CN103923282B - The copolymer and preparation method of the silsesquioxane containing polyoxometallate - Google Patents

本发明创新性的采用开环易位聚合(ROMP)方法将降冰片烯功能化的多金属氧酸盐单体与降冰片烯类衍化的倍半硅氧烷聚合，得到新型的含多金属氧酸盐‑倍半硅氧烷的嵌段共聚物和无规共聚物，并测得其具有可控的分子量和较窄的分子量分布。本发明的优点是简便快捷、高效可控，聚合反应在敞开体系下，几小时内就可以高收率的得到目标聚合物，且后处理简单，分子量也可以精确控制，易于实现工业化。同时，该聚合物保留了无机物多金属氧酸盐和倍半硅氧烷的优异性能，改善了多金属氧酸盐溶解性差、不易加工的缺陷，使这种聚合物在催化、材料、医药等方面都存在潜在的应用价值。

The present invention innovatively uses the ring-opening metathesis polymerization (ROMP) method to polymerize norbornene-functionalized polyoxometalate monomers and norbornene-derived silsesquioxanes to obtain novel polymetallic oxide-containing Block copolymers and random copolymers of salt-silsesquioxanes were tested to have controllable molecular weight and narrow molecular weight distribution. The invention has the advantages of simplicity, quickness, high efficiency and controllability, the target polymer can be obtained with a high yield within a few hours of the polymerization reaction in an open system, the post-treatment is simple, the molecular weight can also be precisely controlled, and industrialization is easy to realize. At the same time, the polymer retains the excellent properties of inorganic polyoxometalates and silsesquioxanes, and improves the defects of poor solubility and difficult processing of polyoxometalates, making this polymer useful in catalysis, materials, medicine etc. have potential application value.

含多金属氧酸盐-倍半硅氧烷的共聚物及制备方法Copolymer containing polyoxometalate-silsesquioxane and preparation method thereof

技术领域technical field

本发明涉及聚合物化学、有机、无机和材料化学，特别是一种采用开环易位聚合法制备含有多金属氧酸盐和倍半硅氧烷杂化聚合物的聚合技术，利用这种聚合方法可以将降冰片烯衍生化的多金属氧酸盐与降冰片烯衍生化的倍半硅氧烷三体聚合，得到新型的含多金属氧酸盐-倍半硅氧烷的嵌段共聚物和无规共聚物。The present invention relates to polymer chemistry, organic, inorganic and material chemistry, especially a kind of polymerization technique that adopts ring-opening metathesis polymerization method to prepare hybrid polymer containing polyoxometalate and silsesquioxane, utilizes this polymerization Method The polyoxometalate derivatized by norbornene can be polymerized with the silsesquioxane derivatized by norbornene to obtain a new block copolymer containing polyoxometalate-silsesquioxane and random copolymers.

背景技术Background technique

随着科学技术的不断进步，单一性能的聚合物材料已经远远达不到人们所期望的性价比高、溶解性好、易加工等要求。共聚物--两种或两种以上不同的单体经聚合反应而得--长期以来被认为是解决这一问题的一种方法。近年来科学家在合成化学和聚合物化学所取得的巨大进展为制备具有特殊功能的材料提供了前所未有的机遇。With the continuous advancement of science and technology, single-performance polymer materials are far from meeting the expectations of high cost performance, good solubility, and easy processing. Copolymers -- made by polymerizing two or more different monomers -- have long been considered a solution to this problem. The great progress scientists have made in synthetic chemistry and polymer chemistry in recent years has provided unprecedented opportunities for the preparation of materials with special functions.

