WO2023226264A1 - 一种超支化聚苯及其制备方法与应用 - Google Patents

一种超支化聚苯及其制备方法与应用 Download PDF

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WO2023226264A1
WO2023226264A1 PCT/CN2022/122045 CN2022122045W WO2023226264A1 WO 2023226264 A1 WO2023226264 A1 WO 2023226264A1 CN 2022122045 W CN2022122045 W CN 2022122045W WO 2023226264 A1 WO2023226264 A1 WO 2023226264A1
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preparation
hyperbranched
hyperbranched polyphenylene
polymerization reaction
monomer
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李红坤
汪露
李永舫
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Suzhou University
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Definitions

  • the invention relates to the field of polymer technology, and in particular to a hyperbranched polyphenylene and its preparation method and application.
  • Hyperbranched polymers are a type of multifunctional macromolecules with dendritic structures. Their unique structures and physical and chemical properties make them have broad application prospects in the fields of chemical sensing, supramolecular assembly, gene delivery, and biomedicine.
  • a commonly used synthesis strategy for hyperbranched polymers is the self-polycondensation reaction of AB n- type (n ⁇ 2) monomers. However, this monomer is difficult to prepare and is prone to self-polymerization during storage, which limits the use of this method. .
  • Other synthesis methods, such as A 2 +B n (n ⁇ 3) polymerization require strict control of the stoichiometric ratio of monomers, otherwise oligomers are easily generated. Therefore, it is of great research significance and application value to develop new polymerization reactions to efficiently prepare hyperbranched polymers.
  • the acetylene [2+2+2] cyclotrimerization reaction is a highly efficient atom-economical reaction.
  • Polymer chemists tried to use it for polymerization and developed a new method for preparing hyperbranched polymers based on cyclotrimerization polymerization of A n (n ⁇ 2) type monomers.
  • Tang's research group used alkynes.
  • a series of functional hyperbranched polyphenylenes were prepared through cyclotrimerization polymerization (Chem. Rev. 2009, 109, 5799-5867). Most of the above polymerization reactions are catalyzed by transition metals, such as palladium, ruthenium, cobalt, nickel and rhodium.
  • hyperbranched polymers with AIE activity Compared with small molecule compounds and linear polymers, there are few reports on hyperbranched polymers with AIE activity (Prog. Polym. Sci. 2020, 100, 101176). In view of the unique topological structure and properties of hyperbranched polymers, the preparation of new structures of AIE-characteristic hyperbranched polymers based on new polymerization reactions has important application value.
  • the present invention provides a hyperbranched polyphenylene and its preparation method and application.
  • the first object of the present invention is to provide a hyperbranched polyphenylene with the following structural formula:
  • R is selected from heterocyclic groups, substituted or unsubstituted aryl groups.
  • said R is selected from the following structures:
  • n is an integer from 1 to 18; * represents the substitution position.
  • the second object of the present invention is to provide a method for preparing the hyperbranched polyphenylene, which includes the following steps: under a protective atmosphere, the binary internal alkyne monomer undergoes a polymerization reaction in a solvent under the action of a catalyst to obtain the desired
  • the hyperbranched polyphenylene; the structural formula of the binary internal alkyne monomer is as follows:
  • R is selected from heterocyclic groups, substituted or unsubstituted aryl groups.
  • the binary internal alkyne monomer is obtained by a Sonogashira coupling reaction between a binary aryl halide and trimethylsilyl acetylene;
  • the binary aryl halide is a binary aryl halide. bromide and/or aryl iodide.
  • the structural formula of the binary aryl bromide is as follows:
  • R is selected from heterocyclic groups, substituted or unsubstituted aryl groups.
  • the catalyst is p-toluenesulfonic acid.
  • the solvent is one or more of 1,2,4-trichlorobenzene, o-dichlorobenzene, chlorobenzene and toluene.
  • the temperature of the polymerization reaction is 90-140°C, and the time is 6-24 hours.
  • the polymerization reaction temperature is 100-120°C and the time is 12-16 hours.
  • the amount of the catalyst is 100-200% of the molar amount of the binary internal alkyne monomer.
  • the amount of the catalyst is 100-120% of the molar amount of the binary internal alkyne monomer.
  • the concentration of the binary internal alkyne monomer is 0.25-1.25 mol/L.
  • the concentration of binary internal alkyne monomer in the polymerization reaction system is 0.75-1.00 mol/L.
  • the hyperbranched polyphenylene is separated from the reaction liquid, specifically including: the reaction liquid is diluted with chloroform and then dripped into petroleum ether/chloroform (20:1, v /v) in a mixed solvent, the hyperbranched polyphenylene is precipitated.
  • the preparation method of hyperbranched polyphenylene specifically includes the following steps:
  • the specific general reaction formula of the present invention is as follows.
  • the polymer expands outward with the structure in the dotted circle.
  • the third object of the present invention is to provide an application of the hyperbranched polyphenylene in detecting polynitroaromatic compounds.
  • the reaction raw materials of the hyperbranched polyphenylene according to the present invention are easily available and can be purchased directly or synthesized through a simple reaction; no by-products are generated during the reaction process, which is in line with atom economy; the reaction has good compatibility with functional groups , can be applied to a variety of monomers; at the same time, hyperbranched polymers also have a large number of terminal functional groups, which can be easily introduced into a variety of functional groups for modification; therefore, this polymerization reaction plays an important role in the synthesis of hyperbranched polymers and functional polymer materials. It has important application value in its preparation.
  • the hyperbranched polyphenylene according to the present invention has good solubility and is soluble in common organic solvents at room temperature, such as chloroform, dichloromethane, N,N-dimethylformamide, tetrahydrofuran, etc., and has Higher thermal stability.
  • Hyperbranched polymers incorporating tetraphenylethylene, cyanostilbene or silole groups have AIE properties, and their fluorescence spectra overlap considerably with the absorption spectra of polynitroaromatic compounds, resulting in energy transfer (FRET).
