WO1999003910A1

WO1999003910A1 - Tube-like organosilicon polymeric complexes and the method for producing the same

Info

Publication number: WO1999003910A1
Application number: PCT/CN1998/000126
Authority: WO
Inventors: Rongben Zhang; Hui Xu; Ping Xie; Letian Wang; Ze Li; Xinyu Cao; 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: CN1206021A; AU8330398A

Abstract

The present invention relates to an organosilicon material with tube-like structure, particularly, the present invention relates to a complex of tube-like organosilicon polymer. It may be prepared by two methods: entrapment in situ and displacement entrapment. Since the tube-like polymers with different molecular dimensions and chemical affinities can selectively entrap guest molecules which match the polymer, diverse complexes may be formed. These complexes may be used in molecular devices, catalysis and separation involving molecule-recognition and so on.

Description

WO 99/03910 _, . PCT/CN98/00126

Tube-like Organosilicon Polymeric Complexes and the Method for

Producing the Same

Field of the Invention

The present invention relates to a organosilicon material with tube-like structure, particularly, the present invention relates to a complex of tube-like organosilicon polymers and the method for producing the same.

Background Art

There have been reported a supermolecular complex based on tube-like cyclodextrins as host molecule (Nature, 1993, 364: 576). In such supermolecular complex, the pore diameter of the tube and chemical affinity of the cavity can not be readily adjusted, therefore, the guest molecules that can be entrapped inside the tube are limited. Entrapment of metal or metal oxide inside a nano-scale carbon tube to form the supermolecular complex has also been report (Chem. Commu., 1995, 1335). However the preparation involves complicated steps and the conditions for the reactions are severe. In addition, the selectivity of entrapment was very poor. Entrapment of polyaniline inside the tube of V₂O₅ gel to form supermolecular complex was reported as well (J. Am. Chem. Soα, 1989, 11 1 , 4319). This complex showed electrical conductivity. However, since this supermolecular complex was a cross-linked system, it was not soluble nor meltable and thus could not be re-processed. In addition, the selectivity of entrapment was very poor too.

Disclosure of Invention

The present invention relates to the synthesis of hybrid organic-inorganic polymeric materials. The host of the complex is a synthetic tube-like organosilicon polymer. The molecular dimension, chemical affinity, and molecular shape of the tube-like polymer can be easily adjusted in accordance with different requirements. Its solubility makes it possible to re-process the material conveniently. The guest molecule which can be entrapped encompasses a wide variety of molecules, therefore building blocks for many functional materials can be obtained.

Previous research relating to this invention is the synthesis of structure- controllable tube-like organosilicon polymers (CN 97 1 12236.9). Its general structure is shown in Figure 1.

The present invention also relates to the preparation of functional supermolecular complexes using tube-like organosilicon polymers as host molecules. Guest molecules, either small molecules or polymers, having sonic, optical, electrical, magnetic, or other properties are entrapped inside the tube-like polymers to form the supermolecular complexes.

The tube-like polymeric complexes of this invention falls into two categories. In one of which a small molecule or a metal ion is entrapped; in the other one a polymer is entrapped. Their general structures are shown in figures 2 and 3, respectively.

The method for producing the tube-like organosilicon polymeric complexes of the present invention includes entrapping the guest molecules into the tube-like organosilicon polymers to form supermolecular complexes. There are two methods for performing the entrapment: entrapment in situ and displacement entrapment. Guest molecules are either small molecules with functionalities or metal ions such as cyclohexanone, tetrahydrofuran (THF), N-(4-nitrophenyl)-2-proline (NPP), azobenzene or its derivatives, fullerene, Schiff bases or frans-stilbene, Pt(l-IV) ions, Eu(lll) ion, Tb(lll) ion, or K(l) ion; or polymers such as poly(ethylene glycol), poly(vinyl alcohol), poly(methylhydrosiloxane), polyaniline, poly pyrrol, polythiophene , poly(acyl imide) or its derivatives, or poly(acrylic acid) or its derivatives.

The entrapment in situ is carried out according to the following procedures. The ladder-like organosilicon polymers, coupling reagents, guest molecules are dissolved in organic solvent. Catalyst is added to the system to induce the coupling reaction. Under the inert atmosphere, the reaction is run at 20 - 140°C, preferable at 40 - 80°C , for 2 - 100 hours, preferable for 20 - 60 hours, during which time the tube-like polymers are formed and the guest molecules are entrapped in situ inside the tube to give the supermolecular complexes. As the ladder-like organosilicon polymers, vinyl ladder-like polymer (Vi-T), allyl ladder-like polymer (Allyl-T), hydrogen ladder-like polymer (H-T), and/or alkoxy ladder-like polymers (RO-T, R = CH₃, CH₃CH₂) may be used.

