JP3882682B2 - Polycarbosilane, method for producing the same, and organosilicon compound - Google Patents
Polycarbosilane, method for producing the same, and organosilicon compound Download PDFInfo
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- JP3882682B2 JP3882682B2 JP2002151607A JP2002151607A JP3882682B2 JP 3882682 B2 JP3882682 B2 JP 3882682B2 JP 2002151607 A JP2002151607 A JP 2002151607A JP 2002151607 A JP2002151607 A JP 2002151607A JP 3882682 B2 JP3882682 B2 JP 3882682B2
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- saturated hydrocarbon
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- 229920003257 polycarbosilane Polymers 0.000 title claims description 31
- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000001931 aliphatic group Chemical group 0.000 claims description 23
- 125000002723 alicyclic group Chemical group 0.000 claims description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 12
- 150000002430 hydrocarbons Chemical group 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 17
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 239000003513 alkali Substances 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-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
- 239000002253 acid Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DLGZGLKSNRKLSM-UHFFFAOYSA-N (4-bromophenoxy)-tert-butyl-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)OC1=CC=C(Br)C=C1 DLGZGLKSNRKLSM-UHFFFAOYSA-N 0.000 description 1
- JWKKXHBGWAQZOK-UHFFFAOYSA-N 1-chloro-1-methylsiletane Chemical compound C[Si]1(Cl)CCC1 JWKKXHBGWAQZOK-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 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
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 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
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003779 heat-resistant material 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
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 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
- 238000000034 method Methods 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、保護されたフェノール性水酸基を有するフェニル基がＳｉに結合した新規なポリカルボシラン及びその製造方法、並びに有機ケイ素化合物に関する。
