电化学聚合漆酚钇的合成及其结构表征

电化学方法合成的聚合漆酚 (EPU )通过与氯化钇的异丙醇溶液作用 ,得到聚合漆酚钇配合物(EPU- Y3 + )。采用红外光谱、荧光光谱、XPS光电子能谱、动态机械热分析 (DMTA)以及差热 -热重(DTA- TG)等手段进行表征 ,确定其配位结构 ,原于发射光谱 (AES)结果表明 ,钇含量达 8.0 1%。配合物的电阻为 8.32× 10 10 Ω(EPU为 7.9× 10 10 Ω)。由于存在配位作用 ,引起配合物进一步交联 ,因而难溶于绝大多数有机溶剂 ,同时玻璃化转变温度和耐热性能均得到提高。     

生漆及漆酚金属聚合物的动态力学性能

测试了生漆及几种典型的漆酚金属聚合物的动态力学性能,并从分子热运动角度解释了其分子结构与性能的关系。实验表明,生漆及漆酚钛、铝、硅、锡、钇、钼等金属聚合物分子中都存在可热交联的基团,在0～360℃范围,模量都在5.0×106Pa以上,大多数在107Pa～109Pa之间,均具有优良的耐热性能。     

漆酚-喔星功能聚合物的合成及特性研究

合成了漆酚喔星功能聚合物(UOXP),对其进行了红外光谱表征。初步研究了该聚合物对几种金属离子的吸附性能,用差示扫描量热法(DSC)研究了吸附金属离子前后聚合物的热稳定性。结果表明,该聚合物能有效吸附Fe3 、Pb2 、Cd2 、Hg2 和Cu2 等金属离子,吸附容量(mgMn /gUOXP)分别为42.6、87.3、110、25.3和92.8;在180℃以下的空气氛围中,吸附金属离子前后的聚合物均具有较好的热稳定性,该聚合物能用于金属离子的吸附分离和作为高分子催化剂的载体。     

Breath Figures法制备漆酚铜聚合物多孔膜

以漆酚铜聚合物(UCP)有机溶液为铸膜液,采用Breath Figures法制备漆酚铜聚合物多孔膜,探讨了溶剂、环境相对湿度和潮湿气体流速等因素对多孔膜形貌的影响,并使用红外光谱和扫描电镜等进行表征。结果表明,以二硫化碳为溶剂,在静态(潮湿气体流速为0mL/min,湿度为95%)或动态(潮湿气体流速为400mL/min,湿度为85%)时,均可制得孔分布均匀、孔型规整、优良耐热性和耐酸碱性的疏水性UCP多孔膜,其平均孔径分别为1.5和0.85μm。     

功能化三联吡啶钌配合物的电化学聚合及其电致变色性质

合成了4-[对-(N-正丁基-N-苯基)苯胺基]-2,2′:6′,2″-三联吡啶钌配合物{[Ru(L)2](PF6)2},利用电化学沉积法在0.1mol/L Bu4 NClO4/CH3CN溶液中制备了导电聚[Ru(L)2]2+膜,并用SEM表征了膜的形貌.交流阻抗谱研究表明,聚合物膜的厚度随扫描圈数的增加而增大,光谱电化学方法研究表明聚[Ru(L)2]2+膜处于中性态是红色而在完全氧化态则几乎无色.研究了聚合物膜的电致变色性质,表明聚[Ru(L)2]2+膜是一种具有潜在应用价值的电致变色材料.     

漆酚甲醛缩聚物无铬化学镀铜

通过改变施镀工艺的pH值、温度、时间以及镀液配方中主盐浓度、还原剂浓度,得到不同条件下的化学镀层厚度、外观和镀速等试验结果,对漆酚甲醛缩聚物(PUF)基材上的化学镀铜工艺进行了研究;并用扫描电镜(SEM)、动态机械热性能(DMTA)、差示扫描量热分析(DSC)和热重分析(TG)等方法研究了镀层的形态与性能.本工艺可在PUF表面镀上一层均匀、色泽光亮的金属铜膜,其粒径匀称、排布规整、镀层致密;金属化聚合物的耐热性显著提高.     

漆酚铁螯合高聚物的合成及其特性研究

用灼烧、红外光谱、质谱、热分析和分光光度法研究了漆酚与FeCl_3的反应关系、产物的组成和结构特征及其性能。由此揭示了传统黑推光漆的内在本质和特性,为黑推光漆的加工及提高性能等,提供了理论依据。此外还对漆酚与FeCl_3的反应机理进行了探讨。     

漆酚甲醛缩聚物水基分散体系的相反转乳化

用复合表面活性剂将漆酚缩甲醛聚合物乳化为水包油型的稳定水基乳液。系统研究了乳化剂种类、乳化剂用量、H LB值和乳化温度等对相反转乳化过程的影响,并用乳液体系电导率变化和黏度变化表征了相反转乳化过程。实验结果表明,复合乳化剂吐温-20/司班-20乳化效果最好;高乳化剂用量和低乳化温度有利于水包油乳液的形成;当水和油的质量比(R)为1.05时,体系开始发生相反转,至R=1.4时,体系由油包水型转化为水包油型。相反转乳液粒径小,分布均匀。     

氟树脂改性漆酚复合涂料的老化性能研究

采用氟树脂对漆酚进行改性,对改性后漆酚涂膜进行了自然老化和人工加速老化测试。通过傅立叶红外光谱(FTIR)、紫外光谱(UV)及扫描电镜(SEM)等手段对老化后的样品进行表征。结果表明,氟树脂含量在30%～90%(wt)时改性样品经过人工加速老化试验后表面出现破坏的时间大于漆酚涂膜,且经模拟太阳光照射120h后,失光率较小;暴露在自然环境中2880h后,表面仍未出现破坏现象。而漆酚涂膜在自然环境中暴露2544h后,表面已被破坏。研究表明,改性漆酚涂膜的耐老化性能较漆酚涂膜有大幅提高。     

耐高温碱水漆酚钛清漆的合成工艺、性能及机理

为开发经济实用的耐高温碱水漆酚钛清漆,以漆酚为基本原料,先通过漆酚与甲醛缩聚,再将钛酸丁酯与前期合成产物反应,从而合成出了漆酚-钛螯合高聚物(漆酚钛树脂),并通过高效液相色谱(HPLC)和傅立叶红外(IR)技术检测了预期产物的合成情况.对该合成反应的机理、工艺进行了分析与讨论,并初步探讨了其在高温碱水中的热稳定性与化学稳定性.结果证明,研制的漆酚钛清漆漆膜在90℃、pH=13的高温碱水中浸泡480 h后外观无变化,表现出良好的性能.     

高吸水性树脂耐盐性研究进展

本文从高吸水性树脂的吸水机理和盐对离子型树脂的影响出发 ,论述了提高吸水性树脂耐盐能力的几种有效方法     

Nanostructured polymer brushes

Nanopatterned polymer brushes with sub-50-nm resolution were prepared by a combination of electron-beam chemical lithography (EBCL) of self-assembled monolayers (SAMs) and surface-initiated photopolymerization (SIPP). As a further development of our previous work, selective EBCL was performed with a highly focused electron beam and not via a mask, to region-selectively convert a SAM of 4'-nitro-1,1'-biphenyl-4-thiol to defined areas of crosslinked 4'-amino-1,1'-biphenyl-4-thiol. These "written" structures were then used to prepare surface-bonded, asymmetric, azo initiator sites of 4'-azomethylmalonodinitrile-1,1'-biphenyl-4-thiol. In the presence of bulk styrene, SIPP amplified the primary structures of line widths from 500 to 10 nm to polystyrene structures of line widths 530 nm down to approximately 45 nm at a brush height of 10 or 7 nm, respectively, as measured by scanning electron microscopy and atomic force microscopy (AFM). The relative position of individual structures was within a tolerance of a few nanometers, as verified by AFM. At line-to-line spacings down to 50-70 nm, individual polymer brush structures are still observable. Below this threshold, neighboring structures merge due to chain overlap.     

耐盐性多元共聚高吸水性树脂的制备及性能研究

采用反相悬浮聚合法,以过硫酸钾为引发剂,N,N-亚甲基双丙烯酰胺为交联剂,通过多元聚合合成了丙烯酸/丙烯酰胺/2-丙烯酰胺基-2-甲基丙磺酸钠/甲基丙烯酸羟丙酯四元共聚高吸水性树脂。探讨了单体组成配比、反应温度、交联剂用量、引发剂用量等共聚反应条件对吸水性能的影响。结果表明,在聚丙烯酸系聚合大分子链上同时引入适当配比的磺酸基、丙烯酰胺基和羟基能产生良好的协同效应,有效提高树脂的耐盐性及吸水性能。所得产品的最高吸蒸馏水率和吸盐水率分别为690g/g和140g/g,热稳定性好。     

Patterned polymer carpets

For the development of polymer carpets as active devices for micro- and nanotechnology, a control of the polymer carpet morphology and especially control of the stimulus responsive polymer brush is needed. Here, we report on the first example for the fabrication of patterned polymer carpets. On a two-dimensional framework of fully crosslinked and chemically patterned nanosheets, polymer brushes of styrene and 4-vinyl pyridine were grafted by self-initiated surface photopolymerization and photografting (SIPGP). It was found that polymer grafting by SIPGP occurred over the entire nanosheets but with a preferred grafting on the amino functionalized nanosheet areas. This results in continuous polymer carpets with an intact nanosheet framework but with amplification of the chemical patterning into a three dimensional topography of the grafted polymer brush. In the case of negative patterned nanosheets, the patterned carpet could be prepared as freestanding ultrathin membranes. Furthermore, swelling experiments with poly(4-vinyl pyridine) carpets showed that the patterns induces a directional buckling of the flexible polymer carpet. This may open the possibility of the development of micro- or nanoactuator devices with anisotropic responds upon environmental changes.     