多金属氧酸盐(polyoxometalates，简称POMs)是一类由钼(Mo)、钨(W)、钒(V)等前过渡金属原子与磷(P)、硅(Si)等中心原子配合而成的一类具有确定结构的单分子簇合物。由于其具有丰富的化学成分、多样的拓扑结构、特殊的氧化还原电位，且在催化、医药以及光、电、磁功能材料等方面展现出其他化合物无法比拟的优异性质，因而受到人们的广泛关注，并得到深入的研究和应用。但由于受其本身的结构特点和固有性质所制约，多金属氧酸盐作为材料具有较差的稳定性、难相容性和不易加工性等缺陷，从而限制了其在实际中的开发和应用。Polyoxometalates (POMs for short) are a class of pre-transition metal atoms such as molybdenum (Mo), tungsten (W), vanadium (V) and central atoms such as phosphorus (P) and silicon (Si). A class of unimolecular clusters with a defined structure. Because of its rich chemical composition, diverse topological structures, special redox potential, and its excellent properties in catalysis, medicine, and optical, electrical, and magnetic functional materials, it has attracted widespread attention. , and has been deeply researched and applied. However, due to its own structural characteristics and inherent properties, polyoxometalates as materials have defects such as poor stability, incompatibility and difficult processability, which limit their development and application in practice. .

倍半硅氧烷(简称POSS)是一类结构简式为(RSiO₁₅)_n的有机-无机杂化的硅氧烷化合物，其核心是由Si-O键组成的笼型无机框架。POSS不仅包含多面体的硅氧纳米结构的特殊刚性骨架，同时又具有优异的性能，如低电解常数、高耐热性、高机械强度、优异的光学性能等，因此，成为近年来材料界研究的热点，并有望用于多种应用领域。Silsesquioxane (POSS for short) is a kind of organic-inorganic hybrid siloxane compound with the simplified structure formula (RSiO ₁₅ ) _n , and its core is a cage-type inorganic framework composed of Si-O bonds. POSS not only contains a special rigid framework of polyhedral silicon-oxygen nanostructure, but also has excellent properties, such as low electrolytic constant, high heat resistance, high mechanical strength, excellent optical properties, etc. Therefore, it has become a research topic in the material field in recent years. hotspot, and is expected to be used in a variety of applications.

聚合物是当代使用最为广泛的有机合成材料，具有易加工、易改性、溶解性好、稳定性高等众多优点，因此采用有机聚合物对多金属盐酸盐进行修饰，期望所得到的材料既能保留多金属氧酸盐的特殊性能，同时也能够改善其不易加工等缺陷。Polymers are the most widely used organic synthetic materials in contemporary times. They have many advantages such as easy processing, easy modification, good solubility, and high stability. Therefore, organic polymers are used to modify polymetallic hydrochlorides. It can retain the special properties of polyoxometalates, and can also improve its defects such as difficult processing.

由于多金属氧酸盐和倍半硅氧烷的溶解性相差极大，人们对于共价键连接的同时含有POMs和POSS的有机-无机杂化聚合物研究甚少。开环易位聚合(ROMP)是环状烯烃在催化下开环进行链增长从而形成聚合物材料的聚合过程，自发现这种高效的活性聚合方法以来，其已被广泛用于制备各种各样的聚合物材料。但是，采用开环易位聚合法制备多金属氧酸盐-倍半硅氧烷的有机-无机杂化聚合物的工作至今仍未见报道。Covalently bonded organic-inorganic hybrid polymers containing POMs and POSS are rarely studied due to the extremely different solubility of polyoxometalates and silsesquioxanes. Ring-opening metathesis polymerization (ROMP) is a polymerization process in which cyclic olefins undergo ring-opening and chain growth under catalysis to form polymer materials. Since the discovery of this efficient living polymerization method, it has been widely used to prepare various type of polymer material. However, the preparation of polyoxometallate-silsesquioxane organic-inorganic hybrid polymers by ring-opening metathesis polymerization has not been reported so far.

发明内容Contents of the invention

本发明的目的：提供一种简便快捷、高效可控的聚合方法制备基于多金属氧酸盐和倍半硅氧烷的有机-无机杂化聚合物，以改善多金属氧酸盐在材料方面的缺陷并提供一类新型的功能高分子材料。The purpose of the present invention: to provide a kind of simple and fast, efficient and controllable polymerization method to prepare organic-inorganic hybrid polymer based on polyoxometalate and silsesquioxane, to improve polyoxometalate in material aspect defects and provide a new class of functional polymer materials.

