JPS6341534A - Polysilane substituted with silyl group - Google Patents
Polysilane substituted with silyl groupInfo
- Publication number
- JPS6341534A JPS6341534A JP18453386A JP18453386A JPS6341534A JP S6341534 A JPS6341534 A JP S6341534A JP 18453386 A JP18453386 A JP 18453386A JP 18453386 A JP18453386 A JP 18453386A JP S6341534 A JPS6341534 A JP S6341534A
- Authority
- JP
- Japan
- Prior art keywords
- polysilane
- substituted
- silyl
- me3si
- 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.)
- Granted
Links
- 229920000548 poly(silane) polymer Polymers 0.000 title claims abstract description 25
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 title description 2
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 150000004756 silanes Chemical class 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- 229910052700 potassium Inorganic materials 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- -1 hebetane Chemical compound 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001923 cyclic compounds Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- JJJKROZNVLOJHB-UHFFFAOYSA-N diphenyl-bis(trimethylsilyl)silane Chemical compound C=1C=CC=CC=1[Si]([Si](C)(C)C)([Si](C)(C)C)C1=CC=CC=C1 JJJKROZNVLOJHB-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- JPXGMXXVGJYDKK-UHFFFAOYSA-N [1,2,2,3,3,4,4-heptakis(trimethylsilyl)tetrasiletan-1-yl]-trimethylsilane Chemical compound C[Si](C)(C)[Si]1([Si](C)(C)C)[Si]([Si](C)(C)C)([Si](C)(C)C)[Si]([Si](C)(C)C)([Si](C)(C)C)[Si]1([Si](C)(C)C)[Si](C)(C)C JPXGMXXVGJYDKK-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- NBCRIQUCROAGJT-UHFFFAOYSA-N dichloro-bis(trimethylsilyl)silane Chemical compound C[Si](C)(C)[Si](Cl)(Cl)[Si](C)(C)C NBCRIQUCROAGJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920003203 poly(dimethylsilylene-co-phenylmethyl- silylene) polymer Chemical group 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- PLUQSKKKNPNZCQ-UHFFFAOYSA-N tetrasiletane Chemical compound [SiH2]1[SiH2][SiH2][SiH2]1 PLUQSKKKNPNZCQ-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、シリル基の置換し友新規なポリシランであり
、ホトレジスト、セラミックス、半導体、光重合開始剤
等々に有用である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is a novel polysilane substituted with silyl groups, which is useful for photoresists, ceramics, semiconductors, photopolymerization initiators, and the like.
従来、ポリシラン化合物としては、メチル基の置換した
ポリメチルポリシランやメチル基、フェニル基の置換し
たポリシラスチレン〔米国特許！ 、 ３．２Ｆ 、
１０／ ）等が知られている。Conventionally, polysilane compounds include polymethylpolysilane substituted with a methyl group and polysilastyrene substituted with a methyl group or a phenyl group [US patent! , 3.2F,
10/) etc. are known.
しかしこれらのポリシランはいづれも主鎖のポリシラン
に直接炭素が結合したものであり、ポリシランの特性を
十分に出し切れていない。However, all of these polysilanes have carbon bonded directly to the main chain of polysilane, and do not fully exhibit the characteristics of polysilane.
本発明は主鎖のポリシランに珪素が結合にしたポリシラ
ン化合物を提供しようとするものである０
〔問題点を解決するための手段〕
本発明者らは、上記実情に鑑み鋭意検討した結果、主鎖
ポリシランにケイ素を置換した新規番
なシリル置換ポリシランを分成し、本発明に到達した。The present invention aims to provide a polysilane compound in which silicon is bonded to polysilane in the main chain. The present invention was achieved by decomposing a new type of silyl-substituted polysilane in which silicon is substituted in a chain polysilane.
すなわち本発明の要旨は、
下記一般式（り
Ｈａ
〔式中 ）（１〜Ｒ６は低級アルキル基を表わし、同一
でも異ってもよい〕
で示される繰返し単位からなり、線状で数平均分子ｉ！
に２００〜２０，０００ のシリル置換ポリシランに
存する。That is, the gist of the present invention is to consist of repeating units represented by the following general formula: i!