氰酸酯/聚甲基丙烯酸甲酯互穿聚合物网络的探究

用同步法合成一系列氰酸酯/聚甲基丙烯酸甲酯(CE/PMMA)体系的互穿聚合物网络(IPN).研究了甲基丙烯酸甲酯(MMA)的含量对CE/PMMA-IPN体系的力学性能及密度的影响.结果表明:CE/PMMA-IPN体系的性能比单一树脂的优异,但其工艺条件有待进一步改进.     

酶催化合成新型功能高分子的研究进展

酶催化聚合是一种新型的聚合方式,它在温和的反应条件下进行,与传统聚合工业中的金属有机催化剂相比,天然的生物酶具有高效性、高选择性,绿色环保性等优点.本研究主要综述酶催化合成新型功能高分子的研究进展.     

锂离子电池凝胶聚合物电解质制备技术进展

综述了近几年锂离子电池凝胶聚合物电解质的制备技术进展,主要介绍了溶液浇铸法、倒相法和现场聚合等工艺的优缺点。现场聚合工艺流程简单、产品成本低,有极其广阔的发展前景。通过添加无机纳米粒子改善凝胶聚合物电解质的性能是目前的研究热点和发展趋势。     

Tailoring the optoelectronic properties of donor-acceptor-donor type π-conjugated polymers via incorporating different electron-acceptor moieties

Syntheses of donor-acceptor-donor type of π-conjugated monomers were performed to examine the effect of the acceptor units' strength on the electrochemical and optoelectrochemical properties of the resulting monomer and polymer. Palladium catalyzed Stille cross-coupling reaction of an organotin reagent with an organic electrophile was used for the synthesis of target monomers, 5,8-bis(4-hexylthiophen-2-yl)-2-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-3-(2,3-dihydrobenzo[b][1,4]dioxin-7-yl)quinoxaline (DBQHT) and 10,13-bis(4-hexylthiophen-2-yl)dibenzo[a,c]phenazine (PHEHT).The presence of the strong electron-donating ethylenedioxy groups on pendant phenyl rings increased electron density on DBQHT, thus the oxidation potential of DBQHT shifts to a lower value than that of PHEHT. The π-π* absorption maximum of PPHEHT was about 40 nm red-shifted compare to that of PDBQHT, which can be attributed to the increase of the effective conjugation and coplanarity of PPHEHT relative to PDBQHT via using phenanthrene fused quinoxaline unit as the acceptor. The electronic band gap of polymer, defined as the onset of the π-π* transition, is found to be 1.65 eV for PPHEHT and 1.82 eV for PDBQHT. Both polymer films showed multi-color electrochromism. PDBQHT can be switched between a red neutral state and a green oxidized state with two intermediate states; purple and brown. PPHEHT also shows multicolored electrochromic behavior with three distinct states: a blue neutral state, a gray intermediate state, and a green oxidized state.     

New fabrication technique of conductive polymer/insulating polymer composite films and evaluation of biocompatibility in neuron cultures

Poly(vinyl alcohol), PVA, produces a flexible composite polymer film with electrical, optical and electrochemical properties very similar to those of polypyrrole (PPy). The rate of electrochemical polymerization depends on the diffusion rate of the electrolyte across the PVA film to the indium tin oxide (ITO) electrode. In particular, a solvent with a hydrophilic nature easily penetrates into the PVA film. By applying this new process, we demonstrate a unique method of forming an electrically conductive pattern in PVA film. It will be possible to develop electrodes for electrical stimulation of the nervous system using the conducting polymer, PPy. Then, by applying a similar technique, we fabricated poly(3,4-ethylenedioxythiophene), PEDOT/PVA, composite films and investigated their basic electrochemical properties. Moreover, in this study, in order to develop a novel cell-culture system which makes it possible to communicate with cultured cells, fibroblasts were cultured on PPy- and PEDOT-coated ITO conductive glass plates for 7 days. The result reveals that the PPy and PEDOT films support the secretory functions of the cells cultured on its surface. The PPy- and PEDOT-coated electrodes may be useful to culture the cells on.