本发明的技术方案：一种降冰片烯修饰的基于降冰片烯单体功能化的多金属氧酸盐单体(I)和降冰片烯修饰的倍半硅氧烷(II)的双嵌段共聚物(III)和无规共聚物(IV)的制备。Technical scheme of the present invention: a norbornene-modified polyoxometalate monomer (I) based on norbornene monomer functionalization and a norbornene-modified silsesquioxane (II) diblock Preparation of Copolymer (III) and Random Copolymer (IV).

本发明是结构通式I、II的降冰片烯衍生物单体和结构通式为III、IV的多金属氧酸盐-倍半硅氧烷杂化聚合物的化合物：The present invention is a norbornene derivative monomer of general structural formula I and II and a polyoxometalate-silsesquioxane hybrid polymer compound of general structural formula III and IV:

其中，n＝1～19；x≥1；y≥1；z≥0；A＝NH，O；R＝ethyl，i-butyl，i-octyl，cyclohexyl.phenyl；POM＝[(n-Bu)₄N]₅HP₂W₁₅O₅₉，[(n-Bu)₄N]₆P₂W₁₅O₅₉。Wherein, n=1～19; x≥1; y≥1; z≥0; A=NH, O; R=ethyl, i-butyl, i-octyl, cyclohexyl.phenyl; POM=[(n-Bu) ₄ N] ₅ HP ₂ W ₁₅ O ₅₉ , [(n-Bu) ₄ N] ₆ P ₂ W ₁₅ O ₅₉ .

本发明基于多金属氧酸盐的嵌段共聚物III的合成路线如下：The synthetic route of the block copolymer III based on polyoxometalate of the present invention is as follows:

其中，Grubbs’III＝[(H₂IMes)(py)₂(Cl)₂Ru＝CHPh](py＝pyridine)；[(H₂IMes)(3-Br-py)₂(Cl)₂Ru＝CHPh](3-Br-py＝3-bromopyridine)；Wherein, Grubbs'III=[(H ₂ IMes)(py) ₂ (Cl) ₂ Ru=CHPh](py=pyridine); [(H ₂ IMes)(3-Br-py) ₂ (Cl) ₂ Ru= CHPh] (3-Br-py=3-bromopyridine);

本发明多金属氧酸盐无规共聚物IV的合成路线如下：The synthetic route of polyoxometalate random copolymer IV of the present invention is as follows:

其中，Grubbs’III＝[(H₂IMes)(py)₂(Cl)₂Ru＝CHPh](py＝pyridine)；[(H₂IMes)(3-Br-py)₂(Cl)₂Ru＝CHPh](3-Br-py＝3-bromopyridine)；Wherein, Grubbs'III=[(H ₂ IMes)(py) ₂ (Cl) ₂ Ru=CHPh](py=pyridine); [(H ₂ IMes)(3-Br-py) ₂ (Cl) ₂ Ru= CHPh] (3-Br-py=3-bromopyridine);

本发明的具体合成路线详细叙述如下：Concrete synthetic route of the present invention is described in detail as follows:

(1)N-十二酸-顺式-5-降冰片烯-外-2，3-二甲酰亚胺(Norb-C₁₁-COOH)的合成(1) Synthesis of N-dodecanoic acid-cis-5-norbornene-exo-2,3-dicarboximide (Norb-C ₁₁ -COOH)

摩尔比为1∶1.1的顺式-5-降冰片烯-外-2，3-二羧酸酐与12-胺基-十二酸，在冰乙酸中回流6小时，旋转蒸发仪除去乙酸，乙酸乙酯再溶解，蒸馏水洗涤，干燥，脱溶，得到目标化合物。(2)N-12-[三(羟甲基)甲胺基]-十二酰胺-顺式-5-降冰片烯-外-2，3-二甲酰亚胺(Norb-C₁₂-tris)的合成cis-5-norbornene-exo-2,3-dicarboxylic acid anhydride and 12-amino-dodecanoic acid in a molar ratio of 1:1.1 were refluxed in glacial acetic acid for 6 hours, and the acetic acid was removed by a rotary evaporator. Ethyl ester was redissolved, washed with distilled water, dried, and desolvated to obtain the target compound. (2) N-12-[tris(hydroxymethyl)methylamino]-dodecamide-cis-5-norbornene-external-2,3-dicarboximide (Norb-C ₁₂ -tris )Synthesis

