WO1999003911A1

WO1999003911A1 - Tube-like organosilicon polymers and the preparation and uses thereof

Info

Publication number: WO1999003911A1
Application number: PCT/CN1998/000127
Authority: WO
Inventors: 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: 1997-07-17
Filing date: 1998-07-16
Publication date: 1999-01-28
Also published as: AU8330498A; CN1206019A

Abstract

The present invention relates to an organosilicon polymer having tube-like structure, particularly the present invention relates to a tube-like organosilicon polymer. It is formed by the reaction of ladder-like organosilicon polymers having reactive groups or by the reaction of ladder-like organosilicon polymers with appropriate coupling reagents. It is soluble in a variety of organic solvents, and has a regular structure and nano-scale pore diameter. The molecular diameter and chemical affinity of which can be adjusted by selecting different ladder-like organosilicon polymers and coupling reagents. Its molecular weight is in the range of 103 - 106. When complexing it with molecules having appropriate dimensions and chemical affinity, complexes which are useful in molecular devices, nano-scale reaction apparatus, catalysis and separation involving molecule-recognition can be obtained.

Description

Tube-like Organosilicon Polymers and the Preparation and Uses Thereof

Technical Field

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.

Background Art

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. In 1995, 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 α, ω-diamine as the coupling reagent. They have the following structure.

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.

Disclosure of Invention

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.

Brief Description of the Drawing:

Figure 1. Shows the general structures of tube-like polymers, wherein

the bridge group connecting main chains of ladder-like

polymers. These bridge groups are: (CH₂)_X, CH₂CH₂(SiMe₂O)χCH₂CH2, CH₂(CH₂)_mC₆H₄(CH₂)mCH₂, CH₂(CH₂)_nOC₆H₄(CH₂)_nCH₂, O(CH₂)_nC₆H₄(CH₂)nO, or OOC(CH₂)nC₆H₄(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.

Preparation of Tube-like Polymers

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.

1. Synthesis of highly regulated ladder-like organosilicon polymers having reactive groups

1 ) Synthesis of Vi-T

To a reaction apparatus vinyltrichlorosilane and dried toluene are added. The concentration of the former is in the range of 0.05 - 0.2 g/mL The reaction temperature is kept at -20 to 0°C. Then p-phenylenediamine in dried acetone (The concentration is about 0.02 - 0.1 g/mL) is added. The molar ratio of trichlorosilane and p-phenylenediamine is 1 :1. After stirring the mixture for 0.5 to 1 hour, dried acetone diluted with water (concentration: 0.02 - 0.1 mL of water/per mL of acetone) is added. 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.

2) Synthesis of Allyl-T To a reaction apparatus are added allyltrichlorosilane and dried toluene. The concentration of the former is in the range of 0.05 - 0.2g/mL. The reaction temperature is kept at -20 to 0°C. Then p-phenylenediamine in dried acetone (The concentration is about 0.02 - 0.1 g/mL) is added. The molar ratio of the allyltrichlorosilane and p-phenylenediamine is 1:1. After stirring the mixture for 0.5 to 1 hour, dried acetone diluted with water (The concentration is 0.02 - 0.1 mL of water/per mL of acetone.) is added. Meanwhile, certain amount of pyridine is added. The molar ratio of water to allyltrichlorosilane is 1.5 - 3 : 1 and the molar ratio of pyridine to allyltrichlorosilane 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.

3) Synthesis of H-T

To a reaction apparatus are added trichlorosilane and dried toluene. The 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. Then p-phenylenediamine in dried acetone (concentration: about 0.02 - 0.1 g/mL) is added. The molar ratio of trichlorosilane and p-phenylenediamine is 1 :1. After stirring the mixture for 0.5 to 1 hour, dried acetone diluted with water (the concentration is 0.02 - 0.1 mL of water/per mL of acetone) is added. The molar ratio of trichlorosilane to water is 1 : 1 - 5. 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. 4) Synthesis of EtO-T

To a reaction apparatus are added ethoxytrichlorosilane and dried toluene. The 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. Then 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. After stirring the mixture for 0.5 to 1 hour, dried acetone diluted with water (The concentration is 0.02 - 0.1 mL of water/per mL of acetone.) is added. Meanwhile, 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.

