JP4161052B2 - Silicon carbide separation membrane and method for producing the same - Google Patents
Silicon carbide separation membrane and method for producing the same Download PDFInfo
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- JP4161052B2 JP4161052B2 JP2003291187A JP2003291187A JP4161052B2 JP 4161052 B2 JP4161052 B2 JP 4161052B2 JP 2003291187 A JP2003291187 A JP 2003291187A JP 2003291187 A JP2003291187 A JP 2003291187A JP 4161052 B2 JP4161052 B2 JP 4161052B2
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- polycarbosilane
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- 229910010271 silicon carbide Inorganic materials 0.000 title claims description 45
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims description 43
- 238000000926 separation method Methods 0.000 title claims description 35
- 239000012528 membrane Substances 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000463 material Substances 0.000 claims description 42
- 229920003257 polycarbosilane Polymers 0.000 claims description 41
- 229920000642 polymer Polymers 0.000 claims description 39
- 239000002243 precursor Substances 0.000 claims description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 33
- 229910052710 silicon Inorganic materials 0.000 claims description 33
- 239000010703 silicon Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 150000002736 metal compounds Chemical class 0.000 claims description 19
- 238000010304 firing Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 238000000197 pyrolysis Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 9
- -1 alkynyl borazine compound Chemical class 0.000 claims description 7
- 150000003058 platinum compounds Chemical class 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000007824 aliphatic compounds Chemical class 0.000 description 7
- 150000001491 aromatic compounds Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MVLGANVFCMOJHR-UHFFFAOYSA-N 1,4-diethynylbenzene Chemical compound C#CC1=CC=C(C#C)C=C1 MVLGANVFCMOJHR-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001558 organosilicon polymer Polymers 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910021426 porous silicon Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CBYDUPRWILCUIC-UHFFFAOYSA-N 1,2-diethynylbenzene Chemical compound C#CC1=CC=CC=C1C#C CBYDUPRWILCUIC-UHFFFAOYSA-N 0.000 description 1
- ISJIEPHLMCICPJ-UHFFFAOYSA-N 1,2-diethynylnaphthalene Chemical compound C1=CC=CC2=C(C#C)C(C#C)=CC=C21 ISJIEPHLMCICPJ-UHFFFAOYSA-N 0.000 description 1
- TZSNBHPFGNSWPO-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;platinum Chemical compound [Pt].[Pt].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1.C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1.C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 TZSNBHPFGNSWPO-UHFFFAOYSA-N 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- IIPDKVKBZNLDMD-UHFFFAOYSA-N 9,10-diethynylanthracene Chemical compound C1=CC=C2C(C#C)=C(C=CC=C3)C3=C(C#C)C2=C1 IIPDKVKBZNLDMD-UHFFFAOYSA-N 0.000 description 1
- NRAKMNFIFIFJNP-UHFFFAOYSA-N C[Pt]C.C1CCC=CC=CC1 Chemical compound C[Pt]C.C1CCC=CC=CC1 NRAKMNFIFIFJNP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 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
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- TXRFFSSLMRVELK-UHFFFAOYSA-N cycloocta-1,3-diene platinum Chemical compound [Pt].C1CCC=CC=CC1.C1CCC=CC=CC1 TXRFFSSLMRVELK-UHFFFAOYSA-N 0.000 description 1
- ILVDYAGPHFWNQI-UHFFFAOYSA-N deca-1,9-diyne Chemical compound C#CCCCCCCC#C ILVDYAGPHFWNQI-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- YFIBSNDOVCWPBL-UHFFFAOYSA-N hexa-1,5-diyne Chemical compound C#CCCC#C YFIBSNDOVCWPBL-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- DMOVPHYFYSASTC-UHFFFAOYSA-N nona-1,8-diyne Chemical compound C#CCCCCCC#C DMOVPHYFYSASTC-UHFFFAOYSA-N 0.000 description 1
- ATBIPMKXEODDBH-UHFFFAOYSA-N octa-1,3-diyne Chemical compound CCCCC#CC#C ATBIPMKXEODDBH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- MDROPVLMRLHTDK-UHFFFAOYSA-N penta-1,4-diyne Chemical compound C#CCC#C MDROPVLMRLHTDK-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- XAFJSPPHVXDRIE-UHFFFAOYSA-L platinum(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Pt+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XAFJSPPHVXDRIE-UHFFFAOYSA-L 0.000 description 1
- SYKXNRFLNZUGAJ-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SYKXNRFLNZUGAJ-UHFFFAOYSA-N 0.000 description 1
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 125000006836 terphenylene group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
- Silicon Polymers (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
本発明は、ケイ素系前駆体ポリマーおよびこれを熱分解及び／または焼成する等して得られる耐熱性、耐候性、耐薬品性に優れた炭化ケイ素系素材、これらの素材から構成され、混合気体のような混合物から特定の物質を分離濃縮することができる分離膜、並びにそれらの製造方法に関するものである。本発明は、化学・機械産業、半導体産業等が対象とされ、物質の分離濃縮、物質のセンシング、強度増加複合材料、光・電子材料、半導体関連材料等の装置に適用しうるものである。 The present invention relates to a silicon-based precursor polymer, a silicon carbide-based material excellent in heat resistance, weather resistance, and chemical resistance obtained by pyrolyzing and / or firing the same, and a mixed gas composed of these materials. The present invention relates to a separation membrane that can separate and concentrate a specific substance from a mixture such as The present invention is intended for the chemical / mechanical industry, the semiconductor industry, and the like, and can be applied to apparatuses such as separation and concentration of substances, sensing of substances, composite materials for increasing strength, optical / electronic materials, and semiconductor-related materials.
