KR100693941B1 - Method for producing hydridopolycarbosilane using porous silica as a catalyst - Google Patents
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- KR100693941B1 KR100693941B1 KR1020050022526A KR20050022526A KR100693941B1 KR 100693941 B1 KR100693941 B1 KR 100693941B1 KR 1020050022526 A KR1020050022526 A KR 1020050022526A KR 20050022526 A KR20050022526 A KR 20050022526A KR 100693941 B1 KR100693941 B1 KR 100693941B1
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- hydridopolycarbosilane
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- methyldichlorosilane
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229920000673 poly(carbodihydridosilane) Polymers 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 18
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005048 methyldichlorosilane Substances 0.000 claims abstract description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- -1 MCM-41 Chemical compound 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
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- 239000008096 xylene Substances 0.000 description 7
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- 239000002243 precursor Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000005055 methyl trichlorosilane Substances 0.000 description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 150000003058 platinum compounds Chemical class 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 229910017090 AlO 2 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- NHBMXLXMVPLQAX-UHFFFAOYSA-N 1,3-disiletane Chemical compound C1[SiH2]C[SiH2]1 NHBMXLXMVPLQAX-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DHEMIMYDNSYZRH-UHFFFAOYSA-N C[SiH](Cl)Cl.C[SiH](Cl)Cl Chemical compound C[SiH](Cl)Cl.C[SiH](Cl)Cl DHEMIMYDNSYZRH-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NWKBSEBOBPHMKL-UHFFFAOYSA-N dichloro(methyl)silane Chemical class C[SiH](Cl)Cl NWKBSEBOBPHMKL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000010438 heat treatment 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- 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
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
본 발명은 다공성실리카를 촉매로 사용하여 메틸디클로로실란과 알칼리 또는 알칼리토금속을 반응시켜 하이드리도폴리카보실란을 제조하는 방법에 관한 것으로서, 본 제조방법에 의하면 기존의 방법에 비하여 낮은 코스트 및 고수율로 하이드리도폴리카보실란을 제조할 수 있다.The present invention relates to a method for preparing hydridopolycarbosilane by reacting methyldichlorosilane with alkali or alkaline earth metal using porous silica as a catalyst, and according to the present method, the method has a lower cost and higher yield than the conventional method. Hydridopolycarbosilanes can be prepared.
하이드리도폴리카보실란, 다공성실리카, 메틸디클로로실란 Hydridopolycarbosilane, porous silica, methyldichlorosilane
Description
도 1은 하이드리도폴리카보실란의 구조를 나타낸 도면이고, 1 is a view showing the structure of the hydridopolycarbosilane,
도 2는 실시예 1에서 얻은 하이드리도폴리카보실란의 FT-IR 챠트이다.2 is an FT-IR chart of hydridopolycarbosilane obtained in Example 1. FIG.
미국특허 제 4,631,179호U.S. Patent 4,631,179
미국특허 제 5,153,295호U.S. Patent 5,153,295
본 발명은 도 1에 나타낸 바와 같은 일반식을 갖는 하이드리도폴리카보실란(hydridopolycarbosilane: HPCS)을 제조하는 방법에 관한 것으로서, 보다 구체적으로는 다공성실리카를 촉매로 사용하여 메틸디클로로실란(methyldichlorosilane)과 알칼리금속 또는 알칼리토금속을 반응시켜 하이드리도폴리카보실란을 제조하는 방 법에 관한 것이다. The present invention relates to a method for preparing hydridopolycarbosilane (HPCS) having a general formula as shown in Figure 1, more specifically, methyldichlorosilane (methyldichlorosilane) and alkali using a porous silica as a catalyst The present invention relates to a method for preparing hydridopolycarbosilane by reacting a metal or alkaline earth metal.
하이드리도폴리카보실란은 세라믹 수율이 높고 상온에서 공기 및 수분에 안정성이 우수하여 주로 내산화성, 내열성을 증진시키기 위한 SiC 코팅, SiC 분말, SiC 복합재료의 전구체 또는 SiC계 연속 섬유를 제조하기 위한 전구체로 널리 이용되고 있다. The hydridopolycarbosilane has a high ceramic yield and excellent stability to air and moisture at room temperature, and is mainly a SiC coating, a SiC powder, a precursor of a SiC composite material, or a precursor for producing a SiC-based continuous fiber to improve oxidation resistance and heat resistance. It is widely used as.
현재 SiC 화학증착(chemical vapor deposition: CVD) 전구체로는 메틸트리클로로실란(Methyltrichrolosilane: MTS)이 주로 사용되어지고 있는데 MTS는 세라믹 수율이 낮으며 발연성 위험이 있고 최종 제품에 염소(Cl) 오염문제 등의 이유로 새로운 전구체 개발이 절실히 요구되고 있다. Currently, methyl trichlorosilane (MTS) is mainly used as a chemical vapor deposition (CVD) precursor, and MTS has a low ceramic yield, a risk of smoke, and a chlorine (Cl) contamination problem in the final product. The development of new precursors is urgently needed.
종래 하이드리도폴리카보실란(HPCS)의 제조방법으로는 미국특허 제4,631,179Conventional method for producing hydridopolycarbosilane (HPCS) US Patent No. 4,631,179
호에 기술되는 바와 같이 1,3-디실라사이클로부탄(1,3-disilacyclobutane)을 출발물질로 하여 백금화합물 촉매를 사용하여 개환(ring opening) 반응에 의해 하이드리도폴리카보실란을 제조하는 방법, 미국특허 제5,153,295호에 기술되는 바와 같이 클로로메틸트리클로로실란(chloromethyltrichlorosilane)을 출발물질로하여 Mg와 반응시켜 폴리클로로카보실란을 일차적으로 제조 한 후 LiAlH4를 사용하여 수소화 반응에 의해 하이드리도폴리카보실란을 제조하는 방법이 알려져 있다. 그러나 이 방법들은 고가의 출발물질과 백금화합물을 촉매를 사용하고 또한 고온 고압에서 반응이 진행되므로 제조코스트가 높고, 대규모 합성이 어렵고 위험하며, 수율이 낮은 문제점이 있다.A method for producing hydridopolycarbosilane by ring opening reaction using a platinum compound catalyst using 1,3-disilacyclobutane as a starting material as described in As described in US Pat. No. 5,153,295, chloromethyltrichlorosilane is used as a starting material to react with Mg to prepare polychlorocarbosilanes first, followed by hydridopolycarbo by hydrogenation using LiAlH 4 . Methods of making silanes are known. However, these methods use a catalyst for expensive starting materials and platinum compounds, and the reaction proceeds at a high temperature and high pressure, and thus has a high manufacturing cost, difficult and dangerous synthesis on a large scale, and a low yield.
본 발명은 상기한 선행기술의 문제점을 해결할 수 있는 새로운 하이드리도폴리카보실란의 제조방법을 제공하는 것을 목적으로 한다. It is an object of the present invention to provide a method for preparing a new hydridopolycarbosilane which can solve the above problems of the prior art.
상기한 목적을 달성하기 위한 본 발명자의 연구에서, 특정의 다공성실리카를 촉매로 사용하면 메틸디클로로실란으로부터 하이드리도폴리카보실란을 제조할 수 있으며, 이 방법은 기존의 방법에 비하여 최종 생성물의 수율이 높고, 출발물질과 촉매의 가격이 저렴하며, 반응온도 및 반응압력이 상대적으로 낮아 보다 안전하면서 경제적으로 하이드리도폴리카보실란을 대규모 합성할 수 있다는 사실을 알게되어 본 발명을 완성하게 된 것이다. In the study of the present inventors for achieving the above object, by using a specific porous silica as a catalyst it is possible to prepare a hydridopolycarbosilane from methyldichlorosilane, the method of the final product yields compared to the conventional method The present invention has been completed by knowing that high, low starting materials and catalysts, relatively low reaction temperature and reaction pressure, and safe and economical synthesis of hydridopolycarbosilane can be achieved.
본 발명의 제1 관점은, 특정의 다공성실리카를 촉매로 사용하여 낮은 압력에서 메틸디클로로실란으로부터 하이드리도폴리카보실란을 제조하는 방법에 관한 것이다.A first aspect of the invention relates to a process for preparing hydridopolycarbosilanes from methyldichlorosilanes at low pressure using certain porous silicas as catalysts.
본 발명의 제2 관점은, Si/Al 비 또는 Si/B비가 0~200인 다공성실리카를 촉매로 사용하는 하이드리도폴리카보실란의 제조 방법에 관한 것이다. The 2nd viewpoint of this invention relates to the manufacturing method of hydrido polycarbosilane which uses porous silica whose Si / Al ratio or Si / B ratio is 0-200 as a catalyst.
본 발명의 제3 관점은, 상기 다공성실리카로 MCM-41, MCM-48등의 메조포러스 실리카 또는 ZSM-5, ZSM-11, ZSM-12, 제올라이트 X, 제올라이트 Y등의 마이크로포러스 실리카를 사용하는 하이드리도폴리카보실란의 제조 방법에 관한 것이다.According to a third aspect of the present invention, mesoporous silica such as MCM-41 and MCM-48 or microporous silica such as ZSM-5, ZSM-11, ZSM-12, zeolite X and zeolite Y are used as the porous silica. A method for producing hydridopolycarbosilane.
본 발명의 제4 관점은, 상기 다공성실리카를 0.1~10중량% 사용하는 하이드리 도폴리카보실란의 제조 방법에 관한 것이다.The 4th viewpoint of this invention relates to the manufacturing method of hydrido polycarbosilane which uses 0.1-10 weight% of said porous silicas.
본 발명의 제5 관점은, 반응 온도가 50~200℃인 하이드리도폴리카보실란의 제조 방법에 관한 것이다.A 5th viewpoint of this invention relates to the manufacturing method of hydrido polycarbosilane whose reaction temperature is 50-200 degreeC.
본 발명의 제6 관점은, 반응 시간이 1~24시간인 폴리카보실란의 제조 방법에 관한 것이다.A 6th viewpoint of this invention relates to the manufacturing method of polycarbosilane whose reaction time is 1 to 24 hours.
이하 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서 촉매로 사용되는 다공성실리카는 실리콘 원자를 중심으로 정사면체의 정점에 산소 원자를 결합시킨 3차원 구조를 갖는 것으로서, 이대로는 산으로 되지 않으나, 실리콘(Si4+) 원자 일부를 보론(B3+) 원자 또는 알루미늄(Al3+) 원자로 치환하면 전하보상을 위하여 다공성실리카의 기공 안에 Na+, K+ 등이 들어가 전체구조의 중성을 유지하게 되어 일반식 Nak(AlO2)m(SiO2)n·xH2O 또는 Kk(AlO2)m(SiO2)n·xH2O 등으로 표시되는 구조를 갖게 된다. 합성 후 Na, K를 암모늄 이온 등과 교환하여 소성하면 브렌스테드산형의 다공성 실리카 촉매로 된다. 이러한 브렌스테드산형 다공성실리카의 표면에 부착되어 있는 하이드록실기가 브렌스테드 산점으로 작용하여 메틸디클로로실란이 하이드리도폴리카보실란으로 전환하는 것을 돕는다. 기존의 백금화합물 촉매에 비해 저렴한 상기 다공성실리카 촉매는 Si/Al 비 또는 Si/B 비를 조정함으로써 촉매의 산도 조절이 가능하고, 최종 생성물의 분자량 조절이 용이하며, 목적하는 하이드리도폴리카보실란의 수율을 높게 하 여 주는 장점이 있다. Si/Al 비 또는 Si/B 비는 0~200의 범위내에서 조정하는 것이 바람직하다.The porous silica used as a catalyst in the present invention has a three-dimensional structure in which oxygen atoms are bonded to the vertices of the tetrahedron around silicon atoms, but it is not an acid, but a part of silicon (Si 4+ ) atoms is boron (B 3). + ) Substituted by atom or aluminum (Al 3+ ) atom enters Na + , K +, etc. into the pores of porous silica to compensate for charge, and maintains the neutrality of the entire structure.The formula Na k (AlO 2 ) m (SiO 2) ) n · xH 2 O or K k (AlO 2 ) m (SiO 2 ) n · xH 2 O or the like. After synthesis, the Na and K are exchanged with ammonium ions and calcined to obtain a brested acid porous silica catalyst. The hydroxyl group attached to the surface of the Brentstead acid type porous silica acts as a Brentstead acid point to help the conversion of methyldichlorosilane to hydridopolycarbosilane. The porous silica catalyst, which is inexpensive compared to the conventional platinum compound catalyst, can adjust the acidity of the catalyst by adjusting the Si / Al ratio or the Si / B ratio, and easily control the molecular weight of the final product, and the desired hydridopolycarbosilane It has the advantage of increasing the yield. It is preferable to adjust Si / Al ratio or Si / B ratio in the range of 0-200.
본 발명에서 사용하는 다공성실리카의 바람직한 예로는 MCM-41, MCM-48등의 메조포러스 실리카 또는 ZSM-5, ZSM-11, ZSM-12, 제올라이트 X, 제올라이트 Y등의 마이크로포러스 실리카 등이 있으나, 상기한 구조에 한정되는 것은 아니다. Preferred examples of the porous silica used in the present invention include mesoporous silica such as MCM-41 and MCM-48, or microporous silica such as ZSM-5, ZSM-11, ZSM-12, zeolite X and zeolite Y. It is not limited to the above structure.
본 발명에 의하면 질소 등의 불활성 분위기하에서, 상기한 다공성 실리카 촉매의 존재하에 메틸디클로로실란을 알칼리 금속 또는 알칼리 토금속, 바람직하게는 나트륨 금속을 사용하여 탈염소반응 및 중합반응(축합 반응)을 거쳐 하이드리도폴리카보실란을 제조한다. According to the present invention, methyldichlorosilane is subjected to dechlorination and polymerization (condensation reaction) using an alkali metal or an alkaline earth metal, preferably sodium metal, in an inert atmosphere such as nitrogen and in the presence of the porous silica catalyst described above. Lidopolycarbosilane is prepared.
특별히 제한하기 위한 것은 아니지만 본 발명을 구현하기에 바람직한 방법의 일예를 들어 보다 구체적으로 설명하면, 우선 자일렌, 테트라하이드로퓨란, 톨루엔 등의 용매에 나트륨 금속을 잘게 썰어 넣은 후 가열 교반하여 나트륨 금속을 완전히 분산시키고, 여기에 메틸디클로로실란을 주입후 가열하여 중합체를 형성한 다음에, 잔여 금속 나트륨 및 용매를 제거하고 상기 중합체를 회수함으로써 하이드리도폴리카보실란을 제조할 수 있다. 메틸디클로로실란을 알칼리 금속과 반응시키면 탈염소반응과 중합반응이 일어나 폴리메틸실란이 생성되고 폴리메틸실란으로부터 일부는 자발적으로 쿠마다 자리옮김(Kumadar rearrangement)이 일어나 하이드리도폴리카보실란으로 전환된다. 다공성 실리카 촉매 존재하에서 위 반응을 진행하는 경우 폴리메틸실란으로부터 하이드리도폴리카보실란으로 전환반응 수율이 급격히 증진된다.Although not particularly limited, one example of a preferred method for implementing the present invention will be described in more detail. First, sodium metal is finely chopped in a solvent such as xylene, tetrahydrofuran, toluene, and then heated and stirred to form sodium metal. The hydridopolycarbosilanes can be prepared by dispersing completely, injecting methyldichlorosilane thereto, followed by heating to form a polymer, then removing residual metal sodium and solvent and recovering the polymer. When methyldichlorosilane is reacted with alkali metal, dechlorination and polymerization occur to produce polymethylsilane, and some of the polymethylsilane spontaneously undergoes Kumadar rearrangement to convert to hydridopolycarbosilane. When the above reaction is carried out in the presence of a porous silica catalyst, the yield of conversion from the polymethylsilane to the hydridopolycarbosilane is rapidly increased.
본 발명의 제조 방법에서, 폴리디메틸실란의 산화를 방지하기 위하여, 반응은 불활성 가스 분위기에서 행하여야 한다. 특별히 제한하기 위한 것은 아니지만 불활성 가스의 바람직한 예로는 질소, 아르곤, 헬륨, 일산화탄소, 이산화탄소 등을 들 수 있다. 또한, 본 발명은 상압하에서 행하는 것이 바람직한 데, 그 이유는 진공하에서 행하면, 저분자량 성분이 반응계로부터 증류, 제거되므로 제품의 수율이 떨어지기 때문이다. In the production method of the present invention, in order to prevent oxidation of the polydimethylsilane, the reaction must be carried out in an inert gas atmosphere. Although not particularly limited, preferred examples of the inert gas include nitrogen, argon, helium, carbon monoxide, carbon dioxide, and the like. In addition, the present invention is preferably carried out at normal pressure, because the low molecular weight component distills and removes from the reaction system when the vacuum is carried out, resulting in a poor product yield.
또한 본 발명의 방법에서, 반응 온도는 50℃~200℃, 바람직하게는 70℃~150℃이다. 반응 온도가 50℃ 보다 낮으면 하이드리도폴리카보실란으로 충분한 전환이 일어나지 않으며, 200℃ 보다 높으면 메틸디클로로실란의 급격한 휘발성에 의해 높은 압력이 발생할 우려가 있다.In the method of the present invention, the reaction temperature is 50 ° C to 200 ° C, preferably 70 ° C to 150 ° C. If the reaction temperature is lower than 50 ° C, sufficient conversion to hydridopolycarbosilane does not occur. If the reaction temperature is higher than 200 ° C, high pressure may occur due to the rapid volatility of methyldichlorosilane.
또한 본 발명의 방법에서, 반응 시간은 통상 1~24 시간, 바람직하게는 5~15시간이다. 반응 시간이 1시간 보다 적은 경우에는 하이드리도폴리카보실란으로 충분한 전환이 일어나지 않으며, 24시간을 초과하는 경우에는 더 이상의 수율 향상을 기대할 수 없다.Moreover, in the method of this invention, reaction time is 1 to 24 hours normally, Preferably it is 5 to 15 hours. If the reaction time is less than 1 hour, sufficient conversion to hydridopolycarbosilane does not occur, and if it exceeds 24 hours, further yield improvement cannot be expected.
또한 본 발명의 방법에서, 다공성실리카는 메틸디클로로실란의 중량에 대하여 0.1~10 중량%가 사용된다. 0.1 중량% 미만 사용하면 전환되지 않는 폴리메틸실란의 비율이 높아 수율이 떨어지며, 10 중량%를 초과하여도 수율의 이득을 기대할 수 없다.Also in the method of the present invention, the porous silica is used 0.1 to 10% by weight based on the weight of methyldichlorosilane. If the amount is less than 0.1% by weight, the yield of polymethylsilane which is not converted is high, and the yield is lowered.
[실시예]EXAMPLE
본 발명의 이해를 돕기 위하여 하기 실시예를 들어 설명하지만, 이들 실시예는 본 발명의 하나의 예시에 해당되며, 본 발명이 이들 실시예로 한정되는 것은 아니다.Although the following examples are given for better understanding of the present invention, these examples correspond to one example of the present invention, and the present invention is not limited to these examples.
본 발명의 다공성실리카 촉매를 사용하여 낮은 압력에서 메틸디클로로실란으로부터 하이드리도폴리카보실란을 제조하는 방법을 설명하기로 한다. 하기 실시예에서 사용된 다공성실리카 촉매는 다음과 같이 제조하였다.A method for preparing hydridopolycarbosilane from methyldichlorosilane at low pressure using the porous silica catalyst of the present invention will be described. The porous silica catalyst used in the examples below was prepared as follows.
촉매의 제조Preparation of the catalyst
<MCM-41 촉매 제조><MCM-41 Catalyst Preparation>
실리콘 원료로는 테트라오르소실리케이트(tetraorthosilicate, TEOS)를 사용하였으며, 구조유도체로 세틸트리메틸암모늄브로마이드(cetyltrimethylammonium bromide: CTMABr)를 사용하였고, pH 조절을 위하여 테트라메틸암모늄 하이드록사이드(tetramethylammonium hydroxide: TMAOH) (25% 수용액)를 사용하였다. 45℃, 20㎖의 증류수에 TMAOH 1.45㎖를 넣고 저어준 후 0.058g~0.116g의 AlCl3를 첨가하여 녹을 때 까지 저어 준 후 2.25g의 CTABr을 첨가하여 CTABr이 다 녹을 때까지 저어준다. CTABr이 다 녹으면 테트라오르소실리케이트 5㎖를 첨가하고 24시간 동안 상온에서 저어주면서 숙성한 후 반응용기(Teflon lined hydrothermal bomb)에 옮겨 넣어 150℃에서 24시간 반응시킨다. 반응이 끝난 후, 에탄올과 증류수로 세척하면서 필터한다. 시료를 60℃에서 건조시킨 후 순수한 Si/Al비 15~30의 MCM-41 촉매 를 얻었다. 600℃에서 4시간 하소하여 MCM-41 기공내에 존재하는 구조유도체를 제거한 후 촉매로 사용하였다.Tetraorthosilicate (TEOS) was used as a silicon raw material, cetyltrimethylammonium bromide (CTMABr) was used as a structural derivative, and tetramethylammonium hydroxide (TMAOH) was used for pH control. (25% aqueous solution) was used. Stir 1.45 ml of TMAOH in 20 ml of distilled water at 45 ° C, stir, add 0.058 g to 0.116 g of AlCl 3 , stir until dissolved, and add 2.25 g of CTABr until the CTABr is completely dissolved. When the CTABr is dissolved, add 5 ml of tetraorthosilicate and stir at room temperature for 24 hours, then transfer to a reaction vessel (Teflon lined hydrothermal bomb) to react at 150 ℃ for 24 hours. After the reaction, the filter is washed with ethanol and distilled water. After drying the sample at 60 ℃ to obtain a pure Si / Al ratio of 15 ~ 30 MCM-41 catalyst. It was calcined at 600 ° C. for 4 hours to remove the structural derivatives present in the pores of MCM-41 and used as a catalyst.
<ZSM-5 제올라이트 촉매 제조><ZSM-5 Zeolite Catalyst Preparation>
테프론 반응 용기에 수산화나트륨(97%) 1.37g과 테트라프로필암모늄 브로마이드(98%) 5.43g과 Na2O·Al2O3·H2O 0.619g을 넣고, 여기에 물 126g을 첨가하여 1시간 동안 저어서 용해하였다. 그 후 여기에 연무 실리카(fumed silica) 12g을 첨가하여 12시간 저어준 후, 상기 테프론 용기를 스테인레스제 용기에 넣고 150℃에서 5일 동안 가열하여 불순물이 함유된 Si/Al비 30의 ZSM-5 제올라이트 촉매를 얻었다. 상기 촉매를 증류수로 수회 세척한 후 100℃ 오븐에서 건조하고, 이어서 상기 촉매에 포함되어 있는 아민을 제거하기 위하여 550℃에서 12시간 소성하고, 또한 상기 촉매에 포함되어 있는 Na이온을 제거하기 위하여 상기 촉매 1g당 0.1M 질산암모늄 수용액 100g을 사용하여 12시간 환류하였다. 그 후, 촉매를 증류수로 수회 세척하고, 오븐에서 건조한 다음, 500℃의 공기 중에서 4시간 더 소성하여, 순수한 Si/Al비 30의 ZSM-5 제올라이트 촉매를 얻었다. Into a Teflon reaction vessel, 1.37 g of sodium hydroxide (97%), 5.43 g of tetrapropylammonium bromide (98%), and 0.619 g of Na 2 O · Al 2 O 3 · H 2 O were added thereto, followed by addition of 126 g of water for 1 hour. Then dissolved. Thereafter, 12 g of fumed silica was added thereto, followed by stirring for 12 hours. Then, the Teflon container was placed in a stainless steel container and heated at 150 ° C. for 5 days, thereby containing ZSM-5 having a Si / Al ratio of 30. Zeolite catalyst was obtained. The catalyst was washed several times with distilled water and then dried in an oven at 100 ° C., and then calcined at 550 ° C. for 12 hours to remove the amine contained in the catalyst, and the Na ions contained in the catalyst were removed. 100 g of 0.1 M aqueous ammonium nitrate solution per g of catalyst was refluxed for 12 hours. Thereafter, the catalyst was washed several times with distilled water, dried in an oven, and further calcined in air at 500 ° C. for 4 hours to obtain a pure Si /
본 발명에서 사용한 하이드리도폴리카보실란은 다음과 같이 제조하였다The hydridopolycarbosilane used in the present invention was prepared as follows.
하이드리도폴리카보실란의 제조Preparation of Hydrido Polycarbosilane
<실시예 1><Example 1>
4목 둥근 플라스크에 자일렌 128ml를 투입한 다음 나트륨 금속 18.4g을 질소 분위기하에서 잘게 썰어 넣고 가열 교반하여 상기 용매에 분산시켰다. 여기에 MCM-41 촉매 0.3g 존재하에서 메틸디클로실란 22ml을 주입하고, 120℃에서 4시간 반응시켜 진한 갈색의 침전물을 얻었다. 이 반응물을 실온으로 냉각하고, 질소하에서 여과하여 침전물을 분리하였다. 침전물은 메틸알콜을 첨가하여 미반응 나트륨 금속과 반응시켜 안정하게 변환시킨 후 폐기하였으며, 여과액을 진공 증류하여 자일렌을 제거함으로써 하이드리도폴리카보실란 5.87g을 얻었다. 이 하이드리도폴리카보실란에 대하여 FT-IR를 측정한 결과는 도 2의 그래프와 같다. 128 ml of xylene was added to a four-necked round flask, and 18.4 g of sodium metal was chopped in a nitrogen atmosphere and heated and stirred to disperse in the solvent. 22 ml of methyldiclosilane was injected in the presence of 0.3 g of MCM-41 catalyst and reacted at 120 ° C. for 4 hours to obtain a dark brown precipitate. The reaction was cooled to room temperature and filtered under nitrogen to separate the precipitate. The precipitate was reacted with unreacted sodium metal by the addition of methyl alcohol to be converted to a stable state and then discarded. 5.87 g of hydridopolycarbosilane was obtained by removing the xylene by vacuum distillation of the filtrate. The FT-IR measurement results of the hydridopolycarbosilane are shown in the graph of FIG. 2.
수득한 하이드리도폴리카보실란은 도 2의 그래프로부터 알수 있는 바와 같이 불순물이 없는 순수한 하이드리도폴리카보실란이었다. IR spectra에서 하이드리도폴리카보실란 합성을 확인 할 수 있는 Si-CH2-Si의 피크가 1030cm-1에서 관찰되었다. 930cm-1과 850cm-1에 나타나는 피이크는 Si-H3 또는 Si-H2 벤딩(bending) 및 스트레칭(stretching)을 나타내며 1245 cm-1에서는 Si-CH3에 의한 피크가 관찰된다. 1350 cm-1, 1390 cm-1은 CH2나 CH3에서의 H stretching이며 비교적 날카로운 피크인 2095 cm-1는 Si-H를 나타낸다. 2900 cm-1 전후에서 나타난 두 개의 피크는 C-H에 의한 것이다. The obtained hydridopolycarbosilane was pure hydridopolycarbosilane free of impurities, as can be seen from the graph of FIG. 2. In IR spectra, the peak of Si-CH2-Si was observed at 1030cm -1 to confirm the hydridopolycarbosilane synthesis. Peaks appearing at 930 cm -1 and 850 cm -1 indicate Si-H 3 or Si-H 2 bending and stretching, and peaks due to Si-CH 3 are observed at 1245 cm -1 . 1350 cm -1 and 1390 cm -1 are H stretching in CH 2 or CH 3 and the relatively sharp peak of 2095 cm -1 represents Si-H. The two peaks appearing before and after 2900 cm −1 are due to CH.
투입 메틸디클롤로실란과 생성 하이드리도폴리카보실란의 중량비로 측정되는 수율은 62.0% 이었다. The yield measured by weight ratio of charged methyldichlorolosilane and produced hydridopolycarbosilane was 62.0%.
<실시예 2><Example 2>
4목 둥근 플라스크에 자일렌 128ml를 투입한 다음 나트륨 금속 18.4g을 질소 분위기하에서 잘게 썰어 넣고 가열 교반하여 상기 용매에 분산시켰다. 여기에 ZSM-5 촉매 0.3g 존재하에서 메틸디클로실란 22ml을 주입하고, 120℃에서 4시간 반응시켜 진한 갈색의 침전물을 얻었다. 이 반응생성물을 실온으로 냉각하고, 질소하에서 여과하여 침전물을 분리하였다. 침전물은 메틸알콜을 첨가하여 미반응된 나트륨 금속과 반응시켜 안정하게 변환시킨 후 폐기하였으며, 여과액을 진공 증류하여 자일렌을 제거함으로써 하이드리도폴리카보실란 7.66g을 얻었다. 이 하이드리도폴리카보실란에 대하여 FT-IR를 측정한 결과 불순물이 없는 순수한 하이드리도폴리카보실란임을 확인할 수 있었다. 128 ml of xylene was added to a four-necked round flask, and 18.4 g of sodium metal was chopped in a nitrogen atmosphere and heated and stirred to disperse in the solvent. 22 ml of methyldiclosilane was injected in the presence of 0.3 g of a ZSM-5 catalyst, and reacted at 120 ° C for 4 hours to obtain a dark brown precipitate. The reaction product was cooled to room temperature and filtered under nitrogen to separate the precipitate. The precipitate was reacted with unreacted sodium metal by the addition of methyl alcohol, converted to stability, and then discarded. 7.66 g of hydridopolycarbosilane was obtained by removing the xylene by vacuum distillation of the filtrate. The FT-IR of this hydridopolycarbosilane was determined to be pure hydridopolycarbosilane without impurities.
투입 메틸디클롤로실란과 생성 하이드리도폴리카보실란의 중량비로 측정되는 수율은 81.0% 이었다. The yield measured by weight ratio of charged methyldichlorolosilane and produced hydridopolycarbosilane was 81.0%.
<비교예 1>Comparative Example 1
4목 둥근 플라스크에 자일렌 128ml를 투입한 다음 나트륨 금속 18.4g을 질소 분위기하에서 잘게 썰어 넣고 가열 교반하여 상기 용매에 분산시켰다. 여기에 메틸디클로실란 22ml을 주입하고, 촉매의 사용이 없이 120℃에서 4시간 반응시켜 역시 진한 갈색의 침전물을 얻었다. 이 반응물을 실온으로 냉각하고, 질소하에서 여 과하여 침전물을 분리하였다. 침전물은 메틸알콜을 첨가하여 미반응된 나트륨 금속과 반응시켜 안정하게 변환시킨 후 폐기하였으며, 여과액을 진공 증류하여 자일렌을 제거함으로써 하이드리도폴리카보실란 4.0g을 얻었다. 이 하이드리도폴리카보실란에 대하여 FT-IR를 측정한 결과 불순물이 없는 순수한 하이드리도폴리카보실란임을 확인할 수 있었다. 128 ml of xylene was added to a four-necked round flask, and 18.4 g of sodium metal was chopped in a nitrogen atmosphere and heated and stirred to disperse in the solvent. 22 ml of methyldiclosilane was added thereto, and the mixture was reacted at 120 ° C. for 4 hours without using a catalyst to obtain a dark brown precipitate. The reaction was cooled to room temperature and filtered off under nitrogen to separate the precipitate. The precipitate was reacted with unreacted sodium metal by the addition of methyl alcohol to be converted to a stable state and then discarded. 4.0 g of hydridopolycarbosilane was obtained by removing the xylene by vacuum distillation of the filtrate. The FT-IR of this hydridopolycarbosilane was determined to be pure hydridopolycarbosilane without impurities.
투입 메틸디클롤로실란과 생성 하이드리도폴리카보실란의 중량비로 측정되는 수율은 42.0% 이었다. The yield measured by weight ratio of charged methyldichlorolosilane and produced hydridopolycarbosilane was 42.0%.
이상 설명한 바와 같이 본 발명에 따라 브렌스테드산형 다공성실리카 촉매를 사용하면 종래 방법에 비해 상당히 낮은 압력과 온도에서 메틸디클로로실란으로부터 하이드리도폴리카보실란을 고수율로 제조할 수 있으며, 또한 상기한 출발물질과 촉매가 저렴하여 제조코스트를 크게 낮출 수 있게 된다. As described above, the use of the Brensted acid type porous silica catalyst according to the present invention enables the preparation of hydridopolycarbosilanes from methyldichlorosilane in a high yield at a significantly lower pressure and temperature than the conventional method. Inexpensive materials and catalysts can significantly lower the manufacturing cost.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3989733A (en) | 1972-12-30 | 1976-11-02 | Shinetsu Chemical Company | Process for the preparation of cyclic polydiorganosiloxanes |
| US5563212A (en) | 1994-05-24 | 1996-10-08 | Exxon Research And Engineering Company | Synthesis of microporous ceramics |
| KR20040100231A (en) * | 2003-05-22 | 2004-12-02 | 주식회사 데크 | The method of producing polycarbosilane using zeolite as catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3989733A (en) | 1972-12-30 | 1976-11-02 | Shinetsu Chemical Company | Process for the preparation of cyclic polydiorganosiloxanes |
| US5563212A (en) | 1994-05-24 | 1996-10-08 | Exxon Research And Engineering Company | Synthesis of microporous ceramics |
| KR20040100231A (en) * | 2003-05-22 | 2004-12-02 | 주식회사 데크 | The method of producing polycarbosilane using zeolite as catalyst |
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