  • FRET energy transfer
  • PET photoinduced electron transfer
  • the present invention also discloses the application of the above-mentioned hyperbranched polyphenylene in the detection of polynitroaromatic hydrocarbon explosives.
  • the monomer of the polymerization reaction of the present invention is an internal acetylenic monomer, and the catalyst is a non-metallic catalyst p-toluenesulfonic acid.
  • the polymerization reaction conditions are simple, convenient and green, and overcome the problem of catalyst residues affecting polymer properties caused by the use of metal catalysts in traditional cyclotrimerization polymerization reactions.
  • the hyperbranched polyphenylene according to the present invention has a high fluorescence quantum yield in the aggregation state due to the typical aggregation-induced emission (AIE) group tetraphenylethylene, which has a fully conjugated structure. Therefore, The hyperbranched polyphenylene can be used as a chemical sensor and has application prospects in polymer light-emitting diodes.
  • AIE aggregation-induced emission
  • the hyperbranched polyphenylene according to the present invention has a microporous structure and has application prospects for gas storage and catalysis.
  • Figure 1 is a structural formula diagram of the hyperbranched polyphenylene of the present invention.
  • Figure 2 is a hydrogen nuclear magnetic resonance spectrum ("*" represents the solvent peak) of the hyperbranched polyphenylene prepared in Example 1 of the present invention and its corresponding monomer in CD 2 Cl 2 ;
  • Figure 3 is a thermal weight loss curve diagram of hyperbranched polyphenylene prepared in Examples 1, 9, 10, and 11 of the present invention. Test conditions: under nitrogen atmosphere, the heating rate is 10°C/min;
  • Figure 4 is an AIE curve of the hyperbranched polyphenylene prepared in Example 1 of the present invention.
  • Figure 5 is a fluorescence spectrum chart for detecting picric acid (PA) in the aggregated state of hyperbranched polyphenylene prepared in Example 1 of the present invention.
  • a hyperbranched polyphenylene and its preparation method specifically include the following steps:
  • Triphenylphosphine (0.32g, 1.2mmol), bistriphenylphosphine palladium dichloride (0.28g, 0.4mmol), copper iodide (0.15g, 0.8mmol), vacuum and vent nitrogen three times, add 20mL of new Steamed tetrahydrofuran and 80 mL of triethylamine were stirred and dissolved, transferred to a 75°C oil bath, and trimethylsilyl acetylene (4.32 g, 40 mmol) was added in three portions.
  • the comparison chart of the hydrogen nuclear magnetic resonance spectrum of the polymer and its corresponding monomer is shown in Figure 2. From the figure, it can be determined that the polymer is a hyperbranched polyphenylene, and the resonance peak of the monomer at ⁇ 0.24 corresponds to its three The methyl hydrogen of methyl silicon disappears in the polymer NMR image, indicating the occurrence of the polymerization reaction. Moreover, the polymer configuration obtained by this polymerization reaction is a single 1,3,5-trisubstituted hyperbranched polyphenylene, which can be further confirmed based on ⁇ 7.68 and ⁇ 7.50, indicating that the polymerization reaction is regionally specific.
  • the branching degree of the polymer was calculated according to the peak area in the NMR spectrum to be 0.64, which is greater than the branching degree of conventional hyperbranched polymers (usually about 0.5) (Macromolecules 1997, 30, 7024-7033), indicating that the polymerization
  • the material has a highly branched structure.
  • the prepared polymer has good solubility and is soluble in common organic solvents at room temperature, such as dichloromethane, tetrahydrofuran, N,N-dimethylformamide, etc.
  • thermogravimetric analysis shows that its 5% mass loss temperature At 400°C, it shows that it has good thermal stability, as shown in Figure 3.
  • a hyperbranched polyphenylene and its preparation method specifically including the following steps:
  • the binary internal acetylenic monomer is the same as in Example 1.
  • a hyperbranched polyphenylene and its preparation method specifically including the following steps:
  • the binary internal acetylenic monomer is the same as in Example 1.
  • a hyperbranched polyphenylene and its preparation method specifically including the following steps:
  • the binary internal acetylenic monomer is the same as in Example 1.
  • a hyperbranched polyphenylene and its preparation method specifically including the following steps:
  • the binary internal acetylenic monomer is the same as in Example 1.
  • a hyperbranched polyphenylene and its preparation method specifically including the following steps:
  • the binary internal acetylenic monomer is the same as in Example 1.
  • a hyperbranched polyphenylene and its preparation method specifically including the following steps:
  • the binary internal alkyne monomer is the same as in Example 1.
  • a hyperbranched polyphenylene and its preparation method specifically including the following steps:
  • the binary internal acetylenic monomer is the same as in Example 1.
  • a hyperbranched polyphenylene and its preparation method specifically including the following steps:
  • Triphenylphosphine (0.32g, 1.2mmol), bistriphenylphosphine palladium dichloride (0.28g, 0.4mmol), copper iodide (0.15g, 0.8mmol), vacuum and vent nitrogen three times, add 20mL of new Steamed tetrahydrofuran and 80 mL of triethylamine were stirred and dissolved, transferred to a 75°C oil bath, and trimethylsilyl acetylene (4.32 g, 40 mmol) was added in three portions. After 24 hours of reaction, the insoluble solid was removed by suction filtration, and petroleum ether was used as the eluent. The product was purified by silica gel column chromatography.
  • thermogravimetric analysis of the prepared polymer shows that its 5% mass loss temperature is 335°C, indicating that it has good thermal stability.
  • a hyperbranched polyphenylene and its preparation method specifically including the following steps:
  • Triphenylphosphine (0.32g, 1.2mmol), bistriphenylphosphine palladium dichloride (0.28g, 0.4mmol), copper iodide (0.15g, 0.8mmol), vacuum and vent nitrogen three times, add 20mL of new Steamed tetrahydrofuran and 80 mL of triethylamine were stirred and dissolved, transferred to a 75°C oil bath, and trimethylsilyne (4.32 g, 40 mmol) was added in three portions. After 24 hours of reaction, the insoluble solid was removed by suction filtration, petroleum ether was used as the eluent, and the product was purified by silica gel column chromatography.