摩尔比为1∶1.2∶1.5的N-十二酸-顺式-5-降冰片烯-外-2，3-二甲酰亚胺(Norb-C₁₁-COOH)，三羟甲基氨基甲烷(tris)，2-乙氧基-1-乙氧碳酰基-1，2-二氢喹啉(EEDQ)溶于乙醇中，回流12小时，脱溶，用20∶1(v／v)二氯甲烷：甲醇的洗脱剂进行柱色谱分离，即可得到白色固体状的目标产物。N-dodecanoic acid-cis-5-norbornene-exo-2,3-dicarboximide (Norb-C ₁₁ -COOH) with a molar ratio of 1:1.2:1.5, trishydroxymethylaminomethane (tris), 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ) was dissolved in ethanol, refluxed for 12 hours, desolvated, and 20:1 (v/v) di Chloromethane: Methanol eluent is subjected to column chromatography to obtain the target product as a white solid.

(3)降冰片烯化的多金属氧酸盐杂化物(Norb-C₁₂-POM)的合成(3) Synthesis of norbornenylated polyoxometalate hybrid (Norb-C ₁₂ -POM)

摩尔比为1.1∶1的N-12-[三(羟甲基)甲胺基]-十二酰胺-顺式-5-降冰片烯-外-2，3-二甲酰亚胺(Norb-C₁₂-tris)和多金属氧酸盐TBA₆H₃P₂W₁₅V₃O₆₂(POM)溶解于N，N-二甲基甲酰胺中，搅拌升温至85℃，反应7天。浓缩，乙醚沉淀，干燥，得到黄色固体。N-12-[tris(hydroxymethyl)methylamino]-dodecylamide-cis-5-norbornene-exo-2,3-dicarboximide (Norb- C ₁₂ -tris) and polyoxometalate TBA ₆ H ₃ P ₂ W ₁₅ V ₃ O ₆₂ (POM) were dissolved in N,N-dimethylformamide, heated to 85°C with stirring, and reacted for 7 days. Concentrate, precipitate with ether, and dry to obtain a yellow solid.

(4)N-倍半硅氧烷-顺式-5-降冰片烯-外-2，3-二甲酰亚胺(Norb-POSS)的合成(4) Synthesis of N-silsesquioxane-cis-5-norbornene-exo-2,3-dicarboximide (Norb-POSS)

摩尔比为1.0∶1.1的顺式-5-降冰片烯-外-2，3-二羧酸酐与POSS-NH₂溶解在甲苯中，分水，回流24小时，旋转蒸发仪除去甲苯，用1∶1(v／v)石油醚：二氯甲烷的洗脱剂进行柱色谱分离，即可得到目标产物。The cis-5-norbornene-exo-2,3-dicarboxylic acid anhydride and POSS-NH with a molar ratio of 1.0:1.1 were dissolved in toluene, separated from water, and refluxed for 24 hours. The toluene was removed by a rotary evaporator, and the toluene was removed with ₁ : 1 (v/v) petroleum ether: dichloromethane eluent for column chromatography to obtain the target product.

(5)多金属氧酸盐-倍半硅氧烷杂化嵌段共聚物Poly(POM)_y-b-Poly(POSS)_x的合成(5) Synthesis of polyoxometalate-silsesquioxane hybrid block copolymer Poly(POM) _y -b-Poly(POSS) _x

降冰片烯化的多金属氧酸盐单体(Norb-C₁₂-POM)溶于DMF溶液中，加入一定量的Grubbs三代催化剂，室温反应2小时，再加入一定量的另一种单体N-倍半硅氧烷-顺式-5-降冰片烯-外-2，3-二甲酰亚胺(Norb-C₃-POSS)的二氯甲烷(DCM)溶液，反应1小时，加入乙烯基乙醚终止反应，甲醇沉淀，得目标嵌段共聚物。The norbornenylated polyoxometalate monomer (Norb-C ₁₂ -POM) was dissolved in DMF solution, and a certain amount of Grubbs third-generation catalyst was added, and reacted at room temperature for 2 hours, and then added a certain amount of another monomer N -Sisesquioxane-cis-5-norbornene-exo-2,3-dicarboximide (Norb-C ₃ -POSS) in dichloromethane (DCM), reacted for 1 hour, added ethylene Diethyl ether was used to terminate the reaction, and methanol was precipitated to obtain the target block copolymer.