2. Introduction of fixing agent and template agent for end-groups of the ladder-like polymers

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(CH₃) O-]_m-OH (m is an integer from 1 to 10), HO(CH₂)_xOH ( 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.

3. Synthesis of structure-controllable tube-like organosilicon polymers by coupling reaction There are three varieties of coupling reactions: (1) hydrosilylation reaction; (2) silane oxidation reaction; (3) silane acyloxlation reaction.

3.1 Hydrosilylation 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. (2) Coupling reaction between two ladder-like polymers having the same functional groups, such as Vi-T and Vi-T, Allyl-T and Ally-T, H-T and H-T, through a coupling reagent.

The synthetic procedure is as follows:

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. 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. 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

H-[Si(CH₃)₂θ-]_x-H (x is an integer from 2 to10), 1 , 4-divinylbenzene, hydroquinone diallyl ether, CH₂=CH-(CH₂)_n-CH=CH₂ (n is an integer from 0 to10), or CH₂=CH- [Si(CH₃)2θ-]_x-CH=CH₂ (x is an integer from 2 to 10) etc. 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 H₂PtCI₆6H₂O, Cp₂PtCI₂, complex of Pt and Vi- SiMe₂OSiMe₂-Vi (Karstedt's catalyst), complexes of Pt °^"ιv 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 %.

3.2 Silane Oxidation Reaction 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 )

(1 ) Coupling reaction between two ladder-like polymers having different functional groups, such as EtO-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. Produced small molecules are removed during the reaction. After the removal of solvent, the tubelike polymer as shown in figure 1a is obtained.

(2) Coupling reaction between two ladder-like polymers having the same functional groups, such as EtO-T and EtO-T, H-T and H-T, through a coupling reagent.

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(CH₃)₂O-]_x-OH (x is an integer from 2 to10), HO(CH₂)_xOH (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%.

3.3 Silane acyloxylation reaction

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.

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 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.

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 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 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 coupling reagents may be used in the silane acyloxylation reaction include HOOC(CH₂)_mCOOH (m is an integer from 1 to 10), HOOC(C₆H₄)_yCOOH (y is 1 or 2), XOC(CH₂)nCOX(n is an integer from 0 to 10), XOC(C₆H₄)_yCOX (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.

Due to their solubility in organic solvents, the tube-like polymers can be further processed easily. These 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.

Best Mode for Carrying Out the Invention

Example 1 : Coupling reaction between two Vi-Ts through HMM

To a 500mL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 100 mL of THF, 1.5 g of Vi-T in toluene (40 mg/mL), and 1.28 of 1 , 1 , 3, 3-tetramethyldisiloxane (HMM) in THF (concentration: 1 mL of HMM/25mL of THF) were injected into the system through syringes. Then 0.5 mg of catalyst Cp₂PtCI₂ was added. The reaction mixture was refluxed at 70°C for 14 hours. Then two third of the solvents was removed below 40°C under vacuum condition.

Removal of the rest solvents below 25°C gave a white product, which can be re-dissolved in THF. In IR spectrum, the Si-H peak at 2280cm^"1 and Vi-Si peak at 1600cm^"1 almost disappeared, indicating the completeness of the reaction. The simulated inner diameter of the tube-like polymer was 5 ~ 9A, and the outer diameter was 10 ~ 1δA. AFM result showed that its outer diameter was 10A.

Example 2: Coupling reaction between two Allyl-Ts through HMM

To a 500mL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 100 mL of cyclohexanone, 100 mL of toluene, 1.76 g of Allyl-T in toluene (40 mg/mL), and 1.28 of 1 , 1 , 3, 3- tetramethyldisiloxane (HMM) in THF (concentration: 1 mL of HMM/25mL of THF) were injected into the system through syringes. Then 5 mg of catalyst Cp₂PtCI₂ was added. The reaction mixture was refluxed at 70°C for 14 hours. Then two third of the solvents was removed below 40°C under vacuum condition. Removal of the rest solvents below 25°C gave a white product, which can be re-dissolved in cyclohexanone. In IR spectrum, the Si-H peak at 2280cm^"1 and Allyl-Si peak at 1600cm^"1 almost disappeared, indicating the completeness of the reaction. The simulated inner diameter of the tube-like polymer was 5 - 10A, and the outer diameter was 10 - 15A, AFM result showed that its outer diameter was 10.9A.