【０００２】
【従来の技術】
高分子主鎖がケイ素と炭素から構成されるポリカルボシランは、種々のものが知られている。ポリカルボシランは、優れた耐熱性、耐分解性を示すため、セラミック材料の前駆体、種々の耐熱性材料として利用されてきた[Chem. Rev. 95, 1443 (1995)]。最近、プラズマ耐性を有するポリカルボシラン[特開平10-150036]及び低誘電性を有する[特開2001-345317]ポリカルボシランにも注目が集められている。
シラシクロブタンの開環重合は、繰り返し単位が制御され、かつ化学構造が明確なポリカルボシランを与えるため、ポリカルボシランの有効な製造手段であり[J. Am. Chem. soc., 117, 8873 (1995)]、種々のポリカルボシランが製造されてきた。
【０００３】
しかし、有機置換基により保護されたフェノール性水酸基を有するフェニル基がＳｉに結合したシラシクロブタンの開環重合により得られるポリカルボシランは知られていない。
【０００４】
【発明が解決しようとする課題】
本発明は、シラシクロブタンの開環重合を利用することにより、有機置換基により保護されたフェノール性水酸基を有するフェニル基がＳｉに結合した新規なポリカルボシラン及びその製造方法を提供するものである。
【０００５】
【課題を解決するための手段】
本発明者は、上記課題を解決するために鋭意検討した結果、特定の有機ケイ素化合物を出発物質として重合することにより、目的とするポリカルボシランを得ることができ、本発明を完成するに至った。
【０００６】
即ち、本発明は、下記一般式［１］で表される繰り返し単位を有するポリカルボシラン及び下記一般式［２］で表される有機ケイ素化合物を重合することを特徴とする上記ポリカルボシランの製造方法である。
【０００８】
【化５】
（式中、Ｒ１、Ｒ２、Ｒ３およびＲ４は、炭素数１から６の一価の有機基であり、脂肪族飽和炭化水素基、脂環族飽和炭化水素基または芳香族炭化水素基であり、Ｒ２〜Ｒ４のうち少なくともひとつは第三級炭素原子を有する脂肪族飽和炭化水素基、炭素数４以上の脂環族飽和炭化水素基又はフェニル基である。）
【００１０】
【発明の実施の形態】
以下、本発明について詳述する。
(1).〔ポリマーの構造〕
本発明のポリカルボシランは下記一般式［１］の繰り返し単位を有するものである。
【００１１】
【化６】
【００１２】
上記Ｒ1、Ｒ2、Ｒ3およびＲ4は、炭素数１から６の、脂肪族飽和炭化水素基、脂環族飽和炭化水素基または芳香族炭化水素基であり、脂肪族飽和炭化水素基は、直鎖状、分岐状の何れでもよい。
好ましいものとして、メチル基、エチル基、プロピル基、ブチル基、ｔert−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基及びフェニル基等がある。
【００１３】
上記Ｒ２〜Ｒ４のうち少なくともひとつは第三級炭素原子を有する脂肪族飽和炭化水素基、炭素数４以上の脂環族飽和炭化水素基又はフェニル基である。もしも、上記Ｒ２〜Ｒ４のうちひとつも第三級炭素原子を有する脂肪族飽和炭化水素基、炭素数４以上の脂環族飽和炭化水素基又はフェニル基でない場合、フェノール性水酸基の保護が不十分になり、ポリマーの安定性が低下し、その結果、本発明のポリカルボシランが有するアルカリ可溶性等の固有の効果を発揮することができなくなる。
【００１４】
原料が得易く、合成が容易なことから、一般にＲ1〜Ｒ3についてはメチル基、Ｒ4についてはtert-ブチル基が好ましい。
【００１５】
有機基で保護されたフェノール性水酸基は、Ｓｉとフェニル基との結合に対して、オルト位、メタ位及びパラ位の何れの位置にあっても良い。
【００１６】
本発明のポリカルボシランは、有機置換基で保護されたフェノール性水酸基による炭素官能性基としての機能やアルカリ可溶性等の固有の機能を損なわない範囲で他の単量体との共重合体であっても良いが、好ましい重合体は、実質的に上記一般式［１］の繰り返し単位からなるものである。
【００１７】
本発明のポリカルボシランは、後述する特定の有機ケイ素化合物を出発物質とすることにより、数平均分子量３,０００〜３００,０００の重合体を容易に得ることができる。
【００１８】
(2).〔ポリマーの製造方法〕
(2)-1.〔モノマーの構造〕
本発明のポリカルボシランを得るには下記一般式［２］で表される有機ケイ素化合物（以下、有機ケイ素化合物［２］と略す）を出発物質として用いることが必要である。
【００１９】
【化７】
（式中、Ｒ１、Ｒ２、Ｒ３およびＲ４は、炭素数１から６の一価の有機基であり、脂肪族飽和炭化水素基、脂環族飽和炭化水素基または芳香族炭化水素基であり、Ｒ２〜Ｒ４のうち少なくともひとつは第三級炭素原子を有する脂肪族飽和炭化水素基、炭素数４以上の脂環族飽和炭化水素基又はフェニル基である。）
【００２１】
上記Ｒ1、Ｒ2、Ｒ3およびＲ4は、炭素数１から６の、脂肪族飽和炭化水素基、脂環族飽和炭化水素基または芳香族炭化水素基であり、脂肪族飽和炭化水素基は、直鎖状、分岐状の何れでもよい。
好ましいものとして、メチル基、エチル基、プロピル基、ブチル基、ｔert−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基及びフェニル基等がある。
【００２２】
Ｒ２〜Ｒ４のうち少なくともひとつは第三級炭素原子を有する脂肪族飽和炭化水素基、炭素数４以上の脂環族飽和炭化水素基又はフェニル基である。もしも、上記Ｒ２〜Ｒ４のうちひとつも第三級炭素原子を有する脂肪族飽和炭化水素基、炭素数４以上の脂環族飽和炭化水素基又はフェニル基でない場合、フェノール性水酸基の保護が不十分になり、保護基の脱離により生成したフェノール性水酸基が重合反応に関与する。その結果、開環重合以外の反応が同時に起こり、一定の構造を有するポリマーを生成しなくなり、本発明のポリカルボシランを得ることができなくなる。原料が得易く、合成が容易なことから、一般にＲ１〜Ｒ３についてはメチル基、Ｒ４についてはｔｅｒｔ−ブチル基が好ましい。好ましい出発物質は下記構造式［３］で表される有機ケイ素化合物である。
【００２３】
【化８】
（式中、Ｍｅはメチル基である。）
【００２５】
有機基で保護されたフェノール性水酸基は、Ｓｉとフェニル基との結合に対して、オルト位、メタ位及びパラ位の何れの位置にあっても良い。
【００２６】
(2)-2.〔モノマーの製造方法〕
上記式［２］で表される有機ケイ素化合物は、新規化合物であり、以下のようにして合成される。
即ち、一般式［４］で表される塩化物と一般式［５］で表される臭素化物とのグリニャール反応により、有機基置換基により保護されたフェノール性水酸基を有する有機ケイ素化合物［２］を得る。
【００２７】
【化９】
【００２８】
【化１０】
（式中、Ｒ２〜Ｒ４は、炭素数１から６の一価の有機基であり、脂肪族飽和炭化水素基、脂環族飽和炭化水素基または芳香族炭化水素基であり、少なくともひとつは第三級炭素原子を有する脂肪族飽和炭化水素基、炭素数４以上の脂環族飽和炭化水素基又はフェニル基である。）
【００３０】
反応に際して、まず、エチレンジブロミドによりマグネシウムを活性化させる。続けて、マグネシウムと一般式［５］で表される臭素化物からグリニャール試薬を調製し、続けて一般式［４］で表される塩化物とのカップリング反応を行う。
好ましい溶媒としては、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフランのようなエーテル類がある。
反応終了後、生成したマグネシウム塩をろ別し、溶媒および揮発成分を留去後、減圧蒸留により有機ケイ素化合物［２］を得る。
【００３１】
(2)-3.〔モノマーの開環重合〕
本発明のポリカルボシランは、有機ケイ素化合物［２］を開環重合させることにより得ることができる。
開環重合は、遷移金属触媒またはアニオン開始剤を用いることにより、容易に行うことができる。工業的な製造方法としては、原料が得易く、重合が容易なことから、遷移金属触媒による重合が好ましい。
【００３２】
(2)-3-1.〔遷移金属触媒による重合〕
反応系を窒素雰囲気下とし、溶媒の存在下又は非存在下で、有機ケイ素化合物［２］に触媒を加え攪拌させる。
好ましい触媒としては、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、金属酸化物等があり、通常、白金系の触媒を使用する。
好ましい白金系触媒としては、塩化白金酸六水和物（H2PtCl6・６H2O）、cis-PtCl2(PhCN)2、白金カーボン、ジビニルテトラメチルジシロキサンが配位した白金錯体(PtDVTMDS)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、有機ケイ素化合物［２］の仕込み量に対して、0.1ｐｐｍから1000ｐｐｍである。
好ましい溶媒としては、ヘキサン、トルエン、キシレン等の非極性溶媒がある。
好ましい反応温度は室温から120℃である。
【００３３】
(2)-3-2.〔アニオン開始剤による重合〕
反応系を窒素雰囲気下とし、有機ケイ素化合物［２］に溶媒、開始剤を加え攪拌させる。
好ましい開始剤としては、n-ブチルリチウム、メチルリチウム、sec-ブチルリチウム、フェニルリチウム等のアルキルリチウム、水酸化ナトリウム、水酸化カリウム、tert-ブトキシカリウム等の固体塩基等があり、通常アルキルリチウムが使用される。
好ましい溶媒としては、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフランのようなエーテル類、ヘキサン、トルエン、キシレン等の非極性溶媒がある。
好ましい反応温度は-78℃から120℃である。
【００３４】
(3).〔ポリマーの有用性〕
本発明のポリカルボシランは、有機置換基により保護されたフェノール性水酸基を有しており、フェノール性水酸基の保護基は、酸性条件下で加水分解により容易に脱離する。
保護基の脱離により生成したフェノール性水酸基は、炭素官能性基またはアルカリ水溶性基として機能する。
また、フェノール性水酸基は、極性官能基と強い水素結合を形成するので、水素結合を利用したポリカルボシランへの展開も図れる。
更にまた、フェノール性水酸基を反応点とし、種々の耐熱性を有する架橋性ポリカルボシランを合成することができる。
本発明のポリカルボシランは、樹脂の改質剤、耐熱性を有するアルカリ可溶性樹脂、樹脂への耐熱性付与剤、耐熱性反応剤、水素結合を利用した疑似架橋剤等への利用が可能である。
【００３５】
【実施例】
以下、本発明を実施例によって具体的に説明する。
【００３６】
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、反応器にマグネシウム2.0g（82.3 mmol）、THF 20mL、及び少量のエチレンジブロミドを仕込み、マグネシウムを活性化させた。
反応系に、THF 30mLに溶かした1-ブロモ-4-tert-ブチルジメチルシリルオキシベンゼン 15.0g (52.2 mmol)を徐々に滴下させ、グリニャール試薬を調製した。
滴下終了後、室温で１時間攪拌し、1-クロロ-1-メチルシラシクロブタン 6.9g (57.4mmol)をゆっくり滴下させ、室温で１時間攪拌した。
生成したマグネシウム塩をろ別し、溶媒を留去後、液体を減圧蒸留で精製した。
以上の操作により、沸点が110〜112℃(253Pa)である無色透明の液体9.4g(62 %)を得た。
この液体について270MHzの1Ｈ-ＮＭＲの測定を行い、第１図のスペクトルを得た。
第１表に示したδ値とその帰属から、得られた液体は、下記構造式［６］で表される有機ケイ素化合物（以下、有機ケイ素化合物［６］と略す）であることが確認された。
【００３７】
【化１１】
【表１】
【化１２】
実施例２
攪拌子を備えた反応器を乾燥窒素雰囲気下にして、反応器に実施例１で合成した有機ケイ素化合物［６］0.2g（0.68mmol）を仕込み、その後ジビニルテトラメチルジシロキサンが配位した白金錯体(PtDVTMDS)のキシレン溶液を有機ケイ素化合物［６］に対し、100ppm滴下した。
80℃、10分攪拌して反応させ、ゲル浸透クロマトグラフィー（GPC）により反応系においてモノマーが消失したこと（転化率100％）を確認し、無色透明の樹脂を得た。
この樹脂について270MHzの1Ｈ-ＮＭＲの測定を行い、第２図のスペクトルを得た。
第２表に示したδ値とその帰属から、得られた樹脂は、下記式［７］で表される繰り返し単位を有するポリカルボシランであることが確認された。
得られた樹脂の分子量（標準ポリスチレンを用いたＧＰＣによる換算分子量）は以下の通りであった。
Mn = 150000、Mw/Mn = 4.1
【００４１】
【化１３】
【表２】
【化１４】
実施例３
反応温度を８０℃から室温に変えた以外、実施例２と同一の条件で反応させた（反応10分後、転化率100%）。
得られた樹脂の分子量（標準ポリスチレンを用いたＧＰＣによる換算分子量）は以下の通りであった。
Mn = 93000、Mw/Mn = 3.1
【００４５】
実施例４
無溶媒反応をトルエン１mlを用いる溶液反応に変えた以外、実施例２と同一の条件で反応させた（反応10分後、転化率98%）。
得られた樹脂の分子量（標準ポリスチレンを用いたＧＰＣによる換算分子量）は以下の通りであった。
Mn = 240000、Mw/Mn = 4.2
【００４６】
実施例５
触媒を白金錯体(PtDVTMDS)から塩化白金酸六水和物（H2PtCl6・６H2O）に換えた以外、実施例２と同一の条件で反応させた（反応10分後、転化率81%）。
得られた樹脂の分子量（標準ポリスチレンを用いたＧＰＣによる換算分子量）は以下の通りであった。
Mn = 75000、Mw/Mn = 3.8
【００４７】
【発明の効果】
本発明によって、保護されたフェノール性水酸基を有するフェニル基がＳｉに結合した新規なポリカルボシランがを提供される。
本発明のポリカルボシランは、樹脂の改質剤、耐熱性を有するアルカリ可溶性樹脂、樹脂への耐熱性付与剤、耐熱性反応剤、水素結合を利用した疑似架橋剤等への利用が可能である。
本発明の製造方法により、保護されたフェノール性水酸基を有するフェニル基がＳｉに結合したポリカルボシランを効率よく製造することができ、数平均分子量３,０００〜３００,０００の範囲で分子量の制御も容易である。
【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。
【図２】第２図は実施例２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 polycarbosilane in which a phenyl group having a protected phenolic hydroxyl group is bonded to Si, a method for producing the same, and an organosilicon compound .
[0002]
[Prior art]
Various polycarbosilanes whose polymer main chain is composed of silicon and carbon are known. Polycarbosilane has been used as a precursor of ceramic materials and various heat resistant materials because it exhibits excellent heat resistance and decomposition resistance [Chem. Rev. 95, 1443 (1995)]. Recently, attention has been focused on polycarbosilane having plasma resistance [JP-A-10-150036] and polycarbosilane having low dielectric properties [JP-A-2001-345317].
Ring-opening polymerization of silacyclobutane is an effective means for producing polycarbosilane because it gives a polycarbosilane having a controlled repeating unit and a well-defined chemical structure [J. Am. Chem. Soc., 117, 8873]. (1995)], various polycarbosilanes have been produced.
[0003]
However, there is no known polycarbosilane obtained by ring-opening polymerization of silacyclobutane in which a phenyl group having a phenolic hydroxyl group protected by an organic substituent is bonded to Si.
[0004]
[Problems to be solved by the invention]
The present invention provides a novel polycarbosilane in which a phenyl group having a phenolic hydroxyl group protected by an organic substituent is bonded to Si by utilizing ring-opening polymerization of silacyclobutane and a method for producing the same. .
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor can obtain the desired polycarbosilane by polymerizing a specific organosilicon compound as a starting material, thereby completing the present invention. It was.
[0006]
That is, this invention polymerizes the polycarbosilane which has a repeating unit represented by the following general formula [1], and the organosilicon compound represented by the following general formula [2]. It is a manufacturing method .
[0008]
[Chemical formula 5]
(Wherein R 1 , R 2 , R 3 and R 4 are monovalent organic groups having 1 to 6 carbon atoms, and are aliphatic saturated hydrocarbon groups, alicyclic saturated hydrocarbon groups or aromatic hydrocarbons. And at least one of R 2 to R 4 is an aliphatic saturated hydrocarbon group having a tertiary carbon atom, an alicyclic saturated hydrocarbon group having 4 or more carbon atoms, or a phenyl group.)
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
(1). [Polymer structure]
The polycarbosilane of the present invention has a repeating unit of the following general formula [1].
[0011]
[Chemical 6]
[0012]
R 1 , R 2 , R 3 and R 4 are an aliphatic saturated hydrocarbon group, alicyclic saturated hydrocarbon group or aromatic hydrocarbon group having 1 to 6 carbon atoms, and an aliphatic saturated hydrocarbon group May be either linear or branched.
Preferable examples include methyl group, ethyl group, propyl group, butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, and phenyl group.
[0013]
At least one of R 2 to R 4 is an aliphatic saturated hydrocarbon group having a tertiary carbon atom, an alicyclic saturated hydrocarbon group having 4 or more carbon atoms, or a phenyl group. If any of R 2 to R 4 is not an aliphatic saturated hydrocarbon group having a tertiary carbon atom, an alicyclic saturated hydrocarbon group having 4 or more carbon atoms, or a phenyl group, the protection of the phenolic hydroxyl group is Insufficient, the stability of the polymer is lowered, and as a result, the inherent effects such as alkali solubility of the polycarbosilane of the present invention cannot be exhibited.
[0014]
In general, a methyl group is preferable for R 1 to R 3 and a tert-butyl group is preferable for R 4 because raw materials are easily obtained and synthesis is easy.
[0015]
The phenolic hydroxyl group protected with an organic group may be in any position of the ortho, meta, and para positions with respect to the bond between Si and the phenyl group.
[0016]
The polycarbosilane of the present invention is a copolymer with other monomers as long as it does not impair the function as a carbon functional group by the phenolic hydroxyl group protected with an organic substituent or the inherent function such as alkali solubility. A preferred polymer may be substantially composed of the repeating unit of the general formula [1].
[0017]
The polycarbosilane of the present invention can easily obtain a polymer having a number average molecular weight of 3,000 to 300,000 by using a specific organosilicon compound described later as a starting material.
[0018]
(2). [Production method of polymer]
(2) -1. [Monomer structure]
In order to obtain the polycarbosilane of the present invention, it is necessary to use an organosilicon compound represented by the following general formula [2] (hereinafter abbreviated as organosilicon compound [2]) as a starting material.
[0019]
[Chemical 7]
(Wherein R 1 , R 2 , R 3 and R 4 are monovalent organic groups having 1 to 6 carbon atoms, and are aliphatic saturated hydrocarbon groups, alicyclic saturated hydrocarbon groups or aromatic hydrocarbons. And at least one of R 2 to R 4 is an aliphatic saturated hydrocarbon group having a tertiary carbon atom, an alicyclic saturated hydrocarbon group having 4 or more carbon atoms, or a phenyl group.)
[0021]
R 1 , R 2 , R 3 and R 4 are an aliphatic saturated hydrocarbon group, alicyclic saturated hydrocarbon group or aromatic hydrocarbon group having 1 to 6 carbon atoms, and an aliphatic saturated hydrocarbon group May be either linear or branched.
Preferable examples include methyl group, ethyl group, propyl group, butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, and phenyl group.
[0022]
At least one of R 2 to R 4 is an aliphatic saturated hydrocarbon group having a tertiary carbon atom, an alicyclic saturated hydrocarbon group having 4 or more carbon atoms, or a phenyl group. If any of R 2 to R 4 is not an aliphatic saturated hydrocarbon group having a tertiary carbon atom, an alicyclic saturated hydrocarbon group having 4 or more carbon atoms, or a phenyl group, the protection of the phenolic hydroxyl group is The phenolic hydroxyl group produced by the elimination of the protecting group becomes insufficient and participates in the polymerization reaction. As a result, reactions other than ring-opening polymerization occur at the same time, and a polymer having a certain structure is not generated, so that the polycarbosilane of the present invention cannot be obtained. Since it is easy to obtain a raw material and it is easy to synthesize, a methyl group is generally preferable for R 1 to R 3 and a tert-butyl group is preferable for R 4 . A preferred starting material is an organosilicon compound represented by the following structural formula [3].
[0023]
[Chemical 8]
(In the formula, Me is a methyl group.)
[0025]
The phenolic hydroxyl group protected with an organic group may be in any position of the ortho, meta, and para positions with respect to the bond between Si and the phenyl group.
[0026]
(2) -2. (Monomer production method)
The organosilicon compound represented by the above formula [2] is a novel compound and is synthesized as follows.
That is, the organosilicon compound [2] having a phenolic hydroxyl group protected by an organic group substituent by a Grignard reaction between the chloride represented by the general formula [4] and the bromide represented by the general formula [5]. Get.
[0027]
[Chemical 9]
[0028]
[Chemical Formula 10]
(Wherein R 2 to R 4 are monovalent organic groups having 1 to 6 carbon atoms, and are an aliphatic saturated hydrocarbon group, an alicyclic saturated hydrocarbon group, or an aromatic hydrocarbon group, and at least one Is an aliphatic saturated hydrocarbon group having a tertiary carbon atom, an alicyclic saturated hydrocarbon group having 4 or more carbon atoms, or a phenyl group.)
