阅读说明：本技术 一种八臂星形热塑性弹性体共聚物及其制备方法 (Eight-arm star-shaped thermoplastic elastomer copolymer and preparation method thereof ) 是由 何金林 王彬 钱强雨 倪沛红 张明祖 于 2019-11-05 设计创作，主要内容包括：本发明公开了一种八臂星形热塑性弹性体共聚物及其制备方法。通过活性阴离子聚合法合成聚苯乙烯-聚异戊二烯锂化合物及聚苯乙烯/二苯基乙烯-聚异戊二烯锂化合物,再利用它们与八烯基多面体齐聚倍半硅氧烷发生偶联反应得到八臂星形共聚物。该方法具有操作便捷、反应效率高、反应条件温和、副反应少的特点,本发明制备的八臂星形聚合物结构及分子量可控,分子量分布窄。由二苯基乙烯(DPE)和苯乙烯(St)共聚得到的聚合物链段作为硬段,使得八臂星形热塑性弹性体共聚物有更为优异的力学性能；同时由DPE和St单元组成的聚合物链段具有比聚苯乙烯更高的玻璃化转变温度,能够提高星形热塑性弹性体共聚物的使用上限温度。(The invention discloses an eight-arm star-shaped thermoplastic elastomer copolymer and a preparation method thereof. Synthesizing polystyrene-polyisoprene lithium compound and polystyrene/diphenylethylene-polyisoprene lithium compound by an active anion polymerization method, and performing coupling reaction on the polystyrene-polyisoprene lithium compound and the diphenylethylene-polyisoprene lithium compound and octaalkenyl polyhedral oligomeric silsesquioxane to obtain the eight-arm star copolymer. The method has the characteristics of convenient operation, high reaction efficiency, mild reaction conditions and less side reactions, and the eight-arm star polymer prepared by the method has controllable structure and molecular weight and narrow molecular weight distribution. A polymer chain segment obtained by copolymerizing Diphenylethylene (DPE) and styrene (St) is used as a hard segment, so that the eight-arm star-shaped thermoplastic elastomer copolymer has more excellent mechanical property; meanwhile, the polymer chain segment composed of DPE and St units has higher glass transition temperature than polystyrene, so that the use upper limit temperature of the star-shaped thermoplastic elastomer copolymer can be increased.)

1. An eight arm star thermoplastic elastomer copolymer characterized by: the chemical structural formula of the eight-arm star-shaped thermoplastic elastomer copolymer is as follows:

in the formula, R₁The chemical structural formula of (A) is as follows:

or

R₂The chemical structural formula of (A) is as follows:

x = 10～200，y = 2～10，z = 5～20，m = 200～600，n = 10～30。

2. a method for preparing the eight-armed star thermoplastic elastomer copolymer as defined in claim 1, comprising the steps of:

(1) in the nitrogen atmosphere, the lithium compound initiates styrene polymerization to obtain a polystyrene lithium compound;

(2) initiating diene polymerization by the polystyrene lithium compound in the step (1) in a nitrogen atmosphere to obtain a polystyrene-polydiene lithium compound;

(3) in a nitrogen atmosphere, reacting the octavinyl polyhedral oligomeric silsesquioxane with the polystyrene-polydiene lithium compound obtained in the step (2) to obtain an eight-arm star-shaped thermoplastic elastomer copolymer;

or comprises the following steps:

(4) in the nitrogen atmosphere, the lithium compound initiates the polymerization of styrene and diphenylethylene to obtain a polystyrene/diphenylethylene lithium compound;

(5) in a nitrogen atmosphere, initiating diene polymerization by the polystyrene/diphenylethylene lithium compound in the step (4) to obtain a polystyrene/diphenylethylene-polydiene lithium compound;

(6) and (3) reacting the octavinyl polyhedral oligomeric silsesquioxane with the polystyrene/diphenylethylene-polydiene lithium compound obtained in the step (5) in a nitrogen atmosphere to obtain the eight-arm star-shaped thermoplastic elastomer copolymer.