分離膜による物質の分離濃縮は、装置や分離操作が単純化できる、相の転移を伴わないためエネルギーの消費の大幅な削減が可能である等の利点があり、環境調和型の分離プロセスとして注目されている。様々なプロセスで分離膜を利用するためには、耐熱性や耐薬品性に優れ、過酷な環境でも長期間使用が可能な耐候性膜材料の開発が不可欠である。このような膜材料として、無機素材を用いたシリカ膜、ゼオライト膜などが注目され、その分離性能等が報告されている。しかしこのような膜材料は、過酷な実使用条件下においてその分離性能等が経時劣化する事が知られており、実用上の要求を必ずしも満足するものではなく、より良い耐候性を有する分離膜材料の開発が要望されている。
さて、炭化ケイ素類は耐熱性および耐候性が極めて高く、超高温環境などでも各種用途に利用可能な材料としてよく知られているが、高強度であるために熱分解・焼成生成後の成形が困難である。これを解決する方法として、有機ケイ素系ポリマーを熱分解・焼成前駆体として用い、高分子状態で紡糸または製膜して成形後に熱分解・焼成して炭化ケイ素類に変換する方法が検討されてきた（特許文献１〜３、非特許文献１〜７）。これらの用途に用いられる有機ケイ素系ポリマーはそのままでは粘度が低く、形態を維持することが困難なので、熱分解・焼成前に架橋反応などの処理を行って例えば架橋型前駆体ポリマーに変換することが必要である。このような架橋反応として、従来は空気中の酸素、水分を酸素源とする酸素架橋反応が用いられてきた。しかし、空気などの酸素源を用いて架橋すると、製造される炭化ケイ素類中に酸素を混入させることにより、得られる炭化ケイ素類の高温での耐候性が低下するという問題があった。
Separation and concentration of substances using a separation membrane has advantages such as simplification of equipment and separation operation, and significant reduction in energy consumption because it does not involve phase transition, and is attracting attention as an environmentally conscious separation process. Has been. In order to use a separation membrane in various processes, it is essential to develop a weather-resistant membrane material that has excellent heat resistance and chemical resistance and can be used for a long time even in harsh environments. As such membrane materials, silica membranes, zeolite membranes and the like using inorganic materials have attracted attention, and their separation performance has been reported. However, it is known that such a membrane material deteriorates over time under severe conditions of actual use, and the separation performance does not always satisfy practical requirements, and has better weather resistance. Development of materials is demanded.
Now, silicon carbides have extremely high heat resistance and weather resistance, and are well known as materials that can be used in various applications even in an ultra-high temperature environment. However, because of their high strength, they can be molded after pyrolysis and firing. Have difficulty. As a method for solving this problem, a method has been studied in which an organosilicon polymer is used as a thermal decomposition / firing precursor, and it is spun or formed into a film in a polymer state and then converted into silicon carbide by thermal decomposition / firing after molding. (Patent documents 1 to 3, non-patent documents 1 to 7). The organosilicon polymer used in these applications is low in viscosity as it is, and it is difficult to maintain its form, so it is necessary to perform a treatment such as a crosslinking reaction before pyrolysis / firing to convert it into a crosslinked precursor polymer, for example. is required. As such a crosslinking reaction, conventionally, an oxygen crosslinking reaction using oxygen in the air and moisture as an oxygen source has been used. However, when crosslinking is performed using an oxygen source such as air, there is a problem that the weather resistance at high temperatures of the resulting silicon carbides is reduced by mixing oxygen into the produced silicon carbides.
本発明は、耐候性を下げる一因とされる酸素の混入を抑制した反応方法により製造したケイ素系前駆体ポリマー、およびそのケイ素系前駆体ポリマーのまたはポリカルボシランと特定のＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類との混合物の熱分解及び／または焼成によって得られる耐熱性、耐薬品性等に優れた分離膜等に用いられる炭化ケイ素系素材、ならびにそれから構成される耐候性等と分離性能の双方に優れた分離膜と、それらの製造方法を提供することを目的とする。 The present invention, oxygen silicon-based precursor polymer was prepared by the reaction method which suppresses contamination of which is a cause of lowering the weather resistance, and its silicon-based precursor polymers or polycarbosilane and a specific B, B ' , B ″ -Trialkynylborazines, silicon carbide materials used for separation membranes and the like obtained by thermal decomposition and / or calcination and excellent in heat resistance, chemical resistance, etc., and weather resistance composed thereof It is an object of the present invention to provide a separation membrane excellent in both of the above and the separation performance, and a method for producing them.
本発明者らは、前記課題を解決すべく鋭意研究を重ねた結果、好ましくは金属化合物の存在下、ケイ素系前駆体ポリマーの一つであるポリカルボシランに特定のＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類を添加した後またはそれらを反応させた後に熱分解・焼成することで、耐候性を下げる一因とされる酸素が構造内に少ない炭化ケイ素系素材が効率的に得られ、また優れた気体透過性能を有する分離膜が調製しうるという新規な事実を見いだし、それに基づいて本発明を完成させるに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have preferably selected B 1 , B ′, B ′ specific to polycarbosilane which is one of silicon-based precursor polymers in the presence of a metal compound. After adding '-trialkynylborazines or reacting them, pyrolysis and firing can efficiently produce a silicon carbide-based material with less oxygen in the structure that contributes to lowering the weather resistance. In addition, the inventors have found a novel fact that a separation membrane having excellent gas permeation performance can be prepared, and based on the fact, the present invention has been completed.
具体的には、以下の手段が提供される。本発明に係るのは以下の（１１）〜（２０）の手段である。
（１）ポリカルボシランと、一般式（Ｉ）
（ＨＣ≡Ｃ）２Ｘ１ （Ｉ）
（式中、Ｘ１は、芳香族もしくは脂肪族化合物またはそれらの結合物の２価の基を示す。）
で表されるジイン類とを反応させて得られるケイ素系前駆体ポリマー。
（２）ポリカルボシランに一般式（Ｉ）
（ＨＣ≡Ｃ）２Ｘ１ （Ｉ）
（式中、Ｘ１は、芳香族もしくは脂肪族化合物またはそれらの結合物の２価の基を示す。）
で表されるジイン類を添加した混合物もしくは（１）項のケイ素系前駆体ポリマーを熱分解及び／または焼成して得られる炭化ケイ素系素材。
（３）ポリカルボシランと、一般式（Ｉ）
（ＨＣ≡Ｃ）２Ｘ１ （Ｉ）
（式中、Ｘ１は、芳香族もしくは脂肪族化合物またはそれらの結合物の２価の基を示す。）
で表されるジイン類とを反応させることを特徴とするケイ素系前駆体ポリマーの製造方法。
（４）前記反応を金属化合物の存在下に行なうことを特徴とする前記（３）項記載の製造方法。
（５）金属化合物が白金化合物であることを特徴とする前記（４）項記載の製造方法。
Specifically, means follows is provided. The following means (11) to (20) relate to the present invention.
(1) Polycarbosilane and general formula (I)
(HC≡C) 2 X 1 (I)
(In the formula, X 1 represents a divalent group of an aromatic or aliphatic compound or a combination thereof.)