  • thermogravimetric analysis of the prepared polymer shows that its 5% mass loss temperature is 251°C, indicating that it has good thermal stability.
  • a hyperbranched polyphenylene and its preparation method specifically including the following steps:
  • Triphenylphosphine (0.32g, 1.2mmol), bistriphenylphosphine palladium dichloride (0.28g, 0.4mmol), copper iodide (0.15g, 0.8mmol), vacuum and vent nitrogen three times, add 20mL of new Steamed tetrahydrofuran and 80 mL of triethylamine were stirred and dissolved, transferred to a 75°C oil bath, and trimethylsilyne (4.32 g, 40 mmol) was added in three portions. After reacting for 24 hours, the insoluble solid was removed by suction filtration, petroleum ether was used as the eluent, and the product was purified on a silica gel chromatography column.
  • thermogravimetric analysis of the prepared polymer shows that its 5% mass loss temperature is 306°C, indicating that it has good thermal stability.
  • the polymer of the present invention shows weak luminescence in THF solution, and the fluorescence is significantly enhanced after adding a poor solvent (water), indicating that the polymer has AIE performance.
  • a poor solvent water
  • the polymer of Example 1 as an example: prepare a series of 10 - A 5 mol/L tetrahydrofuran/water solution of hyperbranched polyphenylene, with a water content controlled from 0 to 90%, was used to quickly test the fluorescence spectrum. The results are shown in Figure 4. The fluorescence intensity of the polymer increased significantly with the increase in water content. The performance Show obvious AIE characteristics.
  • the polymer of the present invention can be used for the detection of nitroaromatic hydrocarbon explosives.
  • the specific experiment is the same as that of the prior art.
  • the specific process is as follows: using picric acid (PA) as a model explosive, the process of detecting PA: first prepare 10 -5 mol/L The tetrahydrofuran aqueous solution of hyperbranched polyphenylene (the volume fraction of water is 90%) is used as the detection substance, and the detection substance PA is added in sequence so that the PA concentration is 0.2, 0.5, 1.0, 2.0, 5.0, 10, 20, 30, 50, 80, 100, 120, 150, 200 ⁇ g/mL, quickly test the fluorescence spectrum, the results are shown in Figure 5: When no PA is added, the fluorescence of the test object is very strong; when PA is added, the fluorescence weakens, and with the addition of PA content increases in sequence, and the fluorescence weakens in sequence.
  • PA picric acid

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Abstract

本发明涉及一种超支化聚苯及其制备方法与应用，涉及高分子技术领域。本发明所述的超支化聚苯的制备方法，包括以下步骤，保护气氛下，二元内炔单体在催化剂作用下，在溶剂中发生聚合反应，得到所述超支化聚苯。本发明所述的聚合反应的单体为内炔类单体，催化剂为非金属催化剂对甲苯磺酸。聚合反应条件简单方便、绿色，克服了传统环三聚聚合反应使用金属催化剂所带来的催化剂残留影响聚合物性能的问题。本发明所述的超支化聚苯由于典型的聚集诱导发光(AIE)基团四苯基乙烯，在聚集状态下拥有较高的荧光量子产率，其具有全共轭结构，因此所述超支化聚苯可以用作化学传感器，具有用于聚合物发光二极管的应用前景。

Description

一种超支化聚苯及其制备方法与应用 技术领域
本发明涉及高分子技术领域，尤其涉及一种超支化聚苯及其制备方法与应用。
背景技术
超支化聚合物是一类具有树枝状结构的多功能大分子，独特的结构和物理化学性质使其在化学传感、超分子组装、基因传递和生物医药等领域有广泛的应用前景。超支化聚合物常用的一个合成策略是AB n型(n≥2)单体的自缩聚反应，然而这种单体较难制备，另外在存储过程中容易发生自聚，限制了该方法的使用。其它合成方法例如A 2+B n(n≥3)聚合则需要严格控制单体化学计量比，否则易生成低聚物。因此开发新的聚合反应用以高效地制备超支化聚合物具有重要的研究意义和应用价值。
乙炔[2+2+2]环三聚反应是一类高效的原子经济性反应。高分子化学家尝试将其用作聚合，并发展了一种新型的基于A n(n≥2)型单体的环三聚聚合反应制备超支化聚合物的方法，其中Tang课题组利用炔的环三聚聚合反应制备了一系列功能性的超支化聚苯(Chem.Rev.2009,109,5799-5867)。以上聚合反应大多采用过渡金属催化，如钯、钌、钴、镍和铑等。然而，这些金属催化剂不仅价格昂贵，残留的金属催化剂也会对聚合物的性能有所影响，大大限制了聚合物的应用范围。另外，目前报道的炔类单体的环三聚聚合反应所使用主要为末端炔类单体，而基于内炔类单体环三聚聚合反应制备超支化聚苯的研究鲜有报道。最近研究报道了铑催化的苯丙炔酸酯类单体的环三聚聚合反应(专利202110687392.3；Macromolecules 2022,55,2456-2462)。但该聚合反应由于需要使用金属催化剂和活化的内炔类单体，限制了其应用范围。
传统的有机和聚合物发光材料在溶液中发光强烈，而在聚集态或固态下发 光减弱或不发光，限制了该类材料在固态下的使用。2001年，香港科技大学Tang课题组报道了一种新颖的光物理现象—聚集诱导发光(Aggregation-induced emission，AIE)，是指一类发光分子在溶液中不发光或发光微弱而在聚集态下发光增强的现象(Chem.Commun.2001,1740-1741)。拥有AIE性质的材料已广泛应用于显示、化学检测及生物传感等领域(Chem.Rev.2015,115,11718-11940)。相比小分子化合物和线形聚合物，具有AIE活性的超支化聚合物的报道还很少(Prog.Polym.Sci.2020,100,101176)。鉴于超支化聚合物具有独特的拓扑结构和性能，基于新型聚合反应制备新结构的AIE特性超支化聚合物具有重要的应用价值。
发明内容
为解决上述技术问题，本发明提供了一种超支化聚苯及其制备方法与应用。
本发明的第一个目的是提供一种超支化聚苯，结构式如下：
Figure PCTCN2022122045-appb-000001
其中，R选自杂环基团、取代或未取代的芳基。
在本发明的一个实施例中，所述R选自以下结构：
Figure PCTCN2022122045-appb-000002
其中，m为1-18的整数；*表示取代位置。
本发明的第二个目的是提供一种所述的超支化聚苯的制备方法，包括以下步骤，保护气氛下，二元内炔单体在催化剂作用下，在溶剂中发生聚合反应，得到所述超支化聚苯；所述二元内炔单体的结构式如下：
Figure PCTCN2022122045-appb-000003
其中，R选自杂环基团、取代或未取代的芳基。
在本发明的一个实施例中，所述二元内炔单体是由二元芳基卤化物和三甲基硅乙炔通过Sonogashira偶联反应得到；所述二元芳基卤化物为二元芳基溴和/或二元芳基碘。
优选地，所述二元芳基溴的结构式如下：
Figure PCTCN2022122045-appb-000004
三甲基硅乙炔的结构式如下：
Figure PCTCN2022122045-appb-000005
其中，R选自杂环基团、取代或未取代的芳基。
在本发明的一个实施例中，所述催化剂为对甲苯磺酸。
在本发明的一个实施例中，所述溶剂为1,2,4-三氯苯、邻二氯苯、氯苯和甲苯中的一种或多种。
在本发明的一个实施例中，所述聚合反应的温度为90-140℃，时间为6-24h。
优选地，所述聚合反应的温度为100-120℃，时间为12-16h。
在本发明的一个实施例中，所述催化剂的用量为所述二元内炔单体摩尔量的100-200％。
优选地，所述催化剂的用量为所述二元内炔单体摩尔量的100-120％。
在本发明的一个实施例中，所述聚合反应体系中，二元内炔单体的浓度为0.25-1.25mol/L。
优选地，所述聚合反应体系中，二元内炔单体的浓度为0.75-1.00mol/L。
在本发明的一个实施例中，聚合反应结束后，还包括从反应液中分离所述的超支化聚苯，具体包括：反应液经氯仿稀释后滴入石油醚/氯仿(20:1，v/v)的混合溶剂中，沉淀得到超支化聚苯。
在本发明的一个实施例中，所述的超支化聚苯的制备方法，具体包括以下步骤，
(1)二元内炔单体的制备
将二溴前体、三苯基膦、双三苯基膦二氯化钯、碘化亚铜溶解于四氢呋喃和三乙胺的混合溶剂中，氮气氛围保护下，分批加入三甲基硅乙炔，75℃下反应18-36h，得到二元内炔单体。
(2)制备超支化聚苯
将二元内炔单体、对甲苯磺酸水合物加入到容器中，抽真空换氮气3次，加入溶剂溶解配制成单体浓度为0.25-1.25mol/L的混合液，90-140℃聚合反应6-24h，反应完毕得到聚合物溶液，再经后处理得到所述的超支化聚苯；后处理为聚合物溶液经氯仿稀释后，滴入石油醚/氯仿(20:1，v/v)混合溶液中，沉淀得到超支化聚苯。
本发明的具体的反应通式如下所示，该聚合物以虚线圈内的结构往外扩展。
Figure PCTCN2022122045-appb-000006
本发明的第三个目的是提供一种所述的超支化聚苯在检测多硝基芳烃类化合物中的应用。
本发明的技术方案相比现有技术具有以下优点：
(1)本发明所述的超支化聚苯，反应原料易得，可以直接购买或者通过简单的反应合成；反应过程中没有副产物生成，符合原子经济性；该反应对官能团的兼容性较好，可以适用多种单体；同时超支化聚合物还有大量末端官能团，可方便的引入多种功能性基团进行修饰；因此，该聚合反应在超支化聚合物的合成及功能性聚合物材料的制备方面具有重要的应用价值。
(2)本发明所述的超支化聚苯具有较好的溶解性，室温下可溶于常见的有机溶剂，如氯仿、二氯甲烷、N,N-二甲基甲酰胺和四氢呋喃等，具有较高的热稳定性。引入四苯基乙烯、氰基二苯乙烯或噻咯基团的超支化聚合物具有AIE性能，其荧光光谱与多硝基芳烃化合物的吸收光谱有相当大的重叠，从而发生能量转移(FRET)和以及光诱导电子转移(PET)，比如可用于检测多硝基芳烃类爆炸物，在防止爆炸袭击方面具有重要的应用前景。因此本发明还公开了上述超支化聚苯在多硝基芳烃类爆炸物的检测中的应用。
(3)本发明所述的聚合反应的单体为内炔类单体，催化剂为非金属催化剂对甲苯磺酸。聚合反应条件简单方便、绿色，克服了传统环三聚聚合反应使用金属催化剂所带来的催化剂残留影响聚合物性能的问题。
(4)本发明所述的超支化聚苯由于典型的聚集诱导发光(AIE)基团四苯基乙烯，在聚集状态下拥有较高的荧光量子产率，其具有全共轭结构，因此所述超支化聚苯可以用作化学传感器，具有用于聚合物发光二极管的应用前景。
(5)本发明所述的超支化聚苯具有微孔结构，具有储气和催化的应用的前景。
附图说明
为了使本发明的内容更容易被清楚地理解，下面根据本发明的具体实施例并结合附图，对本发明作进一步详细的说明，其中：
图1为本发明超支化聚苯的结构式图；
图2为本发明实施例1制备的超支化聚苯及其相应单体在CD 2Cl 2中的核磁共振氢谱(“*”代表溶剂峰)图；
图3为本发明实施例1、9、10、11分别制备的超支化聚苯的热失重曲线图，测试条件：氮气气氛下，升温速率为10℃/min；
图4为本发明实施例1制备的超支化聚苯的AIE曲线图；
图5为本发明实施例1制备的超支化聚苯聚集态下检测苦味酸(PA)的荧光光谱图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
在本发明中，除非另有说明，
Figure PCTCN2022122045-appb-000007
仅表示分子连接关系。
实施例1
参照图1所示，一种超支化聚苯及其制备方法，具体包括以下步骤：
Figure PCTCN2022122045-appb-000008
(1)单体的合成
在500mL双口瓶中加入4-溴二苯甲酮(5.22g，20mmol)和锌粉(5.23g，80mmol)，抽真空充氮气三次，加入100mL新蒸的四氢呋喃，然后在0℃条件下，将四氯化钛(11.38g，60mmol)缓慢加入，恢复至室温，然后加热回流过夜。通过旋转蒸发除去大部分溶剂，加入100mL稀盐酸，用二氯甲烷萃取三次。使用石油醚作为洗脱剂，通过硅胶色谱柱纯化产物，产物真空烘干至恒重，获得1,4-二溴-四苯基乙烯白色固体8.04g(产率为82.2％)，然后， 向250mL双口烧瓶中依次加入(4.90g，10mmol)。三苯基膦(0.32g，1.2mmol)、双三苯基膦二氯化钯(0.28g，0.4mmol)、碘化亚铜(0.15g，0.8mmol)，抽真空通氮气三次，加入20mL新蒸的四氢呋喃和80mL三乙胺，搅拌溶解，转移到75℃的油浴锅中，分三次加入三甲基硅乙炔(4.32g，40mmol)。反应24h后，抽滤除去不溶的固体，通过硅胶色谱柱使用石油醚/乙酸乙酯(200:1，v/v)作为洗脱液纯化粗产物。产物真空烘干至恒重，得到浅绿色固体4.45g(产率为85.0％)。 1H NMR(300MHz,CD 2Cl 2),δ(TMS,ppm):7.26–6.85(m,18H),0.28–0.14(d,J＝3.0Hz,18H).
(2)聚合物的制备
向带有侧臂的10mL聚合管中加入52.4mg(0.10mmol)四苯基乙烯二元内炔单体，38.0mg(0.10mmol)的对甲苯磺酸水合物。通过侧臂对聚合管抽充N 2三次，加入0.1mL 1,2,4-三氯苯，搅拌溶解。将体系置于60℃反应3h，然后置于120℃反应12h，反应结束后，冷却至室温，用3mL三氯甲烷稀释，通过塞有棉花的滴管逐滴滴加到150mL常规搅拌的石油醚/氯仿(20:1，v/v)的混合溶剂中。静置，过滤，碳酸氢钠洗涤，室温干燥至恒重得到聚合物表征数据：黄色固体，产率为82.4％。凝胶渗透色谱(GPC)结果显示：重均分子量(M w)为26800，分子量分布(PDI)为3.40。 1H NMR(300MHz,CD 2Cl 2),δ(TMS,ppm):7.68,7.50,7.12,2.50.
该聚合物与其相对应的单体的核磁共振氢谱对比图如图2所示，从图中可以确定该聚合物为超支化聚苯，其中单体在δ0.24处的共振峰对应其三甲基硅的甲基氢，而在聚合物核磁图中则消失不见，说明该聚合反应的发生。并且该聚合反应得到的聚合物构型为单一的1,3,5-三取代超支化聚苯，可进一步根据δ7.68和δ7.50得到证实，说明该聚合反应具有区域专一性。另外根据核磁谱图中峰面积计算得到该聚合物的支化度为0.64，大于常规超支化聚合物的支化度(通常约为0.5)(Macromolecules 1997,30,7024-7033)，表明该聚合物具有高度的支化结构。
所制备的聚合物具有较好的溶解度，常温下可溶于常见的有机溶剂，如二氯甲烷、四氢呋喃、N,N-二甲基甲酰胺等，此外热失重分析显示其5％质量损失温度在400℃，说明其具有较好的热稳定性，如图3所示。
实施例2
一种超支化聚苯及其制备方法，具体包括以下步骤：
二元内炔单体同实施例1，向带有侧臂的10mL聚合管中加入52.4mg(0.10mmol)四苯基乙烯二元内炔单体，38.0mg(0.10mmol)的对甲苯磺酸水合物。通过侧臂对聚合管抽充N 2三次，加入0.1mL 1,2,4-三氯苯，搅拌溶解。将体系置于60℃反应3h，然后置于120℃反应13h反应结束后，冷却至室温，用3mL三氯甲烷稀释，通过塞有棉花的滴管逐滴滴加到150mL常规搅拌的石油醚/氯仿(20:1，v/v)的混合溶剂中。静置，过滤，碳酸氢钠洗涤，室温干燥至恒重得到聚合物表征数据：黄色固体，产率为84.0％。凝胶渗透色谱(GPC)结果显示：重均分子量(M w)为25500，分子量分布(PDI)为3.30。
实施例3
一种超支化聚苯及其制备方法，具体包括以下步骤：