3. The method for preparing an eight-arm star thermoplastic elastomer copolymer as defined in claim 2, wherein: in the step (1), the molar ratio of the lithium compound to the styrene is 1: 10-200;

in the step (2), the molar ratio of the polystyrene lithium compound to the diene is 1: 210-630;

in the step (3), the molar ratio of the octavinyl polyhedral oligomeric silsesquioxane to the polystyrene-polydienelithium compound is 1: 8.2-9;

in the step (4), the molar ratio of the lithium compound to the styrene to the diphenylethylene is 1: 10-200: 5-20;

in the step (5), the molar ratio of the polystyrene/diphenylethylene lithium compound to the diene is 1: 210-630;

in the step (6), the molar ratio of the octavinyl polyhedral oligomeric silsesquioxane to the polystyrene/diphenylethylene-polydienelithium compound is 1: 8.2-9.

4. The method for preparing an eight-arm star thermoplastic elastomer copolymer as defined in claim 2, wherein: the lithium compound is sec-butyl lithium or n-butyl lithium; the diene is butadiene or isoprene; and (3) no catalyst or catalyst ligand is required to be used in the reaction processes of the steps (1) to (6).

5. The method for preparing an eight-arm star thermoplastic elastomer copolymer as defined in claim 2, wherein: in the step (1), the polymerization is carried out at room temperature for 6-12 hours; in the step (2), the polymerization is carried out at room temperature for 12-24 hours; in the step (3), the reaction is carried out at room temperature for 1-2 hours; in the step (4), the polymerization is carried out at room temperature for 12-24 hours; in the step (5), the polymerization is carried out at room temperature for 12-24 hours; in the step (6), the reaction is carried out at room temperature for 1-2 hours.

6. The method for preparing an eight-arm star thermoplastic elastomer copolymer as defined in claim 2, wherein: after the reactions in the step (3) and the step (6), respectively purifying products, comprising the following steps:

purification treatment of eight-arm star thermoplastic elastomer copolymer: after the reaction is finished, concentrating the reaction solution by using a rotary evaporator, dripping into anhydrous methanol for precipitation, washing precipitates by using the anhydrous methanol, drying in vacuum, dissolving by using toluene to obtain a solution, dripping the anhydrous ethanol until the solution is turbid, heating until the solution is transparent, standing for layering, removing the solvent from a lower transparent phase, precipitating in the anhydrous methanol, and filtering and drying precipitates to obtain the eight-arm star-shaped thermoplastic elastomer copolymer.

7. The method for preparing an eight-arm star thermoplastic elastomer copolymer as defined in claim 2, wherein: the reactions of the steps (1) to (6) are carried out in a solvent.

8. The method for preparing an eight-arm star thermoplastic elastomer copolymer as defined in claim 2, wherein: in the step (3), stopping the reaction by using anhydrous methanol; in the step (6), the reaction was terminated with anhydrous methanol.

9. Use of a lithium compound in the preparation of the eight-arm star thermoplastic elastomer copolymer of claim 1; the lithium compound is sec-butyl lithium or n-butyl lithium.

10. Use of the eight-arm star thermoplastic elastomer copolymer of claim 1 in the preparation of polymeric materials.

Technical Field

The invention belongs to the field of polymer synthesis, and particularly relates to a preparation method of an eight-arm star-shaped thermoplastic elastomer copolymer.

Background

Thermoplastic elastomers (TPEs) are a class of polymeric materials with physical properties intermediate between plastics and rubbers. They exhibit rubber elasticity at normal temperature, can be plasticized and molded at high temperature, have mechanical properties and service properties similar to those of rubber, and can be processed and recovered according to thermoplastic plastics, so that they are known as "third-generation rubber". Because they do not need heat vulcanization similar to rubber, the processing and forming are simple, and the final product can be conveniently prepared by adopting common plastic processing machinery. Moreover, the performance of the product prepared by reprocessing the TPE after recovery has no obvious loss, and compared with the traditional rubber, the product has obvious advantages and is called as a revolution of materials and process technology in the rubber industry. TPEs which have been industrially produced at present include polystyrenes, polyolefins, polyurethanes, polyesters, polyvinyl chlorides, polyamides, organofluorine polymers, silicone polymers and the like, and almost cover all the fields of synthetic rubbers and synthetic resins at present.

