JP6655599B2 - モノ−、ポリ−および/またはオリゴシランにおけるケイ素−ケイ素結合および/またはケイ素−塩素結合の開裂方法 - Google Patents
モノ−、ポリ−および/またはオリゴシランにおけるケイ素−ケイ素結合および/またはケイ素−塩素結合の開裂方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 43
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 title claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 63
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 49
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 33
- 239000000460 chlorine Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 22
- -1 siloxane units Chemical group 0.000 claims description 15
- 238000003776 cleavage reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 230000007017 scission Effects 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- LBAQSKZHMLAFHH-UHFFFAOYSA-N ethoxyethane;hydron;chloride Chemical compound Cl.CCOCC LBAQSKZHMLAFHH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910008045 Si-Si Inorganic materials 0.000 claims description 5
- 229910006411 Si—Si Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 31
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical group [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000012047 saturated solution Substances 0.000 description 5
- 229910003902 SiCl 4 Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000005526 G1 to G0 transition Effects 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- GJCAUTWJWBFMFU-UHFFFAOYSA-N chloro-dimethyl-trimethylsilylsilane Chemical compound C[Si](C)(C)[Si](C)(C)Cl GJCAUTWJWBFMFU-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling 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
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- WDFIBGBTIINTHZ-UHFFFAOYSA-N CCO[SiH2][SiH3] Chemical compound CCO[SiH2][SiH3] WDFIBGBTIINTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- JTBAMRDUGCDKMS-UHFFFAOYSA-N dichloro-[dichloro(methyl)silyl]-methylsilane Chemical compound C[Si](Cl)(Cl)[Si](C)(Cl)Cl JTBAMRDUGCDKMS-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- FHQRQPAFALORSL-UHFFFAOYSA-N dimethylsilyl(trimethyl)silane Chemical compound C[SiH](C)[Si](C)(C)C FHQRQPAFALORSL-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010909 process residue Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-OUBTZVSYSA-N water-17o Chemical compound [17OH2] XLYOFNOQVPJJNP-OUBTZVSYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/10773—Halogenated silanes obtained by disproportionation and molecular rearrangement of halogenated silanes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
- C01B33/10742—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
- C01B33/10742—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material
- C01B33/10757—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/125—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving both Si-C and Si-halogen linkages, the Si-C and Si-halogen linkages can be to the same or to different Si atoms, e.g. redistribution reactions