[0030]
In the reaction, first, magnesium is activated with ethylene dibromide. Subsequently, a Grignard reagent is prepared from magnesium and a bromide represented by the general formula [5], and then a coupling reaction between the chloride represented by the general formula [4] is performed.
Preferred solvents include ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran.
After completion of the reaction, the produced magnesium salt is filtered off, the solvent and volatile components are distilled off, and the organosilicon compound [2] is obtained by distillation under reduced pressure.
[0031]
(2) -3. (Ring-opening polymerization of monomers)
The polycarbosilane of the present invention can be obtained by ring-opening polymerization of the organosilicon compound [2].
Ring-opening polymerization can be easily performed by using a transition metal catalyst or an anionic initiator. As an industrial production method, polymerization with a transition metal catalyst is preferable because raw materials are easily obtained and polymerization is easy.
[0032]
(2) -3-1. [Polymerization with transition metal catalyst]
The reaction system is placed in a nitrogen atmosphere, and a catalyst is added to the organosilicon compound [2] and stirred in the presence or absence of a solvent.
Preferred catalysts include cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum and other group 8-10 group metals, organometallic complexes, metal salts, metal oxides, etc. Use a catalyst.
Preferred platinum-based catalysts include chloroplatinic acid hexahydrate (H 2 PtCl 6 · 6H 2 O), cis-PtCl 2 (PhCN) 2 , platinum carbon, and a platinum complex coordinated with divinyltetramethyldisiloxane (PtDVTMDS). ) Etc. Ph represents a phenyl group.
A preferable amount of the catalyst used is 0.1 ppm to 1000 ppm with respect to the charged amount of the organosilicon compound [2].
Preferred solvents include nonpolar solvents such as hexane, toluene and xylene.
The preferred reaction temperature is from room temperature to 120 ° C.
[0033]
(2) -3-2. [Polymerization with anionic initiator]
The reaction system is placed in a nitrogen atmosphere, and a solvent and an initiator are added to the organosilicon compound [2] and stirred.
Preferred initiators include alkyllithiums such as n-butyllithium, methyllithium, sec-butyllithium, and phenyllithium, solid bases such as sodium hydroxide, potassium hydroxide, and tert-butoxypotassium. used.
Preferable solvents include ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran, and nonpolar solvents such as hexane, toluene and xylene.
The preferred reaction temperature is -78 ° C to 120 ° C.
[0034]
(3). (Usefulness of polymer)
The polycarbosilane of the present invention has a phenolic hydroxyl group protected by an organic substituent, and the protecting group of the phenolic hydroxyl group is easily eliminated by hydrolysis under acidic conditions.
The phenolic hydroxyl group generated by elimination of the protecting group functions as a carbon functional group or an alkali water-soluble group.
In addition, since the phenolic hydroxyl group forms a strong hydrogen bond with the polar functional group, it can be developed into polycarbosilane utilizing the hydrogen bond.
Furthermore, it is possible to synthesize crosslinkable polycarbosilanes having various heat resistances using phenolic hydroxyl groups as reaction sites.
The polycarbosilane of the present invention can be used as a resin modifier, a heat-resistant alkali-soluble resin, a heat-resistance imparting agent to a resin, a heat-resistant reactant, a pseudo-crosslinking agent using hydrogen bonding, and the like. is there.
[0035]
【Example】
Hereinafter, the present invention will be specifically described by way of examples.
[0036]
Example 1
A reactor equipped with a stirrer, a thermometer and a condenser was placed in a dry nitrogen atmosphere, and 2.0 g (82.3 mmol) of magnesium, 20 mL of THF, and a small amount of ethylene dibromide were charged into the reactor to activate the magnesium.
To the reaction system, 15.0 g (52.2 mmol) of 1-bromo-4-tert-butyldimethylsilyloxybenzene dissolved in 30 mL of THF was gradually added dropwise to prepare a Grignard reagent.
