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采用原子转移自由基聚合(ATRP)方法合成了两亲性嵌段共聚物PSt-b-PAA。用1H NMR和GPC等手段对活性聚合进行了确认,对嵌段共聚物的结构进行了表征。两亲性嵌段共聚物在离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BM IM][PF6])中形成胶束溶液。用透射电子显微镜(TEM)观察聚合物在离子液体中形成胶束的纳米结构。当疏水链长固定时,胶束的自组装形状主要依赖于亲水链的长度。两亲性共聚物在离子液体中可自组装成可控制结构的纳米胶束,这种纳米胶束可应用在很多领域。 相似文献
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两亲性聚乙烯醇-b-聚苯乙烯嵌段共聚物的合成及表征 总被引:2,自引:0,他引:2
采用原子转移自由基聚合(ATRP)法合成了具有两亲性的聚乙烯醇-b-聚苯乙烯嵌段共聚物P(VA-b-St)。首先利用调聚反应制备了带三氯甲基端基的聚醋酸乙烯大分子引发剂。以联二吡啶作配体、氯化亚铜为催化剂,引发苯乙烯单体聚合,得到结构明确的P(VAc-b-St)嵌段共聚物,而后通过皂化反应将其水解,从而得到两亲性嵌段共聚物P(VA-b- St);产物采用FT-IR、1H NMR、GPC等方法进行结构表征。P(VA-b-St)在不同浓度溶剂中的自组装行为用TEM进行了观察,结果表明:P(VA-b-St)可在DMF溶剂中形成球状囊泡结构,其尺寸达到纳米级。 相似文献
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简述了嵌段共聚物的几种合成方法,着重介绍了ATRP,RAFT两种可控活性自由基聚合,阐述了其聚合原理,以及最新的研究进展。 相似文献
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通过原子转移自由基聚合反应合成了以丙烯酸正丁酯(nBA)、甲基丙烯酸甲酯(MMA)及甲基丙烯酸缩水甘油酯(GMA)为单体的嵌段共聚物,采用凝胶渗透色谱仪、核磁共振波谱仪和傅立叶红外光谱仪对嵌段共聚物的结构与组成进行了确定。然后用合成的嵌段共聚物对环氧树脂(EP)/4,4′-二氨基二苯甲烷体系进行增韧改性,采用动态热机械分析仪、冲击试验机和扫描电子显微镜对增韧效果进行了表征并对增韧机理做了初步分析。结果表明,嵌段共聚物的加入对体系的主转变温度和模量影响不大;在嵌段共聚物中MMA与nBA的物质的量之比为1∶1时,嵌段共聚物在EP固化时发生微相分离,缺口冲击强度明显提高。 相似文献
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The synthesis and properties of crosslinked diblock copolymers for use as proton‐conducting membranes are presented. A polystyrene‐b‐poly(hydroxyl ethyl methacrylate) diblock copolymer at 56 : 44 wt % was sequentially synthesized via atom transfer radical polymerization. The poly(hydroxyl ethyl methacrylate) (PHEMA) block was thermally crosslinked by sulfosuccinic acid (SA) via the esterification reaction between OH of PHEMA and COOH of SA. Proton nuclear magnetic resonance and Fourier transfer infrared spectra revealed the successful synthesis of the diblock copolymer and the crosslinking reaction under the thermal condition of 120°C for 1 h. The ion‐exchange capacity continuously increased from 0.25 to 0.98 mequiv/g with increasing SA concentration because of the increasing number of charged groups in the membrane. However, the water uptake increased up to an SA concentration of 7.6 wt %, above which it decreased monotonically (maximum water uptake ∼ 27.6%). The membrane also exhibited a maximum proton conductivity of 0.045 S/cm at an SA concentration of 15.2 wt %. The maximum behavior of the water uptake and proton conductivity with respect to the SA concentration was considered to be due to a competitive effect between the increase of ionic sites and the crosslinking reaction according to the SA concentration. All the membranes were thermally quite stable at least up to 250°C, presumably because of the block‐copolymer‐based, crosslinked structure of the membranes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008 相似文献
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采用“活性”自由基聚合的方法合成了不同分子量的苯乙烯和甲基丙烯酸乙酯[polystyrene-block-poly(ethyl methacrylate),PS-b-PEA]嵌段共聚物。并用凝胶渗透色谱(GPC)和红外光谱(FTIR)对所合成的共聚物进行了表征,实验结果显示:在4-羟基-2,2,6,6-四甲基哌啶-1-氧化物自由基(HTEMPO.)和偶氮二异丁腈(AIBN)存在下,苯乙烯聚合反应所得到的聚苯乙烯分子量分布在1.18~1.2范围,分子量随聚合时间的延长而增大(7 200~69 300 g/mol);将该聚苯乙烯溶于甲基丙烯酸乙酯,在(130±2)℃时可以重新引发甲基丙烯酸乙酯的聚合反应,且甲基丙烯酸乙酯的聚合反应具有“活性”聚合的特征,共聚物的数均分子量及分布分别在57 800~107 800 g/mol和1.22~1.26范围,共聚物由FTIR表征显示:在聚苯乙烯接上聚甲基丙烯酸乙酯后,在1 158 cm-1及1 727 cm-1出现其甲基丙烯酸乙酯的特征吸收峰,说明共聚物为嵌段共聚物。 相似文献
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We report here the synthesis of well-defined thermoresponsive diblock copolymer bearing amino acid diamide derivatives, poly(N-acryloyl-l-valine N′-methylamide)-b-poly(ethylene glycol) monomethylether, via click reaction using CuSO4/sodium ascorbate as catalyst in DMF/water mixed solvent. The effects of chain length and water volume fraction in DMF on
coupling efficiency were investigated. For those reactions that both reacting polymers have short chain length, the reaction
efficiency was less affected by water volume fraction and relatively high conversion was achieved. And the higher molecular
weight of reactant polymer performed, the more impressive effects of water content on coupling efficiency appeared. Then,
the thermoresponsive property in terms of the lower critical solution temperature (LCST) of the block copolymer was evaluated
in aqueous solution by UV/vis spectroscopy. Optically active character was detected by circular dichroism instrument under
temperature ranging from 1 to 30 °C, and the spectra undergo one drastic change at the temperature near LCST point. 相似文献
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Polystyrene‐block‐poly(glycidyl methacrylate) reactive diblock copolymer (PS‐b‐PGMA) was synthesized via atom transfer radical polymerization (ATRP). The diblock copolymer was characterized using nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC). The cured epoxy thermosets with 10–20 nm PS particles were prepared by blending the diblock copolymer with epoxy resin. The nanostructures were examined by means of transmission electronic microscopy (TEM) and small angle X‐ray scattering (SAXS). The formation of the nanostructures was caused by the reaction‐induced microphase separation mechanism. It is significant that the glass transition temperatures (Tgs) of these epoxy thermosets were increased by the addition of PS‐b‐PGMA reactive block copolymer as revealed by both differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献
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A series of poly[2-(diisopropylamino)ethyl methacrylate]-block-poly[2-(N-morpholino)ethyl methacrylate], [PDPA-b-PMEMA], have been synthesized by using group transfer polymerization. These novel PDPA-b-PMEMA diblock copolymers dissolved molecularly in aqueous solution at low pH (<6.0) due to the protonation of all tertiary amine residues of both blocks and formed PDPA-core micelles at pH 7.5 by PMEMA block forming the micelle coronas. On the other hand, it was also observed that these diblock copolymers formed near-monodisperse ‘reverse micelles’, PMEMA-core micelles, in n-alkanes with or without requiring cosolvent depending on comonomer ratios. Dynamic light scattering studies indicated monodisperse or near-monodisperse micelles in both cases. The intensity-average radii of the PDPA-core and the PMEMA-core micelles were between 10 nm and 17 nm (polydispersity index, μ2/Γ2 < 0.08) and between 10 nm and 13 nm in n-hexane (μ2/Γ2 < 0.09), respectively. 相似文献
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Synthesis and characterization of perfluorocyclobutyl aryl ether-based amphiphilic diblock copolymer
Liang Tong 《Polymer》2008,49(21):4534-4540
Perfluorocyclobutyl aryl ether-based amphiphilic diblock copolymer containing hydrophilic poly(ethylene glycol) segment was synthesized by atom transfer radical polymerization (ATRP). Perfluorocyclobutyl-containing methacrylate-based monomer, 4-(4′-p-tolyloxyperfluorocyclobutoxy)benzyl methacrylate, was prepared firstly, which can be polymerized by ATRP in a controlled way to obtain well-defined homopolymers with narrow molecular weight distributions (Mw/Mn ≤ 1.30). The molecular weights increased linearly with the conversions of monomer and the apparent polymerization rate exhibited first-order relation with respect to the concentration of monomer. ATRP of 4-(4′-p-tolyloxyperfluorocyclobutoxy)benzyl methacrylate was initiated by PEG-based macroinitiators with different molecular weights to obtain amphiphilic diblock copolymers with narrow molecular weight distributions (Mw/Mn < 1.35) and the number of perfluorocyclobutyl linkage can be tuned by the feed ratio and the conversion of the fluorine-containing methacrylate monomer. The critical micelle concentrations of these amphiphilic diblock copolymers in water and brine were determined by fluorescence probe technique. The morphologies of the micelles were found to be spheres by TEM. 相似文献