聚乙二醇—聚乙烯基咔唑嵌段共聚物的合成及其性质研究
发布时间：2019-03-22 06:36
【摘要】：嵌段共聚物作为高分子研究领域的常青树,因其特异的性能而被广泛研究。聚乙烯基咔唑(PVK)是一种重要的聚合物半导体材料,具有良好的空穴传输能力,被广泛应用于光电子领域。将乙烯基咔唑(NVK)与其他功能分子共聚,构建PVK嵌段共聚物,将会赋予PVK新的性能和应用。本论文采用可逆加成-断裂链转移(RAFT)自由基聚合方法,以聚乙二醇(PEG)大分子RAFT试剂为链转移剂,NVK分别与2-(5-甲氧基-8-羟基喹啉)甲基丙烯酸乙酯(HQHEMA)和N-(2'-甲基丙烯酸乙酯基)-4-(N'-甲基哌嗪基)-1,8-萘酰亚胺(MMPN)共聚,获得一系列两亲性嵌段共聚物:PEG-b-PVK-co-PHQHEMA、PEG-b-PVK-co-Alq3和PEG-b-PVK-co-PMMPN。用傅里叶变换红外(FT-IR)光谱、核磁共振氢(1H NMR)谱、高温凝胶色谱(GPC)、紫外-可见光(UV-Vis)吸收光谱、光致发光(PL)谱和热重分析(TGA)对聚合物的结构和性能进行了表征。(1)合成两种聚合单体:HQHEMA、MMPN。合成出小分子RAFT试剂:S-正十二烷基-S'-(α,α'-二甲基-丙烯酸)-三硫代碳酸酯(DDAT)和大分子RAFT试剂PEG-DDAT。用1H NMR与FT-IR谱确认了化合物的化学结构。(2)通过调控聚合温度、投料比和加料方式,优化NVK聚合条件。在PEG-DDAT调控下,将NVK与HQHEMA共聚,合成出一系列双亲嵌段共聚物:PEG-b-PVK-co-PHQHEMA。用1HNMR和FT-IR 谱对PEG-b-PVK-co-PHQHEMA的结构进行表征。GPC结果表明获得的嵌段共聚物的分子量分布系数低于1.3,表明该RAFT聚合方法可有效地控制聚合物的分子量分布。通过1HNMR谱分析计算出共聚结构单元在共聚物中摩尔分数,并对理论分子量、GPC测得的分子量以及通过1HNMR计算的分子量进行了分析。(3)利用制备的嵌段共聚物PEG-b-PVK-co-PHQHEMA与二喹啉合铝(Pr-i-O-Alq2)螯合形成共聚物PEG-b-PVK-co-Alq3。该共聚物的红外光谱发现铝氧键的存在,其强度随着HQHEMA结构单元含量的增加而增强。TGA结果表明该共聚物的热分解温度超过330℃。由于共聚物在二氯甲烷(DCM)和乙醇中溶解性的差异,在两种溶剂中呈现出不同链构象,共聚物表现出不同的发光性质。(4)采用RAFT自由基聚合方法将NVK与MMPN共聚,制备出共聚物PEG-b-PVK-co-PMMPN。用1HNMR、GPC和FT-IR谱表征共聚物的化学结构并获得MMPN和NVK结构单元在共聚物中的平均组成。由于PVK与萘酰亚胺之间共振能量转移,320nm光激发时,萘酰亚胺的荧光强度增加。探讨pH值和金属离子对PEG-b-PVK-co-PMMPN的发光性能影响,发现共聚物在四氢呋喃溶液中对Cu2+有选择性识别。由于共聚物在水中聚集,PVK与萘酰亚胺之间共振能量转移效率增加,萘酰亚胺的荧光强度显著增加,然而共聚物失去对金属离子的识别。
[Abstract]:Block copolymers are widely studied because of their specific properties as evergreen trees in polymer research field. Poly (vinyl carbazole) (PVK) is an important polymer semiconductor material with good hole transport ability and has been widely used in the field of optoelectronics. The copolymerization of vinyl carbazole (NVK) with other functional molecules to construct PVK block copolymers will give PVK new properties and applications. In this paper, the reversible addition-fragmentation chain transfer (RAFT) radical polymerization method was used, and polyethylene glycol (PEG) macromolecule RAFT reagent was used as chain transfer agent. NVK was copolymerized with 2-(5-methoxy-8-hydroxyquinoline) ethyl methacrylate (HQHEMA) and N-(2-methoxy-ethyl acrylate)-4-(Na-methylpiperazinyl)-1,8-naphthalimide (MMPN), respectively, with 2-(5-methoxy-8-hydroxyquinoline) ethyl methacrylate. Preparation of a series of amphiphilic block copolymers: PEG-b-PVK-co-PHQHEMA,PEG-b-PVK-co-Alq3 and PEG-b-PVK-co-PMMPN. Fourier transform infrared (FT-IR) spectra, nuclear magnetic resonance hydrogen (1H NMR) spectra and high temperature gel chromatography (GPC),) ultraviolet-visible light (UV-Vis) absorption spectra were used. The structure and properties of the polymers were characterized by photoluminescence (PL) spectroscopy and thermogravimetric analysis (TGA). (1) two kinds of polymerized monomers: HQHEMA,MMPN. were synthesized. The small molecule RAFT reagent: s-dodecyl-SS-(伪, 伪'- dimethyl-acrylic acid)-trithiocarbamate (DDAT) and macromolecule RAFT reagent PEG-DDAT. were synthesized. The chemical structure of the compound was confirmed by 1H NMR and FT-IR spectra. (2) the conditions of NVK polymerization were optimized by adjusting the polymerization temperature, feed ratio and feeding mode. A series of amphiphilic block copolymers (PEG-b-PVK-co-PHQHEMA.) were synthesized by copolymerization of NVK with HQHEMA under the control of PEG-DDAT. The structure of PEG-b-PVK-co-PHQHEMA was characterized by 1HNMR and FT-IR spectra. GPC results showed that the molecular weight distribution coefficient of the block copolymer was lower than 1.3, which indicated that the RAFT polymerization method could effectively control the molecular weight distribution of the polymer. The molar fraction of