After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, and 6.9 g (57.4 mmol) of 1-chloro-1-methylsilacyclobutane was slowly added dropwise and stirred at room temperature for 1 hour.
The produced magnesium salt was filtered off, the solvent was distilled off, and the liquid was purified by distillation under reduced pressure.
By the above operation, 9.4 g (62%) of a colorless and transparent liquid having a boiling point of 110 to 112 ° C. (253 Pa) was obtained.
This liquid was subjected to 1 H-NMR measurement at 270 MHz to obtain the spectrum of FIG.
From the δ value shown in Table 1 and its attribution, it was confirmed that the obtained liquid was an organosilicon compound represented by the following structural formula [6] (hereinafter abbreviated as organosilicon compound [6]). It was.
[0037]
Embedded image
[Table 1]
Embedded image
Example 2
A reactor equipped with a stirrer was placed in a dry nitrogen atmosphere, and 0.2 g (0.68 mmol) of the organosilicon compound synthesized in Example 1 was charged into the reactor, and then platinum coordinated with divinyltetramethyldisiloxane was prepared. 100 ppm of a xylene solution of the complex (PtDVTMDS) was added dropwise to the organosilicon compound [6].
The mixture was stirred and reacted at 80 ° C. for 10 minutes, and it was confirmed by gel permeation chromatography (GPC) that the monomer had disappeared in the reaction system (conversion rate: 100%) to obtain a colorless and transparent resin.
The resin was subjected to 1 H-NMR measurement at 270 MHz to obtain the spectrum of FIG.
From the δ value shown in Table 2 and its assignment, it was confirmed that the obtained resin was a polycarbosilane having a repeating unit represented by the following formula [7].
The molecular weight of the obtained resin (converted molecular weight by GPC using standard polystyrene) was as follows.
Mn = 150000, Mw / Mn = 4.1
[0041]
Embedded image
[Table 2]
Embedded image
Example 3
The reaction was carried out under the same conditions as in Example 2 except that the reaction temperature was changed from 80 ° C. to room temperature (10 minutes after the reaction, 100% conversion).
The molecular weight of the obtained resin (converted molecular weight by GPC using standard polystyrene) was as follows.
Mn = 93000, Mw / Mn = 3.1
[0045]
Example 4
The reaction was conducted under the same conditions as in Example 2 except that the solventless reaction was changed to a solution reaction using 1 ml of toluene (conversion rate 98% after 10 minutes of reaction).
The molecular weight of the obtained resin (converted molecular weight by GPC using standard polystyrene) was as follows.
Mn = 240000, Mw / Mn = 4.2
[0046]
Example 5
The reaction was carried out under the same conditions as in Example 2 except that the catalyst was changed from platinum complex (PtDVTMDS) to chloroplatinic acid hexahydrate (H 2 PtCl 6 .6H 2 O). %).
The molecular weight of the obtained resin (converted molecular weight by GPC using standard polystyrene) was as follows.
Mn = 75000, Mw / Mn = 3.8
[0047]
【The invention's effect】
The present invention provides a novel polycarbosilane in which a phenyl group having a protected phenolic hydroxyl group is bonded to Si.
The polycarbosilane of the present invention can be used as a resin modifier, a heat-resistant alkali-soluble resin, a heat-resistance imparting agent to a resin, a heat-resistant reactant, a pseudo-crosslinking agent using hydrogen bonding, and the like. is there.
By the production method of the present invention, a polycarbosilane in which a phenyl group having a protected phenolic hydroxyl group is bonded to Si can be efficiently produced, and the molecular weight can be controlled in the range of a number average molecular weight of 3,000 to 300,000. Is also easy.
[Brief description of the drawings]
FIG. 1 shows the 1 H-NMR spectrum of the product obtained in Example 1. FIG.
FIG. 2 shows the 1 H-NMR spectrum of the product obtained in Example 2 .
Claims (5)
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