二元内炔单体同实施例1，向带有侧臂的10mL聚合管中加入52.4mg(0.10mmol)四苯基乙烯二元内炔单体，38.0mg(0.10mmol)的对甲苯磺酸水合物。通过侧臂对聚合管抽充N 2三次，加入0.1mL 1,2,4-三氯苯，搅拌溶解。将体系置于60℃反应3h，然后置于120℃反应9h，反应结束后，冷却至室温，用3mL三氯甲烷稀释，通过塞有棉花的滴管逐滴滴加到150mL常规搅拌的石油醚/氯仿(20:1，v/v)的混合溶剂中。静置，过滤，碳酸氢钠洗涤，室温干燥至恒重得到聚合物表征数据：黄色固体，产率为57.9％。凝胶渗透色谱(GPC)结果显示：重均分子量(M w)为12800，分子量分布(PDI)为2.34。
实施例4
一种超支化聚苯及其制备方法，具体包括以下步骤：
二元内炔单体同实施例1，向带有侧臂的10mL聚合管中加入52.4mg(0.10 mmol)四苯基乙烯二元内炔单体，38.0mg(0.10mmol)的对甲苯磺酸水合物。通过侧臂对聚合管抽充N 2三次，加入0.1mL 1,2,4-三氯苯，搅拌溶解。将体系置于60℃反应3h，然后置于110℃反应12h，反应结束后，冷却至室温，用3mL三氯甲烷稀释，通过塞有棉花的滴管逐滴滴加到150mL常规搅拌的石油醚/氯仿(20:1，v/v)的混合溶剂中。静置，过滤，碳酸氢钠洗涤，室温干燥至恒重得到聚合物表征数据：黄色固体，产率为55.2％。凝胶渗透色谱(GPC)结果显示：重均分子量(M w)为3200，分子量分布(PDI)为1.21。
实施例5
一种超支化聚苯及其制备方法，具体包括以下步骤：
二元内炔单体同实施例1，向带有侧臂的10mL聚合管中加入52.4mg(0.10mmol)四苯基乙烯二元内炔单体，38.0mg(0.10mmol)的对甲苯磺酸水合物。通过侧臂对聚合管抽充N 2三次，加入0.20mL 1,2,4-三氯苯，搅拌溶解。将体系置于60℃反应3h，然后置于120℃反应12h，反应结束后，冷却至室温，用3mL三氯甲烷稀释，通过塞有棉花的滴管逐滴滴加到150mL常规搅拌的石油醚/氯仿(20:1，v/v)的混合溶剂中。静置，过滤，碳酸氢钠洗涤，室温干燥至恒重得到聚合物表征数据：黄色固体，产率为57.9％。凝胶渗透色谱(GPC)结果显示：重均分子量(M w)为2800，分子量分布(PDI)为1.15。
实施例6
一种超支化聚苯及其制备方法，具体包括以下步骤：
二元内炔单体同实施例1，向带有侧臂的10mL聚合管中加入52.4mg(0.10mmol)四苯基乙烯二元内炔单体，38.0mg(0.10mmol)的对甲苯磺酸水合物。通过侧臂对聚合管抽充N 2三次，加入0.08mL 1,2,4-三氯苯，搅拌溶解。将体系置于60℃反应3h，然后置于120℃反应12h，反应结束后，冷却至室温，用3mL三氯甲烷稀释，通过塞有棉花的滴管逐滴滴加到150mL常规搅拌的石油醚/氯仿(20:1，v/v)的混合溶剂中。静置，过滤，碳酸氢钠洗涤，室温干燥至恒重得到聚合物表征数据：黄色固体，产率为78.9％。凝胶渗透色谱(GPC)结果 显示：重均分子量(M w)为19000，分子量分布(PDI)为1.21。
实施例7
一种超支化聚苯及其制备方法，具体包括以下步骤：
二元内炔单体同实施例1，向带有侧臂的10mL聚合管中加入52.4mg(0.10mmol)四苯基乙烯二元内炔单体，57.0mg(0.10mmol)的对甲苯磺酸水合物。通过侧臂对聚合管抽充N 2三次，加入0.1mL 1,2,4-三氯苯，搅拌溶解。将体系置于60℃反应3h，然后置于120℃反应12h，反应结束后，冷却至室温，用3mL三氯甲烷稀释，通过塞有棉花的滴管逐滴滴加到150mL常规搅拌的石油醚/氯仿(20:1，v/v)的混合溶剂中。静置，过滤，碳酸氢钠洗涤，室温干燥至恒重得到聚合物表征数据：黄色固体，产率为94.7％。凝胶渗透色谱(GPC)结果显示：重均分子量(M w)为10300，分子量分布(PDI)为1.85。
实施例8
一种超支化聚苯及其制备方法，具体包括以下步骤：
二元内炔单体同实施例1，向带有侧臂的10mL聚合管中加入52.4mg(0.10mmol)四苯基乙烯二元内炔单体，76.0mg(0.10mmol)的对甲苯磺酸水合物。通过侧臂对聚合管抽充N 2三次，加入0.1mL 1,2,4-三氯苯，搅拌溶解。将体系置于60℃反应3h，然后置于120℃反应12h，反应结束后，冷却至室温，用3mL三氯甲烷稀释，通过塞有棉花的滴管逐滴滴加到150mL常规搅拌的石油醚/氯仿(20:1，v/v)的混合溶剂中。静置，过滤，碳酸氢钠洗涤，室温干燥至恒重得到聚合物表征数据：黄色固体，产率为84.2％。凝胶渗透色谱(GPC)结果显示：重均分子量(M w)为5100，分子量分布(PDI)为1.38。
实施例9
一种超支化聚苯及其制备方法，具体包括以下步骤：
Figure PCTCN2022122045-appb-000009
(1)单体的制备
在250mL双口瓶中加入芴5.07g(30mmol)，然后加入乙酸、水和浓硫酸(100:20:3，v/v/v)的混合物(100mL)。将反应混合物加热至回流(约140℃)并将固体完全溶解。然后冷却至65℃，加入碘6.38g(25mmol)和碘酸2.91g(12.5mmol)的。将液在65℃下搅拌4h，然后冷却至室温。反应混合物用二氯甲烷萃取，收集的有机层用碳酸钠和硫代硫酸钠溶液洗涤。由乙酸乙酯重结晶后，干燥得到微黄色粉末2,7-二碘-芴3.6g(产率90.6％)；向250mL双口圆底烧瓶中添加2,7-二碘-芴2.11g(5mmol)的，加入DMSO(50mL)。依次添加1-溴辛烷1.44g(7.5mmol)。在室温下搅拌过夜后，用盐酸(1M)中和反应混合物，直到溶液变为淡黄色。然后用乙醚萃取溶液。溶剂蒸发后，通过硅胶色谱柱纯化粗产物。获得了微黄色固体1.84g(产率为50.2％)；向250mL双口烧瓶中依次加入2,7-二碘-9,9-二辛基-芴(6.42g，10mmol)。三苯基膦(0.32g，1.2mmol)、双三苯基膦二氯化钯(0.28g，0.4mmol)、碘化亚铜(0.15g，0.8mmol)，抽真空通氮气三次，加入20mL新蒸的四氢呋喃和80mL三乙胺，搅拌溶解，转移到75℃的油浴锅中，分三次加入三甲基硅乙炔(4.32g，40mmol)。反应24h后，抽滤除去不溶的固体，使用石油醚作为洗脱剂，硅胶柱色谱纯化产物，产物真空烘干至恒重，获得白色固体3.91g(产率为67.6％)。 1H NMR(300MHz,CD 2Cl 2),δ(TMS,ppm):7.67–7.59(d,J＝8.1Hz,2H),7.48–7.39(t,J＝3.7 Hz,4H),2.02–1.90(m,4H),1.27–0.99(m,24H),0.87–0.77(t,J＝6.9Hz,6H),0.30–0.24(s,18H).