200 to 20,000 silyl-substituted polysilanes.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明のシリル置換ポリシランは一般式（「）Ｒ’ −
Ｓｉ −Ｈ”
ｚ−ｓｌ−ｘ （ＩＩ）Ｆ＋４−
Ｓｉ −Ｒ’
〔式中 Ｈ１〜Ｒ６は低級アルキル基を表わし。The silyl-substituted polysilane of the present invention has the general formula (')R'-
Si −H”z−sl−x (II)F+4−
Si -R' [In the formula, H1 to R6 represent a lower alkyl group.
同一でも異ってもよい。Ｘは・・ロゲンを表わす。〕で
示されるハロゲン化シラン化合物の縮合重合によって合
成される。May be the same or different. X represents... Rogen. ] Synthesized by condensation polymerization of halogenated silane compounds.
一般式（ｎ）中、Ｒ１−Ｒ６の低級アルキル基としては
炭素数／−，１のアルキル基が好ｔ Ｌ、 ＜ 、特に
はメチル基が好ましい。゛また％ Ｘとしては、塩素、
臭素、フッ素等が挙げられ、中でも好ましいのは塩素、
臭素である。In the general formula (n), the lower alkyl group represented by R1 to R6 is preferably an alkyl group having a carbon number of /-, 1, and a methyl group is particularly preferred.゛Also, %X is chlorine,
Examples include bromine, fluorine, etc. Among them, chlorine,
It is bromine.
一般式（ＩＩ）で示されるハロゲン化シランのうち、特
に好ましい化合物は、ビストリメチルシリルジクロルシ
ラン（Ｍ８．Ｓｉ ）２Ｓｉｌｌ寓、ビストリメチルシ
リルジブロモシラン（ＭｅｓＳｌ）ｓ ５ｉＢｒｌ
等カ挙げられる。Among the halogenated silanes represented by the general formula (II), particularly preferred compounds are bistrimethylsilyldichlorosilane (M8.Si), bistrimethylsilyldibromosilane (MesSl), and bistrimethylsilyldibromosilane (MesSl).
etc. can be mentioned.
これらのハロゲン化シラン化合物は１例えば次の反応式
で表わされる方法により合成できる。These halogenated silane compounds can be synthesized, for example, by a method represented by the following reaction formula.
２Ｍθ１８１Ｃ！１ ＋ｎ、ｓ１．ｏ：＋鵞−Ｍｅ３Ｓ
ｉＳｉＯｚＳｉｌＪθ。2Mθ181C! 1 +n, s1. o: + Goose-Me3S
iSiOzSilJθ.
ｇ
なお、本明細書１でＭθ はメチル基を、ｙはフェニル
基を示す。g In this Specification 1, Mθ represents a methyl group, and y represents a phenyl group.
ハロゲン化シランの縮合重合は縮合剤の存在下、要すれ
ば適当な溶媒を用いて行なわれる。Condensation polymerization of halogenated silanes is carried out in the presence of a condensing agent, using a suitable solvent if necessary.
縮合剤としてはナトリウム、カリウム又はナトリウム／
カリウム合金が挙げられ、好ましくけナトリウムが用い
られる。As a condensing agent, sodium, potassium or sodium/
Potassium alloys are mentioned, and sodium chloride is preferably used.
縮合剤の使用吋ニノ・ロダン化シラン中のノ・ロゲン原
子に対してλから５当量用いられる。好ましくはコから
３当量用いられる。Use of condensing agent: 5 equivalents are used from λ to the rhogen atoms in the rhodanized silane. Preferably, 3 to 3 equivalents are used.
重合反応においては溶媒の使用は任意であるが好適には
ベンゼン、トルエン、キシレン、ヘベタン、オクタン等
の炭化水素類あるいはテトラヒドロフラン等が使用され
る。溶媒の使用量は、ハロゲン化シラン／ｆ当り、ｌ−
からｔ。In the polymerization reaction, any solvent may be used, but hydrocarbons such as benzene, toluene, xylene, hebetane, and octane, or tetrahydrofuran are preferably used. The amount of solvent used is l- per halogenated silane/f.
From t.
−好ましくはｊ−２０贋ｅである。- Preferably it is j-20 fake.
反応温度は０℃からｌ夕Ｏ℃好１しくはｊＯ℃から１２
０℃である。The reaction temperature is from 0°C to 10°C, preferably from 10°C to 12°C.
It is 0°C.