The coupling reagents may be used include H-[Si(CH₃)₂θ-]_m-H (m is an integer from 2 to 10), 1 , 4-divinylbenzene, hydroquinone diallyl ether, CH2=CH(CH₂)nCH=CH₂ (n is an integer from 0 to 10),

CH=CH₂ (m is an integer from 2 to 10), HO-[Si(CH₃)₂O-]_mOH (m is an integer from 2 to 10), HO(CH₂)_nOH (n is an integer from 2 to 10), hydroquinone, biohenol A, 1 , 4- benzenedimethanol and their alkali salts, HOOC-(CH )_x-COOH (x is an integer from 1 to 10), HOOC-(C₆H₄)_y-COOH ( y is 1 or 2), XOC-(CH₂)_m -COX (m is an integer from 1 to 10; X is a halgen), or XOC-(C₆H₄)_n-COX (n is 1 or 2; X is a halgen).

The molar ratio of the ladder-like polymer and the coupling reagent is in the range of 0.5 - 5.

The solvents may be used include toluene, xylene, ethylene glycol dimethyl ether, poly(vinyl ether), dimethyl o-phthalate, THF, 1 , 4-dioxane, cyclohexanone, acetone, alcohols and a mixture of above solvents.

The catalysts may be used include: platinum catalysts such as H∑PtClβδH∑O, Cρ₂PtCI₂, complex of Pt and Vi-SiMe₂OSiMe₂-Vi (Karstedt's catalyst), and complexse of Pt °^"ιv and alkene compounds, mixture of Pt ²⁺and ethyl acetoacetate/acetone; Pd catalysts such as (Ph₃P)₄Pd, (Ph₃P)₂PdCl2, (PHCN)₂PdCI₂; Rh catalysts such as [RhCI(CO)₂], (Ph₃P)₂(CO)RhCI, (Ph₃P)₃RhCI, (Et₃P)₂(CO)RhCI; chelates of the above mentioned metals and metal colloid catalysts; alkali oxides and hydroxides, sodium alkoxides and phenoxides, organometallic compounds (Zn, Al, B etc); inorganic acid and strong organic acids; halides of alkali metals and other metals (Ni, Fe, Sn, Cu, Cr, Co, Pt, Pd); aluminum, iodine, and colloidal nickel. The amount of the catalyst used is 0.5 - 500 ppm. The weight of guest molecules is 1 - 30% of that of the ladder-like organosilicon polymers.

The displacement entrapment is performed according to the following procedures. The tube-like organosilicon polymers and the guest molecules are dissolved in organic solvent(s). The guest molecules are entrapped inside the tube-like organosilicon polymers by ultrasonic, heating, or by changing the polarity of the solvent, during which the guest molecule is entrapped into the cavity of the tube-like organosilicon polymer and the solvent molecules or other molecules originally entrapped inside the tube were replaced by the guest molecules. The weight of guest molecules is 1 - 200% of that of tube-like organosilicon polymers.

The solvents may used include toluene, xylene, chloroform, ethylene glycol dimethyl ether, ploy(vinyl ether), dimethyl o-phthalate, THF, 1 , 4-dioxane, cyclohexanone, cyclohexanol, methanol, acetone, and acetonitrile. The amount of the solvent used is 5 - 50 ml_ per gram of tube-like polymers.

The frequency of the ultrasonic used is in the range of 1 - 200 kHz.

The temperature is in the range of 20 - 200 °C.

A variety of the tube-like polymeric complexes may be obtained by using the method of the present invention, which is useful in a variety of applications. In this view, these complexes have unique structures which can be readily adjusted, they may act as building blocks for functional materials such as biosensors, supermolecular catalysts, supermolecualr separation membranes, novel nano- scale optical or electronical materials.

The polymeric complexes of the present invention is soluble in a variety of solvents, therefore allows to be further processed. These solvents include toluene, xylene, chloroform, ethylene glycol dimethyl ether, ploy(vinyl ether), dimethyl o- phthalate, THF, 1 , 4-dioxane, cyclohexanone, cyclohexanol, acetone, isopropanol, isobutanol, or a mixture thereof.