(2)聚合物的制备
向带有侧臂的10mL聚合管中加入58.3mg(0.10mmol)芴二元内炔单体，38.0mg(0.10mmol)的对甲苯磺酸水合物。通过侧臂对聚合管抽充N 2三次，加入0.1mL 1,2,4-三氯苯，搅拌溶解。将体系置于60℃反应3h，然后置于120℃反应21h，反应结束后，冷却至室温，用3mL三氯甲烷稀释，通过塞有棉花的滴管逐滴滴加到150mL常规搅拌的石油醚中。静置，过滤，碳酸氢钠洗涤，室温干燥至恒重得到聚合物表征数据：黄色固体，产率为60.0％。凝胶渗透色谱(GPC)结果显示：重均分子量(M w)为22969，分子量分布(PDI)为1.52。 1H NMR(300MHz,CD 2Cl 2),δ(TMS,ppm):8.25–7.38,2.66,2.12,1.11,0.78.
如图3所示，所制备的聚合物的热失重分析显示其5％质量损失温度在335℃，说明其具有较好的热稳定性。
实施例10
一种超支化聚苯及其制备方法，具体包括以下步骤：
Figure PCTCN2022122045-appb-000010
(1)单体的制备
在50mL单口圆底烧瓶中加入4,4′二溴二苯甲酮3.40g(10mmol)，加入甲醇、四氢呋喃(1:10，v/v)的混合物33mL，在0℃下加入硼氢化钠0.76g (20mmol)，反应3h后加水淬灭，用乙酸乙酯萃取，干燥后得到4,4′二溴二苯甲醇，为白色固体3.42g(产率100％)；在100mL双口圆底烧瓶中加入4,4′二溴二苯甲醇3.42g(10mmol)，抽真空充氮气三次，加入新制的二氯甲烷40mL，然后将装置放入冰水浴中，缓慢注入四氯化钛2.08g(11mmol)，恢复至室温，反应过夜，使用石油醚作为洗脱剂，通过凝胶柱纯化产物，产物真空烘干至恒重，获得白色固体3.62g(产率为67.6％)；向250mL双口烧瓶中依次加入(5.02g，10mmol)。三苯基膦(0.32g，1.2mmol)、双三苯基膦二氯化钯(0.28g，0.4mmol)、碘化亚铜(0.15g，0.8mmol)，抽真空通氮气三次，加入20mL新蒸的四氢呋喃和80mL三乙胺，搅拌溶解，转移到75℃的油浴锅中，分三次加入三甲基硅炔(4.32g，40mmol)。反应24h后，抽滤除去不溶的固体，使用石油醚作为洗脱剂，硅胶柱色谱纯化产物，产物真空烘干至恒重，获得白色固体3.73g(产率为69.5％)。 1H NMR(300MHz,CD 2Cl 2),δ(TMS,ppm):7.56–7.47(d,J＝7.9Hz,2H),7.42–7.24(m,4H),7.24–7.08(m,11H),5.17–5.11(s,1H),0.30–0.24(s,7H),0.24–0.18(s,9H),0.12–0.06(s,2H).
(2)聚合物的制备
向带有侧臂的10mL聚合管中加入53.6mg(0.10mmol)茚二元内炔单体，38.0mg(0.10mmol)的对甲苯磺酸水合物。通过侧臂对聚合管抽充N 2三次，加入0.1mL 1,2,4-三氯苯，搅拌溶解。将体系置于60℃反应3h，然后置于120℃反应12h，反应结束后，冷却至室温，用3mL三氯甲烷稀释，通过塞有棉花的滴管逐滴滴加到150mL常规搅拌的石油醚/氯仿(20:1，v/v)的混合溶剂中。静置，过滤，碳酸氢钠洗涤，室温干燥至恒重得到聚合物表征数据：黄色固体，产率为80.0％。凝胶渗透色谱(GPC)结果显示：重均分子量(M w)为14600，分子量分布(PDI)为3.0。 1H NMR(300MHz,CD 2Cl 2),δ(TMS,ppm):8.0–6.9,5.25,2.53.