Star polymers are generally defined as polymers having three or more polymer segments radiating from the core, and are largely divided into regular star-branched polymers having identical blocks and hetero-arm star-branched polymers in which the different blocks are asymmetric. The linear branches that make up the star polymer are referred to as the "arms" of the star polymer, while the central polyfunctional group is referred to as the "core" of the star polymer. However, the synthesis of star polymers with a definite structure, controllable molecular weight and narrow molecular weight distribution is still a challenging task, and there are mainly four methods available for synthesizing star polymers: coupling, precore, forearm, and later-developed iterations. The basic idea of the first three synthetic routes is to achieve the synthesis of star polymers by using multifunctional initiators or coupling agents, and difunctional monomers. The coupling method is to carry out coupling reaction on a linear branched chain with functionalized end group and a multifunctional nucleus to obtain a star polymer, and the method is generally not high in efficiency; the 'first nuclear method' is mainly to initiate monomer polymerization by a polyfunctional initiator so as to obtain a star polymer with consistent arm length, but the method has longer time consumption, and the volume steric effect is increased along with the increase of molecular weight, so that the reaction is difficult to be completely carried out; the "arm-first method" is to synthesize a linear polymer chain having a special end group or having an active end, and then to react with a polyfunctional molecule capable of reacting with the special end group or the active end to prepare a star polymer. The iterative method requires multiple reactions because of the addition of multiple, more complex reagents, and the reaction times are longer as the number of star polymer arms increases. Therefore, the rapid, efficient and convenient preparation of star polymers with regular structure and definite composition, and the precise control of molecular weight and molecular weight distribution thereof still remains a significant challenge in the field of high polymer synthesis nowadays, which needs to develop a new synthetic method for synthesizing the star thermoplastic elastomer TPE copolymer.

Disclosure of Invention

The invention aims to provide an eight-arm star-shaped thermoplastic elastomer copolymer and a preparation method thereof. Polystyrene-polyisoprene lithium compound and polystyrene/diphenylethylene-polyisoprene lithium compound which have accurate structures and narrow molecular weight distribution are prepared by using an active anion polymerization method, and the eight-arm star-shaped thermoplastic elastomer copolymer can be quickly and conveniently prepared by using the polystyrene-polyisoprene lithium compound and the diphenylethylene-polyisoprene lithium compound to perform coupling reaction with octavinyl polyhedral oligomeric silsesquioxane; the method disclosed by the invention has the characteristics of high reaction efficiency, mild reaction conditions, less side reactions and good control on the molecular weight and molecular weight distribution of the polymer.

In order to achieve the purpose, the invention adopts the technical scheme that: an eight-arm star-shaped thermoplastic elastomer copolymer has the following chemical structural formula,

in the formula, a hard segment polymer chain R₁Is composed of

Or

(ii) a Soft segment polymer chain R₂Is as follows; x = 10-200, y = 2-10, z = 5-20, m = 200-600, n = 10-30, and the value types of "x", "y", "z", "m" and "n" are integers, and the value types represent connection sites.

The preparation method of the eight-arm star styrene thermoplastic elastomer copolymer comprises the following steps:

(1) in the nitrogen atmosphere, the lithium compound initiates styrene polymerization to obtain a polystyrene lithium compound;

(2) initiating diene polymerization by the polystyrene lithium compound in the step (1) in a nitrogen atmosphere to obtain a polystyrene-polydiene lithium compound;

(3) and (3) reacting the octavinyl polyhedral oligomeric silsesquioxane with the polystyrene-polydiene lithium compound obtained in the step (2) in a nitrogen atmosphere to obtain the eight-arm star-shaped thermoplastic elastomer copolymer.

Or;

the preparation method of the eight-arm star styrene thermoplastic elastomer copolymer comprises the following steps:

(4) in the nitrogen atmosphere, the lithium compound initiates the polymerization of styrene and diphenylethylene to obtain a polystyrene/diphenylethylene lithium compound;

(5) in a nitrogen atmosphere, initiating diene polymerization by the polystyrene/diphenylethylene lithium compound in the step (4) to obtain a polystyrene/diphenylethylene-polydiene lithium compound;

(6) and (3) reacting the octavinyl polyhedral oligomeric silsesquioxane with the polystyrene/diphenylethylene-polydiene lithium compound obtained in the step (5) in a nitrogen atmosphere to obtain the eight-arm star-shaped thermoplastic elastomer copolymer.

In the technical scheme, in the step (1), the molar ratio of the lithium compound to the styrene is 1: 10-200;

in the step (2), the molar ratio of the polystyrene lithium compound to the diene is 1: 210-630;

in the step (3), the molar ratio of the octavinyl polyhedral oligomeric silsesquioxane to the polystyrene-polydienelithium compound is 1: 8.2-9;

in the step (4), the molar ratio of the lithium compound to the styrene to the diphenylethylene is 1: 10-200: 5-20;

in the step (5), the molar ratio of the polystyrene/diphenylethylene lithium compound to the diene is 1: 210-630;

in the step (6), the molar ratio of the octavinyl polyhedral oligomeric silsesquioxane to the polystyrene/diphenylethylene-polydienelithium compound is 1: 8.2-9.

In the technical scheme, in the step (1), the polymerization is carried out at room temperature for 6-12 hours; in the step (2), the polymerization is carried out at room temperature for 12-24 hours; in the step (3), the reaction is carried out at room temperature for 1-2 hours; in the step (4), the polymerization is carried out at room temperature for 12-24 hours; in the step (5), the polymerization is carried out at room temperature for 12-24 hours; in the step (6), the reaction is carried out at room temperature for 1-2 hours.

In the technical scheme, the reactions in the steps (1) to (6) are carried out in a solvent; the lithium compound is sec-butyl lithium or n-butyl lithium; the diene is butadiene or isoprene; and (3) no catalyst or catalyst ligand is required to be used in the reaction processes of the steps (1) to (6).

In the technical scheme, in the step (3), the reaction is terminated by anhydrous methanol; in the step (6), the reaction was terminated with anhydrous methanol. Preferably, in the step (3), the molar ratio of the eight-arm star-shaped polystyrene-polyisoprene lithium compound to the anhydrous methanol is 1: 16-80; in the step (6), the molar ratio of the eight-arm star-shaped polystyrene/diphenylethylene-polyisoprene lithium compound to the anhydrous methanol is 1: 16-80.

The preparation method of the eight-arm star styrene thermoplastic elastomer copolymer specifically comprises the following steps:

(1) preparing a polystyrene lithium compound: in a nitrogen atmosphere, taking styrene as a monomer, sec-butyl lithium as an initiator and anhydrous benzene or cyclohexane as a solvent, and carrying out anionic polymerization reaction at room temperature to obtain a polystyrene lithium compound;

(2) preparation of polystyrene-polyisoprene lithium compound: in a nitrogen atmosphere, taking the polystyrene lithium compound in the step (1) as a macroinitiator, taking anhydrous benzene or cyclohexane as a solvent, taking isoprene as a monomer, and carrying out an anionic polymerization reaction at room temperature to obtain a polystyrene-polyisoprene lithium compound;

(3) preparation of eight-arm radial polystyrene-polyisoprene thermoplastic elastomer copolymer: and (3) in a nitrogen atmosphere, taking anhydrous benzene or cyclohexane as a solvent, reacting the octavinyl polyhedral oligomeric silsesquioxane with the polystyrene-polyisoprene lithium compound in the step (2) at room temperature, and terminating with anhydrous methanol to obtain the eight-arm star-shaped polystyrene-polyisoprene thermoplastic elastomer copolymer.

Or;

the preparation method of the eight-arm star styrene thermoplastic elastomer copolymer specifically comprises the following steps:

(4) preparation of polystyrene/lithium diphenylethylene compound: in the nitrogen atmosphere, styrene and diphenylethylene are taken as monomers, sec-butyl lithium is taken as an initiator, anhydrous benzene or cyclohexane is taken as a solvent, and the anionic polymerization reaction is carried out at room temperature to obtain a polystyrene/diphenylethylene lithium compound;

(5) preparation of polystyrene/diphenylethylene-polyisoprene lithium compound: in a nitrogen atmosphere, taking the polystyrene/diphenylethylene lithium compound in the step (4) as a macromolecular initiator, taking anhydrous benzene or cyclohexane as a solvent, taking isoprene as a monomer, and carrying out an anionic polymerization reaction at room temperature to obtain a polystyrene/diphenylethylene-polyisoprene lithium compound;

(6) preparation of eight-arm radial polystyrene/diphenylethylene-polyisoprene thermoplastic elastomer copolymer: and (3) in a nitrogen atmosphere, taking anhydrous benzene or cyclohexane as a solvent, reacting the octavinyl polyhedral oligomeric silsesquioxane with the polystyrene/diphenylethylene-polyisoprene lithium compound in the step (5) at room temperature, and terminating with anhydrous methanol to obtain the eight-arm star-shaped polystyrene/diphenylethylene-polyisoprene thermoplastic elastomer copolymer.

In the invention, after the reactions in the step (3) and the step (6), the products are respectively purified, and the method comprises the following steps:

purification treatment of eight-arm star thermoplastic elastomer copolymer: after the reaction is finished, concentrating the reaction solution by using a rotary evaporator, dripping into anhydrous methanol for precipitation, washing precipitates by using the anhydrous methanol, drying in vacuum, dissolving by using toluene to obtain a solution, dripping the anhydrous ethanol until the solution is turbid, heating until the solution is transparent, standing for layering, removing the solvent from a lower transparent phase, precipitating in the anhydrous methanol, and filtering and drying precipitates to obtain the eight-arm star-shaped thermoplastic elastomer copolymer.

The invention discloses application of sec-butyl lithium or n-butyl lithium in preparation of the eight-arm star-shaped thermoplastic elastomer copolymer and application of the eight-arm star-shaped thermoplastic elastomer copolymer in preparation of a high polymer material.

According to the invention, the eight-arm star-shaped thermoplastic elastomer copolymer can be rapidly and efficiently prepared under mild reaction conditions by using a living anion polymerization method, and the structure of the star-shaped polymer can be accurately controlled; the molecular weight and molecular weight distribution of the polymer can be more accurately controlled by using a living anion polymerization method, and side reactions are basically avoided; the octavinyl polyhedral oligomeric silsesquioxane and the polymer active chain are quickly subjected to high-efficiency coupling reaction, so that the preparation time of the octavinyl polyhedral oligomeric silsesquioxane-based star thermoplastic elastomer copolymer can be greatly shortened.

In the technical scheme, the preparation method specifically comprises the following steps:

(1) preparation of polystyrene lithium compound (PS-Li): in a nitrogen atmosphere, sec-butyllithium (b), (c) and (d)sec-BuLi) initiator is added into a reaction device, styrene is taken as monomer, anhydrous benzene or cyclohexane is taken as solvent, and anion polymerization reaction is carried out for 12 hours at room temperature, so as to obtain polystyrene lithium compound (PS-Li), wherein the reaction formula is as follows:

(2) preparation of polystyrene-polyisoprene lithium compound (PS-PI-Li): in a nitrogen atmosphere, using the polystyrene lithium compound (PS-Li) in the step (1) as a macroinitiator, using anhydrous benzene or cyclohexane as a solvent, using isoprene as a monomer, and carrying out an anionic polymerization reaction for 12 hours at room temperature to obtain a polystyrene-polyisoprene lithium compound (PS-PI-Li), wherein the reaction formula is as follows:

(3) preparation of eight-arm Star-shaped polystyrene-polyisoprene thermoplastic elastomer copolymer ((PS-PI)₈POSS): in a nitrogen atmosphere, using anhydrous benzene or cyclohexane as a solvent, reacting octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) with the polystyrene-polyisoprene lithium compound (PS-PI-Li) in the step (2) at room temperature for 1-2 hours, and terminating with anhydrous methanol to obtain the eight-arm star-shaped polystyrene-polyisoprene thermoplastic elastomer copolymer ((PS-PI)₈POSS), the reaction formula is as follows:

(4) preparation of polystyrene/lithium diphenylethyleneoxide compound (PSD-Li): in a nitrogen atmosphere, sec-butyllithium (b), (c) and (d)secBuLi) initiator is added into a reaction device, anhydrous benzene or cyclohexane is taken as a solvent, diphenylethylene is added firstly, then styrene is added, and the reaction is carried out at room temperatureCarrying out anionic polymerization for 12 hours to obtain a polystyrene/diphenylethylene lithium compound (PSD-Li) with the following reaction formula:

(5) preparation of polystyrene/diphenylethylene-polyisoprene lithium compound (PSD-PI-Li): in a nitrogen atmosphere, taking the polystyrene/diphenylethylene lithium compound (PSD-Li) in the step (4) as a macroinitiator, taking anhydrous benzene or cyclohexane as a solvent, taking isoprene as a monomer, and carrying out an anionic polymerization reaction for 12 hours at room temperature to obtain the polystyrene/diphenylethylene-polyisoprene lithium compound (PSD-PI-Li), wherein the reaction formula is as follows:

(6) preparation of eight-arm Star-shaped polystyrene/diphenylethylene-polyisoprene thermoplastic elastomer copolymer ((PSD-PI)₈POSS): in a nitrogen atmosphere, using anhydrous benzene or cyclohexane as a solvent, reacting octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) with the polystyrene/diphenylethylene-polyisoprene lithium compound (PSD-PI-Li) in the step (5) at room temperature for 1-2 hours, and terminating with anhydrous methanol to obtain the eight-arm star-shaped polystyrene/diphenylethylene-polyisoprene thermoplastic elastomer copolymer ((PSD-PI)₈POSS), the reaction formula is as follows:

the eight-arm star-shaped thermoplastic elastomer copolymer has the advantages that due to the unique topological branched structure, the hydrodynamic volume of the star-shaped polymer is highly limited, so that the polymer has less winding state compared with a linear polymer in a solution or molten state, and therefore, the eight-arm star-shaped thermoplastic elastomer copolymer has lower viscosity, smaller hydrodynamic volume, smaller rotating radius, low crystallinity and the like, and has good processability, and therefore, the eight-arm star-shaped thermoplastic elastomer copolymer becomes an excellent raw material for preparing TPE materials.

In the above technical scheme, in the steps (3) and (6), after the reaction is completed, the products are respectively purified, and the specific purification process includes the following steps:

3) eight-arm star polystyrene-polyisoprene thermoplastic elastomer copolymer ((PS-PI)₈POSS) purification treatment: after the reaction is ended, concentrating the reaction liquid by using a rotary evaporator, dropwise adding the reaction liquid into anhydrous methanol to precipitate and separate out, washing the reaction liquid for three times by using the anhydrous methanol, putting the reaction liquid into a vacuum drying oven, and performing vacuum drying for 12-24 hours at the temperature of 30-40 ℃ to obtain a crude product. Dissolving the crude product with toluene until the crude product is transparent, dropwise adding absolute ethyl alcohol until the solution is turbid, then treating the solution at the temperature of 30-35 ℃ until the solution is transparent, transferring the solution into a separating funnel while the solution is hot, standing and layering the solution, removing the solvent from a lower transparent phase, precipitating the lower transparent phase in absolute methyl alcohol, and filtering and drying the precipitate to obtain a semitransparent elastic blocky solid;

6) eight-arm star polystyrene/diphenylethylene-polyisoprene thermoplastic elastomer copolymer ((PSD-PI)₈POSS) purification treatment: after the reaction is ended, concentrating the reaction liquid by using a rotary evaporator, dropwise adding the reaction liquid into anhydrous methanol to precipitate and separate out, washing the reaction liquid for three times by using the anhydrous methanol, putting the reaction liquid into a vacuum drying oven, and performing vacuum drying for 12-24 hours at the temperature of 30-40 ℃ to obtain a crude product. And dissolving the crude product with toluene until the crude product is transparent, dropwise adding absolute ethyl alcohol until the solution is turbid, then treating the solution at the temperature of 30-35 ℃ until the solution is transparent, transferring the solution into a separating funnel while the solution is hot, standing and layering the solution, removing the solvent from a lower transparent phase, precipitating the lower transparent phase in absolute methyl alcohol, and filtering and drying the precipitate to obtain a semitransparent elastic blocky solid.

Due to the application of the scheme, compared with the prior art, the invention has the following advantages:

1. the invention adopts a living anion polymerization method to efficiently synthesize the eight-arm star-shaped thermoplastic elastomer copolymer which can accurately control the molecular weight and the molecular weight distribution;

2. the invention introduces the diphenylethylene unit into the hard segment unit of the thermoplastic elastomer copolymer, can improve the glass transition temperature of the hard segment of the elastomer, and can simply adjust the glass transition temperature of the obtained elastomer copolymer by adjusting the dosage of the diphenylethylene unit.

Drawings

FIG. 1 shows PS (A), PS-PI (B), pre-purification (C) and post-purification (D) (PS-PI) in example I₈(ii) a gel permeation chromatography efflux curve for POSS in Tetrahydrofuran (THF);

FIG. 2 shows PS (A), PS-PI (B) and the purified (PS-PI) in example I₈Nuclear magnetic resonance hydrogen spectrogram of POSS (polyhedral oligomeric silsesquioxane) (C) with deuterated chloroform (CDCl) as solvent₃）；

FIG. 3 shows PS (A), PS-PI (B) and the purified (PS-PI) in example I₈(iii) an infrared spectrogram of poss (c);

FIG. 4 shows PS (A), PS-PI (B) and the purified (PS-PI) in example I₈Thermal weight loss curve of POSS (polyhedral oligomeric silsesquioxane) (C), nitrogen and 10 ℃/min;

FIG. 5 shows the purification of example I (PS-PI)₈The tensile rate of a stress-strain curve of POSS is 50 mm/min;

FIG. 6 is a PSD of the second embodiment_0.54(molar ratio of DPE to St units 0.54:1), PSD_0.37(molar ratio of DPE to St units 0.37:1) and PSD_0.16(DPE to St units molar ratio 0.16:1) in Tetrahydrofuran (THF);

FIG. 7 is a PSD of the second embodiment_0.16（A）、PSD_0.37(B) And PSD_0.54(C) The solvent is deuterated chloroform (CDCl)₃）；

FIG. 8 shows PS (A) in the first embodiment and PSD in the second embodiment_0.16（B）、PSD_0.37(C) And PSD_0.54(D) The differential scanning calorimetry curve of (1), nitrogen, 10 ℃/min;

FIG. 9 is a PSD of the second embodiment_0.54-PI（A）、PSD_0.37-PI (B) and PSD_0.16Nuclear magnetic resonance hydrogen spectrum of PI (C) with deuterated chloroform (CDC) as solventl₃）；

FIG. 10 is a PSD of the second embodiment_0.16（A）、PSD_0.16PI (B), pre-purification (C) and post-purification (D) (PSD)_0.16-PI)₈(ii) a gel permeation chromatography efflux curve for POSS in Tetrahydrofuran (THF);

FIG. 11 is a PSD of the second embodiment_0.37（A）、PSD_0.37PI (B), pre-purification (C) and post-purification (D) (PSD)_0.37-PI)₈(ii) a gel permeation chromatography efflux curve for POSS in Tetrahydrofuran (THF);

FIG. 12 is a PSD of the second embodiment_0.54（A）、PSD_0.54PI (B), pre-purification (C) and post-purification (D) (PSD)_0.54-PI)₈(ii) a gel permeation chromatography efflux curve for POSS in Tetrahydrofuran (THF);

FIG. 13 is a diagram of a second embodiment (PSD)_0.16-PI)₈A stress-strain curve of POSS (PSD: PI molecular weight ratio of 1: 4.0) with a stretching rate of 50 mm/min;

FIG. 14 shows a PSD of the second embodiment_0.37-PI)₈A stress-strain curve of POSS (PSD: PI molecular weight ratio of 1: 3.4) with a stretching rate of 50 mm/min;

FIG. 15 is a diagram of a second embodiment (PSD)_0.54-PI)₈A stress-strain curve of POSS (PSD: PI molecular weight ratio of 1: 3.2) (C) with a tensile rate of 50 mm/min;

FIG. 16 is the gel permeation chromatography elution profiles of PS, PS-PI, and PS-PI-PS of example III, with Tetrahydrofuran (THF);

FIG. 17 is a schematic diagram showing a film formed by volatilization of a solvent for PS-PI-PS according to the third example;

FIG. 18 shows a first embodiment (PS-PI)₈And POSS adopts solvent volatilization to form a dumbbell-shaped membrane material object diagram.

Detailed Description

The invention is further described with reference to the following figures and examples: