WO2021088942A1 - 一种八臂星形热塑性弹性体共聚物及其制备方法 - Google Patents

一种八臂星形热塑性弹性体共聚物及其制备方法 Download PDF

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WO2021088942A1
WO2021088942A1 PCT/CN2020/126878 CN2020126878W WO2021088942A1 WO 2021088942 A1 WO2021088942 A1 WO 2021088942A1 CN 2020126878 W CN2020126878 W CN 2020126878W WO 2021088942 A1 WO2021088942 A1 WO 2021088942A1
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lithium compound
polystyrene
thermoplastic elastomer
arm star
elastomer copolymer
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PCT/CN2020/126878
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English (en)
French (fr)
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何金林
王彬
钱强雨
倪沛红
张明祖
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苏州大学
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Priority to US17/774,833 priority Critical patent/US20230025095A1/en
Publication of WO2021088942A1 publication Critical patent/WO2021088942A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • the invention belongs to the field of polymer synthesis, and specifically relates to a preparation method of an eight-arm star-shaped thermoplastic elastomer copolymer.
  • Thermoplastic Elastomer is a type of polymer material with physical properties between plastic and rubber. They show rubber elasticity at room temperature, can be plasticized and formed at high temperature, have mechanical properties and use properties similar to rubber, and can be processed and recycled as thermoplastics, so they are known as the "third-generation rubber.” Because they do not require thermal vulcanization similar to rubber, they are relatively simple to process and shape, and the final product can be easily made by ordinary plastic processing machinery. Moreover, there is no obvious loss in performance of the product produced by reprocessing after TPE recycling. This has obvious advantages over traditional rubber, which can be regarded as a revolution in materials and technology in the rubber industry.
  • TPEs that have been industrially produced include polystyrene, polyolefin, polyurethane, polyester, polyvinyl chloride, polyamide, organic fluoropolymer, silicone polymer, etc., which almost cover the current synthesis All areas of rubber and synthetic resins.
  • Star polymer is generally defined as a polymer with three or more polymer segments radiating from the core. It is mainly divided into regular star-branched polymers with the same block and asymmetrical different blocks. The hetero-arm star-branched polymer. The linear branches that make up the star polymer are called the "arms" of the star polymer, and the multifunctional group in the center is called the "core” of the star polymer.
  • the linear branches that make up the star polymer are called the "arms" of the star polymer, and the multifunctional group in the center is called the "core" of the star polymer.
  • 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 bifunctional monomers.
  • the "coupling method” uses the functionalized linear branch of the terminal group to carry out the coupling reaction with the multifunctional nucleus to obtain the star polymer. This method is generally not efficient; the "pre-nucleus method” mainly uses a multifunctional initiator The monomer polymerization is initiated to obtain a star polymer with more uniform arm lengths.
  • the "first arm method” is the first Synthesize linear polymer chains with special end groups or active ends, and then use multi-functional molecules that can react with special end groups or active ends to realize the preparation of star polymers.
  • This method can easily control the star arms The molecular weight and molecular weight distribution of the resulting star polymers with relatively consistent arm lengths are obtained.
  • this method takes a long time to polymerize into star polymers, and sometimes the reaction is difficult to complete.
  • the iterative rule requires the addition of a variety of more complex reagents and multi-step reactions, and as the number of arms of the star polymer increases, the reaction time becomes longer and longer. Therefore, it is still a major challenge in the field of polymer synthesis to be able to quickly, efficiently and conveniently prepare a star polymer with a regular structure and a clear composition, and to accurately control its molecular weight and molecular weight distribution. This also requires the development of new synthetic methods. For the synthesis of star-shaped thermoplastic elastomer TPE copolymer.
  • the purpose of the present invention is to provide an eight-arm star-shaped thermoplastic elastomer copolymer and a preparation method thereof.
  • the living anionic polymerization method is used to prepare polystyrene-polyisoprene lithium compound and polystyrene/diphenylethylene-polyisoprene lithium compound with precise structure and narrow molecular weight distribution, and use it to align with the octavinyl polyhedron.
  • the polysilsesquioxane undergoes a coupling reaction, and an eight-arm star-shaped thermoplastic elastomer copolymer can be prepared quickly and conveniently; the method disclosed in the present invention has high reaction efficiency, mild reaction conditions, few side reactions, and a high molecular weight The characteristics of good molecular weight distribution control.
  • the technical solution adopted by the present invention is: an eight-arm star-shaped thermoplastic elastomer copolymer, the chemical structure of which is as follows: .
  • the hard segment polymer chain R 1 is or ;
  • the method for preparing the eight-arm star-shaped styrene thermoplastic elastomer copolymer includes the following steps.
  • the lithium compound initiates styrene polymerization to obtain a polystyrene lithium compound.
  • the polystyrene lithium compound of step (1) initiates diene polymerization to obtain a polystyrene-polydiene lithium compound.
  • the octavinyl polyhedral oligomeric silsesquioxane reacts with the polystyrene-polydiene lithium compound of step (2) to obtain an eight-arm star-shaped thermoplastic elastomer copolymer.
  • the method for preparing the eight-arm star-shaped styrene-based thermoplastic elastomer copolymer includes the following steps: (4) In a nitrogen atmosphere, the lithium compound initiates the polymerization of styrene and diphenylethylene to obtain polystyrene/diphenylethylene Ethylene lithium compound.
  • step (4) In a nitrogen atmosphere, the polystyrene/diphenylethylene lithium compound in step (4) initiates diene polymerization to obtain a polystyrene/diphenylethylene-polydiene lithium compound.
  • the octavinyl polyhedral oligomeric silsesquioxane reacts with the polystyrene/diphenylethylene-polydiene lithium compound of step (5) to obtain an eight-arm star-shaped thermoplastic elastomer copolymer .
  • step (1) the molar ratio of the lithium compound to the styrene is 1:(10-200).
  • step (2) the molar ratio of the polystyrene lithium compound to the diene is 1: (210-630).
  • step (3) the molar ratio of the octavinyl polyhedral oligomeric silsesquioxane to the polystyrene-polydiene lithium compound is 1:(8.2-9).
  • step (4) the molar ratio of the lithium compound, styrene, and diphenylethylene is 1: (10 to 200): (5 to 20).
  • step (5) the molar ratio of the polystyrene/diphenylethylene lithium compound to the diene is 1: (210-630).
  • step (6) the molar ratio of the octavinyl polyhedral oligomeric silsesquioxane to the polystyrene/diphenylethylene-polydiene lithium compound is 1:(8.2-9).
  • step (1) the polymerization is room temperature reaction for 6 to 12 hours; in step (2), the polymerization is room temperature reaction for 12 to 24 hours; in step (3), the reaction is room temperature reaction for 1 to 2 hours; In step (4), the polymerization is room temperature reaction for 12 to 24 hours; in step (5), the polymerization is room temperature reaction for 12 to 24 hours; in step (6), the reaction is room temperature reaction for 1 to 2 hours.
  • the reactions in steps (1) to (6) are carried out in a solvent; the lithium compound is sec-butyllithium or n-butyllithium; the diene is butadiene or isoprene; the steps ( There is no need to use catalysts and catalyst ligands in the reaction process from 1) to (6).
  • step (3) anhydrous methanol is used to terminate the reaction; in step (6), anhydrous methanol is used to terminate the reaction.
  • the molar ratio of the eight-arm star-shaped polystyrene-polyisoprene lithium compound to anhydrous methanol is 1: (16 to 80); in step (6), the The molar ratio of the eight-arm star-shaped polystyrene/diphenylethylene-polyisoprene lithium compound to anhydrous methanol is 1: (16-80).
  • the method for preparing the eight-arm star-shaped styrene thermoplastic elastomer copolymer specifically includes the following steps.
  • polystyrene lithium compound In a nitrogen atmosphere, styrene is used as the monomer, sec-butyl lithium is used as the initiator, and anhydrous benzene or cyclohexane is used as the solvent, and anionic polymerization reaction is carried out at room temperature to obtain Polystyrene lithium compound.
  • step (2) Preparation of polystyrene-polyisoprene lithium compound: In a nitrogen atmosphere, use the polystyrene lithium compound in step (1) as a macroinitiator, and anhydrous benzene or cyclohexane as a solvent, Using isoprene as a monomer, an anionic polymerization reaction is carried out at room temperature to obtain a polystyrene-polyisoprene lithium compound.
  • the method for preparing the eight-arm star-shaped styrene-based thermoplastic elastomer copolymer specifically includes the following steps: (4) Preparation of polystyrene/diphenylethylene lithium compound: in a nitrogen atmosphere, styrene and diphenylethylene Phenylethylene is a monomer, sec-butyllithium is an initiator, anhydrous benzene or cyclohexane is used as a solvent, and anionic polymerization is carried out at room temperature to obtain a polystyrene/diphenylethylene lithium compound.
  • step (4) Preparation of polystyrene/diphenylethylene-polyisoprene lithium compound: In a nitrogen atmosphere, use the polystyrene/diphenylethylene lithium compound in step (4) as a macroinitiator to Anhydrous benzene or cyclohexane is used as a solvent, isoprene is used as a monomer, and anionic polymerization reaction is performed at room temperature to obtain a polystyrene/diphenylethylene-polyisoprene lithium compound.
  • the product is purified separately, including the following steps: Purification of eight-arm star-shaped thermoplastic elastomer copolymer: After the reaction, the reaction liquid is rotated After being concentrated by the evaporator, it was dropped into anhydrous methanol to precipitate. The precipitate was washed with anhydrous methanol and dried in vacuum, and then dissolved in toluene to obtain a solution. Then, anhydrous ethanol was added dropwise until the solution appeared turbid, and then heated until the solution was transparent, and then stood still. After layering, the lower transparent phase is removed from the solvent and then precipitated in anhydrous methanol. The precipitate is filtered and dried to obtain an eight-arm star-shaped thermoplastic elastomer copolymer.
  • the invention discloses the application of sec-butyl lithium or n-butyl lithium in the preparation of the above-mentioned eight-arm star-shaped thermoplastic elastomer copolymer and the application of the above-mentioned eight-arm star-shaped thermoplastic elastomer copolymer in the preparation of polymer materials.
  • the present invention uses the living anionic polymerization method to quickly and efficiently prepare the eight-arm star-shaped thermoplastic elastomer copolymer under mild reaction conditions, and realizes the precise control of the structure of the star polymer; the living anionic polymerization method can control the polymer The molecular weight and molecular weight distribution are controlled more precisely, and there are basically no side reactions; the use of octavinyl polyhedral oligomeric silsesquioxane and the active chain of the polymer can quickly and efficiently couple the reaction, which can greatly shorten the eight-arm star-shaped thermoplastic elastomer Preparation time of the copolymer.
  • PSD-PI-Li polystyrene/diphenylethylene-polyisoprene lithium compound
  • PSD-Li polystyrene/diphenylethylene lithium compound in step (4)
  • anhydrous benzene or cyclohexane is used as solvent
  • isoprene is used as monomer
  • anionic polymerization is carried out at room temperature for 12 hours to obtain polystyrene/diphenyl Ethylene-polyisoprene lithium compound (PSD-PI-Li)
  • the reaction formula is as follows.
  • the eight-arm star-shaped thermoplastic elastomer copolymer of the present invention benefits from its unique topological branched structure, and the hydrodynamic volume of the star-shaped polymer is highly restricted, making this type of polymer in a solution or molten state compared to linear
  • the polymer has less winding state, which gives it lower viscosity, smaller hydrodynamic volume, smaller radius of rotation, low crystallinity, etc., and has good processing properties, thus becoming an excellent preparation for TPE materials.
  • Raw materials are used.
  • the present invention has the following advantages compared with the prior art.
  • the invention adopts a living anionic polymerization method to efficiently synthesize an eight-arm star-shaped thermoplastic elastomer copolymer capable of accurately controlling molecular weight and molecular weight distribution.
  • the present invention introduces diphenylethylene units into the hard segment units of the thermoplastic elastomer copolymer, which can increase the glass transition temperature of the elastomer hard segments, and can easily adjust the resulting elasticity by adjusting the amount of diphenylethylene units The glass transition temperature of the bulk copolymer.
  • Figure 1 shows the gel permeation chromatography elution curves of PS (A), PS-PI (B), before purification (C) and after purification (D) (PS-PI) 8 POSS in Example 1.
  • the solvent is tetrahydrofuran (THF) ).
  • Figure 2 shows the proton nuclear magnetic resonance spectra of PS (A), PS-PI (B) and purified (PS-PI) 8 POSS (C) in Example 1, and the solvent is deuterated chloroform (CDCl 3 ).
  • Figure 3 shows the infrared spectra of PS (A), PS-PI (B) and purified (PS-PI) 8 POSS (C) in Example 1.
  • Figure 4 is the thermal weight loss curve of PS (A), PS-PI (B) and purified (PS-PI) 8 POSS (C) in Example 1, nitrogen, 10°C/min.
  • Figure 5 shows the stress-strain curve of (PS-PI) 8 POSS after purification in Example 1, and the stretching rate is 50 mm/min.
  • Figure 6 shows the PSD 0.54 (DPE to St unit molar ratio of 0.54:1), PSD 0.37 (DPE to St unit molar ratio of 0.37:1) and PSD 0.16 (DPE to St unit molar ratio of 0.16:1) in Example 2. ) Gel permeation chromatography elution curve, the solvent is tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • Figure 7 shows the proton nuclear magnetic resonance spectra of PSD 0.16 (A), PSD 0.37 (B) and PSD 0.54 (C) in Example 2, and the solvent is deuterated chloroform (CDCl 3 ).
  • Figure 8 shows the differential scanning calorimetry curves of PS (A) in Example 1 and PSD 0.16 (B), PSD 0.37 (C) and PSD 0.54 (D) in Example 2, nitrogen, 10°C/min.
  • Fig. 9 shows the proton nuclear magnetic resonance spectra of PSD 0.54 -PI (A), PSD 0.37 -PI (B) and PSD 0.16 -PI (C) in Example 2, and the solvent is deuterated chloroform (CDCl 3 ).
  • Figure 10 shows the gel permeation chromatography elution curves of PSD 0.16 (A), PSD 0.16 -PI (B), before purification (C) and after purification (D) (PSD 0.16 -PI) 8 POSS in Example 2, the solvent is Tetrahydrofuran (THF).
  • Figure 11 shows the gel permeation chromatography elution curves of PSD 0.37 (A), PSD 0.37 -PI (B), before purification (C) and after purification (D) (PSD 0.37 -PI) 8 POSS in Example 2.
  • the solvent is Tetrahydrofuran (THF).
  • Figure 12 shows the gel permeation chromatography elution curves of PSD 0.54 (A), PSD 0.54 -PI (B), before purification (C) and after purification (D) (PSD 0.54 -PI) 8 POSS in Example 2.
  • the solvent is Tetrahydrofuran (THF).
  • Figure 13 is the stress-strain curve of (PSD 0.16 -PI) 8 POSS (PSD:PI molecular weight ratio is 1:4.0) in Example 2, and the stretching rate is 50 mm/min.
  • Figure 14 is the stress-strain curve of (PSD 0.37 -PI) 8 POSS (PSD:PI molecular weight ratio is 1:3.4) in Example 2, and the stretching rate is 50 mm/min.
  • Figure 15 is the stress-strain curve of (PSD 0.54 -PI) 8 POSS (PSD:PI molecular weight ratio is 1:3.2) (C) in Example 2, and the tensile rate is 50 mm/min.
  • Figure 16 shows the gel permeation chromatography elution curves of PS, PS-PI, and PS-PI-PS in Example 3, and the solvent is tetrahydrofuran (THF).
  • Fig. 17 is a physical picture of the PS-PI-PS film formed by solvent volatilization in Example 3.
  • Fig. 18 is a physical picture of the dumbbell-shaped film obtained by using solvent volatilization to form a (PS-PI) 8 POSS film in Example 1.
  • Example 1 Preparation of eight-arm star-shaped thermoplastic elastomer copolymer ((PS-PI) 8 POSS).