Example 3: Coupling reaction between two Allyl-Ts through H(SiMe₂O)₃H

To a 500mL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 100 mL of cyclohexanone, 100 mL of toluene, 1.86 g of Allyl-T in toluene (40 mg/mL), and 1.87 g of H(SiMe₂O)₃H in THF (concentration: 1mL /25mL of THF) were injected into the system through syringes. Then 5 mg of catalyst Cp₂PtCI was added. The reaction mixture was refluxed at 70°C for 14 hours. Then two third of the solvents was removed below 40°C under vacuum condition. Removal of the rest solvents below 25°C gave a white product, which can be re-dissolved in cyclohexanone. In IR spectrum, the Si-H peak at 2280cm^"1 and Allyl-Si peak at 1600cm^"1 essentially disappeared, indicating the completeness of the reaction.

Example 4: Coupling reaction between H-T and Vi-T via hydrosilylation

To a 500mL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 100 mL of THF, 100 mL of cyclohexanone, 1.5 g of Vi-T in toluene (40 mg/mL), and 1.1 g of H-T in toluene (10mg/mL) were injected into the system through syringes. Then 4 mg of Karstedt's catalyst was added. The reaction mixture was refluxed at 60°C for 36 hours. THF and some of cyclohexanone were removed below 40°C under vacuum condition. Removal of the rest solvents below 25°C gave a white product. The simulated inner diameter of the tube-like polymer was 1 - 2A, and the outer diameter was 6 ~ 9A. AFM result showed that its outer diameter was 6.5A.

Example 5: Coupling reaction between H-T and Allyl-T via hydrosilylation

To a 500mL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 100 mL of THF, 100 mL of cyclohexanone, 1.7g of Allyl-T in toluene (40 mg/mL), and 1.1 g of H-T in toluene (10mg/mL) were injected into the system through syringes. Then 6 mg of catalyst H₂PtC₆6H₂O was added. The reaction mixture was refluxed at 70°C for 40 hours. After that period of time THF and some of cyclohexanone were removed below 40°C under vacuum condition. Removal of the rest solvents below 25°C gave a white product. The simulated inner diameter of the tube-like polymer was 2 - 3A, and the o o outer diameter was 8 ~ 12A. AFM result showed that its outer diameter was 8.2A.

Example 6: Coupling reaction between lateral vinyl groups on the main chains of a Vi-T polymer through HMM

To a three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 300 mL of THF, 100 mL of xylene, 1.5 g of Vi-T in toluene (20 mg/mL), and 1.28 of 1 , 1 , 3, 3-tetramethyldisiloxane (HMM) in THF (concentration: 1mL of HMM/25mL of THF) were injected into the system through syringes. Then 5 mg of Pt/C catalyst was added. The reaction mixture was refluxed at 70°C for 36 hours. Then THF was removed below 40°C under vacuum condition. Removal of the rest solvents below 25°C gave a white product, which can be re- dissolved in THF. In IR spectrum, the Si-H peak at 2280cm^"1 and Allyl-Si peak at 1600cm^"1 almost disappeared, indicating the completeness of the reaction. The simulated inner diameter of the tube-like polymer was 1 - 2A, and the outer diameter was 6 ~ 9A. AFM result showed that its outer diameter was 6.5A.

Example 7: Coupling reaction between lateral allyl groups on the main chains of a Allyl-T polymer through HMM

To a three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 300 mL of THF, 100 mL of xylene, 1.7 g of Allyl-T in toluene (40 mg/mL), and 1.28 of 1 , 1 , 3, 3-tetramethyldisiloxane (HMM) in THF (concentration: 1 mL of HMM/25mL of THF) were injected into the system through syringes. Then 5 mg of catalyst Cp₂PtCI₂ was added. The reaction mixture was refluxed at 60 - 70°C for 36 hours. Then THF was removed below 40°C under vacuum condition. Removal of the rest solvents below 25°C gave a white product, which can be re-dissolved in THF. In IR spectrum, the Si-H peak at 2280cm^'1 and allyl-Si peak at 1600cm^"1 almost disappeared, indicating the completeness of the reaction. The simulated inner diameter of the tube-like polymer was 2 - 3λ, and the outer diameter was 8 ~ 12A. AFM result showed that its outer diameter was 9.3A.

Example 8: Coupling reaction between two H-Ts through Vi-MM

To a 500mL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 300 mL of THF, 1.4g of 1 , 1 , 3, 3- tetramethyl-1 , 3-divinyldisiloxane (Vi-MM) in THF (concentration: 0.04mg of Vi- MM/1 mL of THF) were injected into the system through syringes. Then 5 mg of catalyst H₂PtCI₆6H₂O and 0.81 mL of H-T in toluene (concentration: 13.4gmg/1ml of toluene) were added. The reaction mixture was refluxed at 60 - 70°C for 36 hours. Evaporation of solvents gave a homogeneous and transparent film. In IR spectrum, the Si-H peak at 2280cm^"1 and Vi-Si peak at 1600cm^'1 almost disappeared, indicating the completeness of the reaction. The simulated inner diameter of the

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 9: Coupling reaction between H-T and EtO-T

To a 500mL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 50 mL of THF, 150 mL of ethylene glycol dimethyl ether, 2 g of EtO-T in THF (30 mg/ per mL of THF), and 1 g of H-T in THF (15 mg/per mL of THF) were injected into the system through syringes. Then a mixture of 0.2 mL of 5% aqueous NaOH and 20 mL of acetone was added. The reaction mixture was first kept at 25°C for 3 hours, and slowly heated until some solvents were distilled out. The mixture was then refluxed for 48 hours during which time the produced ethyl alcohol was distilled out. The product was washed with water until neutral. The solvents were removed and the product was washed with methanol several times and dried to give the final product. In IR spectrum, the heights of the peaks from original ethoxy and Si-H groups decreased more than 90%, and the peak of hydroxy group was also very weak. All these indicated that most of the ethoxy groups were coupled.

Example 10: Coupling of lateral groups on the main chains of a EtO-T through hydroquinone

To a lOOOmL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 250 mL of toluene, 250 mL of ethylene glycol dimethyl ether, 2 g of EtO-T in THF (30 mg/ per mL of THF)were injected into the system through syringes. Then 2 g of hydroquinone and 0.05 g of disodium hydroquinoxide dispersed in 20 mL of THF were slowly added at 50°C to the reaction system. When one third of the above mixture had been added, the reaction temperature was slowly increased until solvent was distilled out slowly. After the addition of the above mixture, the reaction mixture was refluxed for 48 hours, during which time the produced ethyl alcohol was distilled out. After removing the solvents, the product was washed with methanol several times and dried to give the final product. In IR and H-NMR spectra, the heights of the peaks from original ethoxy and Si-H groups decreased 85%, and the peak of hydroxy group was also very weak. All these indicated that most of the ethoxy groups were coupled. The simulated inner diameter of the tube-like polymer was 2 ~ 3 A, and the outer was 5 - 8A. AFM result showed that its outer diameter was 7A. Example 11 : Coupling reaction between two EtO-T through 1 , 4- benzenedimethanol

To a 500mL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 250 mL of toluene, 2 g of EtO-T in THF (30 mg/ per mL of THF) were injected into the system through syringes. Then 2.4g of 1 , 4-benzenedimethanol and 0.1 g of disodium hydroquinoxide dispersed in 20 mL of THF were slowly added at 25°C to the reaction system. When one third of the above mixture has been added, the reaction temperature was slowly increased until some solvent was distilled out slowly. After the addition of the above mixture, the reaction mixture was refluxed for 48 hours, during which time the produced ethyl alcohol was distilled out. After removing the solvents, the product was washed with methanol several times and dried to give the final product. In IR and H-NMR spectra, the heights of the peaks from original ethoxy and Si-H groups decreased 80%, and the peak of hydroxy group was also very weak. All these indicated that most of the ethoxy groups were consumed and the two ladder-like polymers were coupled. The simulated inner diameter of the tube-like polymer was 5 ~ δA, and the outer diameter was 10 ~ 12A. AFM result showed that its outer diameter was 9.5A.

Example 12: Coupling reaction between two H-T through HOOC(CH₂)₄COOH

To a 500mL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 200 mL of xylene, 2 g of H-T in THF (10 mg/ per mL of THF) were injected into the system through syringes. Then 2.6g of adipic acid and 0.015 g of Cp₂PtCI₂ were slowly added at 30°C to the reaction system. When one third of the above mixture has been added, the reaction temperature was slowly increased to 60°C. After the addition of the above mixture, the reaction mixture was refluxed for 12 hours. After removing the solvents, the product was washed with methanol several times and dried to give the final product. In IR and H-NMR spectra, the heights of the peaks from Si-H group decreased 90%, and the peak of hydroxy group was also very weak, indicating that most of the Si- H were coupled.

Example 13: Coupling of lateral groups on the same H-T polymer through HOOC(CH₂)₄COOH

To a 10OOmL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 600 mL of xylene, 2 g of H-T in THF (10 mg/ per mL of THF) were injected into the system through syringes. Then 2.5g of adipic acid and 0.015 g of Cp₂PtCI₂ were slowly added at 30°C to the reaction system. When one third of the above mixture has been added, the reaction temperature was slowly increased to 50°C. After the addition of the above mixture, the reaction mixture was refluxed for 12 hours. After removing the solvents, the product was washed with methanol several times and dried to give the final product. In IR and H-NMR spectra, the heights of the peaks from Si-H group decreased 90%, and the peak of hydroxy group was also very weak, indicating that most of the Si- H were coupled.

Example 14: Coupling reaction between H-T and EtO-T through CIOC(CH₂)₄COCI

To a 500mL three-necked flask was placed a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere, 100 mL of xylene, 100 mL of ethylene glycol dimethyl ether, 1 g of H-T in THF (15mg/per mL THF), and 1.8 g of EtO-T in THF (10 mg/ per mL of THF) were injected into the system through syringes. Then 5.2 g of CIOC(C₆H₄)COCI, 0.01 g of Cp₂PtCI₂, and a small particle of iodine were added at 25°C. The reaction temperature was slowly increased to 70°C and kept at this temperature for 24 hours. After reaction, the product was washed with water for five times and the solvents were removed. The product was then washed with methanol and dried to give final product. In IR and H-NMR spectra, the heights of the Si-H peaks and ethoxy peaks decreased 85%, and the peak of hydroxy group was also very weak, indicating that two ladder-like polymers were coupled.

Claims

What is claimed is:

1. A tube-like organosilicon polymer having the following structure:

a

wherein, is the bridge group connecting main chains of ladder-like

polymers; these bridge groups are:

(CH₂)_X, CH₂CH₂(SiMe2╬╕)_mCH₂CH2, CH₂(CH₂)_mC₆H₄(CH₂)_mCH2,

CH₂(CH₂)_nOC₆H₄O(CH₂)_╧ÇCH2, O(CH₂)_nC₆H₄(CH₂)_nO, or OOC(CH₂)_nC₆H₄(CH₂)_nCOO, wherein x is an integer form 2 to 10, m is an integer form 1 to 10, n is an integer form 0 to 10; the above structure "a" is the tube-like polymer formed either by reaction between two ladder-like polymers or by coupling reaction of the two ladder-like polymers through coupling reagents; the above structure "b" is the tube-like polymer formed by the coupling reaction between reactive groups on the main chains of the same ladder-like polymer having same functional groups through coupling reagents.

2. A tube-like polymer as set forth in claim 1 , wherein the structure "a" is the tube- like polymer formed by coupling reaction between two ladder-like polymers having different functional groups.

3. A tube-like polymer as set forth in claim 1 , wherein the structure "a" is the tubelike polymer formed by the coupling reaction between two ladder-like polymers having the same functional groups through coupling reagents.

4. A method for preparing the tube-like polymer of claim 1 , comprising the steps of: (1 ) synthesizing the highly regulated ladder-like organosilicon polymer R-T containing reactive groups, wherein R is Vi, Allyl, H, or EtO. (2) synthesizing the tube-like organosilicon polymers by one of the three coupling reactions: the hydrosilylation reaction, silane oxidation reaction, and silane acyloxylation reaction.

5. A method for preparing the tube-like polymer as set forth in claim 4, wherein the hydrosilylation coupling reaction is performed by firstly dissolving the ladder-like polymers Vi-T and H-T or Allyl-T and H-T in dried solvents, respectively, then under the protection of inert gas atmosphere, putting them into a reaction apparatus with the molar ratio of 1 : 0.8 to 1 : 1.5; adding solvent and catalyst such as Pt ┬░^"╬╣v compound or complex of Pt ┬░^"╬╣ and alkene into the reaction mixture, the concentrations of the reactants are in the range of 10 - 40 mg/mL; and allowing the reaction to proceed at 50 -120┬░C for 12 - 72 hours.

6. A method for preparing the tube-like polymer as set forth in claim 4, wherein the hydrosilylation coupling reaction is performed by firstly dissolving the ladder-like polymer Vi-T, Allyl-T or H-T in dried solvent, then under the protection of inert gas atmosphere, putting dissolved ladder-like polymer into a reaction apparatus; adding solvent, coupling reagent such as H(SiMe₂)O)_mH, CH₂=CH(SiMe₂O)_mCH=CH₂, CH2=CHCH2(SiMe₂O)_mCH₂CH=CH2, or CH2=CHC₆H₄CH=CH₂, wherein m is an integer from 1 to 10 and n is an integer from

0 to 10, and catalyst such as Pt┬░^"╬╣v compound or complex of Pt┬░^"╬╣v and alkene into the reaction apparutus, the concentrations of reactants are in the range of 5 - 40 mg/mL; and allowing the reaction to proceed at 30 -100┬░C for 12 - 72 hours.

7. A method for preparing the tube-like polymer as set forth in claim 4, wherein the silane oxidation coupling reaction is performed by firstly dissolving two ladder-like polymers EtO-T and H-T in dried solvents, respectively, then under the protection of inert gas atmosphere, putting them into a reaction apparatus with the molar ratio of

1 : 0.8 to 1 : 1.5; adding solvent and basic catalyst into the reaction mixture, the concentrations of reactants are in the range of 10 - 40 mg/mL; and allowing the reaction to proceed at 50 -120┬░C for 12 - 72 hours.

8. A method for preparing the tube-like polymer as set forth in claim 4, wherein the silane oxidation coupling reaction is performed by firstly dissolving ladder-like polymer H-T or EtO-T in dried solvent, then under the protection of inert gas atmosphere, putting it into a reaction apparatus; adding coupling reagent hydroquinone or 1 , 4-benzene dimethanol and catalyst such as basic compound or sodium phenoxide into the reaction mixture, the concentrations of reactants are in the range of 5 - 40 mg/mL; and allowing the reaction to proceed at 30 -100┬░C for 12 - 72 hours.

9. A method for preparing the tube-like polymer as set forth in claim 4, wherein the silane acyloxylation coupling reaction is performed by firstly dissolving two ladderlike polymers EtO-T and H-T in dried solvents, respectively, then under the protection of inert gas atmosphere, putting them into a reaction apparatus with the molar ratio of 1 : 0.8 to 1 : 1.5; adding solvent, Pt complex and iodine as catalyst into the reaction mixture, the concentrations of reactants are in the range of 10 - 40 mg/mL; and allowing the reaction to proceed at 50 -120┬░C for 12 - 72 hours.

10. A method for preparing the tube-like polymer as set forth in claim 4, wherein the silane acyloxylation coupling reaction is performed by firstly dissolving the ladder- like polymer H-T or EtO-T in dried solvent, then under the protection of inert gas atmosphere, putting it into a reaction apparatus; adding coupling reagent such as HOOC(CH₂)_xCOOH (x is an integer from 2 to 10), XOC(C₆H₄)COX (X is a halogen) and catalyst Pt complex and iodine into the reaction mixture, the concentrations of reactants are in the range of 5 - 40 mg/mL; and allowing the reaction to proceed at 30 -100┬░C for 12 - 72 hours.

11. A method for preparing the tube-like polymer as set forth in any one of claims 6, 8, and 10, wherein the concentrations of reactant for the coupling of two ladder-like polymers are in the range of 10 - 40 mg/mL.

12. A method for preparing the tube-like polymer as set forth in any one of claims 6, 8, and 10, wherein the concentration of the reactant for the coupling of lateral groups on the same ladder-like polymer is in the range of 5 - 10 mg/mL.

13. A method for preparing the tube-like polymer as set forth in any one of claims 6, 8, 10, 11 , and 12, wherein the molar ratio of coupling reagent and R-T is in the range of 1.5 - 0.8 for the above-mentioned hydrosilylation reaction, silane oxidation reaction, and silane acyloxylation reaction.

14. Use of the tube-like polymer of claim 1 in the preparation of biosensors, supermolecular catalysts, supermolecular separation membranes, and new optical and electronical materials.