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- 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
- C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
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- Chemical Kinetics & Catalysis (AREA)
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- Silicon Polymers (AREA)
- Silicon Compounds (AREA)
Description
Si2Cl6≧SiCl4>Si3Cl8>イソ−Si4Cl10≒ネオ−Si5Cl12
Si2Cl6≧SiCl4>Si3Cl8>イソ−Si4Cl10≒ネオ−Si5Cl12
Si2Cl6>HSiCI3>HSi(SiCl3)3>H2Si(SiCl3)2>H2SiCl2 および他の高分子量不溶性ポリシランとして得られた。
Si2Cl6>>HSi(SiCl3)3|HSiCl3|H2Si(SiCl3)2|Si3Cl8|H2SiCl2+「より高分子量の」未確認H/Cl−オリゴ−またはポリシラン。
HSi(SiCl3)3>ClSi(SiCl3)3>Si2Cl6>Si3Cl8>HSiCl3>H2Si(SiCl3)2>H2SiCl2の混合物。
NMR分析はBruker社のAV500分光計で行った。GC−MS分析は、Thermo Fisher Scientific社のガスクロマトグラフィーTrace GC Ultraに結合された質量分光計ITQ 900 MSで行った。固定相(Macherey−Nagel社のPERMABONDシラン)は長さ50m、内径0.32mmであった。1μlの試料溶液が注入されると、1/25がヘリウムをキャリアガスとして用いて、1.7mL/minの流量で固定相を通して搬送される。固定相の温度は最初の10分間は50℃であり、次いで20℃/minの割合で250℃まで増大され、さらに10分間にわたりこの最終温度に留め置かれる。カラムを出た後、試料は70eVでイオン化され、それぞれ34〜600および34〜900の範囲にあるカチオン性フラグメントの電荷質量比m/zが測定された。
ジエチルエーテル(p.a.グレード、ブチルヒドロキシトルエンで安定化)を前もってナトリウム/ベンゾフェノンで乾燥し、蒸留した。次いで、ガス流入管を備えたシュレンクフラスコ中で、前もって濃硫酸をくぐらせたHClガスをジエチルエーテルへと導入した。溶液の僅かな温度上昇が生じた。排出されるガスの量が導入されるガスの量と等しい場合(バブルカウンターによって示される)に、飽和状態が認識可能であった。完了させるため、この状態をさらに30分間維持した。
T−PCS(真空中で可能な限りSiCl4を除去する;64.64g)を、ジエチルエーテル中のHCl飽和溶液(5M、113mL)と、氷冷(0℃)しながら反応させた(a)。その茶色がかった溶液を16時間にわたって撹拌し、室温(24℃)まで徐々に加温したところ、淡黄色への色の変化が生じた。
図1
P−PCS(真空中で可能な限りSiCl4を除去する;4.9g)を、ジエチルエーテル中のHCl飽和溶液(5M,2.5mL)と、氷冷(0℃)しながら反応させた(a)。その赤茶色の溶液を14時間にわたって撹拌し、室温(24℃)まで徐々に加温したところ、僅かな変色のみが生じた。
図2
この方法では、「開裂可能な」ジシランMexSi2Cl6−x(x=0〜3)および「開裂可能でない」ジシラン(x=4〜6)が、単一の反応段階において官能性シランモノマーへと開裂され、これは次いで、交換反応Si−X→Si−OEt(X=H,Cl)の後に、好ましくはメチル置換環状シロキサンへと、および/または次善のエトキシ置換環状シロキサンへと、直接に変換可能である。ここでSi−Si結合およびSi−Cl結合の開裂に用いられる試薬は、HClガスで飽和されたジエチルエーテル溶液(HCl/Et2O)である。
MeSi>トリ官能性シロキサン
Me2Si>ジ官能性シロキサン、連鎖延長
Me3Si>モノ官能性シロキサン、封鎖剤
a)Me2SiCl2のHCl/Et2Oとの、120℃における67時間の反応は、以下の環状シロキサンをもたらす(GC−MS分析、図3)。
図3
図4
図5
図6
Claims (15)
- ポリ−および/またはオリゴシランにおける、ケイ素−ケイ素結合および/またはケイ素−塩素結合の開裂のための方法であって、ポリ−および/またはオリゴシランがエーテルまたはエーテル−塩化水素溶液に溶解または懸濁されることを特徴とする方法。
- ハロゲン化ポリシラン、特に塩素化ポリシラン、とりわけ過塩素化ポリシラン(PCS)から、ケイ素−ケイ素結合の開裂によって、ハロゲン化オリゴシラン、特に塩素化オリゴシランが調製されることを特徴とする、請求項1に記載の方法。
- ハロゲン化ポリシランがエチルエーテル(Et2O)またはエチルエーテル−塩化水素溶液、特にジエチルエーテルまたはジエチルエーテル−塩化水素溶液に溶解または懸濁されることを特徴とする、請求項1または2に記載の方法。
- ハロゲン化オリゴシランとして、nが2から5の整数である式SinX2n+2を有するハロゲン化オリゴシラン、特に式SinCl2n+2によって表されるハロゲン化オリゴシランが調製される、請求項1から3のいずれか1項記載の方法。
- 熱処理により製造されたハロゲン化ポリシラン、特に過塩素化ポリシラン(T−PCS)が反応させられる、請求項1から4のいずれか1項記載の方法。
- プラズマ化学的に製造されたハロゲン化ポリシラン、特に過塩素化ポリシラン(P−PCS)が反応させられる、請求項1から4のいずれか1項記載の方法。
- Si2Cl6の調製のために、T/P−PCS、特にT−PCSがEt2OまたはEt2O中の塩化水素のそれぞれと反応されることを特徴とする、請求項5または6に記載の方法。
- XSi(SiCl3)3(X=H,Cl)の調製のために、T/P−PCSがEt2O中の塩化水素と反応されることを特徴とする、請求項5または6に記載の方法。
- X2Si(SiCl3)2(X=H,Cl)の調製のために、T/P−PCSがEt2O中の塩化水素と反応されることを特徴とする、請求項5または6に記載の方法。
- 反応から得られた溶液が単離されることを特徴とする、請求項の1から9のいずれか1項記載の方法。
- 得られた溶液から、少なくとも1つのハロゲン化オリゴシランが単離されることを特徴とする、請求項1から10のいずれか1項記載の方法。
- ポリ−および/またはオリゴシランの開裂、およびシロキサンの形成に用いられることを特徴とする、請求項1から11のいずれか1項記載の方法。