(6)多金属氧酸盐-倍半硅氧烷杂化无规共聚物Poly(POM)_y-r-Poly(POSS)_x+z的合成(6) Synthesis of polyoxometalate-silsesquioxane hybrid random copolymer Poly(POM) _y -r-Poly(POSS) _x+z

降冰片烯化的多金属氧酸盐杂化物(Norb-C₁₂-POM)和N-倍半硅氧烷-顺式-5-降冰片烯-外-2，3-二甲酰亚胺(Norb-C₃-POSS)溶于DMF和DCM混合溶液中，加入一定量的Grubbs三代催化剂，室温反应2小时，加入乙烯基乙醚终止反应，甲醇沉淀，得目标嵌段共聚物。Norbornenylated polyoxometalate hybrid (Norb-C ₁₂ -POM) and N-silsesquioxane-cis-5-norbornene-exo-2,3-dicarboximide ( Norb-C ₃ -POSS) was dissolved in DMF and DCM mixed solution, added a certain amount of Grubbs third-generation catalyst, reacted at room temperature for 2 hours, added vinyl ether to terminate the reaction, precipitated with methanol, and obtained the target block copolymer.

本发明的优点是：本发明通过用共价键将降冰片烯衍生物修饰到多金属氧酸盐和倍半硅氧烷上，制备了同时含有多金属氧酸盐和倍半硅氧烷的降冰片烯化的有机-无机杂化物单体，首次采用开环易位聚合(ROMP)法直接对所得到的单体进行嵌段共聚和无规共聚得到线性高分子聚合物。该方法合成工艺简单、条件温和、易于操作、反应容易控制、产物纯度高、便于实现工业化生产和推广应用。The advantage of the present invention is that: the present invention prepares polyoxometalate and silsesquioxane by covalently modifying norbornene derivatives to polyoxometalate and silsesquioxane The norbornene-based organic-inorganic hybrid monomer is first used to directly carry out block copolymerization and random copolymerization of the obtained monomer by the ring-opening metathesis polymerization (ROMP) method to obtain a linear polymer. The method has the advantages of simple synthesis process, mild conditions, easy operation, easy reaction control, high product purity, and convenient industrial production and popularization and application.

附图说明Description of drawings

图1为采用实施例4中所述分子的¹H NMR谱图。Figure 1 is a ¹ H NMR spectrum using the molecule described in Example 4.

图2为采用实施例4中所述分子的¹³C NMR谱图。FIG. 2 is a ¹³ C NMR spectrum using the molecule described in Example 4. FIG.

图3为采用实施例5中所述聚合物的¹H NMR谱图。FIG. 3 is a ¹ H NMR spectrum using the polymer described in Example 5. FIG.

图4为采用实施例5中所述聚合物的³¹P NMR谱图。Figure 4 is a ³¹ P NMR spectrum using the polymer described in Example 5.

图5为采用实施例6中所述聚合物的¹H NMR谱图。FIG. 5 is a ¹ H NMR spectrum using the polymer described in Example 6. FIG.

图6为采用实施例6中所述聚合物的³¹P NMR谱图。FIG. 6 is a ³¹ P NMR spectrum using the polymer described in Example 6. FIG.

图7为采用实施例5中所述嵌段聚合物的GPC谱图。Figure 7 is a GPC spectrum using the block polymer described in Example 5.

图8为采用实施例6所述无规聚合物的GPC谱图。Figure 8 is a GPC spectrogram using the random polymer described in Example 6.

