JP2005023006A - Cyclic organosilicon compound and method for producing the same - Google Patents
Cyclic organosilicon compound and method for producing the same Download PDFInfo
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- JP2005023006A JP2005023006A JP2003189050A JP2003189050A JP2005023006A JP 2005023006 A JP2005023006 A JP 2005023006A JP 2003189050 A JP2003189050 A JP 2003189050A JP 2003189050 A JP2003189050 A JP 2003189050A JP 2005023006 A JP2005023006 A JP 2005023006A
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- -1 Cyclic organosilicon compound Chemical class 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- YEDDVXZFXSHDIB-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoropropan-1-ol Chemical group OC(F)(F)C(F)(F)C(F)F YEDDVXZFXSHDIB-UHFFFAOYSA-N 0.000 abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 6
- 125000004122 cyclic group Chemical group 0.000 abstract description 5
- 125000005370 alkoxysilyl group Chemical group 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- QYCGBAJADAGLLK-UHFFFAOYSA-N 1-(cyclohepten-1-yl)cycloheptene Chemical group C1CCCCC=C1C1=CCCCCC1 QYCGBAJADAGLLK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 0 O[S+](*(CC(C1)C2)CC1C2C1)OC1(C(F)(F)F)C(F)(F)F Chemical compound O[S+](*(CC(C1)C2)CC1C2C1)OC1(C(F)(F)F)C(F)(F)F 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 125000005371 silicon functional group Chemical group 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、ヘキサフルオロプロパノ−ル基が分子内でシリル化保護された、新規な環状有機ケイ素化合物及びその製造方法に関する。
本発明の化合物は、アルカリ可溶性ケイ素系樹脂組成物に利用されるケイ素系モノマーの主剤として有用である。
【０００２】
【従来の技術】
ヘキサフルオロプロパノ−ル基を有するアルコキシシランとして、例えば、下記有機ケイ素化合物（５）は公知である（特許文献１）。
【０００３】
【化５】
【０００４】
【特許文献１】
特開２００２−１２８７８８号公報
【特許文献２】
特開２００２−３０８９９０号公報
【０００５】
【発明が解決しようとする課題】
本発明者らは、アルカリ可溶性のポリシルセスキオキサンを、効率よく安全に製造できるような新規な有機ケイ素化合物に関して鋭意検討した結果、ヘキサフルオロプロパノ−ル基が分子内でシリル化保護された、環状アルコキシシラン化合物が有用であることに着目した。
本発明は、ヘキサフルオロプロパノ−ル基の水素原子が同一分子内のアルコキシシリル基で置換されている環状アルコキシシラン化合物及びその工業的製造方法を提供するものである。
【０００６】
【課題を解決するための手段】
本発明の化合物は、下記一般式（１）で表される環状有機ケイ素化合物であり、ヘキサフルオロプロパノ−ル基の水素原子が同一分子内のアルコキシシリル基で置換されている環状アルコキシシラン化合物（以下、本発明ケイ素系化合物）である。
【０００７】
【化６】
（式中、Ｒ１およびＲ２は炭素数１から４のアルキル基を示す。Ｓｉ原子はビシクロ［２．２．１］ヘプタン環の２−位又は３−位に結合している。）
【０００９】
以下、本発明について詳述する。
【００１０】
【発明の実施の形態】
本発明の化合物を表す上記一般式（１）において、Ｒ１およびＲ２は炭素数１から４のアルキル基であり、好ましい具体例として、メチル基、エチル基、プロピル基、ブチル基などがある。
本発明の化合物は、合成の容易なことおよび原料の入手のしやすさ、毒性の低さから、Ｒ１およびＲ２がエチル基である下記化合物（６）が最も好ましい。
【００１１】
【化７】
本発明の環状有機ケイ素化合物は、下記の反応［Ａ］及び反応［Ｂ］を行うことにより製造することができる。
反応［Ａ］：下記化合物（２）と下記トリアルコキシシラン（３）とを縮合反応させて、下記化合物（４）を得る。
【００１３】
【化８】
【化９】
（式中、Ｒ１、Ｒ２およびＲ３は炭素数１から４のアルキル基を示す。）
【００１６】
【化１０】
反応［Ｂ］：ハイドロシリレーション反応触媒の存在下で、上記化合物（４）を分子内ハイドロシリレーション反応させて上記化合物（１）を得る。
【００１８】
反応［Ａ］において、化合物（２）とトリアルコキシシラン（３）との反応仕込み割合の好ましい範囲は、化合物（２）の１モル当たり、トリアルコキシシラン（３）の１〜１０モルである。
反応［Ａ］は、特に触媒を必要としない反応であるが、塩基を反応系に存在させると、ヘキサフルオロプロパノ−ルの水素を引き抜くことによって反応を促進することができる。
好ましい塩基として、水酸化カリウム、水酸化ナトリウム、水酸化リチウム、トリエチルアミン、ピリジン及びジイソプロピルエチルアミン等がある。
塩基の好ましい濃度は、化合物（２）の１モル当たり１〜４モルである。
反応［Ａ］の好ましい反応温度は、４０〜２００℃であり、より好ましくは１００〜１８０℃であり、好ましい反応時間は１〜５０時間である。
【００１９】
反応［Ｂ］では、末端Ｓｉ−Ｈとビシクロヘプテン環における末端オレフィンによる分子内ハイドロシリレーションにより、目的化合物（１）が生成する。
【００２０】
ハイドロシリレーションの好ましい触媒として、コバルト、ニッケル、ルテニウム、ロジウム、パラジウム、イリジウム、白金等の第８属から第１０属金属の単体、有機金属錯体、金属塩及び金属酸化物等があり、通常、白金系の触媒が使用される。好ましい白金系触媒としては、白金−ジビニルテトラメチルジシロキサン錯体、塩化白金酸六水和物（Ｈ２ＰｔＣｌ６・６Ｈ２Ｏ）、ｃｉｓ−ＰｔＣｌ２（ＰｈＣＮ）２、白金カーボン等がある。なお、Ｐｈはフェニル基を表わす。触媒の好ましい使用量は、化合物（４）の量に対して、０．１ｐｐｍ〜１０，０００ｐｐｍである。
【００２１】
反応［Ｂ］の好ましい反応温度は、６０〜２００℃であり、好ましい反応時間は１〜５０時間である。反応温度が６０℃未満ではヒドロシリレーション反応が円滑に継続されず、２００℃を超えると、暴走反応が引き起こされる恐れがある。
【００２２】
ハイドロシリレーション反応触媒が存在しない系では、ハイドロシリレーションは進行しないため、ハイドロシリレーション反応触媒を存在させないで反応［Ａ］を行い、化合物（２）とトリアルコキシシラン（３）から選択的に化合物（４）を生成させることができる。反応［Ａ］の生成物である化合物（４）を単離して、反応［Ｂ］により分子内ハイドロシリレーションを行って、目的物（１）を得ることもできるし、また反応［Ａ］の生成物である化合物（４）を単離せず、そのまま反応［Ｂ］により、目的物（１）を得ることもできる。
【００２３】
反応［Ａ］と反応［Ｂ］により得られた本発明の化合物（１）は、通常、減圧蒸留によって単離される。減圧蒸留の際に、ニトロソアミン系又はハイドロキノン系等の重合禁止剤を用いると化合物（１）の収率を高める効果がある。
【００２４】
【発明の効果】
本発明によって、ヘキサフルオロプロパノ−ル基の水素原子が同一分子内のアルコキシシリル基で置換されている、新規な環状アルコキシシラン化合物が提供される。
本発明の化合物は、ケイ素官能基及びシリル基で保護された炭素官能基を有するので、ケイ素官能性及び保護された炭素官能性をもつ複反応性ケイ素化合物として機能する。
即ち、本発明の化合物は、ケイ素原子に結合した加水分解性のアルコキシ基が存在するため、他の有機ケイ素化合物（ポリマーを含む）との反応によりシロキサン結合を形成したり、それ自身でポリシロキサンやポリシルセスキオキサン化合物となる。また、本発明の化合物は、無機化合物中のシラノール基とカップリング反応させることができる。
また、ヘキサフルオロプロパノ−ル基の水素原子と置換しているシリル基は、酸性ないしアルカリ性の条件下で加水分解により容易に脱離させることができ、その結果フリーのヘキサフルオロプロパノ−ル基が発現し、炭素官能性基またはアルカリ水溶性基として機能する。従って、本発明の化合物から得られるポリシルセスキオキサンは、アルカリ可溶性である。
本発明のケイ素系化合物は、そのため、有機合成の中間原料、ポリマー樹脂の合成原料、ポリマーの改質剤、無機化合物の表面処理剤、各種材料のカップリング剤として有用である。
【００２５】
【実施例】
以下、本発明を参考例および実施例によって具体的に説明する。
【００２６】
実施例１
攪拌機、温度計及び冷却管を備えた反応器を乾燥窒素雰囲気下にして、化合物（２）２５．０ｇ（９１ ｍｍｏｌ）、トリエトキシシラン６４．０ｇ （３９０ ｍｍｏｌ）を仕込み、系内を攪拌させながらオイルバスで１５０℃に加熱した。加熱攪拌を３時間行った。内温度が１４０℃以上であることを確認し、塩化白金酸六水和物（０．２ Ｍ イソプロパノ−ル溶液）０．２ｍＬ加えた。５時間、１５０℃で攪拌放置した。その後、減圧精留によって、沸点８０〜８５℃／１３３Ｐａで無色透明の液体３０．５ｇを得た。収率は理論量に対して８５％であった。
この液体について、１Ｈ−ＮＭＲの測定を行ったところ、第１図のスペクトルを得た。化合物（２）におけるノルボルネンのオレフィンプロトン（６．０ ｐｐｍ）が消失し、ハイドロシリレーション反応が進行したことを確認した。δ値とその帰属は第１表のとおりであった。また、マススペクトル（ＥＩ、ＣＩ）によれば、それぞれ３９２（Ｍ＋， ＥＩ）、３９３（Ｍ ＋ Ｈ＋， ＣＩ）の親ピークが観測された。これらの分析結果により、得られた液体は、ヘキサフルオロプロパノ−ル基の水素原子が同一分子内のシリル基で置換されている環状アルコキシシランである化合物（６）であることが確認できた。
【００２７】
【化１１】
【表１】
【化１２】
実施例２
攪拌機、温度計及び冷却管を備えた反応器を乾燥窒素雰囲気下にして、化合物（２）２５．０ｇ（９１ ｍｍｏｌ）、トリエトキシシラン６４．０ｇ （３９０ ｍｍｏｌ）、重合禁止剤（Ｎ−ニトロソフェニルヒドロキシアミン アルミニウム塩）２５ ｍｇを仕込み、系内を攪拌させながらオイルバスで１５０℃に加熱した。加熱攪拌を３時間行った。内温度が１４０℃以上であることを確認し、塩化白金酸六水和物（０．２ Ｍ イソプロパノ−ル溶液）０．２ｍＬ加えた。５時間、１５０℃で攪拌放置した。その後、減圧精留によって、沸点８０〜８５℃／１３３Ｐａで無色透明の液体３２．０ｇを得た。収率は理論量に対して８９％であった。
【図面の簡単な説明】
【図１】第１図は、実施例１で得られた生成物の１Ｈ−ＮＭＲスペクトルを示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel cyclic organosilicon compound in which a hexafluoropropanol group is protected by silylation in the molecule and a method for producing the same.
The compound of the present invention is useful as a main component of a silicon monomer used in an alkali-soluble silicon resin composition.
[0002]
[Prior art]
As an alkoxysilane having a hexafluoropropanol group, for example, the following organosilicon compound (5) is known (Patent Document 1).
[0003]
[Chemical formula 5]
[0004]
[Patent Document 1]
JP 2002-128788 A [Patent Document 2]
Japanese Patent Laid-Open No. 2002-308990
[Problems to be solved by the invention]
As a result of intensive studies on a novel organosilicon compound capable of efficiently and safely producing an alkali-soluble polysilsesquioxane, the present inventors found that the hexafluoropropanol group was silylated and protected in the molecule. In addition, it was noted that cyclic alkoxysilane compounds are useful.
The present invention provides a cyclic alkoxysilane compound in which a hydrogen atom of a hexafluoropropanol group is substituted with an alkoxysilyl group in the same molecule, and an industrial production method thereof.
[0006]
[Means for Solving the Problems]
The compound of the present invention is a cyclic organosilicon compound represented by the following general formula (1), wherein a hydrogen atom of a hexafluoropropanol group is substituted with an alkoxysilyl group in the same molecule (Hereinafter, the silicon-based compound of the present invention).
[0007]
[Chemical 6]
(In the formula, R 1 and R 2 represent an alkyl group having 1 to 4 carbon atoms. The Si atom is bonded to the 2-position or 3-position of the bicyclo [2.2.1] heptane ring.)
[0009]
Hereinafter, the present invention will be described in detail.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the above general formula (1) representing the compound of the present invention, R 1 and R 2 are alkyl groups having 1 to 4 carbon atoms, and preferred specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. .
The compound of the present invention is most preferably the following compound (6) in which R 1 and R 2 are ethyl groups because of easy synthesis, availability of raw materials, and low toxicity.
[0011]
[Chemical 7]
The cyclic organosilicon compound of the present invention can be produced by performing the following reaction [A] and reaction [B].
Reaction [A]: The following compound (2) and the following trialkoxysilane (3) are subjected to a condensation reaction to obtain the following compound (4).
[0013]
[Chemical 8]
[Chemical 9]
(In the formula, R 1 , R 2 and R 3 represent an alkyl group having 1 to 4 carbon atoms.)
[0016]
Embedded image
Reaction [B]: In the presence of a hydrosilylation reaction catalyst, the compound (4) is subjected to an intramolecular hydrosilylation reaction to obtain the compound (1).
[0018]
In reaction [A], the preferable range of the reaction charge ratio of compound (2) and trialkoxysilane (3) is 1 to 10 moles of trialkoxysilane (3) per mole of compound (2).
The reaction [A] is a reaction that does not particularly require a catalyst. However, when a base is present in the reaction system, the reaction can be promoted by extracting hydrogen of hexafluoropropanol.
Preferred bases include potassium hydroxide, sodium hydroxide, lithium hydroxide, triethylamine, pyridine and diisopropylethylamine.
A preferred concentration of the base is 1 to 4 moles per mole of the compound (2).
The preferable reaction temperature of the reaction [A] is 40 to 200 ° C, more preferably 100 to 180 ° C, and the preferable reaction time is 1 to 50 hours.
[0019]
In the reaction [B], the target compound (1) is produced by intramolecular hydrosilylation with the terminal Si—H and the terminal olefin in the bicycloheptene ring.
[0020]
Preferred catalysts for hydrosilylation include simple substances of
[0021]
A preferable reaction temperature for the reaction [B] is 60 to 200 ° C., and a preferable reaction time is 1 to 50 hours. If the reaction temperature is less than 60 ° C, the hydrosilylation reaction does not continue smoothly. If the reaction temperature exceeds 200 ° C, a runaway reaction may occur.
[0022]
In a system in which no hydrosilylation reaction catalyst is present, hydrosilylation does not proceed. Therefore, reaction [A] is carried out without the presence of the hydrosilylation reaction catalyst, and the compound (2) and trialkoxysilane (3) are selectively used. Compound (4) can be produced. Compound (4), which is a product of reaction [A], is isolated and subjected to intramolecular hydrosilylation by reaction [B] to obtain target product (1). The target compound (1) can also be obtained by reaction [B] without isolating the product compound (4).
[0023]
The compound (1) of the present invention obtained by the reaction [A] and the reaction [B] is usually isolated by distillation under reduced pressure. When a polymerization inhibitor such as nitrosamine or hydroquinone is used during distillation under reduced pressure, there is an effect of increasing the yield of compound (1).