重合操作は、チッ素、アルゴン等の不活性ガス雰囲気中
で行なうことが好ましい。The polymerization operation is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon.
例えば、前記のビストリメチルシリルジクロルシランを
原料にして重合した場合、以下の反−番 一
応により本発明の目的とするケイ素置換ポリシラン及び
環状化合物（Ｉｌｌ）が生成する。For example, when the above-mentioned bistrimethylsilyldichlorosilane is used as a raw material for polymerization, the silicon-substituted polysilane and the cyclic compound (Ill) targeted by the present invention are produced by the following reaction.
（１） （［）
重合反応終了後は、ｎ−へキサンのような環状化合物（
ＩＩＩ）の貧溶媒に注ぎ、溶媒の一部を留去して、上記
式（Ｕ）のび員環化合物を析出させ、口過分離後、残り
の溶媒を留去して目的とするシリル置換ポリシラン（１
）を得る。あるいは、ｌ員環化合物を析出させ１口過分
離後、口液をメタノール中に注ぎ、シリル置換ポリシラ
ン（Ｉ）を沈殿させて得ることも出来る。(1) ([) After the polymerization reaction is completed, a cyclic compound such as n-hexane (
III), and part of the solvent is distilled off to precipitate the long-membered ring compound of the above formula (U). After separation, the remaining solvent is distilled off to obtain the desired silyl-substituted polysilane. (1
). Alternatively, the l-membered ring compound can be precipitated and separated in one mouth, followed by pouring the mouth liquid into methanol to precipitate the silyl-substituted polysilane (I).
このようにして、数平均分子量２００〜λｏ、ｏｏｏ穆
度の本発明のシリル置換ポリシランを得ることができる
。In this way, the silyl-substituted polysilane of the present invention having a number average molecular weight of 200 to λo and a degree of smoothness of ooo can be obtained.
次に本発明を実施例により更に具体的に説明するが１本
発明はその要旨を越えない限り、以下の実施例に限定さ
れるものではない。Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
参考例１
会構塩化水素ガス導入管、かくはん機、還流冷却器を備
えた／１三つロフラスコにビス（トリメチルシリル）ジ
フェニルシラン（ｒｔｉｙ。Reference Example 1 Bis(trimethylsilyl)diphenylsilane (rtiy) was placed in a three-hole flask equipped with a hydrogen chloride gas inlet tube, a stirrer, and a reflux condenser.
０、／ ７ ｍｏｌ ） 、塩化アルミニウム（ｔ、２
ｆ。0,/7 mol), aluminum chloride (t, 2
f.
０．０４ｔ ｊ ｍｏｌ ）、ベンゼｙ （Ｊ’ ００
ｍｌ ）を仕込み、これに室温にて７時間塩化水素を
通じた。0.04t j mol), benzene y (J' 00
ml) and hydrogen chloride was passed through it at room temperature for 7 hours.
次いで反応混合物にヘキサンをｊｏｏｍ加え、塩化アル
ミニウムを析出させｆ別した。アセトンｌ−を加え、Ｆ
液を蒸留し収量３３ｆ（収率ｒθ％）で目的物を得た。Next, hexane was added to the reaction mixture, and aluminum chloride was precipitated and separated. Add acetone l-, F
The liquid was distilled to obtain the desired product in a yield of 33f (yield rθ%).
生成物の物性は次の通りである。ｂｐ ４ ｊ ℃／！
ｍｍＨｇ ０、ＨＮＭＲ（００１４）δ：０．２７
ｐｐｍ（ｓ、ＢｉＭｅ）ＩＲ（ｎｅａｔ）； ／、２
ｔＯ（ｓ）（ＳｉＭｅ）、／Ｊ４’ｊｍ ’（ｖｓ）
（ＳｉＭｅ）
ｎ普０／、４！１００（文献値ｎ、 ／、４＃００）
参考例コ
合成
ｉｔ三ツロフラスコにビス（トリメチルシリル）ジフェ
ニルシラン（ｔｏｘｙ、０，３λｍｏｌ）。The physical properties of the product are as follows. bp 4 j ℃/!
mmHg 0, HNMR (0014) δ: 0.27
ppm(s, BiMe)IR(neat); /, 2
tO(s) (SiMe), /J4'jm' (vs)
(SiMe) nP0/, 4!100 (Literature value n, /, 4#00)
Reference Example Co-synthesis: Bis(trimethylsilyl)diphenylsilane (toxy, 0.3λmol) was placed in a three-way flask.