具体实施方式Detailed ways

实施例1：N-十二酸-顺式-5-降冰片烯-外-2，3-二甲酰亚胺(Norb-C₁₁-COOH)的合成Example 1: Synthesis of N-dodecanoic acid-cis-5-norbornene-exo-2,3-dicarboximide (Norb-C ₁₁ -COOH)

25mL单口圆底烧瓶中，加入164.1mg(1mmol)顺式-5-降冰片烯-外-2，3-二羧酸酐，237.0mg(1.1mmol)12-胺基-十二酸，10mL冰乙酸，回流6h，停止反应，旋蒸出去溶剂。用20mL乙酸乙酯再溶解，分别用蒸馏水和饱和食盐水洗涤三次，无水硫酸钠干燥，过滤，旋干，乙酸乙酯重结晶，得白色固体343mg(0.95mmol)，收率95％。In a 25mL single-necked round bottom flask, add 164.1mg (1mmol) cis-5-norbornene-exo-2,3-dicarboxylic anhydride, 237.0mg (1.1mmol) 12-amino-dodecanoic acid, 10mL glacial acetic acid , Refluxed for 6h, stopped the reaction, and the solvent was removed by rotary evaporation. It was redissolved in 20 mL of ethyl acetate, washed three times with distilled water and saturated brine respectively, dried over anhydrous sodium sulfate, filtered, spin-dried, and recrystallized from ethyl acetate to obtain 343 mg (0.95 mmol) of a white solid with a yield of 95%.

实施例2：N-12-[三(羟甲基)甲胺基]-十二酰胺-顺式-5-降冰片烯-外-2，3-二甲酰亚胺(Norb-C₁₂-tris)的合成Example 2: N-12-[tris(hydroxymethyl)methylamino]-dodecamide-cis-5-norbornene-exo-2,3-dicarboximide (Norb-C ₁₂ - tris) synthesis

在100mL单口圆底烧瓶中，将1.09g(3.02mmol)N-十二酸-顺式-5-降冰片烯-外-2，3-二甲酰亚胺，0.44g(3.63mmol)三羟甲基氨基甲烷，1.12g(4.53mmol)溶于50mL无水乙醇中，回流12h。旋干，二氯甲烷溶解，过滤以除去过量的三羟甲基氨基甲烷，以20∶1(v／v)二氯甲烷：甲醇为洗脱剂，通过硅胶(100～200目)柱层析分离得到目标化合物998mg(2.15mmol)，收率71％。In a 100 mL single-necked round bottom flask, 1.09 g (3.02 mmol) of N-dodecanoic acid-cis-5-norbornene-exo-2,3-dicarboximide, 0.44 g (3.63 mmol) of trihydroxy Methylaminomethane, 1.12g (4.53mmol) was dissolved in 50mL of absolute ethanol, and refluxed for 12h. Spin dry, dissolve dichloromethane, filter to remove excess trishydroxymethylaminomethane, use 20:1 (v/v) dichloromethane:methanol as eluent, and pass through silica gel (100-200 mesh) column chromatography 998 mg (2.15 mmol) of the target compound were isolated with a yield of 71%.

实施例3：降冰片烯化的多金属氧酸盐杂化物(Norb-C₁₂-POM)的合成Example 3: Synthesis of norbornenylated polyoxometalate hybrids (Norb-C ₁₂ -POM)

50mL单口圆底烧瓶中，加入46mg(0.098mmol)N-12-[三(羟甲基)甲胺基]-十二酰胺-顺式-5-降冰片烯-外-2，3-二甲酰亚胺，484mg(0.089mmol)[(n-Bu)₄N]₆H₃P₂W₁₅V₃O₆₂，20mLN，N-二甲基甲酰胺，85℃下反应7天。浓缩，乙醚沉淀，离心，得到黄色固体510mg，收率98％。In a 50mL single-necked round bottom flask, add 46mg (0.098mmol) N-12-[tris(hydroxymethyl)methylamino]-dodecylamide-cis-5-norbornene-exo-2,3-dimethyl Imide, 484 mg (0.089 mmol) [(n-Bu) ₄ N] ₆ H ₃ P ₂ W ₁₅ V ₃ O ₆₂ , 20 mL N,N-dimethylformamide, reacted at 85°C for 7 days. Concentrate, precipitate with ether, and centrifuge to obtain 510 mg of a yellow solid with a yield of 98%.

