磷钨酸对对苯撑乙烯撑寡聚物-b-聚(2-乙烯基吡啶)自晶种行为的影响※

doi:10.6023/A21120557

摘要/Abstract

自晶种具有操作简便和聚合物组装基元适用性广的优点, 它是利用结晶-柔性(crystalline-coil)两嵌段共聚物活性结晶驱动自组装制备长度和组成可控的聚合物纳米纤维的重要策略. 而多金属氧酸及其衍生物具有独特的化学组成和几何结构以及优异的电/磁/光等物理性能. 以对苯撑乙烯撑寡聚物-b-聚(2-乙烯基吡啶)(OPV₅-b-P2VP₄₂)和磷钨酸(H₃O₄₀PW₁₂)分别为模型结晶-柔性两嵌段共聚物和多金属氧酸, 系统考察了磷钨酸对OPV₅-b-P2VP₄₂自晶种行为的影响. 研究发现OPV₅-b-P2VP₄₂的种子纤维在加热退火时的抗溶解能力随着磷钨酸的量增大而增强. 这可能是由于P2VP中的吡啶基元与磷钨酸金属原子间的络合作用, 而非吡啶与磷钨酸间的氢键作用, 使P2VP链间发生交联/聚集, 这不仅可平衡或减弱P2VP链间的排斥力和拉伸作用, 还将提升种子纤维断裂和解离所需的能量.

关键词: 活性结晶驱动自组装, 自晶种, 纳米纤维, 多金属氧酸, 共轭聚合物

Self-seeding route of living crystallization-driven self-assembly with merits of easily-handling and excellent compatibility with various block copolymers (BCPs) has been considered as one of the most important strategies to generate uniform nanofibers of controlled length and composition. Polyoxometalates with unique structure and shape are usually endowed with attractive electric/magnetic/optical properties. Herein, the influence of phosphotungstic acid (H₃O₄₀PW₁₂) on the self-seeding of oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine) (OPV₅-b-P2VP₄₂, the subscripts represent the number of repeat unit of each block) was systematically examined aiming to get more insight on the effect of polyoxometalates on living crystallization-driven self-assembly. Uniform fiber-like micelles of OPV₅-b-P2VP₄₂ are formed with addition of different molar ratios of phosphotungstic acid to pyridyls of P2VP, α_acid/v, from 0 to 0.20. The percentage of surviving seed micelles decreased exponentially with increasing annealing temperature regardless of α_acid/v from 0 to 0.10, demonstrating the typical characteristics of self-seeding behaviors. The most striking finding of this work is that the resistance of seed micelles toward the dissolution upon annealing is enhanced significantly with the increasing of α_acid/v, leading to the formation of shorter fiber-like micelles with a higher α_acid/v. For example, fiber-like micelles with average length of 1325, 232, 137 and 73 nm were formed with α_acid/v of 0, 0.01, 0.05 and 0.10, respectively, upon the heating of seed micelles of OPV₅-b-P2VP₄₂ with average length of 22 nm at 60 ℃ for 45 min, followed by cooling/aging at 30 ℃ for 24 h. It is likely that the coordination, instead of hydrogen bonding interaction, between phosphotungstic acid and pyridyls, contributes to the enhancement of resistance of seed micelles toward the dissolution. The tight and multi-dentate coordination between phosphotungstic acid and pyridyls of P2VP chains would make the P2VP chain crosslink. The crosslinking would weaken the repulsion within P2VP chains and increase the energy for the dissolution of micelles. This work not only provides more information to deepen our understanding on the influence of nature of corona chains on living crystallization-driven self-assembly (CDSA), especially self-seeding process, but also presents a new platform to generate uniform hybrid polyoxometalate/polymer nanofibers of controlled length.

Key words: living crystallization-driven self-assembly, self-seeding, nanofiber, polyoxometalate, π-conjugated polymer

引用此文

王志琴, 项博, 黄晓宇, 陆国林, 冯纯. 磷钨酸对对苯撑乙烯撑寡聚物-b-聚(2-乙烯基吡啶)自晶种行为的影响^※[J]. 化学学报, 2022, 80(3): 297-302.

Zhiqin Wang, Bo Xiang, Xiaoyu Huang, Guolin Lu. Effect of Phosphotungstic Acid on Self-seeding of Oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine)^※[J]. Acta Chimica Sinica, 2022, 80(3): 297-302.

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图/表 5

图1. OPV5-b-P2VP42和磷钨酸的结构示意图

Figure 1. Schematic illustration of structures of OPV5-b-P2VP42 and phosphotungstic acid

图2. (A) OPV5-b-P2VP42种子纤维(0.05 mg/mL的乙醇溶液)以及αacid/v分别为(B) 0、(C) 0.03和(D) 0.15, 退火温度为50 ℃时, 利用自晶种制备得到的OPV5-b-P2VP42纤维状胶束的TEM照片、(E)通过自晶种制备得到的OPV5-b-P2VP42纤维状胶束的长度和(F)对应的种子存活率(Ps)与αacid/v的关系图

Figure 2. TEM images of (A) seed micelles of OPV5-b-P2VP42 (0.05 mg/mL in ethanol) and obtained fiber-like micelles by self-seeding with annealing temperature of 50 ℃ and αacid/v of (B) 0, (C) 0.03 and (D) 0.15, (E) dependence of Ln of obtained fiber-like micelles and (F) corresponding Ps on αacid/v in self-seeding of OPV5-b-P2VP42 with annealing temperature of 50 ℃

图3. 退火温度为60 ℃, αacid/v为(A) 0、(B) 0.01、(C) 0.05和(D) 0.10, 利用自晶种制备所得OPV5-b-P2VP42纤维状胶束的TEM照片、(E) αacid/v分别为0、0.01、0.05和0.10时, 通过自晶种制备所得OPV5-b- P2VP42纤维状胶束的长度和(F)对应的种子存活率与退火温度的关系图

Figure 3. TEM images of fiber-like micelles of OPV5-b-P2VP42 obtained by self-seeding with annealing temperature of 60 ℃ and αacid/v of (A) 0, (B) 0.01, (C) 0.05 and (D) 0.10, (E) dependence of Ln of obtained fiber-like micelles and (F) corresponding Ps on annealing temperature in self-seeding with different αacid/v of 0, 0.01, 0.05 and 0.10

图4. OPV5-b-P2VP42的胶束种子溶液(0.05 mg/mL的乙醇溶液)中加入柠檬酸的量αacid/v分别为(A) 0、(B) 0.01、(C) 0.05、(D) 0.10、(E) 0.15和(F) 0.20后, 种子胶束溶液在55 ℃加热45 min, 随后在30 ℃下静置24 h所得胶束的TEM照片、(G) OPV5-b-P2VP42的种子胶束溶液(0.05 mg/mL的乙醇溶液)在55 ℃加热45 min, 随后在30 ℃下静置24 h所得纤维状胶束的长度和种子存活率与加入柠檬酸的量的关系图及(H)加入不同磷钨酸后的P2VP的乙醇溶液(0.05 mg/mL)的照片

Figure 4. TEM images of the micelles formed by annealing the OPV5-b-P2VP42 seed solution (0.05 mg/mL in ethanol) at 55 ℃, followed by aging at 30 ℃ for 24 h with addition of citric acid with αacid/v of (A) 0, (B) 0.01, (C) 0.05, (D) 0.10, (E) 0.15 and (F) 0.20, (G) dependence of Ln of obtained fiber-like micelles and corresponding Ps on αacid/v of citric acid for self-seeding of OPV5-b-P2VP42 (0.05 mg/mL in ethanol) with annealing temperature of 55 ℃ and (H) photograph of ethanol solution of P2VP (0.05 mg/mL) with addition of different amount of phosphotungstic acid

图式1. 在加入磷钨酸后, OPV5-b-P2VP42自晶种过程的示意图

Scheme 1. Schematic illustration of self-seeding of OPV5-b-P2VP42 in the presence of phosphotungstic acid

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