the copolymer structure unit in the copolymer was calculated by 1HNMR spectrum analysis, and the molecular weight of the copolymer was calculated. The molecular weight measured by GPC and calculated by 1HNMR were analyzed. (3) the block copolymer PEG-b-PVK-co-PHQHEMA was chelated with diquinoline aluminum (Pr-i-O-Alq2) to form the copolymer PEG-. B / PVK / Alq3. The IR spectra of the copolymer show that the Al-O bond exists and the strength of the copolymer increases with the increase of the content of HQHEMA structural units. The results show that the thermal decomposition temperature of the copolymer is more than 330 鈩，
本文编号：2445349
[Abstract]:Block copolymers are widely studied because of their specific properties as evergreen trees in polymer research field. Poly (vinyl carbazole) (PVK) is an important polymer semiconductor material with good hole transport ability and has been widely used in the field of optoelectronics. The copolymerization of vinyl carbazole (NVK) with other functional molecules to construct PVK block copolymers will give PVK new properties and applications. In this paper, the reversible addition-fragmentation chain transfer (RAFT) radical polymerization method was used, and polyethylene glycol (PEG) macromolecule RAFT reagent was used as chain transfer agent. NVK was copolymerized with 2-(5-methoxy-8-hydroxyquinoline) ethyl methacrylate (HQHEMA) and N-(2-methoxy-ethyl acrylate)-4-(Na-methylpiperazinyl)-1,8-naphthalimide (MMPN), respectively, with 2-(5-methoxy-8-hydroxyquinoline) ethyl methacrylate. Preparation of a series of amphiphilic block copolymers: PEG-b-PVK-co-PHQHEMA,PEG-b-PVK-co-Alq3 and PEG-b-PVK-co-PMMPN. Fourier transform infrared (FT-IR) spectra, nuclear magnetic resonance hydrogen (1H NMR) spectra and high temperature gel chromatography (GPC),) ultraviolet-visible light (UV-Vis) absorption spectra were used. The structure and properties of the polymers were characterized by photoluminescence (PL) spectroscopy and thermogravimetric analysis (TGA). (1) two kinds of polymerized monomers: HQHEMA,MMPN. were synthesized. The small molecule RAFT reagent: s-dodecyl-SS-(伪, 伪'- dimethyl-acrylic acid)-trithiocarbamate (DDAT) and macromolecule RAFT reagent PEG-DDAT. were synthesized. The chemical structure of the compound was confirmed by 1H NMR and FT-IR spectra. (2) the conditions of NVK polymerization were optimized by adjusting the polymerization temperature, feed ratio and feeding mode. A series of amphiphilic block copolymers (PEG-b-PVK-co-PHQHEMA.) were synthesized by copolymerization of NVK with HQHEMA under the control of PEG-DDAT. The structure of PEG-b-PVK-co-PHQHEMA was characterized by 1HNMR and FT-IR spectra. GPC results showed that the molecular weight distribution coefficient of the block copolymer was lower than 1.3, which indicated that the RAFT polymerization method could effectively control the molecular weight distribution of the polymer. The molar fraction of the copolymer structure unit in the copolymer was calculated by 1HNMR spectrum analysis, and the molecular weight of the copolymer was calculated. The molecular weight measured by GPC and calculated by 1HNMR were analyzed. (3) the block copolymer PEG-b-PVK-co-PHQHEMA was chelated with diquinoline aluminum (Pr-i-O-Alq2) to form the copolymer PEG-. B / PVK / Alq3. The IR spectra of the copolymer show that the Al-O bond exists and the strength of the copolymer increases with the increase of the content of HQHEMA structural units. The results show that the thermal decomposition temperature of the copolymer is more than 330 鈩，
本文编号：2445349
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