[0024]
【The invention's effect】
The present invention provides a novel cyclic alkoxysilane compound in which a hydrogen atom of a hexafluoropropanol group is substituted with an alkoxysilyl group in the same molecule.
Since the compound of the present invention has a silicon functional group and a carbon functional group protected with a silyl group, it functions as a double-reactive silicon compound having silicon functionality and protected carbon functionality.
That is, since the compound of the present invention has a hydrolyzable alkoxy group bonded to a silicon atom, a siloxane bond is formed by reaction with another organosilicon compound (including a polymer), or a polysiloxane itself. Or a polysilsesquioxane compound. Moreover, the compound of this invention can be made to carry out a coupling reaction with the silanol group in an inorganic compound.
Further, the silyl group substituted with the hydrogen atom of the hexafluoropropanol group can be easily removed by hydrolysis under acidic or alkaline conditions, and as a result, free hexafluoropropanol can be removed. The group is expressed and functions as a carbon functional group or an alkali water-soluble group. Therefore, the polysilsesquioxane obtained from the compound of the present invention is alkali-soluble.
Therefore, the silicon-based compound of the present invention is useful as an organic raw material for organic synthesis, a synthetic raw material for polymer resin, a polymer modifier, a surface treatment agent for inorganic compounds, and a coupling agent for various materials.
[0025]
【Example】
Hereinafter, the present invention will be specifically described with reference examples and examples.
[0026]
Example 1
A reactor equipped with a stirrer, a thermometer and a condenser tube was placed in a dry nitrogen atmosphere, and 25.0 g (91 mmol) of compound (2) and 64.0 g (390 mmol) of triethoxysilane were charged, and the system was stirred. The mixture was heated to 150 ° C. in an oil bath. Heating and stirring were performed for 3 hours. After confirming that the internal temperature was 140 ° C. or higher, 0.2 mL of chloroplatinic acid hexahydrate (0.2 M isopropanol solution) was added. The mixture was left stirring at 150 ° C. for 5 hours. Thereafter, 30.5 g of a colorless and transparent liquid having a boiling point of 80 to 85 ° C./133 Pa was obtained by vacuum rectification. The yield was 85% based on the theoretical amount.
When 1 H-NMR measurement was performed on this liquid, the spectrum of FIG. 1 was obtained. It was confirmed that the norbornene olefinic proton (6.0 ppm) in compound (2) disappeared and the hydrosilylation reaction proceeded. The δ value and its attribution are shown in Table 1. Further, according to mass spectra (EI, CI), parent peaks of 392 (M + , EI) and 393 (M + H + , CI) were observed, respectively. From these analysis results, it was confirmed that the obtained liquid was a compound (6) which is a cyclic alkoxysilane in which a hydrogen atom of a hexafluoropropanol group is substituted with a silyl group in the same molecule. .
[0027]
Embedded image
[Table 1]
Embedded image
Example 2
A reactor equipped with a stirrer, a thermometer and a condenser was placed in a dry nitrogen atmosphere, and 25.0 g (91 mmol) of compound (2), 64.0 g (390 mmol) of triethoxysilane, a polymerization inhibitor (N-nitroso) Phenylhydroxyamine aluminum salt) 25 mg was charged and heated to 150 ° C. in an oil bath while stirring the system. Heating and stirring were performed for 3 hours. After confirming that the internal temperature was 140 ° C. or higher, 0.2 mL of chloroplatinic acid hexahydrate (0.2 M isopropanol solution) was added. The mixture was left stirring at 150 ° C. for 5 hours. Thereafter, 32.0 g of a colorless transparent liquid having a boiling point of 80 to 85 ° C./133 Pa was obtained by vacuum rectification. The yield was 89% based on the theoretical amount.
[Brief description of the drawings]
FIG. 1 shows the 1 H-NMR spectrum of the product obtained in Example 1. FIG.
Claims (2)
反応［Ａ］：下記化合物（２）と下記トリアルコキシシラン（３）とを縮合反応させて、下記化合物（４）を得る。
Reaction [A]: The following compound (2) and the following trialkoxysilane (3) are subjected to a condensation reaction to obtain the following compound (4).
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