Brief Description of Drawings Figure 1 shows the general structure of tube-like organosilicon polymers, wherein 1 represents -CH₂CH₂-, -CH₂(CH2)nCH2-, -(CH₂CH2(SiMe2O)_mCH₂CH2-, -CH₂CH₂C6H₄CH₂CH₂-, -CH₂(CH₂)_nOC₆H₄(CH₂)_nCH₂-, -O(CH₂)_nC₆H₄(CH₂)nO-, or OOC(CH₂)_nC₆H₄(CH₂)_nCOO-. Figure 2 shows the general structure of the tube-like organosilicon polymeric complex in which the entrapped molecules are small molecules or metal ions. Wherein 1 represents the entrapped small molecules or metal ions, and 2 represent the same thing as that 1 in figure 1 represents.

Figure 3 shows the general structure of the tube-like organosilicon polymeric complex in which the entrapped molecules are polymers. Wherein 1 represents the entrapped polymers, and 2 represents the same thing as that 1 in figure 1 represents.

Best Mode for Carrying Out the Invention

Example 1 Entrapment in-situ of poly(vinyl alcohol)

To a Schlenk flask were placed poly(vinyl alcohol), 6 mg(MW - 5000), and a magnetic stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for more than three times. Under the argon atmosphere 10 mL of isopropanol was injected into the system through a syringe. After poly(vinyl alcohol) was dissolved completely, 1 mL of a solution of Vi-T in toluene (concentration: 40 mg/mL), 0.1 mg of Cp₂PtCI₂, and 1.2 mL of a solution of 1 ,1 ,3,3-tetramethyldisiloxane (HMM) in THF (concentration: 0.04 mL of HMM/1 mL of THF) were added into the system successively. The reaction temperature was controlled at 60 - 80°C for 24 hours. The product was washed with water and methanol. The IR spectrum of the product indicated the completeness of the reaction. The Tg peak of poly(vinyl alcohol) disappeared on DSC measurement. The peaks of poly(vinyl alcohol) appeared in the ¹H-NMR spectrum. All these results indicated that poly(vinyl alcohol) was entrapped inside the tube-like polymers. Example 2 Entrapment in-situ of azobenzene

To a 500 mL of three-necked flask was placed a 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 isopropanol was injected into the system through a syringe. Then 50 mL of a solution of Allyl-T in THF (concentration: 30 mg/1 mL of THF), 4 mg of (Ph₃P)₄Pd, 0.1 g of azobenzene and 11 mL of a solution of HMM in THF (concentration: 1 mL of HMM/10 mL of THF) were added into the system successively. The reaction was carried out at 60 - 70°C for 36 - 48 hours.

After reaction the majority of the solvent was evaporated and the product was precipitated from methanol for several times. Re-dissolving of the precipitate in THF and casting it on glass gave a homogeneous and transparent film. The IR spectrum of the product indicated the completeness of the reaction. The melting point peak of azobenzene disappeared on DSC measurement. The benzene peaks of azobenzene appeared in the IR spectrum. All these results indicated that azobenzene was entrapped inside the tube-like polymers.

Example 3 Entrapment in-situ of poly(ethylene glycol)

To a Schlenk flask were placed poly(ethylene glycol), 10 mg(MW ~ 800) and a stir bar. The reaction system was vacuumized and refilled with argon. This process was repeated for more than three times. Under the argon atmosphere 10 mL of THF was injected into the system through a syringe. After poly(ethylene glycol) was dissolved completely, 1 mL of a solution of Vi-T in toluene (concentration: 40 mg/1 mL), 0.1 mg of Cp₂PtCI₂₎ and 1.2 mL of a solution of HMM in THF (concentration: 0.04 mL of HMM/1 mL of THF) were added into the system successively. The reaction temperature was controlled at 30 - 40°C for 36 hours. The product was washed with water and methanol. The IR spectrum of the product indicated the completeness of the reaction. The peaks of poly(ethylene glycol) appeared in the ¹H-NMR spectrum and these peaks were broadened and shifted to up-field, indicating that poly(ethylene glycol) was entrapped inside the tube-like polymers.

Example 4 Entrapment in-situ of (s)-(-1 )-(-4)-nitrophenyl(-2-pyrroidine methanol) (NPP)

To a 100 mL of three-necked flask were placed 50 mg of NPP and a stir bar. The reaction system was vacumized and refilled with argon. This process was repeated for three times. Under the argon atmosphere 60 mL of THF was injected into the system through a syringe. After poly(ethylene glycol) was dissolved completely, 10 mL of a solution of Allyl-T in THF (concentration: 30 mg/1 mL), 1 mg of Cp₂PtCI₂, and 2 mL of a solution of HMM in THF (concentration: 1 mL of HMM/10 mL of THF) were added into the system successively. The reaction was carried out at 40 - 50°C for 36 - 48 hours. After the reaction the majority of the solvent was evaporated and the product was precipitated from methanol for several times. The product was washed with methanol for several times. The IR spectrum of the product indicated the completeness of the reaction. The melting point peak of NPP disappeared on DSC measurement. The peaks of benzene appeared in the IR spectrum. All these results indicated that NPP was entrapped inside the tube-like polymers.

Example 5 Entrapment in-situ of frans-stilbene

To a 500 mL of three-necked flask were placed 40 mg of fraπs-stilbene and 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 was injected into the system through a syringe. Then 2 g of EtO-T in THF (concentration: 30 mg/1 mL), 2.4 g of 1 , 4-benzenedimethanol and 0.1 g 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 had 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 of the product there were benzene and carbon-carbon double bond peaks. It was found that the fluorescence did not disappear when the product was irradiated by the UV light and then tested with a fluorophotometer. All these indicated that the frans-stilbene was entrpapped inside tube-like polymers to form supermolecular complexes.

Example 6 Entrapment in-situ of Ceo molecules

To a 500 mL of three-necked flask were placed 2 mg of Ceo molecules and 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 was injected into the system through a syringe. 2 g of H-T in THF (concentration: 10 mg/1 mL of THF) was added. Then 2.6g of sebacic acid and 0.02 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 ¹³C-NMR spectrum of the product there was a peak of Ceo molecule. Comparing the fluorescence spectra of the complex and the pure Ceo compound it was found that the peak of the former was broadened and stronger than that of the latter. All these indicated that Ceo molecule was entrapped inside tube-like polymers.

Example 7 Displacement entrapment of cyclohexanone

1 g of dried solid tube-like organosilicon polymers was dissolved in 20 mL of cyclohexanone. The solution was ultrosonicated for two hours and then stayed overnight. The cyclohexanone was first evaporated to almost dryness and then evaporated to dryness under vacuum. In ¹H-NMR spectrum of the product there were peaks of cyclohexanone molecule, which were broadened and shifted about 0.1 ppm up-field compared to the those of pure cyclohexanone. In addition, the peaks of THF originally entrapped inside the polymers became smaller. All these indicated that cyclohexanone molecule was entrapped inside tube-like polymers.

Example 8 Displacement entrapment of poly(methylhydrosiloxane)

1 g of dried solid tube-like organosilicon polymers was dissolved in 20 mL of chloroform. Then 1 ml of poly(hydrogen methyl siloxane) was added.

The mixture was ultrosonicated for two hours and then stayed overnight. Methanol was added to the solution to precipitate the tube-like complexes. The solution was then centrifuged. The top layer was decanted and the precipitate was washed with methanol three times. The solvent was evaporated to dryness to give the complexes. In IR spectrum there was absorption peak of Si-H bond and it was shifted to red for about 2 wavenumbers. In ²⁹Si-NMR spectrum the Si-H peak shifted about 3 - 4 ppm down-field. In GPC spectrum the peak of guest molecules disappeared. All these indicated that poly(methylhydrosiloxane) was entrapped inside tube-like organosilicon polymers to form supermolecular complexes.

Example 9 Displacement entrapment of polyaniline

1 g of dried solid tube-like organosilicon polymers was dissolved in 20 mL of cyclohexanol. Then 100 mg of polyaniline was added. The mixture was ultrosonicated for two hours and then stayed overnight. The cyclohexanol was first evaporated to almost dryness and then evaporated to dryness under vacuum. The product was washed with methanol several times. In IR and ¹H-NMR spectra there are peaks of poly aniline. In UV spectrum the absorption peaks of polyaniline shifted to blue. All these indicated that polyaniline was entrapped inside tube-like polymers. Example 10 Displacement entrapment of Eu³⁺ ion

1 g of dried solid tube-like organosilicon polymers was dissolved in 20 mL of acetonit le. Then 4 mg of Eu(NO₃)₃6H₂O was added. The mixture was heated at 50 - 60°C for 24 hours. Upon cooling down, 2 mL of the reaction solution was taken and tested by fluorophotometer. It was found that the fluorescence of the Eu³⁺ ion disappeared, indicating that Eu³⁺ was entrapped inside tube-like organosilicon polymers to form supermolecular complexes.

Example 1 1 Displacement entrapment of Schiff base type liquid crystal molecules

1 g of dried solid tube-like organosilicon polymers was dissolved in 20 mL of THF. Then 50 mg of Schiff base type liquid crystal molecules was added. The mixture was ultrosonicated for two hours at room temperature and then heated for 10 - 20 hour. Upon cooling, the methanol was added to precipitate the product. The precipitate was washed with methanol several times and dried under vacuum. On DSC measurement the melting point of the Schiff base type liquid crystal molecules disappeared. In ¹H-NMR spectrum there are peaks of bezene ring, and these peaks were broadened. All these indicated that the Schiff base type liquid crystal molecules were entrapped inside tube-like organosilicon polymers.

Example 12 Displacement entrapment of poly(acrylic acid)

1 g of dried solid tube-like organosilicon polymers was dissolved in 20 mL of

THF. Then 100 mg of poly(acrylic acid) was added. The mixture was ultrosonicated at room temperature for two hours and then stayed overnight. Methanol was added to the solution to precipitate the tube-like complexes. The solution was then centrifuged. The top layer was decanted and the precipitate was washed with methanol three times and then with water several time. The product was dried under vacuum. In IR spectrum there was a strong peak of carbonyl group and was shifted to red for 5 wavenumbers. In ¹³C-NMR spectrum the COOH peak was shifted about 2 - 3 ppm down-field. All these indicated that poly(acrylic acid) was entrapped inside tube-like organosilicon polymers to form supermolecular complexes.

Claims

What is claimed is:

1. A tube-like organosilicon polymeric complex, wherein the host molecule of the tube-like organosilicon polymeric complex is a tube-like organic silicon polymer, and the guest molecule entrapped inside the tube is a small molecule, a metal ion, or a polymer.

2. A tube-like organosilicon polymeric complex as set forth in claim 1 , wherein said small molecule is one or more selected from the group consisting of cyclohexanone, tetrahydrofuran (THF), N-(4-nitrophenyl)-2-proline (NPP), azobenzene and its derivatives, fullerene, Schiff bases, and frans-stilbene.

3. A tube-like organosilicon polymeric complex as set forth in claim 1 wherein said metal ion is Eu(lll).

4. A tube-like organosilicon polymeric complex as set forth in claim 1 , wherein said polymer is one or more selected from the group consisting of poly(ethylene glycol), poly(vinyl alcohol), poly(methylhydrosiloxane), polyaniline, polypyrrol, polythiophene, poly(acyl imide) and its derivatives, and poly(acrylic acid) and its derivatives.

5. A method for producing the tube-like organosilicon polymeric complex of claim 1 , wherein the guest molecule is entrapped into the tube-like polymer by entrapment in situ or by displacement entrapment.

6. A method for producing the tube-like organosilicon polymeric complex as set forth in claim 5, wherein the entrapment in situ is carried out according to the following procedures: dissolving the ladder-like organosilicon polymer, coupling reagent, and guest molecule in organic solvent; adding catalyst to initiate coupling reaction; under the inert atmosphere, allowing the reaction to proceed at 40 - 80┬░C for 20 - 60 hours to form tube-like polymer; meanwhile, the guest molecule is entrapped inside the cavity of the tube to form the supermolecular complex.

7. A method for producing the tube-like organosilicon polymeric complex as set forth in claim 6, wherein the weight of the guest molecule is 1 - 30 % of that of the ladder-like organosilicon polymer.

8. A method for producing the tube-like organosilicon polymeric complex as set forth in claim 5, wherein the displacement entrapment is carried out according to the following procedures: the ladder-like organosilicon polymer and the guest molecule are dissolved in organic solvent; the guest molecule is entrapped inside the cavity of the tube by ultrasonic, heat, or by changing the polarity of the solvent.

9. A method for producing the tube-like organosilicon polymeric complex as set forth in claim 8, wherein the weight of the guest molecule is 1 - 200 % of that of the tube-like polymer.

10. A method for producing the tube-like organosilicon polymeric complex as set forth in claim 8, wherein the solvents is one or more selected from the group consisting of toluene, chloroform, ethylene glycol dimethyl ether, THF, 1 , 4- dioxane, cyclohexanone, cyclohexanol, methanol, acetone, and acetonitrile, the amount of which is 5 - 50 mL per gram of the tube-like polymer.