- Si−Si結合および/またはSi−Cl結合の各々がジエチルエーテル中の塩化水素で熱的に開裂され、シロキサン単位に変換されることを特徴とする、請求項12に記載の方法。
- Me n Si 2 Cl 6−n (n=1〜6)から、環状、かご状、および/または鎖状のシロキサンが生成されることを特徴とする、請求項12または13に記載の方法。
- Me n Si 2 Cl 6−n (n=1〜6)の混合物、特に塩素化モノシランとの混合物の分解のために使用されることを特徴とする、請求項14に記載の方法。
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EP3543211B1 (en) | 2016-11-16 | 2022-04-20 | IHI Corporation | Method for hydrolyzing chlorosilane polymers |
US11008349B2 (en) * | 2017-09-20 | 2021-05-18 | Momentive Performance Materials Inc. | Process for the production of organohydridochlorosilanes |
CN109686802A (zh) * | 2018-11-09 | 2019-04-26 | 惠州凯珑光电有限公司 | 一种电子元器件和模组的封装工艺 |
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US3012006A (en) * | 1958-04-24 | 1961-12-05 | Dow Corning | Fluorinated alkyl silanes and their use |
US3878234A (en) * | 1973-07-30 | 1975-04-15 | Dow Corning | Preparation of hydrocarbon silanes from polysilanes |
US4855473A (en) | 1986-05-27 | 1989-08-08 | Bayer Aktiengesellschaft | Process for the preparation of organooxychlorosilanes |
GB8629593D0 (en) | 1986-12-11 | 1987-01-21 | Dow Corning Ltd | Polysilanes |
US5025075A (en) | 1988-07-22 | 1991-06-18 | Dow Corning Corporation | Methylpolysilanes and method for their preparation |
DE4220151A1 (de) | 1992-06-19 | 1993-12-23 | Wacker Chemie Gmbh | Verfahren zur Gewinnung von Methylchlorsilanen aus hochsiedenden Rückständen der Methylchlorsilansynthese |
US5292912A (en) | 1993-07-19 | 1994-03-08 | Dow Corning Corporation | Catalytic conversion of direct process high-boiling component to chlorosilane monomers in the presence of hydrogen chloride |
US5473037A (en) * | 1993-08-18 | 1995-12-05 | Shin-Etsu Chemical Co. Ltd. | Method of producing dimethylpolysiloxanes |
JP3644703B2 (ja) * | 1993-08-18 | 2005-05-11 | 信越化学工業株式会社 | 環状ジメチルポリシロキサンの製造方法 |
JP3362630B2 (ja) * | 1997-02-28 | 2003-01-07 | 信越化学工業株式会社 | 直接法メチルクロルシラン合成より副生する高沸点成分からのモノシラン類の製造方法 |
US6337415B1 (en) * | 1999-11-04 | 2002-01-08 | Shin-Etsu Chemical Co., Ltd. | Process for preparing tetrakis (trimethylsily) silane and tris (trimethysilyl) silane |
DE10039172C1 (de) | 2000-08-10 | 2001-09-13 | Wacker Chemie Gmbh | Verfahren zum Aufarbeiten von Rückständen der Direktsynthese von Organochlorsilanen |
DE10354262A1 (de) | 2003-11-20 | 2005-06-23 | Wacker-Chemie Gmbh | Verfahren zur Herstellung von Alkylchlorsilanen aus den Rückständen der Direktsynthese von Alkylchlorsilanen |
DE102006034061A1 (de) * | 2006-07-20 | 2008-01-24 | REV Renewable Energy Ventures, Inc., Aloha | Polysilanverarbeitung und Verwendung |
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DE102008042934A1 (de) * | 2008-10-17 | 2010-04-22 | Wacker Chemie Ag | Verfahren zur Herstellung von Neopentasilanen |
RU2499801C2 (ru) * | 2008-12-03 | 2013-11-27 | Доу Корнинг Корпорейшн | Способ получения трихлорсилана и тетрахлорсилана |
DE102009027194A1 (de) | 2009-06-25 | 2010-12-30 | Wacker Chemie Ag | Verfahren zur Herstellung von Dodecahalogenneopentasilanen |
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