实施例4：N-倍半硅氧烷-顺式-5-降冰片烯-外-2，3-二甲酰亚胺(Norb-POSS)的合成Example 4: Synthesis of N-silsesquioxane-cis-5-norbornene-outer-2,3-dicarboximide (Norb-POSS)

装有分水器的100mL双口圆底烧瓶中，加入164mg(1.0mmol)顺式-5-降冰片烯-外-2，3-二羧酸酐，962mg(1.1mmol)3-氨基-1-倍半硅氧烷，50mL甲苯，回流24h，停止反应，旋干。以1∶1(v／v)石油醚：二氯甲烷为洗脱剂，通过硅胶(100～200目)柱层析分离得到842mg(0.83mmol)白色固体状目标化合物，收率83％。In a 100mL double-necked round bottom flask equipped with a water separator, add 164mg (1.0mmol) cis-5-norbornene-exo-2,3-dicarboxylic anhydride, 962mg (1.1mmol) 3-amino-1- Silsesquioxane, 50mL toluene, reflux for 24h, stop the reaction, spin dry. Using 1:1 (v/v) petroleum ether:dichloromethane as the eluent, 842 mg (0.83 mmol) of the target compound was obtained as a white solid through silica gel (100-200 mesh) column chromatography, with a yield of 83%.

实施例5：多金属氧酸盐-倍半硅氧烷的嵌段共聚物Poly(POM)₂₀-b-Poly(POSS)₂₀的合成Example 5: Synthesis of polyoxometalate-silsesquioxane block copolymer Poly(POM) ₂₀ -b-Poly(POSS) ₂₀

敞开体系下，向带有塞子的2mL小瓶中加入200.7mg(0.034mmol)Norb-C₁₂-POM，0.38mL DMF，1.7mg(0.0034mmol)Grubbs III催化剂，室温反应2h，再加入0.34mL0.1mmol／mLDMF∶DCM＝1∶1的Norb-POSS溶液，继续反应1h。加入乙烯基乙醚停止反应，搅拌10min。甲醇中沉淀，得黄色固体228.4mg，收率97％， With the system open, add 200.7mg (0.034mmol) Norb-C ₁₂ -POM, 0.38mL DMF, 1.7mg (0.0034mmol) Grubbs III catalyst to a 2mL vial with a stopper, react at room temperature for 2h, then add 0.34mL0.1mmol /mLDMF:DCM=1:1 Norb-POSS solution, continue to react for 1h. Vinyl ether was added to stop the reaction and stirred for 10 min. Precipitate in methanol to obtain 228.4mg of yellow solid, yield 97%,

实施例6：多金属氧酸盐-倍半硅氧烷的无规共聚物Poly(POM)20-r-Poly(POSS)₂₀的合成Embodiment 6: Synthesis of random copolymer Poly(POM)20-r-Poly(POSS) ₂₀ of polyoxometalate-silsesquioxane

敞开体系下，向带有塞子的2mL小瓶中加入158.0mg(0.027mmol)Norb-C₁₂-POM，27.6mg(0.027mmol)Norb-POSS，1.2mg(0.0014mmol)Grubbs III催化剂，0.2mLDMF：DCM的混合溶液，室温反应2h。加入乙烯基乙醚停止反应，搅拌10min。乙醚中沉淀，得黄色固体177.5mg，收率96％， Under an open system, add 158.0mg (0.027mmol) Norb-C ₁₂ -POM, 27.6mg (0.027mmol) Norb-POSS, 1.2mg (0.0014mmol) Grubbs III catalyst, 0.2mL DMF:DCM to a 2mL vial with a stopper The mixed solution was reacted at room temperature for 2h. Vinyl ether was added to stop the reaction and stirred for 10 min. Precipitate in diethyl ether to obtain 177.5mg of yellow solid, yield 96%,