臭化アルミニウム（ＩＩ、Ｏｒ、 ０．０ ／ ｊ ｍ
ｏｌ ）、ベンゼン（／ｌ）を入れ、かくはんしながら
、室温にてこれに臭化水素を４時間通じた。次いで反応
混合物に１１のヘキサンを加え ｆ−１過し、析出した
アルミニウム塩を除いた。アセトン／ｍｌを加えＦ液を
蒸留して収量ｒ、ｒｙ （収率７り％）で目的物を得た
。その物性は以下の通りであった。ｂｐ １００℃／Ｉ
ＩｔｒｎｒｎＨｇｌ ＨＮＭＲ（００１４）δ；θ、Ｊ
Ｏｐｐｍ （ｓ、ＳｉＭｅ）ＩＲ（ｎｅａｔ）； ／λ
６０（ｓ）（ＳｉＭｅ）μ２弘ｊ（ｖｓ）（ＳｉＭｅ）
、ｆｆ４’、２＞ ’（ｖｓ）元素分析値 ０＠Ｈ４
＠Ｂｒ１Ｓｉ３として−グ −
実施例１
かくはん機、滴下漏斗、還流冷却器を備えた／１三つロ
フラスコにナトリウム（’ｙ、ｔ ｙ ｒｏ、３４ｔｍ
ｏｌ ） とトルエ：ｙ （３ｊ ０ｗ１）を入れ、
Ｉ１０’Ｃまで加熱した。これにビス（トリメチルシリ
ル）ジブｃ１そシラ７（！０．Ｏｆ、０．／！ｍ０１）
のトルエン（１００ｗｌ）溶液を１時間かけて、かくは
んしながら滴下した。反応混合物を２時間加熱還流後冷
却し、ヘキサン（１００荒ｅ）を加え析出した塩をＰ別
した。エタノール（／ ｒｒｔｌ ）を加えてから溶媒
の一部を留去し、析出したシクロテトラシランをｆ別し
た。更に溶媒を留去しポリ（ビストリメチルシリルシリ
レン）を得た。収量／コｆ（収率Ｊ４ｔ％）で、その物
性値は以下の通りであった。Aluminum bromide (II, Or, 0.0/j m
ol) and benzene (/l) were added thereto, and hydrogen bromide was passed therein for 4 hours at room temperature while stirring. Next, 11 hexane was added to the reaction mixture, and the mixture was filtered f-1 to remove the precipitated aluminum salt. Acetone/ml was added and solution F was distilled to obtain the desired product in yields r and ry (yield 7%). Its physical properties were as follows. bp 100℃/I
ItrnrnHgl HNMR (0014) δ; θ, J
Oppm (s, SiMe)IR(neat); /λ
60 (s) (SiMe) μ2 Hiroj (vs) (SiMe)
, ff4', 2>' (vs) elemental analysis value 0@H4
As @Br1Si3 - Example 1 Sodium ('y, tyro, 34tm
ol) and Torue:y (3j 0w1),
Heated to I10'C. To this, bis(trimethylsilyl) dib c1 sosila 7 (!0.Of, 0./!m01)
A toluene (100 wl) solution of was added dropwise over 1 hour while stirring. The reaction mixture was heated under reflux for 2 hours, then cooled, and hexane (100 ml) was added to separate the precipitated salt. After adding ethanol (/rrtl), a portion of the solvent was distilled off, and the precipitated cyclotetrasilane was separated. Further, the solvent was distilled off to obtain poly(bistrimethylsilylsilylene). The physical property values in terms of yield/cof (yield J4t%) were as follows.