A silicon-based precursor polymer obtained by reacting with a diyne represented by the formula:
(2) General formula (I) in polycarbosilane
(HC≡C) 2 X 1 (I)
(In the formula, X 1 represents a divalent group of an aromatic or aliphatic compound or a combination thereof.)
A silicon carbide-based material obtained by thermally decomposing and / or firing a mixture added with diynes represented by formula (1) or a silicon-based precursor polymer of item (1).
(3) Polycarbosilane and general formula (I)
(HC≡C) 2 X 1 (I)
(In the formula, X 1 represents a divalent group of an aromatic or aliphatic compound or a combination thereof.)
A process for producing a silicon-based precursor polymer, characterized by reacting with a diyne represented by the formula:
(4) The method according to (3) above, wherein the reaction is carried out in the presence of a metal compound.
(5) The method according to (4), wherein the metal compound is a platinum compound.
（６）ポリカルボシランに一般式（Ｉ）
（ＨＣ≡Ｃ）２Ｘ１ （Ｉ）
（式中、Ｘ１は、芳香族もしくは脂肪族化合物またはそれらの結合物の２価の基を示す。）
で表されるジイン類を添加して混合物を得るか、またはポリカルボシランと前記ジイン類とを反応させてケイ素系前駆体ポリマーを得て、そして前記混合物またはケイ素系前駆体ポリマーを熱分解及び／または焼成することを特徴とする炭化ケイ素系素材の製造方法。
（７）前記添加または反応を金属化合物の存在下に行なうことを特徴とする前記（６）項記載の製造方法。
（８）金属化合物が白金化合物であることを特徴とする前記（７）項記載の製造方法。
（９）前記（２）項記載の炭化ケイ素系素材から構成された炭化ケイ素系分離膜。
（１０）ポリカルボシランに一般式（Ｉ）
（ＨＣ≡Ｃ）２Ｘ１ （Ｉ）
（式中、Ｘ１は、芳香族もしくは脂肪族化合物またはそれらの結合物の２価の基を示す。）
で表されるジイン類を添加して混合物を得るか、またはポリカルボシランと前記ジイン類とを反応させてケイ素系前駆体ポリマーを得て、前記混合物もしくはケイ素系前駆体ポリマーを基材に塗布し、または前記混合物もしくはケイ素系前駆体ポリマーに基材を浸漬もしくは接触させた後、熱分解及び／または焼成することにより、膜状の炭化ケイ素系素材から構成された炭化ケイ素系分離膜を得ることを特徴とする炭化ケイ素系分離膜の製造方法。
（１１）ポリカルボシランと、一般式（ＩＩ）
(6) General formula (I) in polycarbosilane
(HC≡C) 2 X 1 (I)
(In the formula, X 1 represents a divalent group of an aromatic or aliphatic compound or a combination thereof.)
To obtain a mixture by reacting polycarbosilane with the diynes to obtain a silicon-based precursor polymer, and pyrolyzing the mixture or the silicon-based precursor polymer. A method for producing a silicon carbide-based material, characterized by firing.
(7) The production method as described in (6) above, wherein the addition or reaction is carried out in the presence of a metal compound.
(8) The method according to (7), wherein the metal compound is a platinum compound.
(9) A silicon carbide separation membrane composed of the silicon carbide material according to (2).
(10) General formula (I) in polycarbosilane
(HC≡C) 2 X 1 (I)
(In the formula, X 1 represents a divalent group of an aromatic or aliphatic compound or a combination thereof.)
A diene compound represented by the formula (1) is added to obtain a mixture, or polycarbosilane and the diynes are reacted to obtain a silicon-based precursor polymer, and the mixture or silicon-based precursor polymer is applied to a substrate. Alternatively, after the substrate is immersed or brought into contact with the mixture or the silicon-based precursor polymer, thermal decomposition and / or baking are performed to obtain a silicon carbide-based separation membrane composed of a film-shaped silicon carbide-based material. A method for producing a silicon carbide-based separation membrane.
(11) Polycarbosilane and general formula (II)
（式中、Ｒ１はアルキル基、アリール基、アラルキル基または水素原子を示し、Ｒ２はアルキル基、アリール基、アラルキル基または水素原子を示す。）
で表されるＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類とを反応させて得られるケイ素系前駆体ポリマー。
（１２）ポリカルボシランに一般式（ＩＩ）
(In the formula, R 1 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R 2 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom.)
A silicon-based precursor polymer obtained by reacting B, B ′, B ″ -trialkynylborazines represented by the formula:
(12) General formula (II) for polycarbosilane
（式中、Ｒ１はアルキル基、アリール基、アラルキル基または水素原子を示し、Ｒ２はアルキル基、アリール基、アラルキル基または水素原子を示す。）
で表されるＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類を添加した混合物もしくは（１１）項のケイ素系前駆体ポリマーを熱分解及び／または焼成して得られる炭化ケイ素系素材。
（１３）ポリカルボシランと、一般式（ＩＩ）
(In the formula, R 1 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R 2 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom.)
A silicon carbide-based material obtained by thermally decomposing and / or firing a mixture of B, B ′, B ″ -trialkynylborazines represented by the formula (1) or a silicon-based precursor polymer of item (11).
(13) Polycarbosilane and general formula (II)
（式中、Ｒ１はアルキル基、アリール基、アラルキル基または水素原子を示し、Ｒ２はアルキル基、アリール基、アラルキル基または水素原子を示す。）
で表されるＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類とを反応させることを特徴とするケイ素系前駆体ポリマーの製造方法。
（１４）前記反応を金属化合物の存在下に行なうことを特徴とする前記（１３）項記載の製造方法。
（１５）金属化合物が白金化合物であることを特徴とする前記（１４）項記載の製造方法。
（１６）ポリカルボシランに一般式（ＩＩ）
(In the formula, R 1 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R 2 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom.)
A process for producing a silicon-based precursor polymer, which comprises reacting with B, B ′, B ″ -trialkynylborazines represented by the formula:
(14) The process according to the above (13), wherein the reaction is carried out in the presence of a metal compound.
(15) The production method as described in (14) above, wherein the metal compound is a platinum compound.