如图3所示，所制备的聚合物的热失重分析显示其5％质量损失温度在251℃，说明其具有较好的热稳定性。
实施例11
一种超支化聚苯及其制备方法，具体包括以下步骤：
Figure PCTCN2022122045-appb-000011
(1)单体的制备
在250mL双口瓶中加入1,2-二苯甲烷2.02g(12mmol)，抽真空充氮气三次，加入50mL新蒸的四氢呋喃，在-78℃环境下加入正丁基锂6.9mL(11mmol)，恢复至室温，反应30min后，将1,2-二溴二苯甲酮3.40g(10mmol)溶于四氢呋喃后加入体系中，室温反应过夜，饱和氯化铵溶液处理，二氯甲烷萃取三次，无水硫酸镁干燥，产物真空烘干至恒重，得到白色固体α,α-双(4-溴苯基)-β-苯基苯乙醇5.03g(产率为98.9％)；向装有油水分离器的500mL双口烧瓶中加入，α,α-双(4-溴苯基)-β-苯基苯乙醇5.08g(10mmol)，对甲苯磺酸0.285g(1.5mmol)，加入甲苯75mL，130℃回流过夜，旋干溶剂，使用石油醚作为洗脱剂，通过凝胶柱纯化产物，产物真空烘干至恒重，获得白色固体二溴四苯基乙烯1.98g(产率为40.5％)；向250mL双口烧瓶中依次加入二溴四苯基乙烯(6.42g，10mmol)。三苯基膦(0.32g，1.2mmol)、双三苯基膦二氯化钯(0.28g，0.4mmol)、碘化亚铜(0.15g，0.8mmol)，抽真空通氮气三次，加入20mL新蒸的四氢呋喃和80mL三乙胺，搅拌溶解，转移到75℃的油浴锅中，分三次加入三甲基硅炔(4.32g，40mmol)。反应24h后，抽滤除去不溶的固体，使用石油醚作为洗脱剂，硅胶色谱柱纯化产物，产物真空烘干至恒重，获得白色固体3.53g(产率为67.5％)。 1H NMR(300MHz,CD 2Cl 2), δ(TMS,ppm):7.24–6.87(m,18H),0.25–0.19(s,18H).
(2)聚合物的制备
向带有侧臂的10mL聚合管中加入52.4mg(0.10mmol)四苯基乙烯二元内炔单体，38.0mg(0.10mmol)的对甲苯磺酸水合物。通过侧臂对聚合管抽充N 2三次，加入0.1mL 1,2,4-三氯苯，搅拌溶解。将体系置于60℃反应3h，然后置于120℃反应12h，反应结束后，冷却至室温，用3mL三氯甲烷稀释，通过塞有棉花的滴管逐滴滴加到150mL常规搅拌的石油醚/氯仿(20:1，v/v)的混合溶剂中。静置，过滤，碳酸氢钠洗涤，室温干燥至恒重得到聚合物表征数据：黄色固体，产率为87.0％。凝胶渗透色谱(GPC)结果显示：重均分子量(M w)为32200，分子量分布(PDI)为2.36。 1H NMR(300MHz,CD 2Cl 2),δ(TMS,ppm):7.68,7.51,7.12,2.50.
如图3所示，所制备的聚合物的热失重分析显示其5％质量损失温度在306℃，说明其具有较好的热稳定性。
应用例
本发明的聚合物表现出在THF溶液中发光微弱，加入不良溶剂(水)后荧光显著增强的现象，表明该聚合物具有AIE性能，以实施例1的聚合物为例：配制一系列10 -5mol/L的超支化聚苯的四氢呋喃/水溶液，含水量控制为0到90％，快速测试荧光光谱，结果如图4所示，聚合物的荧光强度随水含量的增加而明显增强，表现出明显的AIE特性。
由于拥有AIE性能，本发明聚合物可以用于硝基芳烃类爆炸物的检测。以实施例10的聚合物为例，具体实验与现有技术一样，具体过程如下：以苦味酸(picric acid，PA)为模型爆炸物，检测PA的过程：首先配制10 -5mol/L的超支化聚苯的四氢呋喃水溶液(水的体积分数为90％)作为检测物，依次加入被检测物PA，使PA浓度分别为0.2、0.5、1.0、2.0、5.0、10、20、30、50、80、100、120、150、200μg/mL，快速测试荧光光谱，结果如图5所示：当不加PA时，检测物的荧光非常强；加入PA时，荧光减弱，并且随着加入PA含量的依次增 大，荧光依次减弱，PA浓度为0.2μg/mL就可以看出荧光减弱，其在0-30μg/mL的PA浓度范围内的荧光猝灭常数为25266M -1，这说明其对PA检测的灵敏度较高。表明本发明的超支化聚苯可以作为传感器用检测硝基芳烃类爆炸物。
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

  1. 一种超支化聚苯，其特征在于，结构式如下：
    Figure PCTCN2022122045-appb-100001
    其中，R选自杂环基团、取代或未取代的芳基。
  2. 根据权利要求1所述的超支化聚苯，其特征在于，所述R选自以下结构：
    Figure PCTCN2022122045-appb-100002
    其中，m为1-18的整数；*表示取代位置。
  3. 一种权利要求1或2所述的超支化聚苯的制备方法，其特征在于，包括以下步骤，保护气氛下，二元内炔单体在催化剂作用下，在溶剂中发生聚合反 应，得到所述超支化聚苯；所述二元内炔单体的结构式如下：
    Figure PCTCN2022122045-appb-100003
    其中，R选自杂环基团、取代或未取代的芳基。
  4. 根据权利要求3所述的超支化聚苯的制备方法，其特征在于，所述二元内炔单体是由二元芳基卤化物和三甲基硅乙炔通过Sonogashira偶联反应得到；所述二元芳基卤化物为二元芳基溴和/或二元芳基碘。
  5. 根据权利要求3所述的超支化聚苯的制备方法，其特征在于，所述催化剂为对甲苯磺酸。
  6. 根据权利要求3所述的超支化聚苯的制备方法，其特征在于，所述溶剂为1,2,4-三氯苯、邻二氯苯、氯苯和甲苯中的一种或多种。
  7. 根据权利要求3所述的超支化聚苯的制备方法，其特征在于，所述聚合反应的温度为90-140℃，时间为6-24h。
  8. 根据权利要求3所述的超支化聚苯的制备方法，其特征在于，所述催化剂的用量为所述二元内炔单体摩尔量的100-200％。
  9. 根据权利要求3所述的超支化聚苯的制备方法，其特征在于，所述聚合反应体系中，二元内炔单体的浓度为0.25-1.25mol/L。
  10. 一种权利要求1或2所述的超支化聚苯在检测多硝基芳烃类化合物中的应用。
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