Ｉ Ｒ（ｎｅａｔ） ；コタ！０（ｖｅ）、 、２ｒｒ
Ｏ（ｖｅ）’ ＨＮＭＲ（ＯＯ’１４）δ； Ｏ，／
ｌ（ｓ、ＪＨ，ＳｉＭｅ）０．２ｊｐｐｍ（ｍ、ｔＬｔ
、ｔＨ，ＳｉＭｅ）数平均分子量 ７００
実施例コ
かくはん機１滴下漏斗、還流冷却器を備えた１００Ｗ１
１三つロフラスコにナトリウム（／、３９゜！ ｊ ｍ
ｍｏｌ ） と） ルエン（Ｊ Ｏｗｌ ）を入れ。I R (neat) ; Kota! 0(ve), ,2rr
O(ve)'HNMR(OO'14)δ; O,/
l(s, JH, SiMe) 0.2jppm(m, tLt
, tH, SiMe) Number average molecular weight 700 Example co-stirrer 1 dropping funnel, 100W1 with reflux condenser
Sodium (/, 39°! j m
mol) and) luene (J Owl).
ｉｉｏ″Ｃｔで加熱した。こ、れに、ビス（トリメチル
シリル）ジクロロシラン（６，６９、λ７ｍｍｏｌ ）
のトルエン（ｔｏｔａｌ）溶液をかくけんしながら
１時間かけて滴下した。反応混合物を２３時間加熱還流
させて冷却した。ヘキサン（２００，１）を加え、生成
した塩を析出させｒ別した。エタノール１ｗ、ｌを加え
た後、Ｐ液を水洗し、無水硫酸マグネシウムで乾燥した
。溶媒の一部を留去し析出したオクタキス（トリメチル
シリル）シクロテトラシランをｆ別技、溶媒を留去し、
ポリ（ビストリメチルシリルシリレン）を得た。収量０
．ｊ ／ ｆ （収率／／％）〔発明の効果〕
本発明のシリル置換ポリシランは主鎖ポリシランのケイ
素に直接ケイ素原子が置換しており、従来のケイ素原子
に直接炭素原子が置換したポリシランに比し電子的、立
体的特性の異なる新しい性質のポリシランとして期待さ
れる。Heated at iio''Ct. To this, bis(trimethylsilyl)dichlorosilane (6,69, λ7 mmol)
A toluene (total) solution of was added dropwise over 1 hour with stirring. The reaction mixture was heated to reflux for 23 hours and cooled. Hexane (200,1) was added, and the resulting salt was precipitated and separated. After adding 1 w, 1 of ethanol, the P solution was washed with water and dried over anhydrous magnesium sulfate. Part of the solvent was distilled off, and the precipitated octakis(trimethylsilyl)cyclotetrasilane was separated by a separate technique, and the solvent was distilled off.
Poly(bistrimethylsilylsilylene) was obtained. Yield 0
．． j/f (yield//%) [Effect of the invention] The silyl-substituted polysilane of the present invention has a silicon atom directly substituted on the silicon of the main chain polysilane, and is different from the conventional polysilane in which a silicon atom is directly substituted with a carbon atom. It is expected to be a polysilane with new properties with different electronic and steric properties.
Claims (1)
一でも異つてもよい） で示される繰返し単位からなり、線状で数平均分子量２
００〜２０，０００のシクル置換ポリシラン。(1) From the repeating unit represented by the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 to R^6 represent lower alkyl groups and may be the same or different.) It is linear and has a number average molecular weight of 2.
00-20,000 cycle substituted polysilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18453386A JPH0676495B2 (en) | 1986-08-06 | 1986-08-06 | Silyl-substituted polysilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18453386A JPH0676495B2 (en) | 1986-08-06 | 1986-08-06 | Silyl-substituted polysilane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6341534A true JPS6341534A (en) | 1988-02-22 |
| JPH0676495B2 JPH0676495B2 (en) | 1994-09-28 |
Family
ID=16154863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18453386A Expired - Lifetime JPH0676495B2 (en) | 1986-08-06 | 1986-08-06 | Silyl-substituted polysilane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0676495B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039593A (en) * | 1986-10-31 | 1991-08-13 | Zeigler John K | Poly(silyl silane) homo and copolymers |
| JP2007106894A (en) * | 2005-10-13 | 2007-04-26 | Nippon Soda Co Ltd | Method for producing polysilane |
-
1986
- 1986-08-06 JP JP18453386A patent/JPH0676495B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039593A (en) * | 1986-10-31 | 1991-08-13 | Zeigler John K | Poly(silyl silane) homo and copolymers |
| JP2007106894A (en) * | 2005-10-13 | 2007-04-26 | Nippon Soda Co Ltd | Method for producing polysilane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0676495B2 (en) | 1994-09-28 |
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