ (III -3) Represents a hydrocarbon group of
（式（Ｉ−１−１）中、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１同士及びＲ３同士はそれぞれ同一の炭化水素基であることを、Ｒ１とＲ３間はそれぞれ異なる炭化水素基であることを表す。）
（式（ＩＩ−１−１）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１及びＲ３は式（Ｉ−１−１）のＲ１及びＲ３とそれぞれ同一の炭化水素基であることを表す。）The oligosiloxane represented by the formula (I-1) is an oligosiloxane represented by the following formula (I-1-1), and the oligosiloxane represented by the formula (II-1) is The manufacturing method of the polysiloxane of Claim 1 which is an oligo siloxane represented by Formula (II-1-1).
(In Formula (I-1-1), R 1 and R 3 represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. And R 1 and R 3 are the same hydrocarbon group, and R 1 and R 3 are different hydrocarbon groups.)
(In formula (II-1-1), R is each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 and R 3 are at least one selected from the group consisting of an oxygen atom and a halogen atom contain atoms represents a hydrocarbon group which may having 1 to 20 carbon atoms, that R 1 and R 3 are each identical hydrocarbon radicals as R 1 and R 3 of one of formulas (I-1-1) Represents.)
（式（ＩＩＩ−１−１）中、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１同士及びＲ３同士はそれぞれ同一の炭化水素基であることを、Ｒ１とＲ３間はそれぞれ異なる炭化水素基であることを表す。）
（式（ＩＶ−１−１）中、Ｒはそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ１及びＲ３は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１〜２０の炭化水素基を表し、Ｒ１及びＲ３は式（ＩＩＩ−１−１）のＲ１及びＲ３とそれぞれ同一の炭化水素基であることを表す。）The oligosiloxane represented by the formula (III-1) is an oligosiloxane represented by the following formula (III-1-1), and the oligosiloxane represented by the formula (IV-1) is The manufacturing method of the polysiloxane of Claim 2 which is an oligosiloxane represented by Formula (IV-1-1).
(In the formula (III-1-1), R 1 and R 3 each represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom And R 1 and R 3 are the same hydrocarbon group, and R 1 and R 3 are different hydrocarbon groups.)
(In formula (IV-1-1), R is each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 and R 3 are at least one selected from the group consisting of an oxygen atom and a halogen atom contain atoms represents a hydrocarbon group which may having 1 to 20 carbon atoms, that R 1 and R 3 are each identical hydrocarbon radicals as R 1 and R 3 of formula (III-1-1) Represents.)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015185965 | 2015-09-18 | ||
| JP2015185965 | 2015-09-18 | ||
| PCT/JP2016/077135 WO2017047652A1 (en) | 2015-09-18 | 2016-09-14 | Method for producing periodic polysiloxane by polycondensation of symmetric oligosiloxanes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2017047652A1 JPWO2017047652A1 (en) | 2018-07-05 |
| JP6550626B2 true JP6550626B2 (en) | 2019-07-31 |
Family
ID=58288928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017539946A Active JP6550626B2 (en) | 2015-09-18 | 2016-09-14 | Process for producing periodic polysiloxanes by polycondensation of symmetrical oligosiloxanes |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6550626B2 (en) |
| WO (1) | WO2017047652A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10975107B2 (en) | 2017-03-02 | 2021-04-13 | National Institute Of Advanced Industrial Science And Technology | Sequence-controlled oligosiloxane and manufacturing method and oligosiloxane synthesizer therefor |
| US11643506B2 (en) * | 2018-12-21 | 2023-05-09 | Dow Silicones Corporation | Polyfunctional organosiloxanes, compositions containing same, and methods for the preparation thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7064173B2 (en) * | 2002-12-30 | 2006-06-20 | General Electric Company | Silicone condensation reaction |
-
2016
- 2016-09-14 WO PCT/JP2016/077135 patent/WO2017047652A1/en active Application Filing
- 2016-09-14 JP JP2017539946A patent/JP6550626B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017047652A1 (en) | 2017-03-23 |
| JPWO2017047652A1 (en) | 2018-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101028348B1 (en) | Branched polymers from organohydrogensilicon compounds | |
| TW201116557A (en) | Terminal vinyl polysiloxane containing isocyanuric ring | |
| JP6550626B2 (en) | Process for producing periodic polysiloxanes by polycondensation of symmetrical oligosiloxanes | |
| EP0669363B1 (en) | Process for preparing polyorganosilane | |
| Samthong et al. | Synthesis and characterization of organic/inorganic epoxy nanocomposites from poly (aminopropyl/phenyl) silsesquioxanes | |
| US6492480B1 (en) | Method of polymerizing a silalkylenesiloxane | |
| Rathore et al. | A photocurable, photoluminescent, polycarbosilane obtained by acyclic diene metathesis (ADMET) polymerization | |
| JP3848260B2 (en) | Method for producing hydroxyalkylpolysiloxane | |
| Fuchise et al. | Organocatalytic controlled/living ring-opening polymerization of 1, 3, 5-triphenyl-1, 3, 5-tri-p-tolylcyclotrisiloxane for the precise synthesis of fusible, soluble, functionalized, and solid poly [phenyl (p-tolyl) siloxane] s | |
| WO2018051792A1 (en) | Process for producing polysiloxane-structure-containing compound, and polymer composition | |
| US6291623B1 (en) | Fluoroalkylsubstituted cyclotrisiloxanes, their use for preparation of new polymers and novel polymers | |
| Zhou et al. | Highly heat resistant and thermo-oxidatively stable borosilane alkynyl hybrid polymers | |
| WO2019204041A1 (en) | Alkyl ether substituted cyclotrisiloxanes and preparation method thereof | |
| Interrante et al. | Polycarbosilanes | |
| JP6493268B2 (en) | Method for producing organopolysiloxane having arylene group in main chain | |
| Minato et al. | One-pot synthesis of polysiloxanes using catalytic reaction of dihydroorganosilanes with DMF: A new approach to functional polysiloxanes | |
| Wang et al. | Carborane‐incorporated poly (silyleneethynylenephenyleneethynylene) s with different side groups | |
| EP3781579B1 (en) | Hydridosiloxanyl substituted cyclotrisiloxanes, preparation method thereof, and polymeric products derived therefrom | |
| Pavelka et al. | Addition polymerization of 1, 1-dimesitylneopentylsilene: Synthesis of a polysilene | |
| TW200916507A (en) | New silicone compound, and raw material thereof and method for producing the silicone compound | |
| JP6390473B2 (en) | Silacyclobutane ring-opened polymer modified at both ends and method for producing the same | |
| JP6299638B2 (en) | Method for producing organopolyfluorosiloxane | |
| Ziatdinov et al. | Anionic ring-opening polymerization of trimethylsiloxy-substituted 1-oxa-2, 5-disilacyclopentanes: Synthesis of trimethylsiloxy-substituted poly [1-oxa-2, 5-disila-1, 5-pentanylene] s | |
| Vasnev et al. | Recent Advances in the Field of Polycarboranesiloxanes Synthesis | |
| Rieger et al. | Polysilanes, Polycarbosilanes, Dioxadisilacyclohexane, and Polysiloxanes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20180130 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180316 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190528 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190610 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6550626 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |