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WO1999003911A1 - Polymeres organosilicies de forme tubulaire, leur preparation et leurs utilisations - Google Patents

Polymeres organosilicies de forme tubulaire, leur preparation et leurs utilisations Download PDF

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Publication number
WO1999003911A1
WO1999003911A1 PCT/CN1998/000127 CN9800127W WO9903911A1 WO 1999003911 A1 WO1999003911 A1 WO 1999003911A1 CN 9800127 W CN9800127 W CN 9800127W WO 9903911 A1 WO9903911 A1 WO 9903911A1
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WO
WIPO (PCT)
Prior art keywords
reaction
polymer
tube
ladder
coupling
Prior art date
Application number
PCT/CN1998/000127
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English (en)
Inventor
Rongben Zhang
Xinyu Cao
Ping Xie
Ze Li
Hui Xu
Letian Wang
Ming Cao
Daorong Dai
Original Assignee
Institute Of Chemistry, Chinese Academy Of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute Of Chemistry, Chinese Academy Of Sciences filed Critical Institute Of Chemistry, Chinese Academy Of Sciences
Priority to AU83304/98A priority Critical patent/AU8330498A/en
Publication of WO1999003911A1 publication Critical patent/WO1999003911A1/fr

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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
    • C08G77/48—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 at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • 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
    • C08G77/48—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 at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—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 at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages

Definitions

  • the present invention relates to a organosilicon polymer having tube-like structure, particularly the present invention relates to a tube-like organosilicon polymers and preparation and uses thereof.
  • Known tube-like polymers includes, for example, those reported by S. lijima in 1991 ⁇ Nature, 1991, 354, 56.), in which the preparation and structure of nano-scale carbon tubes is described.
  • This tube-like polymer is an inorganic nano-scale tube.
  • Recently Akira Harada et al reported the formation of tube-like polymers by using naturally occurring cyclodextrins as the raw materials. Because the dimension and the shape of the cyclodextrin unit are fixed, the diameter and affinity of the tube-like polymers resulting from cyclodextrins are also fixed and difficult to control.
  • H. Nakamura et al reported a tube-like polymer prepared by using siloxane gel as starting materials. However, the polymer is not soluble nor meltable. For the above reasons, the applications of these tube-like polymers are limited.
  • Chinese Patent No. CN 941005071 disclosed the highly regulated ladder-like hydrogen polysilsesquioxanes and copolymers and their preparations.
  • Japanese Patent No. JP 08188649 disclosed the highly regulated ladder-like polysilsesquoxanes and copolymers containing reactive groups and their preparations. They are synthesized via pre-coupling and stepwise hydrolyzation, condensation by using organosilicon monomers containing reactive groups, such as trichlorosilane, vinyltrichlorosilane, allylthchlorosilane, ethoxytrichlorosilane etc as starting materials, and employing ⁇ , ⁇ -diamine as the coupling reagent. They have the following structure.
  • R-T Structure of ladder-like polysilsesquioxanes (R-T) (R and R' are the same or different groups selected from vinyl, allyl, hydrogen, alkoxane, and the like). It is a double chain ladder-like polymer and shows no tube-like structure.
  • the present invention is directed to solving the problems of above-mentioned inorganic polymers, polymers of naturally occurring materials or insoluble and unmeltable polymers of cross-linked system by providing a method of synthesizing tube-like organosilicon polymers. Its molecular dimension, chemical affinity, and shape can be readily adjusted by selecting the coupling reagents and the solvents. Its solubility in a wide variety of solvent makes it possible to re-process the material conveniently.
  • the tube-like polymer is formed by the coupling reaction of the reactive groups on the side chains of the ladder-like organosilicon polymer.
  • the instant invention thus provides a soluble tube-like organosilicon polymer with controllable microstructures (i.e., the diameter and chemical affinity of the tube).
  • the structure of the tube-like polymer is shown in Figure 1.
  • the tube-like structure shown in figure 1 a is formed either by the coupling reaction between two ladder-like polymers having different functional groups, such as Allyl-T and H-T, Vi-T and H-T, H-T and EtO-T, and so on; or by the coupling reaction between two ladder-like polymers with the same functional groups, such as Vi-T and Vi-T, Allyl-T and Allyl-T, EtO-T and EtO-T, through a coupling reagent.
  • the tube-like structure in figure 1b is formed by the coupling reaction between reactive groups on the side chain of the same ladder-like polymer through a coupling reagent.
  • Figure 1 Shows the general structures of tube-like polymers, wherein
  • bridge groups are: (CH 2 ) X , CH 2 CH 2 (SiMe 2 O) ⁇ CH 2 CH2, CH 2 (CH 2 ) m C 6 H 4 (CH 2 )mCH 2 , CH 2 (CH 2 ) n OC 6 H 4 (CH 2 ) n CH 2 , O(CH 2 ) n C 6 H 4 (CH 2 )nO, or OOC(CH 2 )nC 6 H 4 (CH2)nCOO, wherein x is an integer from 2 to 10, m is an integer from 1 to 10, n is an integer from 0 to 10.
  • the preparation of the tube-like polymers of the present invention is carried out according to following steps: (1 ) Synthesis of highly regulated ladder-like organosilicon polymers having reactive groups; (2) Introduction of fixing agent and template agent for end-groups of the ladder-like polymers; (3) Soluble tube-like polymer is formed by the coupling reaction.
  • the molar ratio of water to vinyltrichlorosilane is 1.5 - 3 : 1.
  • the mixture is then stirred at 25°C for 1 to 2 hours.
  • the ammonium salt is filtered off and the filtrate is washed with water until neutral and dried over anhydrous sodium sulfate.
  • trichlorosilane and dried toluene To a reaction apparatus are added trichlorosilane and dried toluene.
  • concentration of the former is in the range of 0.05 - 0.1 g/mL.
  • the reaction temperature is kept at -30 to 0°C.
  • p-phenylenediamine in dried acetone Concentration: about 0.02 - 0.1 g/mL
  • the molar ratio of trichlorosilane and p-phenylenediamine is 1 :1.
  • dried acetone diluted with water the concentration is 0.02 - 0.1 mL of water/per mL of acetone
  • ethoxytrichlorosilane To a reaction apparatus are added ethoxytrichlorosilane and dried toluene.
  • concentration of the former is in the range of 0.05 - 0.1 g/mL.
  • the reaction temperature is kept at -30 to 0°C.
  • p-phenylenediamine in dried acetone (The concentration is about 0.02 - 0.1 g/mL) is added.
  • the molar ratio of the ethoxytrichlorosilane to p-phenylenediamine is 1 :1.
  • dried acetone diluted with water The concentration is 0.02 - 0.1 mL of water/per mL of acetone.
  • certain amount of pyridine is added.
  • the molar ratio of ethoxytrichlorosilane to water is 1 : 1 - 5 and the molar ratio of pyridine to ethoxyltrichlorosilane is 1 - 2 : 1.
  • the mixture is then stirred at 25°C for 1 to 2 hours.
  • the ammonium salt is filtered off and the filtrate is washed with water until neutral and dried over anhydrous sodium sulfate.
  • the fixing agent for end-groups of ladder-like polymer is the bifunctional molecule which can react with the terminal hydroxy group on ladder-like polymers, such as HO-[Si(CH 3 ) O-] m -OH (m is an integer from 1 to 10), HO(CH 2 ) x OH ( x is an integer from 2 to 10), hydroquinone etc.
  • the template agents introduced are: (1 ) molecule which can form hydrogen bond with ladder-like polymers; (2) electron-rich and electron-poor groups which can be partially introduced into ladder-like polymers; (3) ion which can form complex with ladder-like polymers by coordination reaction.
  • the hydrosilylation reaction is the addition reaction of hydrogen silane to unsaturated hydrocarbons.
  • Ladder-like polymers having lateral groups of vinyl, allyl, and hydrogen can be coupled to form tube-like polymers via hydrosilysation reaction.
  • Ladder-like polymers can be coupled by the following three methods.
  • Table 1 (1) Coupling reaction between two ladder-like polymers having different functional groups, such as Allyl-T and H-T, Vi-T and H-T.
  • the synthetic procedure is as follows: Two ladder-like polymers are dissolved in dried solvents, respectively. Then under the inert gas atmosphere they are added with the molar ratio of 1 : 0.8 to 1 : 1.5 into a reaction apparatus. Solvent and catalyst are added to the reaction mixture.
  • the concentrations of reactants are in the range of 10 - 40 mg/mL.
  • the reaction is allowed to proceed at 50 -120°C for 12 - 72 hours. After the removal of solvent, the tube-like polymer as shown in figure 1a is obtained.
  • Two ladder-like polymers are dissolved in dried solvent. Then under the inert gas atmosphere they are added into a reaction apparatus. Solvent, catalyst, and coupling reagent are added to the reaction mixture. The concentrations of reactants are in the range of 10 - 40 mg/mL. The reaction is carried out at 30 -100°C for 12 - 72 hours. After the removal of solvent, the tube-like polymer as shown in figure 1 a is obtained. (3) Coupling reaction between reactive groups on the main chains of the same ladder-like polymer through coupling reagents, such as H-T, Vi-T, and Allyl-T The synthetic procedure is as follows: The ladder-like polymer is dissolved in dried solvent. Then under the inert gas atmosphere it is added into a reaction apparatus.
  • Solvent, catalyst, and coupling reagent are added to the reaction mixture.
  • concentrations of reactants are in the range of 5 - 10 mg/mL.
  • the reaction is carried out at 30 -100°C for 12 - 72 hours. After the removal of solvent, the tube-like polymer as shown in figure 1 b is obtained.
  • the solvents may be used in hydrosilylation reaction include toluene, xylene, ethylene glycol dimethyl ether, poly(allyl ether), dimethyl o-phthalate, tetrahydrofuran (THF), 1 , 4-dioxane, cyclohexanone, acetone, alcohols, or a mixture of above solvents.
  • the amount of the solvent(s) is 50 - 500 mL/per gram of R-T.
  • the coupling reagents may be used in the hydrosilylation reaction include
  • the molar ratio of coupling reagent to R-T is 1.5 - 0.8 : 1 .
  • the catalysts may be used in this invention for hydrosilylation reaction are those catalysts that have the effect on the hydrosilylation reaction, especially those transition metal complexes, which show high selectivity for the hydrosilylation reaction such as platinum catalysts H 2 PtCI 6 6H 2 O, Cp 2 PtCI 2 , complex of Pt and Vi- SiMe 2 OSiMe 2 -Vi (Karstedt's catalyst), complexes of Pt ° " ⁇ v and alkenes, complexes of Pd and Rh, chelate complexes of the above-mentioned metals, and colloidal metal catalysts.
  • the amount of catalyst is 0.5 ppm - 1 %.
  • the silane oxidation reaction is the reaction of hydrosilane, alkoxysilane, or the hydroxysilane formed from hydrosilane or ethoxysilane with dihydroxy alcohol, diphenol, silanediol to produce silyl ether (alkoxy/phenoxy silane) by dehydration, dehydrogenation or dealcoholization. This reaction is applicable to the ladder-like polymers with hydrogen and alkoxy as reactive groups.
  • Ladder-like polymers may be coupled by the following three methods. (Table 1)
  • Two ladder-like polymers are dissolved in dried solvents, respectively. Then under the inert gas atmosphere they are added with the molar ratio of 1 : 0.8 to 1 : 1.5 into a reaction apparatus. Solvent and catalyst are added to the reaction mixture. The concentrations of reactants are in the range of 10 - 40 mg/mL. The reaction is allowed to proceed at 50 -120°C for 12 - 72 hours. Produced small molecules are removed during the reaction. After the removal of solvent, the tubelike polymer as shown in figure 1a is obtained.
  • the synthetic procedure is as follows.
  • Two ladder-like polymers are dissolved in the dried solvent. Then under the inert gas atmosphere they are added into a reaction apparatus. Solvent, catalyst, and coupling reagent are added to the reaction mixture. The concentrations of reactants are in the range of 10 - 40 mg/mL. The reaction is allowed to proceed at 30 -100°C for 12 - 72 hours. Small molecules produced during the reaction are removed. Removal of solvent yielded the tube-like polymer as shown in figure 1a. (3) Coupling reaction between reactive groups on the main chains of the same ladder-like polymer having the same functional groups, such as H-T or EtO-T, through a coupling reagent.
  • the synthetic procedure is as follows: The ladder-like polymer is dissolved in dried solvent. Then under the inert gas atmosphere it is added into a reaction apparatus. Catalyst and coupling reagent are added to the reaction mixture. The concentrations of reactants are in the range of 5 - 10 mg/mL. The reaction is carried out at 30 -100°C for 12 - 72 hours. Produced small molecules are removed during the reaction. Removal of solvent yielded the tube-like polymer as shown in figure 1 b.
  • the oxidation coupling reagents used in the silane oxidation reaction include HO-[Si(CH 3 ) 2 O-] x -OH (x is an integer from 2 to10), HO(CH 2 ) x OH (x is an integer from 2 to 10), hydroquinone, biphenol A, 1 , 4-benzenedimethanol, and the alkali salts of those compounds.
  • the molar ratio of the coupling reagent to R-T is 1.5 - 0.8 to 1.
  • the solvents used in the above silane oxidation coupling reaction are the same as those used in the hydrosilylation reaction, except that the alcohols are limited to those mixed solvents with low boiling points.
  • the catalysts for the above silane oxidation reaction are oxides of alkalis, hydroxides of alkalis, sodium salts of alcohols, sodium salts of phenols, inorganic acids, strong organic acids, halides, or amines.
  • the amount of catalyst is in the range of 0.1- 10%.
  • the silane acyloxylation reaction is the reaction of alkoxysilane, or the hydroxysilane formed from the hydrolysis of alkoxysilane and hydrogen silane, with diprotic acid or diacyl chloride to produce acyloxysilane (silyl ester) and byproducts such as acetic acid or hydrogen chloride.
  • This reaction is applicable to the ladder-like polymers with hydrogen and ethoxy as reactive groups.
  • Ladder-like polymers may be coupled by the following three methods. (Table 1 ) (1) Coupling reaction between two ladder-like polymers having different functional groups, such as EtO-T and H-T.
  • Two ladder-like polymers are dissolved in dried solvents, respectively. Then under the inert gas atmosphere, they are added with the molar ratio of 1 : 0.8 to 1 : 1.5 into a reaction apparatus. Solvent and catalyst are added to the reaction mixture. The concentrations of reactants are in the range of 10 - 40 mg/mL. The reaction is carried out at 50 -120°C for 12 - 72 hours. Produced small molecules are removed during the reaction. Removal of solvent yielded the tube-like polymer as shown in figure 1a.
  • Two ladder-like polymers are dissolved in the dried solvent. Then under the inert gas atmosphere they are added to a reaction apparatus. Catalyst and coupling reagent are added to the reaction mixture. The concentrations of reactants are in the range of 10 - 40 mg/mL. The reaction is carried out at 30 -100°C for 12 - 72 hours. Produced mall molecules are removed during the reaction. Removal of solvent yielded the tube-like polymer as shown in figure 1a. (3) Coupling reaction between reactive groups on the main chains of the same ladder-like polymer having the same functional groups, such as H-T or EtO-T, through a coupling reagent.
  • the ladder-like polymer is dissolved in dried solvent. Then under the inert gas atmosphere it is added into a reaction apparatus. Catalyst and coupling reagent are added to the reaction mixture. The concentrations of reactants are in the range of 5 - 10 mg/mL. The reaction is carried out at 30 -100°C for 12 - 72 hours. Produced small molecules are removed during the reaction. Removal of solvent yielded the tube-like polymer as shown in figure 1 b.
  • the coupling reagents may be used in the silane acyloxylation reaction include HOOC(CH 2 ) m COOH (m is an integer from 1 to 10), HOOC(C 6 H 4 ) y COOH (y is 1 or 2), XOC(CH 2 )nCOX(n is an integer from 0 to 10), XOC(C 6 H 4 ) y COX (y is 1 or 2; X is a halogen), and so on.
  • the molar ratio of the coupling reagent to R-T is 1.5 - 0.8 : 1.
  • the solvents may be used in the silane acyloxylation reaction are the same as those used in the hydrosilylation reaction, except the alcohols.
  • the catalysts may be used in the silane acyloxylation reaction are strong inorganic acids, aluminum, iodine, colloidal nickel, and the metals and their complexes in Group VIII.
  • the amount of the catalyst is 0.1- 10%.
  • the micro-scale dimension and affinity of the tube-like organosilicon polymers of this invention can be adjusted and controlled. (Table 1 )
  • AFM data are from those bright parts observed.
  • the AFM pictures showed that molecules are streak arranged.
  • the data on the table are the distances between the two bright lines. These distances represent, to some extend, the width of molecular chains; but it is a little shorter than the real distance. From the data of DSC and light scattering results, it can be seen that the tube-like polymers have rod-like structures with certain rigidity.
  • the tube-like polymers can be further processed easily.
  • solvents include toluene, xylene, ethylene glycol dimethyl ether, poly(allyl ether), dimethyl o-phthalate, THF, 1 , 4-dioxane, cyclohexanone, acetone, isopropanol, isobutanol, or a mixture of above solvents.
  • These new tubelike polymers can form complexes with guest molecules; thus may be used in a variety of applications. Because of its unique and controllable structure, it can be used as functional materials, such as biosensors, supermolecular catalysts, supermolecular separation membranes, new optical and electronical materials.
  • Example 6 Coupling reaction between lateral vinyl groups on the main chains of a Vi-T polymer through HMM
  • Example 7 Coupling reaction between lateral allyl groups on the main chains of a Allyl-T polymer through HMM
  • 0 o tube-like polymer was 5 ⁇ 10A, and the outer diameter was 12 ⁇ 16A.
  • AFM result showed that its outer diameter was 10.3A.
  • Example 12 Coupling reaction between two H-T through HOOC(CH 2 ) 4 COOH
  • Example 13 Coupling of lateral groups on the same H-T polymer through HOOC(CH 2 ) 4 COOH

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne un polymère organosilicié présentant une structure tubulaire, plus particulièrement un polymère organosilicié de forme tubulaire. On prépare ce polymère en faisant réagir les polymères organosiliciés en échelle présentant des groupes réactifs ou en faisant réagir les polymères organosiliciés en échelle avec des réactifs de couplage. Ce polymère est soluble dans une variété de solvants organiques et présente une structure régulière et un diamètre nanométrique des pores. On peut régler le diamètre moléculaire et l'affinité chimique de celui-ci en sélectionnant différents polymères organosiliciés en échelle et réactifs de couplage. son poids moléculaire est compris entre 10?3 et 106¿. Lorsqu'on forme des complexes en les mélangeant avec des molécules présentant des dimensions et une affinité chimique adéquates, on peut obtenir des complexe utiles dans les dispositifs moléculaires, dans les appareils de réaction nanométriques, lors de la catalyse et de la séparation faisant intervenir la reconnaissance des molécules.
PCT/CN1998/000127 1997-07-17 1998-07-16 Polymeres organosilicies de forme tubulaire, leur preparation et leurs utilisations WO1999003911A1 (fr)

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Application Number Priority Date Filing Date Title
AU83304/98A AU8330498A (en) 1997-07-17 1998-07-16 Tube-like organosilicon polymers and the preparation and uses thereof

Applications Claiming Priority (2)

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CN97112236.9 1997-07-17
CN 97112236 CN1206019A (zh) 1997-07-17 1997-07-17 有机硅管状高分子及其制备方法和用途

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0982344A2 (fr) * 1998-08-27 2000-03-01 Dow Corning Corporation Polymères du type feuille et tube ayant des groupes siloxane pendants
US6423772B1 (en) 1999-07-16 2002-07-23 Institute Of Chemistry, Chinese Academy Of Sciences Organo-bridged ladderlike polysiloxane, tube-like organosilicon polymers, complexes thereof, and the method for producing the same
CN101024691B (zh) * 2006-08-14 2010-07-07 南京大学 一种自组装生长的聚倍半硅氧烷纳米管及纳米线的制法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60110726A (ja) * 1983-11-18 1985-06-17 Mitsubishi Electric Corp シリコ−ン化合物の製法
JPS61278532A (ja) * 1985-06-05 1986-12-09 Mitsubishi Electric Corp 末端ヒドロキシフエニルラダ−ポリシロキサンの製法
JPH0641307A (ja) * 1992-01-23 1994-02-15 Showa Denko Kk グラフト変性ラダーシリコーンおよびその組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60110726A (ja) * 1983-11-18 1985-06-17 Mitsubishi Electric Corp シリコ−ン化合物の製法
JPS61278532A (ja) * 1985-06-05 1986-12-09 Mitsubishi Electric Corp 末端ヒドロキシフエニルラダ−ポリシロキサンの製法
JPH0641307A (ja) * 1992-01-23 1994-02-15 Showa Denko Kk グラフト変性ラダーシリコーンおよびその組成物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0982344A2 (fr) * 1998-08-27 2000-03-01 Dow Corning Corporation Polymères du type feuille et tube ayant des groupes siloxane pendants
EP0982344A3 (fr) * 1998-08-27 2001-04-11 Dow Corning Corporation Polymères du type feuille et tube ayant des groupes siloxane pendants
US6423772B1 (en) 1999-07-16 2002-07-23 Institute Of Chemistry, Chinese Academy Of Sciences Organo-bridged ladderlike polysiloxane, tube-like organosilicon polymers, complexes thereof, and the method for producing the same
CN101024691B (zh) * 2006-08-14 2010-07-07 南京大学 一种自组装生长的聚倍半硅氧烷纳米管及纳米线的制法

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CN1206019A (zh) 1999-01-27

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