(16) General formula (II) in polycarbosilane
（式中、Ｒ１はアルキル基、アリール基、アラルキル基または水素原子を示し、Ｒ２はアルキル基、アリール基、アラルキル基または水素原子を示す。）
で表されるＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類を添加して混合物を得るか、またはポリカルボシランと前記Ｂ，Ｂ’，Ｂ”−トリアルキニルボラジン類とを反応させてケイ素系前駆体ポリマーを得て、そして前記混合物またはケイ素系前駆体ポリマーを熱分解及び／または焼成することを特徴とする炭化ケイ素系素材の製造方法。
（１７）前記添加または反応を金属化合物の存在下に行なうことを特徴とする前記（１６）項記載の製造方法。
（１８）金属化合物が白金化合物であることを特徴とする前記（１７）項記載の製造方法。
（１９）前記（１２）項記載の炭化ケイ素系素材から構成された炭化ケイ素系分離膜。
（２０）ポリカルボシランに一般式（ＩＩ）
(In the formula, R 1 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R 2 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom.)
A B, B ′, B ″ -trialkynylborazines represented by the following formula is added to obtain a mixture, or polycarbosilane and the B, B ′, B ″ -trialkynylborazines are reacted to form a silicon system A method for producing a silicon carbide-based material, comprising obtaining a precursor polymer and thermally decomposing and / or firing the mixture or the silicon-based precursor polymer.
(17) The production method as described in (16) above, wherein the addition or reaction is carried out in the presence of a metal compound.
(18) The production method as described in (17) above, wherein the metal compound is a platinum compound.
(19) A silicon carbide-based separation membrane composed of the silicon carbide-based material according to (12).
(20) General formula (II) in polycarbosilane
（式中、Ｒ１はアルキル基、アリール基、アラルキル基または水素原子を示し、Ｒ２はアルキル基、アリール基、アラルキル基または水素原子を示す。）
で表されるＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類を添加して混合物を得るか、またはポリカルボシランと前記Ｂ，Ｂ’，Ｂ”−トリアルキニルボラジン類とを反応させてケイ素系前駆体ポリマーを得て、前記混合物もしくはケイ素系前駆体ポリマーを基材に塗布し、または前記混合物もしくはケイ素系前駆体ポリマーに基材を浸漬もしくは接触させた後、熱分解及び／または焼成することにより、膜状の炭化ケイ素系素材から構成された炭化ケイ素系分離膜を得ることを特徴とする炭化ケイ素系分離膜の製造方法。
（２１）分離対象物が、例えば水素、ヘリウム、二酸化炭素、一酸化炭素、酸素、窒素などの気体を含む混合物、並びに、例えば水、エタノールなどの揮発性有機化合物の蒸気などの蒸気及び／または液体を含む混合物から選ばれる少なくとも二種であることを特徴とする前記（９）または（１９）項記載の分離膜および分離濃縮装置。
(In the formula, R 1 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R 2 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom.)
A B, B ′, B ″ -trialkynylborazines represented by the following formula is added to obtain a mixture, or polycarbosilane and the B, B ′, B ″ -trialkynylborazines are reacted to form a silicon system Obtaining a precursor polymer, applying the mixture or silicon-based precursor polymer to a substrate, or immersing or contacting the substrate in the mixture or silicon-based precursor polymer, followed by pyrolysis and / or baking. A method for producing a silicon carbide-based separation membrane, comprising obtaining a silicon carbide-based separation membrane composed of a membrane-like silicon carbide-based material.
(21) The separation target is a mixture containing a gas such as hydrogen, helium, carbon dioxide, carbon monoxide, oxygen, nitrogen, and / or a vapor such as a vapor of a volatile organic compound such as water or ethanol, and / or The separation membrane and the separation concentration apparatus according to (9) or (19) above, wherein the separation membrane is at least two kinds selected from a mixture containing a liquid.
本発明によれば、好ましくは金属化合物の存在下、ポリカルボシランを特定のＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類と混合した後またはそれらを反応させた後に熱分解・焼成することで、耐熱性材料等、各種材料の製造に有用な炭化ケイ素系素材、及び前記炭化ケイ素系素材で構成された気体ー気体分離膜を効率よく安全に製造することができる。
また、本発明の炭化ケイ素系素材は、耐熱性材料等、各種材料の製造に有用なものであり、特に分離膜に用いると、分離能に加えて高温での耐候性にも優れる。
また、本発明のケイ素系前駆体ポリマーは、前記炭化ケイ素系素材を与える前駆体として好適なものである。
したがって、本発明の工業的意義は多大である。
According to the present invention, the polycarbosilane is preferably pyrolyzed and calcined after mixing with specific B 1 , B ′, B ″ -trialkynylborazines or after reacting them in the presence of a metal compound. Thus, it is possible to efficiently and safely manufacture a silicon carbide-based material useful for manufacturing various materials such as a heat-resistant material and a gas-gas separation membrane composed of the silicon carbide-based material.
In addition, the silicon carbide-based material of the present invention is useful for the production of various materials such as heat-resistant materials. In particular, when used for a separation membrane, the silicon carbide-based material is excellent in weather resistance at high temperatures in addition to separation ability.
In addition, the silicon-based precursor polymer of the present invention is suitable as a precursor for providing the silicon carbide-based material.
Therefore, the industrial significance of the present invention is great.
本発明のケイ素系前駆体ポリマーは、耐熱性があり、そのまま気体分離膜として使用されるものであるか、あるいはその熱分解・焼成処理により気体分離性のある炭化ケイ素系素材の膜を生成するものであれば、その材質は特に限定されない。好ましくは、ポリメチレンシリレンなどのポリカルボシランに、特定のジイン類またはＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類を反応させることにより得られるポリマーが挙げられる。
本発明では、原料化合物のポリカルボシランに、好ましくは金属化合物の存在下で、一般式（Ｉ）のジイン類もしくは一般式（ＩＩ）のＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類を添加して混合物を得るか、またはポリカルボシランと前記ジイン類もしくはＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類とを反応させてケイ素系前駆体ポリマーを得て、その後に熱分解・焼成することによって、炭化ケイ素系素材を得ることができる。
本発明において、前記の「反応」とは、例えばポリカルボシランが分子内のＳｉ−Ｈ結合によって、ジイン類やＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類の炭素−炭素三重結合の少なくとも１個に付加する反応をいう。したがって、ジイン類やＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類の必ずしも全てが反応していなくてもよい。
また、前記「熱分解」においては、主としてＳｉ−Ｃ結合の切断、転移が起こるが、それ以外にも架橋反応を含む多様な反応も生起することがある。前記「焼成」においては、例えば１２００℃以上程度の温度まで加熱する時は、全ての水素原子を最終生成物から除くこともできる。
本発明で用いるポリカルボシランは、常法によりポリジメチルシランなどのポリシラン類を熱転移・熱分解して製造することができる。ポリカルボシランは、分子内に少なくともＳｉ−Ｈ結合を有するものである。
なお、ポリカルボシラン中の単位ユニットの繰り返し数は、好ましくは２以上である。
The silicon-based precursor polymer of the present invention has heat resistance and is used as a gas separation membrane as it is, or generates a gas-separable silicon carbide-based material membrane by pyrolysis and baking treatment. If it is a thing, the material will not be specifically limited. Preferably, the polymer obtained by making polycarbosilane, such as polymethylenesilylene, react with specific diynes or B, B ′, B ″ -trialkynylborazines.
In the present invention, diynes of general formula (I) or B, B ′, B ″ -trialkynylborazines of general formula (II) are added to polycarbosilane as a raw material compound, preferably in the presence of a metal compound. To obtain a mixture, or to react polycarbosilane with the diynes or B, B ′, B ″ -trialkynylborazines to obtain a silicon-based precursor polymer, which is then pyrolyzed and calcined. Thus, a silicon carbide-based material can be obtained.
In the present invention, the above-mentioned “reaction” means, for example, that at least one of carbon-carbon triple bonds of diynes and B, B ′, B ″ -trialkynylborazines by polycarbosilane by an intramolecular Si—H bond. This refers to a reaction to be added to each individual.
In the “thermal decomposition”, Si—C bond cleavage and rearrangement mainly occur, but various other reactions including a crosslinking reaction may also occur. In the “calcination”, for example, when heating to a temperature of about 1200 ° C. or higher, all hydrogen atoms can be removed from the final product.
The polycarbosilane used in the present invention can be produced by heat transfer / pyrolysis of polysilanes such as polydimethylsilane by a conventional method. Polycarbosilane has at least a Si—H bond in the molecule.
In addition, the number of repeating unit units in polycarbosilane is preferably 2 or more.
前記一般式（Ｉ）のジイン中の基Ｘ１は、炭素数が好ましくは６〜２０、より好ましくは６〜１２の芳香族化合物の２価の基であるか、または、炭素数が好ましくは１〜２０、より好ましくは１〜１２の脂肪族化合物の２価の基であるか、またはこれらの芳香族化合物と脂肪族化合物との結合体で形成される化合物の２価の基である。これらの２価の基においては、２つの結合手の位置関係には特に制限はない。基Ｘ１の具体例としては、フェニレン基、ナフチレン基、ビフェニレン基、テルフェニレン基、アントリレン基、メチレン基、エチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、デカメチレン基、ドデカメチレン基、エイコサメチレン基、ジメチレンフェニレン基等が挙げられ、それら基の水素原子の一部が、アルキル基、アリール基、アラルキル基、シクロアルキル基等の基で置換されていても差し支えない。したがって、それらの置換基等を有する一般式（Ｉ）で表されるジイン類としては、ジエチニルベンゼン、ジエチニルナフタレン、ジエチニルアントラセン、1,4−ペンタジイン、1,5−ヘキサジイン、1,7−オクタジイン、1,8−ノナジイン、1,9−デカジイン、1,11−ドデカジイン、1,13−テトラデカジイン等が挙げられるが、これらに限定されるものではない。 Before SL group X 1 in diyne of the general formula (I), or preferably a carbon number 6 to 20, a divalent group and more preferably 6 to 12 aromatic compound, or, preferably carbon atoms Is a divalent group of an aliphatic compound of 1 to 20, more preferably 1 to 12, or a divalent group of a compound formed by a conjugate of an aromatic compound and an aliphatic compound. . In these divalent groups, the positional relationship between the two bonds is not particularly limited. Specific examples of the group X 1 include phenylene group, naphthylene group, biphenylene group, terphenylene group, anthrylene group, methylene group, ethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, decamethylene group, Examples include dodecamethylene group, eicosamethylene group, dimethylenephenylene group, etc., and some of the hydrogen atoms of these groups may be substituted with groups such as alkyl groups, aryl groups, aralkyl groups, cycloalkyl groups, etc. Absent. Accordingly, the diynes represented by the general formula (I) having those substituents and the like include diethynylbenzene, diethynylnaphthalene, diethynylanthracene, 1,4-pentadiyne, 1,5-hexadiyne, 1,7 Examples include, but are not limited to, octadiyne, 1,8-nonadiyne, 1,9-decadiyne, 1,11-dodecadiine, 1,13-tetradecadiine and the like.
本発明で用いるＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類は一般式（ＩＩ） The B, B ', B "-trialkynylborazines used in the present invention are represented by the general formula (II)
で表される。式中、Ｒ１はアルキル基、アリール基、アラルキル基または水素原子を示す。アルキル基の炭素数は１〜２４、好ましくは１〜１２である。アリール基の炭素数は６〜２０、好ましくは６〜１０である。アラルキル基の炭素数は７〜２４、好ましくは７〜１２である。
前記Ｒ１を例示すると、メチル基、エチル基、イソプロピル基、ｔ−ブチル基、オクチル基等のアルキル基、フェニル基、ナフチル基、ビフェニル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基、水素原子等が挙げられる。
It is represented by In the formula, R 1 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom. The alkyl group has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. The aryl group has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. The aralkyl group has 7 to 24 carbon atoms, preferably 7 to 12 carbon atoms.
Examples of R 1 include alkyl groups such as methyl group, ethyl group, isopropyl group, t-butyl group, and octyl group, aryl groups such as phenyl group, naphthyl group, and biphenyl group, and aralkyl groups such as benzyl group and phenethyl group. And a hydrogen atom.
前記一般式（ＩＩ）において、Ｒ２はアルキル基、アリール基、アラルキル基または水素原子を示す。アルキル基の炭素数は１〜２４、好ましくは１〜１２である。アリール基の炭素数は６〜２０、好ましくは６〜１０である。アラルキル基の炭素数は７〜２４、好ましくは７〜１２である。
前記Ｒ２を例示すると、メチル基、エチル基、イソプロピル基、ｔ−ブチル基、オクチル基等のアルキル基、フェニル基、ナフチル基、ビフェニル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基、水素原子等が挙げられる。
複数のＲ１は、互いに同一でも異なっていてもよく、また、複数のＲ２は、互いに同一でも異なっていてもよい。また、Ｒ１とＲ２は、互いに同一でも異なっていてもよい。
In the general formula (II), R 2 represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom. The alkyl group has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. The aryl group has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. The aralkyl group has 7 to 24 carbon atoms, preferably 7 to 12 carbon atoms.
Examples of R 2 include alkyl groups such as methyl group, ethyl group, isopropyl group, t-butyl group and octyl group, aryl groups such as phenyl group, naphthyl group and biphenyl group, and aralkyl groups such as benzyl group and phenethyl group. And a hydrogen atom.
A plurality of R 1 may be the same or different from each other, and a plurality of R 2 may be the same or different from each other. R 1 and R 2 may be the same as or different from each other.
これらの置換基を有し、一般式（ＩＩ）で表されるＢ，Ｂ’，Ｂ”−トリアルキニルボラジン類の具体例としては、Ｂ，Ｂ’，Ｂ”−トリエチニルボラジン、Ｂ，Ｂ’，Ｂ”−トリエチニル−Ｎ，Ｎ’，Ｎ”−トリメチルボラジン、Ｂ，Ｂ’，Ｂ”−トリ（１−プロピニル）ボラジン、Ｂ，Ｂ’，Ｂ”−トリフェニルエチニルボラジン、Ｂ，Ｂ’，Ｂ”−トリフェニルエチニル−Ｎ，Ｎ’，Ｎ”−トリメチルボラジン、Ｂ，Ｂ’，Ｂ”−トリエチニル−Ｎ，Ｎ’，Ｎ”−トリフェニルボラジン、Ｂ，Ｂ’，Ｂ”−トリフェニルエチニル−Ｎ，Ｎ’，Ｎ”−トリフェニルボラジン、Ｂ，Ｂ’，Ｂ”−トリエチニル−Ｎ，Ｎ’，Ｎ”−トリベンジルボラジン等が挙げられるが、これらに限定されるものではない。 Specific examples of B, B ′, B ″ -trialkynylborazines having these substituents and represented by the general formula (II) include B, B ′, B ″ -triethynylborazine, B, B ', B ″ -triethynyl-N, N ′, N ″ -trimethylborazine, B, B ′, B ″ -tri (1-propynyl) borazine, B, B ′, B ″ -triphenylethynylborazine, B, B ', B "-triphenylethynyl-N, N', N" -trimethylborazine, B, B ', B "-triethynyl-N, N', N" -triphenylborazine, B, B ', B "- Examples include triphenylethynyl-N, N ′, N ″ -triphenylborazine, B, B ′, B ″ -triethynyl-N, N ′, N ″ -tribenzylborazine, and the like. Absent.
Ｂ，Ｂ’，Ｂ''−トリアルキニルボラジン類は、それぞれ１種類を単独で使用することもできるが、それぞれ２種類以上を混合して使用することも本発明の有利な形態に含まれる。 Each of B 1 , B ′, B ″ -trialkynylborazines can be used alone, but the use of a mixture of two or more of them is also included in the advantageous form of the present invention.
前記の添加または反応における原料化合物の量関係は、ポリカルボシランに対しての、一般式（Ｉ）のジイン類、または一般式（ＩＩ）で表されるＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類のモル比が０．０００１〜５０、好ましくは０．００１〜２０の範囲である。 The amount relationship between the raw material compound before SL addition or reaction, with respect to polycarbosilane, B represented by the diyne of the general formula (I), or the general formula (II), B ', B ''- The molar ratio of trialquinylborazines is in the range of 0.0001-50, preferably 0.001-20.
前記の添加、反応、熱分解、焼成において、各種金属化合物を用いることができる。これは触媒又は添加物として作用する。中でもヒドロシリル化反応に使用される任意の白金化合物を用いることは、本発明の有利な態様に含まれる。これを例示すると、白金ジビニルテトラメチルジシロキサン、白金環状ジビニルメチルシロキサン、塩化白金酸、ジクロロ白金、白金カーボン、トリス（ジベンジリデンアセトン）二白金、ビス（エチレン）テトラクロロ二白金、シクロオクタジエンジクロロ白金、ビス（シクロオクタジエン）白金、シクロオクタジエンジメチル白金、ビス（トリフェニルホスフィン）ジクロロ白金、テトラキス（トリフェニルホスフィン）白金等が挙げられるが、これらに限定されるものではない。これらの金属化合物は、１種を単独で用いてもよく、２種以上を組み合わせて用いることもできる。
金属化合物は、ジイン類またはＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類に対する、金属化合物中の金属原子のモル比として、通常０．０００１〜５の範囲である。
Added before reporting, reaction, thermal decomposition, firing, it is possible to use various metal compounds. This acts as a catalyst or additive. Among these, the use of any platinum compound used in the hydrosilylation reaction is included in an advantageous embodiment of the present invention. For example, platinum divinyltetramethyldisiloxane, platinum cyclic divinylmethylsiloxane, chloroplatinic acid, dichloroplatinum, platinum carbon, tris (dibenzylideneacetone) diplatinum, bis (ethylene) tetrachlorodiplatinum, cyclooctadienedichloro Examples include, but are not limited to, platinum, bis (cyclooctadiene) platinum, cyclooctadienedimethylplatinum, bis (triphenylphosphine) dichloroplatinum, tetrakis (triphenylphosphine) platinum, and the like. These metal compounds may be used alone or in combination of two or more.
The metal compound is usually in the range of 0.0001 to 5 as the molar ratio of the metal atom in the metal compound to the diynes or B, B ′, B ″ -trialkynylborazines.
前記の反応には、ヒドロシリル化反応に用いられる種々の溶媒を用いることができる。例えば芳香族炭化水素系、飽和炭化水素系、脂肪族エーテル系、芳香族エーテル系等の溶媒が挙げられる。 Various solvents used in the hydrosilylation reaction can be used for the above reaction. For example, aromatic hydrocarbon type, saturated hydrocarbon type, aliphatic ether type, aromatic ether type solvents and the like can be mentioned.
前記の反応は一般的に室温（０〜３５℃程度の温度）で容易に進行するが、ジイン類またはＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類の構造により、好ましい反応速度を達するために−２０℃から２００℃の範囲で冷却または加熱することもできる。もしくは反応の完了を待たずに次の加熱処理（熱分解・焼成処理）に進むことも可能である。 The above reaction generally proceeds easily at room temperature (a temperature of about 0 to 35 ° C.), but a preferable reaction rate is achieved by the structure of diynes or B, B ′, B ″ -trialkynylborazines. Further, it can be cooled or heated in the range of -20 ° C to 200 ° C. Alternatively, it is possible to proceed to the next heat treatment (pyrolysis / firing treatment) without waiting for completion of the reaction.
上記の熱分解・焼成条件は、有機ケイ素系ポリマーから炭化ケイ素類へ熱変換させるための任意の熱分解・焼成条件を用いることができる。焼成は通常室温から加熱を始められる。加熱最終温度は４００℃〜２０００℃の範囲で行われるが、好ましくは６００℃〜１６００℃の範囲である。加熱速度は毎分０．１℃〜毎分１００℃までの範囲で選ばれるが、段階的な加熱や加熱処理の途中または最終段階で一定温度の加熱を維持することも、本発明の態様に含まれる。熱分解・焼成処理は、例えばアルゴンガス、窒素ガス等の不活性ガス雰囲気下あるいは真空下で行なうことが好ましい。 As the above pyrolysis / firing conditions, any pyrolysis / firing conditions for thermally converting an organosilicon polymer to silicon carbide can be used. Firing can usually be started from room temperature. The final heating temperature is 400 ° C to 2000 ° C, and preferably 600 ° C to 1600 ° C. The heating rate is selected in the range of 0.1 ° C./min to 100 ° C./min. However, maintaining a constant temperature in the middle or in the final stage of stepwise heating or heat treatment is also an aspect of the present invention. included. The thermal decomposition / firing treatment is preferably performed in an inert gas atmosphere such as argon gas or nitrogen gas or in vacuum.
本発明により提供される炭化ケイ素系素材から、さまざまな耐候性材料を得ることができる。その形状としては、膜状、糸状、塊状等各種のものが可能である。特に前２者の形態においては、高温下などの過酷な条件で利用可能な分離濃縮膜素材として適用可能である。膜状、糸状または塊状の炭化ケイ素系素材は、例えば、セラミックスなどの基材上に、反応させたポリカルボシランすなわち前記ケイ素系前駆体ポリマーあるいはその溶液を塗布し、または前記ポリカルボシランあるいはその溶液に基材を浸漬もしくは接触させた後、基材上で該ポリカルボシランを加熱することによってさらに反応を進め、膜状で、あるいは紡糸によって糸状で、あるいは特に基材を用いないことによって塊状で、それぞれ得ることができる。また、上記操作において、前記予め反応させたポリカルボシラン（ケイ素系前駆体ポリマー）やその溶液に代えて、ポリカルボシランとＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類との混合物を用いて、この混合物を基材上に塗布し、またはこの混合物に基材を浸漬もしくは接触させた後、基材上で該混合物を加熱処理するか、あるいは該混合物を紡糸するか、あるいは基材を用いないで該混合物を加熱することによっても、炭化ケイ素系素材を所定の形状で得ることができる。上記操作において、セラミックスとして多孔性の基材を用いることによって、水素等のガス分離膜などとして用いることができる膜状の炭化ケイ素系素材を得ることもできる。 Various weather-resistant materials can be obtained from the silicon carbide-based material provided by the present invention. Various shapes such as a film shape, a thread shape, and a lump shape are possible as the shape. In particular, the former two forms are applicable as a separation and concentration membrane material that can be used under severe conditions such as high temperatures. The film-like, thread-like, or massive silicon carbide-based material is prepared by, for example, applying a reacted polycarbosilane, that is, the silicon-based precursor polymer or a solution thereof on a substrate such as ceramics, or the polycarbosilane or the After the substrate is immersed in or brought into contact with the solution, the reaction is further promoted by heating the polycarbosilane on the substrate, in the form of a film, by spinning, or in the form of a lump by not using the substrate. Can be obtained respectively. Moreover, in the said operation, it replaced with the said polycarbosilane (silicon-type precursor polymer) and its solution which were made to react beforehand, and used the mixture of polycarbosilane and B , B ', B''-trialkynylborazines. The mixture is applied onto the substrate, or the substrate is dipped or contacted with the mixture, and then the mixture is heated on the substrate, the mixture is spun, or the substrate is The silicon carbide-based material can be obtained in a predetermined shape by heating the mixture without using it. In the above operation, by using a porous substrate as the ceramic, a film-like silicon carbide-based material that can be used as a gas separation membrane such as hydrogen can also be obtained.
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.
＜参考例１＞
日本カーボン社製ポリカルボシランＳタイプ０．２ｇ（商品名、４．７ｍｍｏｌモノマー単位）、1,4−ジエチニルベンゼン（Ｉ−ａ）０．２３ｍｍｏｌおよびシクロオクタジエンジメチル白金０．００２３ｍｍｏｌのトルエン１５ｍｌ溶液を、窒素下、室温で７２時間攪拌することによって、1,4−ジエチニルベンゼンが付加したケイ素系前駆体ポリマーを得た。なお、反応の進行は添加剤の減量をガスクロマトグラフィーで追跡することによって確認した。得られた付加ポリマーをアルゴン気流中、毎分１０℃の昇温速度で６００℃まで加熱したところ、二酸化炭素プローブ分子が大量に吸着しうる多孔性の炭化ケイ素系素材が得られた。
< Reference Example 1>
Nippon Carbon Co., Ltd. polycarbosilane S type 0.2 g (trade name, 4.7 mmol monomer unit), 1,4-diethynylbenzene (Ia) 0.23 mmol and cyclooctadiene dimethyl platinum 0.0023 mmol toluene 15 ml The solution was stirred at room temperature for 72 hours under nitrogen to obtain a silicon-based precursor polymer to which 1,4-diethynylbenzene was added. The progress of the reaction was confirmed by monitoring the weight loss of the additive by gas chromatography. When the obtained addition polymer was heated to 600 ° C. in a stream of argon at a temperature rising rate of 10 ° C. per minute, a porous silicon carbide-based material capable of adsorbing a large amount of carbon dioxide probe molecules was obtained.
＜実施例１＞
1,4−ジエチニルベンゼン（Ｉ−ａ）の代わりにB,B',B''−トリエチニル−N,N',N''−トリメチルボラジン（ＩＩ−ａ）を等モル量で用いたこと以外は、参考例１と同様に付加反応および熱分解及び／または焼成処理を行ったところ、B,B',B''−トリエチニル−N,N',N''−トリメチルボラジンを付加したケイ素系前駆体ポリマーが得られ、この付加ポリマーをアルゴン気流中、毎分１０℃の昇温速度で６００℃まで加熱したところ、二酸化炭素プローブ分子が大量に吸着しうる多孔性の炭化ケイ素系素材が得られた。
<Example 1 >
B, B ′, B ″ -triethynyl-N, N ′, N ″ -trimethylborazine (II-a) was used in equimolar amounts instead of 1,4-diethynylbenzene (Ia) Except for the above, when addition reaction and thermal decomposition and / or calcination treatment were performed in the same manner as in Reference Example 1, silicon added with B, B ′, B ″ -triethynyl-N, N ′, N ″ -trimethylborazine When this addition polymer is heated to 600 ° C. at a rate of temperature increase of 10 ° C./min in an argon stream, a porous silicon carbide material capable of adsorbing a large amount of carbon dioxide probe molecules is obtained. Obtained.
＜実施例２＞
実施例１で調製したB,B',B''−トリエチニル−N,N',N''−トリメチルボラジンと反応させたポリカルボシランのトルエン溶液にセラミック多孔基材チューブ（長さ５０ｍｍ、外径２．９ｍｍ、チューブ壁厚０．７ｍｍ）を浸漬し、乾燥後、アルゴン気流中600℃で熱処理することによって炭化ケイ素系分離膜を調製した。この分離膜の水素および窒素ガスの透過速度を、高真空タイムラグ法により温度100℃で測定した結果、H２透過速度＝16ｘ10−１０[mol/m２・sec・Pa]、N２透過速度＝0.14ｘ10−１０[mol/m２・sec・Pa]、H２/N２透過速度比=114[-]となり、水素/窒素の透過速度比が高く、水素の選択透過性に優れていることがわかった。
<Example 2 >
B prepared in Example 1, B ', B'' - Toriechiniru -N, N', N '' - Se in a toluene solution of polycarbosilane reacted with trimethyl borazine ceramic porous substrate tube (length 50 mm, A silicon carbide separation membrane was prepared by immersing an outer diameter of 2.9 mm and a tube wall thickness of 0.7 mm , followed by drying and heat treatment at 600 ° C. in an argon stream. As a result of measuring the permeation rate of hydrogen and nitrogen gas through this separation membrane at a temperature of 100 ° C. by the high vacuum time lag method, H 2 permeation rate = 16 × 10 −10 [mol / m 2 · sec · Pa], N 2 permeation rate = 0.14 × 10 −10 [mol / m 2 · sec · Pa], H 2 / N 2 permeation rate ratio = 114 [-], hydrogen / nitrogen permeation rate ratio is high, and excellent hydrogen selective permeability I understood.
Claims (10)
で表されるＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類とを前記ポリカルボシランの分子内のＳｉ−Ｈ結合を前記一般式（ＩＩ）で表されるＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類の炭素−炭素三重結合の少なくとも１個に付加反応させて得られる、熱分解及び／又は焼成して炭化ケイ素系素材を与えるケイ素系前駆体ポリマー。 Polycarbosilane and general formula (II)
B, B ′, B ″ -trialkynylborazines represented by the formula: B—B ′, B ″ represented by the general formula (II) in the Si—H bond in the polycarbosilane molecule. -A silicon-based precursor polymer obtained by subjecting an addition reaction to at least one carbon-carbon triple bond of trialkynylborazines to give a silicon carbide-based material by pyrolysis and / or calcination .
で表されるＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類を添加した混合物もしくは請求項１のケイ素系前駆体ポリマーを熱分解及び／または焼成して得られる炭化ケイ素系素材。 General formula (II) for polycarbosilane
A silicon carbide-based material obtained by thermally decomposing and / or calcining a mixture to which B, B ′, B ″ -trialkynylborazines represented by the formula ( 1 ) or a silicon-based precursor polymer according to claim 1 is added.
で表されるＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類とを反応させるにあたり前記ポリカルボシランの分子内のＳｉ−Ｈ結合を前記一般式（ＩＩ）で表されるＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類の炭素−炭素三重結合の少なくとも１個に付加反応させることを特徴とする熱分解及び／又は焼成して炭化ケイ素系素材を与えるケイ素系前駆体ポリマーの製造方法。 Polycarbosilane and general formula (II)
In represented by B, B ', B'' - B represented by the Si-H bonds in the molecule of the polycarbosilane Upon reacting the tri alkynyl borazine compound formula (II), B', A method for producing a silicon-based precursor polymer, which comprises subjecting at least one carbon-carbon triple bond of B ″ -trialkynylborazines to an addition reaction to give a silicon carbide-based material by pyrolysis and / or calcination .
で表されるＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類を添加して混合物を得るか、またはポリカルボシランと前記Ｂ，Ｂ’，Ｂ''−トリアルキニルボラジン類とを反応させてケイ素系前駆体ポリマーを得て、そして前記混合物またはケイ素系前駆体ポリマーを熱分解及び／または焼成することを特徴とする炭化ケイ素系素材の製造方法。 General formula (II) for polycarbosilane
A mixture is obtained by adding B, B ′, B ″ -trialkynylborazines represented by the following formula, or by reacting polycarbosilane with the B, B ′, B ″ -trialkynylborazines. A method for producing a silicon carbide-based material, comprising obtaining a silicon-based precursor polymer and thermally decomposing and / or firing the mixture or the silicon-based precursor polymer.
で表されるＢ，Ｂ’，Ｂ''−トリアルキニルボラジン類を添加して混合物を得るか、またはポリカルボシランと前記Ｂ，Ｂ’，Ｂ''−トリアルキニルボラジン類とを反応させてケイ素系前駆体ポリマーを得て、前記混合物もしくはケイ素系前駆体ポリマーを基材に塗布し、または前記混合物もしくはケイ素系前駆体ポリマーに基材を浸漬もしくは接触させた後、熱分解及び／または焼成することにより、膜状の炭化ケイ素系素材から構成された炭化ケイ素系の気体−気体の分離膜を得ることを特徴とする炭化ケイ素系分離膜の製造方法。 General formula (II) for polycarbosilane
A mixture is obtained by adding B, B ′, B ″ -trialkynylborazines represented by the following formula, or by reacting polycarbosilane with the B, B ′, B ″ -trialkynylborazines. Obtaining a silicon-based precursor polymer and applying the mixture or silicon-based precursor polymer to a substrate, or dipping or contacting the substrate in the mixture or silicon-based precursor polymer, followed by thermal decomposition and / or baking A method for producing a silicon carbide-based separation membrane comprising obtaining a silicon carbide-based gas-gas separation membrane composed of a film-like silicon carbide-based material .
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