  • PS-PI-Li polystyrene-polyisoprene lithium compound
  • the PS-PI-Li solution obtained in the above step (2) and octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) (73.5 mg, 0.12 mmol) in benzene (10 mL) solution was subjected to the coupling reaction at room temperature for 2 hours, and the reaction was terminated with anhydrous methanol.
  • the reaction solution was concentrated with a rotary evaporator and precipitated in anhydrous methanol, and the filtered solid was dried in a vacuum oven at 35° C. for 24 hours to obtain a crude product.
  • the crude product is purified by fractional precipitation to obtain a transparent elastic block solid, which is an eight-arm star-shaped thermoplastic elastomer copolymer.
  • FIG. 1 H NMR proton nuclear magnetic resonance spectroscopy
  • FT-IR infrared spectroscopy
  • GPC gel permeation chromatography
  • Figure 1 (C), Figure 1 (D), Figure 2 (C) and Figure 3 (C) are the gel permeation chromatography (GPC) elution curves of the crude product of (PS-PI) 8 POSS, respectively.
  • PS-PI POSS pure product by gel permeation chromatography (GPC) elution curve, 1H NMR (1 H NMR) and infrared spectroscopy
  • FIG (FT-IR) FIG verified (PS-PI) 8 POSS is Chemical structure.
  • FIG. 4 shows the thermal decomposition curves of three polymers of PS, PS-PI and (PS-PI) 8 POSS, showing that the eight-arm star elastomer copolymer (PS-PI) 8 POSS is compared with the linear polymer PS- PI has a high thermal decomposition temperature and good thermal stability.
  • Figure 5 shows the stress-strain curve of the eight-arm star elastomer copolymer (PS-PI) 8 POSS. It can be seen from the figure that its elongation at break is 900% and the average breaking strength is 1.2 MPa.
  • Example 2 Preparation of eight-arm star-shaped thermoplastic elastomer copolymer ((PSD-PI) 8 POSS) containing DPE units.
  • PSD 0.37 sec-butyl lithium ( sec- BuLi, 0.55 mL, 0.7 mmol), diphenylethylene (2.5 mL, 14.2 mmol), styrene (2.6 mL, 22.7 mmol); PSD 0.54 : sec-butyl lithium ( sec -BuLi, 0.48 mL, 0.71 mmol), diphenylethylene (2.5 mL, 14.2 mmol), styrene (1.9 mL, 17 mmol).
  • the polymer was characterized by proton nuclear magnetic resonance spectroscopy ( 1 H NMR) and gel permeation chromatography (GPC).
  • Figures 6 and 7 are gel permeation chromatography (GPC) elution curves and proton nuclear magnetic resonance spectroscopy ( 1 H NMR) graphs of PSD polymers with different DPE unit content, respectively, verifying the chemistry of PSD with different monomer molar ratios structure.
  • the glass transition temperature of the polymer is also increased correspondingly, that is, the glass transition temperature of the polymer can be adjusted by changing the content of the DPE unit.
  • PSD 0.16 -PI solution was concentrated with a rotary evaporator and added dropwise Precipitate in anhydrous methanol, stand still for layering, and dry the filtered solid in a vacuum oven at 35°C for 24 hours to obtain a white sticky solid PSD 0.16 -PI.
  • PSD 0.37 -PI and PSD 0.54 -PI were prepared by this method, and the amount of raw material monomer can be changed.
  • PSD 0.37 -PI isoprene (14.43 g, 211.9 mmol); PSD 0.54 -PI: isoprene (11.7 g, 172 mmol).
  • Figure 13, Figure 14, Figure 15 respectively correspond to the stress-strain curves of (PSD 0.16 -PI) 8 POSS, (PSD 0.37 -PI) 8 POSS and (PSD 0.54 -PI) 8 POSS, which can be seen from the figure Their breaking elongation and breaking strength are: (PSD 0.16 -PI) 8 POSS (2060%, 7.2 MPa); (PSD 0.37 -PI) 8 POSS (1880%, 7.7 MPa); (PSD 0.54 -PI) 8 POSS (1610%, 6.4 MPa).
  • the method disclosed by the invention has the advantages of rapid and efficient reaction, mild conditions, fewer side reactions, controllable polymer molecular weight and molecular weight distribution, etc.
  • the obtained eight-arm star-shaped thermoplastic elastomer copolymer has a clear structure;
  • the polymer segment obtained by copolymerization of DPE) and styrene (St) is used as the hard segment, which makes the eight-arm star-shaped thermoplastic elastomer copolymer have more excellent stress-strain characteristics; at the same time, diphenylethylene (DPE) and styrene ( St)
  • DPE diphenylethylene
  • St styrene
  • the polymer segment obtained by copolymerization has a higher glass transition temperature than that of polystyrene, which can increase the upper limit temperature of the star-shaped thermoplastic elastomer copolymer, and the molar ratio of the two monomers can be changed.
  • the present invention does not require catalysts and
  • GPC gel permeation chromatography
  • PS-PI-Li polystyrene-polyisoprene lithium compound
  • GPC gel permeation chromatography
  • Example 3 Dissolve the PS-PI-PS in Example 3 and the (PS-PI) 8 POSS in Example 1 in a beaker with 40 mL of benzene solvent, stir for 0.5 h to fully dissolve, and cast in a polytetrafluoroethylene square tank Inside, cover the upper tank cover to slowly evaporate the solvent for 3 days, then place the square tank in a vacuum oven at 35°C for 12 hours to fully remove the solvent to obtain PS-PI-PS and (PS-PI) 8 POSS films; 17 is a photo of the PS-PI-PS physical film, which has poor mechanical properties and cannot be made into a dumbbell-shaped sample for mechanical performance testing; Figure 18 is a physical photo of the (PS-PI) 8 POSS film, which can prepare a dumbbell-shaped sample, corresponding to the attached Figure 5 Sample strips used for testing.

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Abstract

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，所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，能够提高八臂星形热塑性弹性体共聚物的使用上限温度。

Description

一种八臂星形热塑性弹性体共聚物及其制备方法 技术领域
本发明属于高分子合成领域，具体涉及一种八臂星形热塑性弹性体共聚物的制备方法。
 背景技术
热塑性弹性体（Thermoplastic Elastomer, TPE）是物理性能介于塑料和橡胶之间的一类高分子材料。它们在常温下显示橡胶弹性、高温下又能塑化成型，具有类似于橡胶的力学性能及使用性能、又能按热塑性塑料进行加工和回收，因此被誉为“第三代橡胶”。由于它们不需要类似于橡胶那样的热硫化，因而加工成型比较简单，采用普通的塑料加工机械即可方便地制得最终产品。而且TPE回收后重新加工制得的产品性能并没有明显的损失，这相对于传统橡胶优势十分明显，堪称是橡胶工业的一次材料和工艺技术的革命。目前已经工业化生产的TPE有聚苯乙烯类、聚烯烃类、聚氨酯类、聚酯类、聚氯乙烯类、聚酰胺类、有机氟聚合物类、有机硅聚合物类等，几乎涵盖了目前合成橡胶与合成树脂的所有领域。
星形聚合物一般被定义为具有三个及三个以上从核心辐射发散出来的聚合物链段的聚合物，主要分为具有相同嵌段的规则星形支化聚合物和不同嵌段不对称的杂臂星形支化聚合物。组成星形聚合物的线形支链称为星形聚合物的“臂”，而中心的多官能基团称为星形聚合物的“核”。然而，合成结构明确、分子量可控、分子量分布较窄的星形聚合物仍是富有挑战性的工作，目前可用于合成星形聚合物的方法主要有四种：偶联法、先核法、先臂法以及后来出现的迭代法等。前三种合成路线的基本思路是通过使用多官能团的引发剂或偶联剂、以及双官能团的单体来实现星形聚合物的合成。“偶联法”是用端基功能化的线形支链与多官能化的核进行偶联反应得到星形聚合物，该方法一般效率不高；“先核法”主要是通过多官能团引发剂引发单体聚合，从而得到臂长较为一致的星形聚合物，但该方法耗时比较长，且随分子量增加，体积位阻效应变大，反应难以进行完全；“先臂法”则是先合成具有特殊端基或带有活性末端的线形聚合物链，再利用能与特殊端基或活性末端反应的多官能团分子与之反应实现星形聚合物的制备，此方法可方便地控制星臂的分子量和分子量分布从而得到臂长较为一致的星形聚合物，但是此方法在聚合成星形聚合物时所需时间较长，有时反应难以完全。迭代法则因为需要加入多种较复杂的试剂，需要多步反应，而且随着星形聚合物臂数增加，反应时间越来越长。因此，能够快速高效便捷制备结构规整、组成明确的星形聚合物，并且可以精确控制其分子量和分子量分布，仍然是现今高分子合成领域的一重大挑战，这也就需要研发新的合成方法用于合成星形热塑性弹性体TPE共聚物。
 技术问题
本发明的目的在于提供一种八臂星形热塑性弹性体共聚物及其制备方法。利用活性阴离子聚合法制备结构精确、分子量分布窄的聚苯乙烯-聚异戊二烯锂化合物和聚苯乙烯/二苯基乙烯-聚异戊二烯锂化合物，利用其与八乙烯基多面体齐聚倍半硅氧烷发生偶联反应，可以快速便捷制得八臂星形热塑性弹性体共聚物；本发明公开的方法具有反应效率高、反应条件温和、副反应少、对聚合物的分子量和分子量分布控制好的特点。
 技术解决方案
为达到上述目的，本发明采取的技术方案为：一种八臂星形热塑性弹性体共聚物，其化学结构式如下，
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。
式中，硬段聚合物链R 1 为
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或
Figure 150152dest_path_image003
；软段聚合物链R 2 为；x = 10～200，y = 2～10，z = 5～20，m = 200～600，n = 10～30，“x”、“y”、“z”、“m”和“n”的取值类型均为整数，*表示连接位点。
上述八臂星形苯乙烯类热塑性弹性体共聚物的制备方法，包括以下步骤。
（1）氮气氛围中，锂化合物引发苯乙烯聚合，得到聚苯乙烯锂化合物。
（2）氮气氛围中，步骤(1)的聚苯乙烯锂化合物引发二烯聚合，得到聚苯乙烯-聚二烯锂化合物。
（3）氮气氛围中，八乙烯基多面体齐聚倍半硅氧烷与步骤(2)的聚苯乙烯-聚二烯锂化合物反应，得到八臂星形热塑性弹性体共聚物。
或者，上述八臂星形苯乙烯类热塑性弹性体共聚物的制备方法，包括以下步骤：（4）氮气氛围中，锂化合物引发苯乙烯、二苯基乙烯聚合，得到聚苯乙烯/二苯基乙烯锂化合物。
（5）氮气氛围中，步骤(4)的聚苯乙烯/二苯基乙烯锂化合物引发二烯聚合，得到聚苯乙烯/二苯基乙烯-聚二烯锂化合物。
（6）氮气氛围中，八乙烯基多面体齐聚倍半硅氧烷与步骤(5)的聚苯乙烯/二苯基乙烯-聚二烯锂化合物反应，得到八臂星形热塑性弹性体共聚物。
上述技术方案中，步骤(1)中，锂化合物与苯乙烯的摩尔比为1∶(10～200)。
步骤(2)中，聚苯乙烯锂化合物与二烯的摩尔比为1∶(210～630)。
步骤(3)中，八乙烯基多面体齐聚倍半硅氧烷与聚苯乙烯-聚二烯锂化合物的摩尔比为1∶(8.2～9)。
步骤(4)中，所述锂化合物、苯乙烯、二苯基乙烯的摩尔比为1∶(10～200)∶(5～20)。
步骤(5)中，所述聚苯乙烯/二苯基乙烯锂化合物与二烯的摩尔比为1∶(210～630)。
步骤(6)中，所述八乙烯基多面体齐聚倍半硅氧烷与聚苯乙烯/二苯基乙烯-聚二烯锂化合物的摩尔比为1∶(8.2～9)。
上述技术方案中，步骤(1)中，聚合为室温反应6～12小时；步骤(2)中，聚合为室温反应12～24小时；步骤(3)中，反应为室温反应1～2小时；步骤(4)中，聚合为室温反应12～24小时；步骤(5)中，聚合为室温反应12～24小时；步骤(6)中，反应为室温反应1～2小时。
上述技术方案中，所述步骤(1)～(6)反应在溶剂中进行；锂化合物为仲丁基锂或者正丁基锂；二烯为丁二烯或者异戊二烯；所述步骤(1)～(6)的反应过程中不需要使用催化剂和催化剂配体。
上述技术方案中，步骤(3)中，以无水甲醇终止反应；步骤(6)中，以无水甲醇终止反应。优选的，步骤(3)中，所述八臂星形聚苯乙烯-聚异戊二烯锂化合物与无水甲醇的摩尔比为1∶(16～80)；步骤(6)中，所述八臂星形聚苯乙烯/二苯基乙烯-聚异戊二烯锂化合物与无水甲醇的摩尔比为1∶(16～80)。
上述八臂星形苯乙烯类热塑性弹性体共聚物的制备方法中，具体包括以下步骤。
（1）制备聚苯乙烯锂化合物：在氮气氛围中，以苯乙烯为单体，仲丁基锂为引发剂，无水苯或环己烷为溶剂，在室温条件下进行阴离子聚合反应，得到聚苯乙烯锂化合物。
（2）制备聚苯乙烯-聚异戊二烯锂化合物：在氮气氛围中，用步骤（1）中的聚苯乙烯锂化合物作为大分子引发剂，以无水苯或环己烷为溶剂，以异戊二烯为单体，在室温条件下进行阴离子聚合反应，得到聚苯乙烯-聚异戊二烯锂化合物。
（3）制备八臂星形聚苯乙烯-聚异戊二烯热塑性弹性体共聚物：在氮气氛围中，以无水苯或环己烷为溶剂，在室温条件下，以八乙烯基多面体齐聚倍半硅氧烷与步骤（2）中的聚苯乙烯-聚异戊二烯锂化合物反应，以无水甲醇终止后即得到八臂星形聚苯乙烯-聚异戊二烯热塑性弹性体共聚物。
或者，上述八臂星形苯乙烯类热塑性弹性体共聚物的制备方法中，具体包括以下步骤：（4）制备聚苯乙烯/二苯基乙烯锂化合物：在氮气氛围中，以苯乙烯和二苯基乙烯为单体，仲丁基锂为引发剂，以无水苯或环己烷为溶剂，在室温条件下进行阴离子聚合反应，得到聚苯乙烯/二苯基乙烯锂化合物。
（5）制备聚苯乙烯/二苯基乙烯-聚异戊二烯锂化合物：在氮气氛围中，用步骤（4）中的聚苯乙烯/二苯基乙烯锂化合物为大分子引发剂，以无水苯或环己烷为溶剂，以异戊二烯为单体，在室温条件下进行阴离子聚合反应，得到聚苯乙烯/二苯基乙烯-聚异戊二烯锂化合物。
（6）制备八臂星形聚苯乙烯/二苯基乙烯-聚异戊二烯热塑性弹性体共聚物：在氮气氛围中，以无水苯或环己烷为溶剂，在室温条件下，以八乙烯基多面体齐聚倍半硅氧烷与步骤（5）中的聚苯乙烯/二苯基乙烯-聚异戊二烯锂化合物反应，以无水甲醇终止后即得到八臂星形聚苯乙烯/二苯基乙烯-聚异戊二烯热塑性弹性体共聚物。
本发明中，所述步骤（3）、步骤（6）反应后，分别对产物进行提纯处理，包括以下步骤：八臂星形热塑性弹性体共聚物的提纯处理：反应结束后，反应液用旋转蒸发仪浓缩后滴入无水甲醇中沉淀析出，析出物用无水甲醇洗涤后真空干燥，再用甲苯溶解得到溶液，然后滴加无水乙醇至溶液出现混浊，再加热至溶液透明，然后静置分层，然后将下层透明相除去溶剂后在无水甲醇中沉淀，沉淀物经过抽滤、烘干，得到八臂星形热塑性弹性体共聚物。
本发明公开了仲丁基锂或者正丁基锂在制备上述八臂星形热塑性弹性体共聚物中的应用以及上述八臂星形热塑性弹性体共聚物在制备高分子材料中的应用。
本发明利用活性阴离子聚合方法可以实现在温和反应条件下快速高效制备八臂星形热塑性弹性体共聚物，并实现了对星形聚合物结构的精确控制；利用活性阴离子聚合法可以对聚合物的分子量和分子量分布进行更加精确的控制，且基本没有副反应；利用八乙烯基多面体齐聚倍半硅氧烷与聚合物活性链快速发生高效偶联反应，能够大大缩短八臂星形热塑性弹性体共聚物的制备时间。
上述技术方案中，具体的制备为。
(1) 制备聚苯乙烯锂化合物（PS-Li）：在氮气氛围中，将仲丁基锂（ sec-BuLi）引发剂加入反应装置内，以苯乙烯为单体，以无水苯或环己烷为溶剂，在室温条件下进行阴离子聚合反应12小时，得到聚苯乙烯锂化合物（PS-Li），反应式如下。
 
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。
(2) 制备聚苯乙烯-聚异戊二烯锂化合物（PS-PI-Li）：在氮气氛围中，用步骤(1)中的聚苯乙烯锂化合物（PS-Li）为大分子引发剂，以无水苯或环己烷为溶剂，以异戊二烯为单体，在室温条件下进行阴离子聚合反应12小时，得到聚苯乙烯-聚异戊二烯锂化合物（PS-PI-Li），反应式如下。
 
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。
(3) 制备八臂星形聚苯乙烯-聚异戊二烯热塑性弹性体共聚物（(PS-PI) 8POSS）：在氮气氛围中，以无水苯或环己烷为溶剂，在室温条件下，以八乙烯基多面体齐聚倍半硅氧烷（OVPOSS）与步骤(2)中的聚苯乙烯-聚异戊二烯锂化合物（PS-PI-Li）反应1～2小时，用无水甲醇终止后即得到八臂星形聚苯乙烯-聚异戊二烯热塑性弹性体共聚物（(PS-PI) 8POSS），反应式如下。
 
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。
 (4) 制备聚苯乙烯/二苯基乙烯锂化合物（PSD-Li）：在氮气氛围中，将仲丁基锂（ sec-BuLi）引发剂加入反应装置内，以无水苯或环己烷为溶剂，先加入二苯基乙烯，后加入苯乙烯，在室温条件下进行阴离子聚合反应12小时，得到聚苯乙烯/二苯基乙烯锂化合物（PSD-Li），反应式如下。
 
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。
 (5) 制备聚苯乙烯/二苯基乙烯-聚异戊二烯锂化合物（PSD-PI-Li）：在氮气氛围中，用步骤(4)中的聚苯乙烯/二苯基乙烯锂化合物（PSD-Li）为大分子引发剂，以无水苯或环己烷为溶剂，以异戊二烯为单体，在室温条件下进行阴离子聚合反应12小时，得到聚苯乙烯/二苯基乙烯-聚异戊二烯锂化合物（PSD-PI-Li），反应式如下。
 
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。
 (6) 制备八臂星形聚苯乙烯/二苯基乙烯-聚异戊二烯热塑性弹性体共聚物（(PSD-PI) 8POSS）：在氮气氛围中，以无水苯或环己烷为溶剂，在室温条件下，以八乙烯基多面体齐聚倍半硅氧烷（OVPOSS）与步骤(5)中的聚苯乙烯/二苯基乙烯-聚异戊二烯锂化合物（PSD-PI-Li）反应1～2小时，用无水甲醇终止后即得到八臂星形聚苯乙烯/二苯基乙烯-聚异戊二烯热塑性弹性体共聚物（(PSD-PI) 8POSS），反应式如下。
 
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。
本发明八臂星形热塑性弹性体共聚物得益于其独特的拓扑支化结构，星形聚合物的流体动力学体积被高度限制，使得此类聚合物在溶液或熔融状态下相比于线形聚合物有较少的缠绕状态，从而赋予其较低的粘度、较小的流体动力学体积、较小的旋转半径、低结晶度等，且有着良好的加工性能，从而成为制备TPE材料的优良原材料。
上述技术方案中，所述步骤(3)、(6)中，反应完成后，分别对产物进行提纯处理，具体的纯化过程包括以下步骤。
(3)八臂星形聚苯乙烯-聚异戊二烯热塑性弹性体共聚物（(PS-PI) 8POSS）的提纯处理：终止反应结束后，反应液用旋转蒸发仪浓缩，逐滴滴入无水甲醇中沉淀析出，并用无水甲醇洗涤三次，放入真空干燥烘箱，在30～40 ℃抽真空干燥12～24小时后得到粗产物。然后将粗产物用甲苯溶解至透明，并滴加无水乙醇至溶液出现混浊，然后于30～35 ℃处理至溶液透明，再趁热将溶液转移到分液漏斗中，静置分层，下层透明相除去溶剂后在无水甲醇中沉淀，沉淀物经过抽滤、烘干，得到半透明弹性块状固体。
(6)八臂星形聚苯乙烯/二苯基乙烯-聚异戊二烯热塑性弹性体共聚物。（(PSD-PI) 8POSS）的提纯处理：终止反应结束后，反应液用旋转蒸发仪浓缩，逐滴滴入无水甲醇中沉淀析出，并用无水甲醇洗涤三次，放入真空干燥烘箱，在30～40 ℃抽真空干燥12～24 h后得到粗产物。然后将粗产物用甲苯溶解至透明，并滴加无水乙醇至溶液出现混浊，然后于30～35 ℃处理至溶液透明，再趁热将溶液转移到分液漏斗中，静置分层，下层透明相除去溶剂后在无水甲醇中沉淀，沉淀物经过抽滤、烘干，得到半透明弹性块状固体。
有益效果
由于上述方案运用，本发明与现有技术相比，具有以下优点。
1．本发明采用活性阴离子聚合法，高效合成能够精确控制分子量和分子量分布的八臂星形热塑性弹性体共聚物。
2. 本发明将二苯基乙烯单元引入热塑性弹性体共聚物的硬段单元中，可以提高弹性体硬段的玻璃化转变温度，而且能够通过调整二苯基乙烯单元的用量来简易调节所得弹性体共聚物的玻璃化转变温度。
 附图说明
图1为实施例一中PS（A）、PS-PI（B）、纯化前（C）和纯化后（D）(PS-PI) 8POSS的凝胶渗透色谱流出曲线，溶剂为四氢呋喃（THF）。
图2为实施例一中PS（A）、PS-PI（B）和 纯化后(PS-PI) 8POSS（C）的核磁共振氢谱图，溶剂为氘代氯仿（CDCl 3）。
图3为实施例一中PS（A）、PS-PI（B）和 纯化后(PS-PI) 8POSS（C）的红外光谱谱图。
图4为实施例一中PS（A）、PS-PI（B）和 纯化后(PS-PI) 8POSS（C）的热失重曲线，氮气，10℃/min。
图5为实施例一中纯化后(PS-PI) 8POSS的应力应变曲线，拉伸速率为50 mm/min。
图6为实施例二中PSD 0.54 (DPE与St单元摩尔比为0.54:1)、PSD 0.37 (DPE与St单元摩尔比为0.37:1)和PSD 0.16 (DPE与St单元摩尔比为0.16:1)的凝胶渗透色谱流出曲线，溶剂为四氢呋喃（THF）。
图7为实施例二中PSD 0.16（A）、PSD 0.37（B）和PSD 0.54（C）的核磁共振氢谱图，溶剂为氘代氯仿（CDCl 3）。
图8为实施例一中PS（A）及实施例二中PSD 0.16（B）、PSD 0.37（C）和PSD 0.54（D）的差示扫描量热曲线，氮气，10℃/min。
图9为实施例二中PSD 0.54-PI（A）、PSD 0.37-PI（B）和PSD 0.16-PI（C）的核磁共振氢谱图，溶剂为氘代氯仿（CDCl 3）。
图10为实施例二中PSD 0.16（A）、PSD 0.16-PI（B）、纯化前（C）和纯化后（D）(PSD 0.16-PI) 8POSS的凝胶渗透色谱流出曲线，溶剂为四氢呋喃（THF）。
图11为实施例二中PSD 0.37（A）、PSD 0.37-PI（B）、纯化前（C）和纯化后（D）(PSD 0.37-PI) 8POSS的凝胶渗透色谱流出曲线，溶剂为四氢呋喃（THF）。
图12为实施例二中PSD 0.54（A）、PSD 0.54-PI（B）、纯化前（C）和纯化后（D）(PSD 0.54-PI) 8POSS的凝胶渗透色谱流出曲线，溶剂为四氢呋喃（THF）。
图13为实施例二中(PSD 0.16-PI) 8POSS（PSD:PI分子量之比为1:4.0）的应力应变曲线，拉伸速率为50 mm/min。
图14为实施例二中(PSD 0.37-PI) 8POSS（PSD:PI分子量之比为1:3.4）的应力应变曲线，拉伸速率为50 mm/min。
图15为实施例二中 (PSD 0.54-PI) 8POSS（PSD:PI分子量之比为1:3.2）（C）的应力应变曲线，拉伸速率为50 mm/min。
图16为实施例三中 PS、PS-PI、PS-PI-PS的凝胶渗透色谱流出曲线，溶剂为四氢呋喃（THF）。
图17为实施例三中 PS-PI-PS采用溶剂挥发成膜所得膜的实物图。
图18为实施例一中(PS-PI) 8POSS采用溶剂挥发成膜所得哑铃状膜实物图。
本发明的实施方式
下面结合附图及实施例对本发明作进一步描述。
实施例一：八臂星形热塑性弹性体共聚物（(PS-PI) 8POSS）的制备。
(1)聚苯乙烯锂化合物（PS-Li）的制备。
在氮气氛围中，用仲丁基锂（ sec-BuLi，0.7 mL，0.77 mmol）作为引发剂，苯（100 mL）作溶剂，在室温下引发苯乙烯（4.0 mL, 34.9 mmol）进行活性阴离子聚合反应12小时，得到聚苯乙烯锂化合物（PS-Li）溶液，存放在密封瓶中用于下一步反应，并取2 mL 反应溶液用无水甲醇终止，得到聚苯乙烯（PS）溶液，用作测试表征。如果将苯替换为同量的四氢呋喃，可以得到产物聚苯乙烯锂化合物，但进行后续偶联反应效率很差，几乎无法得到八臂星形聚合物。
用旋转蒸发仪将PS溶液浓缩，逐滴滴入甲醇中沉淀，静置分层，过滤后的固体放在真空烘箱中35 ℃干燥24小时，得到白色粉末PS。利用核磁共振氢谱（ 1H NMR）、凝胶渗透色谱（GPC）和红外光谱（FT-IR）对其进行表征。附图1（A）、附图2（A）和附图3（A）分别为上述PS聚合物的凝胶渗透色谱（GPC）流出曲线、核磁共振氢谱（ 1H NMR）图和红外光谱（FT-IR）图，验证了PS的化学结构。从 1H NMR谱图中可以找到对应于聚合物结构上的质子峰归属，从GPC流出曲线（
Figure 308623dest_path_image010
= 3.9 kg•mol -1，
Figure 407029dest_path_image011
= 1.05）中可以看到得到的PS聚合物的峰形对称、分子量分布窄。
(2)聚苯乙烯-聚异戊二烯锂化合物（PS-PI-Li）的制备。
在氮气氛围中，往上述步骤(1)中得到的PS-Li溶液中加入异戊二烯（15.5 g, 227.2 mmol）和苯（200 mL），在室温条件下进行活性阴离子聚合反应12小时，得到聚苯乙烯-聚异戊二烯锂化合物（PS-PI-Li）溶液，存放在密封瓶中用于下一步反应，并取2 mL PS-PI-Li溶液用无水甲醇终止，得到聚苯乙烯-聚异戊二烯（PS-PI）溶液，用作测试表征。
用旋转蒸发仪将PS-PI溶液浓缩，逐滴滴入甲醇中沉淀，静置分层，过滤后的固体放在真空烘箱中35 ℃干燥24小时，得到白色黏状固体PS-PI。利用核磁共振氢谱（ 1H NMR）、红外光谱（FT-IR）和凝胶渗透色谱（GPC）对其进行表征。附图1（B）、附图2（B）和附图3（B）分别为上述PS-PI聚合物的凝胶渗透色谱（GPC）流出曲线、核磁共振氢谱（ 1H NMR）图及红外光谱（FT-IR）图，验证了PS-PI的化学结构。从 1H NMR谱图中可以找到对应于聚合物结构上的质子峰归属，从GPC流出曲线（
Figure 502024dest_path_image012
= 28.6 kg•mol -1，
Figure 889143dest_path_image013
= 1.03）中可以看到纯化得到的PS-PI聚合物的峰形对称、分子量分布窄。
(3)八臂星形聚苯乙烯-聚异戊二烯热塑性弹性体共聚物（(PS-PI) 8POSS）的制备。
在氮气氛围中，将上述步骤(2)中得到的PS-PI-Li溶液和八乙烯基多面体齐聚倍半硅氧烷（OVPOSS）（73.5 mg, 0.12 mmol）的苯（10 mL）溶液在室温条件下进行偶联反应2小时，用无水甲醇终止反应。反应结束后，将反应溶液用旋转蒸发仪浓缩，并在无水甲醇中进行沉淀，将过滤所得固体在真空烘箱中35 ℃干燥24小时，得到粗产物。再通过分级沉淀，对粗产物进行提纯，得到透明状弹性块状固体，为八臂星形热塑性弹性体共聚物。
利用核磁共振氢谱（ 1H NMR）、红外光谱（FT-IR）、凝胶渗透色谱（GPC）对其进行了表征。附图1（C）、附图1（D）、附图2（C）和附图3（C）分别为上述(PS-PI) 8POSS粗产物的凝胶渗透色谱（GPC）流出曲线，(PS-PI) 8POSS纯净产物的凝胶渗透色谱（GPC）流出曲线、核磁共振氢谱（ 1H NMR）图及红外光谱（FT-IR）图，验证了(PS-PI) 8POSS的化学结构。从 1H NMR谱图中可以找到对应于聚合物结构上的质子峰归属；从GPC流出曲线中可以看到纯化前得到的粗产物有多组峰，纯化后得到的(PS-PI) 8POSS峰形对称、分子量分布窄（
Figure 180316dest_path_image014
= 168.5 kg•mol -1，
Figure 805332dest_path_image015
= 1.12）。附图4是PS、PS-PI和(PS-PI) 8POSS三种聚合物的热分解曲线，表明八臂星形弹性体共聚物(PS-PI) 8POSS相较于线形聚合物PS-PI有着较高的热分解温度和良好的热稳定性。附图5为八臂星形弹性体共聚物(PS-PI) 8POSS的应力应变曲线，从图中可以看出其断裂伸长率为900%，断裂强度平均值为1.2 MPa。
实施例二：含DPE单元的八臂星形热塑性弹性体共聚物（(PSD-PI) 8POSS）的制备。
(1)    聚苯乙烯/二苯基乙烯锂化合物（PSD-Li）的制备。
以苯乙烯与二苯基乙烯的摩尔比为1:0.16（St:DPE = 1:0.16）为例。在氮气氛围中，以仲丁基锂（ sec-BuLi，0.44 mL，0.56 mmol）作为引发剂，苯（100 mL）作溶剂，在室温条件下,依次加入二苯基乙烯（1.2 mL, 6.79 mmol）和苯乙烯（2.6 mL, 22.7 mmol）进行活性阴离子聚合反应12小时，得到聚苯乙烯/二苯基乙烯锂化合物（PSD 0.16-Li）溶液，存放在密封瓶中用于下一步反应，并取2 mL PSD 0.16-Li溶液用无水甲醇终止，得到聚苯乙烯/二苯基乙烯（PSD 0.16）溶液，用作测试表征；用旋转蒸发仪将PSD溶液浓缩，逐滴滴入无水甲醇中沉淀，静置分层，过滤后的固体放在真空烘箱中35 ℃干燥24小时，得到白色粉末PSD 0.16。另外两个样品PSD 0.37和PSD 0.54均用此方法制备，更换原料比例即可。PSD 0.37：仲丁基锂（ sec-BuLi，0.55 mL，0.7 mmol），二苯基乙烯（2.5 mL, 14.2 mmol），苯乙烯（2.6 mL, 22.7 mmol）；PSD 0.54：仲丁基锂（ sec-BuLi，0.48 mL，0.71 mmol），二苯基乙烯（2.5 mL, 14.2 mmol），苯乙烯（1.9 mL, 17 mmol）。
利用核磁共振氢谱（ 1H NMR）和凝胶渗透色谱（GPC）对聚合物进行表征。附图6和附图7分别为具有不同DPE单元含量的PSD聚合物的凝胶渗透色谱（GPC）流出曲线和核磁共振氢谱（ 1H NMR）图，验证了不同单体摩尔比PSD的化学结构。从GPC流出曲线（PSD 0.54，
Figure 399125dest_path_image016
= 5.9 kg•mol -1，
Figure 742381dest_path_image017
= 1.11，PSD 0.37，
Figure 587977dest_path_image016
= 6.0 kg•mol -1，
Figure 598659dest_path_image017
= 1.14，PSD 0.16，
Figure 301036dest_path_image016
= 7.6 g•mol -1，
Figure 193905dest_path_image017
= 1.14）上可以看到PSD聚合物的峰形对称、分子量分布窄，从 1H NMR谱图中可以找到对应于聚合物结构上的质子峰归属。附图8为不同DPE单元含量的PSD聚合物的差式扫描量热曲线，可以看到随着DPE单元含量的增加，从1:0（A）、1:0.16（B）、1:0.37（C）到1:0.54（D），聚合物的玻璃化转变温度也相应的提高，即可以通过改变DPE单元的含量来调节聚合物的玻璃化转变温度。
(2) 聚苯乙烯/二苯基乙烯-聚异戊二烯锂化合物（PSD-PI-Li）的制备。
以苯乙烯与二苯基乙烯的摩尔比为1:0.16（St:DPE = 1:0.16）为例。在氮气氛围中，往上述步骤(1)中得到的PSD 0.16-Li溶液中加入异戊二烯（13.0 g, 191.0 mmol）和苯（200 mL），在室温条件下进行活性阴离子聚合反应12小时，得到聚苯乙烯/二苯基乙烯-聚异戊二烯锂化合物（PSD 0.16-PI-Li）溶液，存放在密封瓶中用于下一步反应；并取2 mL PSD 0.16-PI-Li溶液用无水甲醇终止，得到聚苯乙烯/二苯基乙烯-聚异戊二烯（PSD 0.16-PI）溶液，用作测试表征，用旋转蒸发仪将PSD 0.16-PI溶液浓缩，逐滴滴入无水甲醇中沉淀，静置分层，过滤后的固体放在真空烘箱中35 ℃干燥24小时，得到白色黏状固体PSD 0.16-PI。另外两个样品PSD 0.37-PI和PSD 0.54-PI均用此方法制备，更换原料单体用量即可。PSD 0.37-PI：异戊二烯（14.43 g, 211.9 mmol）；PSD 0.54-PI：异戊二烯（11.7 g, 172 mmol）。
利用核磁共振氢谱（ 1H NMR）和凝胶渗透色谱（GPC）对其进行表征。附图9、附图10（B）、附图11（B）和附图12（B）分别为具有不同DPE单元含量的PSD 0.16-PI、PSD 0.37-PI和PSD 0.54-PI的核磁共振氢谱（ 1H NMR）和凝胶渗透色谱（GPC）流出曲线，验证了PSD-PI的化学结构。从 1H NMR谱图中可以找到对应于聚合物结构上的质子峰归属，从GPC流出曲线（PSD 0.54-PI，
Figure 639930dest_path_image016
= 41.5 kg•mol -1，
Figure 505118dest_path_image017
= 1.03，PSD 0.37-PI，
Figure 565347dest_path_image016
= 47.2 kg•mol -1，
Figure 883195dest_path_image017
= 1.03，PSD 0.16-PI，
Figure 929649dest_path_image016
= 56.1 kg•mol -1，
Figure 914922dest_path_image017
= 1.03）中可以看到聚合物的峰形对称、分子量分布窄。
(3) 八臂星形聚苯乙烯/二苯基乙烯-聚异戊二烯热塑性弹性体共聚物（(PSD-PI) 8POSS）的制备。
以苯乙烯与二苯基乙烯的摩尔比为1:0.16（St:DPE = 1:0.16）为例。在氮气氛围中，将上述步骤(2)中得到的PSD 0.16-PI-Li溶液和八乙烯基多面体齐聚倍半硅氧烷（OVPOSS）（36 mg, 0.057 mmol）的苯（10 mL）溶液在室温条件下进行偶联反应2小时，用无水甲醇终止反应。反应结束后，将反应溶液用旋转蒸发仪浓缩，并在无水甲醇中进行沉淀，将过滤所得固体在真空烘箱中35 ℃干燥24小时，得到粗产物。再通过分级沉淀，对粗产物进行提纯，得到透明状弹性块状固体(PSD 0.16-PI) 8POSS。另外两个样品(PSD 0.37-PI) 8POSS和(PSD 0.54-PI) 8POSS均用此方法制备，更换原料OVPOSS用量即可。(PSD 0.37-PI) 8POSS：OVPOSS（50 mg, 0.079 mmol）；PSD 0.54-PI：OVPOSS（40 mg, 0.063 mmol）。
利用凝胶渗透色谱（GPC）对其进行了表征。附图10（C、D）、附图11（C、D）和附图12（C、D）分别为所得(PSD-PI) 8POSS粗产物和纯净产物的凝胶渗透色谱（GPC）流出曲线，验证了(PSD-PI) 8POSS的化学结构。从GPC流出曲线中可以看到纯化前得到的聚合物的峰有多组，纯化后得到的聚合物峰形对称、且分子量分布窄（(PSD 0.16-PI) 8POSS：
Figure 959102dest_path_image016
= 322 kg•mol -1，
Figure 701930dest_path_image017
= 1.11；(PSD 0.37-PI) 8POSS：
Figure 489757dest_path_image016
= 265.7 kg•mol -1，
Figure 329537dest_path_image017
= 1.12；(PSD 0.54-PI) 8POSS：
Figure 606935dest_path_image016
= 232.6 kg•mol -1，
Figure 633797dest_path_image017
= 1.10）。附图13、附图14、附图15分别对应(PSD 0.16-PI) 8POSS、(PSD 0.37-PI) 8POSS和(PSD 0.54-PI) 8POSS的应力应变曲线，从图中可以看出它们的断裂伸长率和断裂强度分别为：(PSD 0.16-PI) 8POSS（2060%，7.2 MPa）；(PSD 0.37-PI) 8POSS（1880%，7.7 MPa）；(PSD 0.54-PI) 8POSS（1610%，6.4 MPa）。表明相比于实施例一中的(PS-PI) 8POSS八臂星形弹性体共聚物，引入DPE单元的(PSD-PI) 8POSS八臂星形弹性体共聚物具有更优的力学性能。
本发明公开的方法具有反应快速高效、条件温和、副反应较少、聚合物的分子量和分子量分布可控等优点，得到的八臂星形热塑性弹性体共聚物结构明确；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应力应变特性；同时二苯基乙烯（DPE）和苯乙烯（St）共聚得到的聚合物链段有相比于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，而且可以通过改变两种单体的投料摩尔比来调整硬段聚合物链的玻璃化转变温度；尤其是本发明每一步都无需催化剂、催化剂配体。
实施例三 线形三嵌段热塑性弹性体共聚物（PS-PI-PS）的制备。
(1)聚苯乙烯锂化合物（PS-Li）的制备。
在氮气氛围中，用仲丁基锂（ sec-BuLi，0.12 mL，0.08 mmol）作为引发剂，苯（100 mL）作溶剂，在室温下引发苯乙烯（1.30 mL, 11.4 mmol）进行活性阴离子聚合反应12小时，得到聚苯乙烯锂化合物（PS-Li）溶液，存放在密封瓶中用于下一步反应，并取2 mL 反应溶液用无水甲醇终止，得到聚苯乙烯（PS）溶液，用作测试表征。
用旋转蒸发仪将PS溶液浓缩，逐滴滴入甲醇中沉淀，静置分层，过滤后的固体放在真空烘箱中35 ℃干燥24小时，得到白色粉末PS。附图16为上述PS聚合物的凝胶渗透色谱（GPC）流出曲线，从GPC流出曲线（
Figure dest_path_image018
= 18 kg•mol -1，
Figure 412266dest_path_image017
= 1.06）中可以看到得到的PS聚合物的峰形对称、分子量分布窄。
(2)聚苯乙烯-聚异戊二烯锂化合物（PS-PI-Li）的制备。
在氮气氛围中，往上述步骤(1)中得到的PS-Li溶液中加入异戊二烯（8.17 g, 120.0 mmol）和苯（200 mL），在室温条件下进行活性阴离子聚合反应12小时，得到聚苯乙烯-聚异戊二烯锂化合物（PS-PI-Li）溶液，存放在密封瓶中用于下一步反应，并取2 mL PS-PI-Li溶液用无水甲醇终止，得到聚苯乙烯-聚异戊二烯（PS-PI）溶液，用作测试表征。
用旋转蒸发仪将PS-PI溶液浓缩，逐滴滴入甲醇中沉淀，静置分层，过滤后的固体放在真空烘箱中35 ℃干燥24小时，得到白色黏状固体PS-PI。附图16为上述PS-PI聚合物的凝胶渗透色谱（GPC）流出曲线，从GPC流出曲线（
Figure 840973dest_path_image018
= 238.7 kg•mol -1，
Figure 289272dest_path_image017
= 1.03）中可以看到纯化得到的PS-PI聚合物的峰形对称、分子量分布窄。
(3)线形聚苯乙烯-聚异戊二烯热塑性弹性体共聚物（PS-PI-PS）的制备。
在氮气氛围中，往上述步骤(2)中得到的PS-PI-Li溶液中加入苯乙烯（1.30 mL, 11.4 mmol），在室温条件下进行活性阴离子聚合反应12小时，反应结束后，用无水甲醇终止，得到聚苯乙烯-聚异戊二烯-聚苯乙烯（PS-PI-PS）溶液，用作测试表征。用旋转蒸发仪将PS-PI-PS溶液浓缩，逐滴滴入甲醇中沉淀，静置分层，过滤后的固体放在真空烘箱中35 ℃干燥24小时，得到白色固体产物PS-PI-PS。附图16为上述PS-PI-PS的凝胶渗透色谱（GPC）流出曲线，峰形对称、分子量分布窄（
Figure 69009dest_path_image018
= 248.3 kg•mol -1，
Figure 136322dest_path_image017
= 1.06）。
将实施例三中的PS-PI-PS、实施例一中的(PS-PI) 8POSS，分别用40 mL苯溶剂溶解在烧杯中，搅拌0.5 h充分溶解，浇铸于聚四氟乙烯方槽内，盖上方槽盖使溶剂缓慢挥发3天，再将方槽放在真空烘箱中35 ℃干燥12小时，充分除去溶剂，得到PS-PI-PS和(PS-PI) 8POSS膜；附图17是PS-PI-PS实物膜照片，机械性能差，无法制成哑铃状样品进行机械性能测试；附图18是(PS-PI) 8POSS膜实物照片，可以制备哑铃状样品，对应于附图5测试所用样品条。

Claims (10)

  1. 一种八臂星形热塑性弹性体共聚物，其特征在于：所述八臂星形热塑性弹性体共聚物的化学结构式如下：
    Figure 4940dest_path_image001
    式中，R 1的化学结构式如下：
    Figure 187660dest_path_image002
    或
    Figure 232976dest_path_image003
    R 2的化学结构式如下：
    Figure 18399dest_path_image004
    x = 10～200，y = 2～10，z = 5～20，m = 200～600，n = 10～30。
  2. 权利要求1所述八臂星形热塑性弹性体共聚物的制备方法，其特征在于，包括以下步骤：
    （1）氮气氛围中，锂化合物引发苯乙烯聚合，得到聚苯乙烯锂化合物；
    （2）氮气氛围中，步骤(1)的聚苯乙烯锂化合物引发二烯聚合，得到聚苯乙烯-聚二烯锂化合物；
    （3）氮气氛围中，八乙烯基多面体齐聚倍半硅氧烷与步骤(2)的聚苯乙烯-聚二烯锂化合物反应，得到八臂星形热塑性弹性体共聚物；
    或者包括以下步骤：
    （4）氮气氛围中，锂化合物引发苯乙烯、二苯基乙烯聚合，得到聚苯乙烯/二苯基乙烯锂化合物；
    （5）氮气氛围中，步骤(4)的聚苯乙烯/二苯基乙烯锂化合物引发二烯聚合，得到聚苯乙烯/二苯基乙烯-聚二烯锂化合物；
    （6）氮气氛围中，八乙烯基多面体齐聚倍半硅氧烷与步骤(5)的聚苯乙烯/二苯基乙烯-聚二烯锂化合物反应，得到八臂星形热塑性弹性体共聚物。
  3. 根据权利要求2所述八臂星形热塑性弹性体共聚物的制备方法，其特征在于：步骤(1)中，锂化合物与苯乙烯的摩尔比为1∶(10～200)；
    步骤(2)中，聚苯乙烯锂化合物与二烯的摩尔比为1∶(210～630)；
    步骤(3)中，八乙烯基多面体齐聚倍半硅氧烷与聚苯乙烯-聚二烯锂化合物的摩尔比为1∶(8.2～9)；
    步骤(4)中，所述锂化合物、苯乙烯、二苯基乙烯的摩尔比为1∶(10～200)∶(5～20)；
    步骤(5)中，所述聚苯乙烯/二苯基乙烯锂化合物与二烯的摩尔比为1∶(210～630)；
    步骤(6)中，所述八乙烯基多面体齐聚倍半硅氧烷与聚苯乙烯/二苯基乙烯-聚二烯锂化合物的摩尔比为1∶(8.2～9)。
  4. 根据权利要求2所述八臂星形热塑性弹性体共聚物的制备方法，其特征在于：锂化合物为仲丁基锂或者正丁基锂；二烯为丁二烯或者异戊二烯；所述步骤(1)～(6)的反应过程中不需要使用催化剂和催化剂配体。
  5. 根据权利要求2所述八臂星形热塑性弹性体共聚物的制备方法，其特征在于：步骤(1)中，聚合为室温反应6～12小时；步骤(2)中，聚合为室温反应12～24小时；步骤(3)中，反应为室温反应1～2小时；步骤(4)中，聚合为室温反应12～24小时；步骤(5)中，聚合为室温反应12～24小时；步骤(6)中，反应为室温反应1～2小时。
  6. 根据权利要求2所述八臂星形热塑性弹性体共聚物的制备方法，其特征在于：所述步骤(3)、步骤(6)反应后，分别对产物进行提纯处理，包括以下步骤：
    八臂星形热塑性弹性体共聚物的提纯处理：反应结束后，反应液用旋转蒸发仪浓缩后滴入无水甲醇中沉淀析出，析出物用无水甲醇洗涤后真空干燥，再用甲苯溶解得到溶液，然后滴加无水乙醇至溶液出现混浊，再加热至溶液透明，然后静置分层，然后将下层透明相除去溶剂后在无水甲醇中沉淀，沉淀物经过抽滤、烘干，得到八臂星形热塑性弹性体共聚物。
  7. 根据权利要求2所述八臂星形热塑性弹性体共聚物的制备方法，其特征在于：所述步骤(1)～(6)反应在溶剂中进行。
  8. 根据权利要求2所述八臂星形热塑性弹性体共聚物的制备方法，其特征在于：步骤(3)中，以无水甲醇终止反应；步骤(6)中，以无水甲醇终止反应。
  9. 锂化合物在制备权利要求1所述八臂星形热塑性弹性体共聚物中的应用；锂化合物为仲丁基锂或者正丁基锂。
  10. 权利要求1所述八臂星形热塑性弹性体共聚物在制备高分子材料中的应用。
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