三嵌段离子液体共聚物P2VP(Bu)TFSI-b-PS-b-P(POEGMA)合成与表征

在链转移剂S-十二烷基-S′-(α,α′-二甲基-α″-乙酸)-三硫代碳酸酯的调控下,偶氮二异丁腈引发单体2-乙烯基吡啶、苯乙烯和聚乙二醇单甲醚甲基丙烯酸酯连续聚合,制备了含有聚2-乙烯基吡啶(P2VP)、聚苯乙烯(PS)和聚(聚乙二醇单甲醚甲基丙烯酸酯)[P(POEGMA)]链段的三嵌段共聚物P2VP105-b-PS189-b-P(POEGMA)22(下标为聚合度),凝胶渗透色谱法测试结果表明其数均相对分子量为35550,多分散指数为2.10。采用核磁共振氢谱仪、傅里叶变换红外光谱仪对共聚物的结构进行了确认,根据核磁共振氢谱测试结果表明共聚物的数均相对分子量为45500。该三嵌段共聚物依次与溴代正丁烷和双三氟甲基磺酰亚胺锂(LiTFSI)进行季铵化和阴离子交换,得到离子液体共聚物P2VP105(Bu)TFSI-b-PS189-b-P(POEGMA)22,离子电导率为1.55×10^–3 S/cm。测试结果表明,P(POEGMA)链段的引入可以改善离子液体共聚物的离子传导性,与不含P(POEGMA)链段的离子液体共聚物相比,其离子电导率提高了332.96%。     

基于超支化聚对氯甲基苯乙烯聚合离子液体共混体系的制备与表征

以对氯甲基苯乙烯/乙烯基苄基氯(CMS/VBC)、甲基丙烯酸甲酯(MMA)、甲基丙烯酸缩水甘油酯(GMA)、1?甲基咪唑(MIm)、双三氟甲烷磺酰亚胺锂(LITFSI)等为原料,通过活性/可控自由基聚合制备了超支化接枝多臂共聚物h?PCMS?g?PMMA、功能性嵌段共聚物PMMA?b?PGMA、离子液体嵌段共聚物PMM...     

利用原子转移自由基聚合制备水溶性含氟嵌段共聚物

利用原子转移自由基聚合技术合成了相对分子质量可控,相对分子质量分布较窄的丙烯酸叔丁酯与氟烷基（甲基）丙烯酸酯的嵌段共聚物。进一步将嵌段共聚物的丙烯酸叔丁酯链段在酸性条件下水解,制备了水溶性含氟嵌段共聚物,借助核磁共振氢谱和红外光谱对嵌段共聚物进行了表征。     

BAMO/AMMO三嵌段共聚物的合成、表征及热分解动力学

以三氟化硼.乙醚/1,4丁二醇作引发体系,利用阳离子开环共聚合的方法合成出3,3′-双叠氮甲基环氧丁烷/3-叠氮甲基-3′-甲基环氧丁烷(BAMO/AMMO)三嵌段共聚物。用FTIR、1HNMR和GPC对共聚物的结构和相对分子质量进行了表征,用DSC测定了共聚物的玻璃化转变温度。结果表明,合成的BAMO/AMMO三嵌段共聚物的相对分子质量可控、且分布窄,并具有含能热塑性弹性体的性质。同时用Vyazovkin的非线性无模型函数方法研究其热分解动力学,得到叠氮基团的分解活化能约为150kJ/mol。三嵌段共聚物在叠氮基团分解之后形成了交联网络结构。     

PMMA-b-PVBMIm的制备及其在CNT/PMMA复合材料中的应用

碳纳米管(CNT)作为一种一维结构的纳米材料,具有优良的力学、电学、热学性能,且拥有与炭黑相似的表面结构和化学组成,可作为一种纳米填料,用于改善聚合物的性能.但容易团聚这一特性限制了它的大规模应用.为了解决这个问题,本研究通过可逆-加成断裂链转移(RAFT)聚合方法合成了聚甲基丙烯酸甲酯和聚对氯甲基苯乙烯嵌段共聚物(P...     

丙烯酸酯嵌段共聚物合成及其改性环氧树脂的研究

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。     

“活性”原子转移自由基聚合向活性正离子开环聚合转化制备苯乙烯—2 …

以苯乙烯的ＡＴＲＰ聚合制备含卤端基的聚苯乙烯，再以此含卤端基的聚苯乙烯引发２－甲基－２－恶唑啉的正离子开环聚合，合成了苯乙烯与２－甲基－２－恶唑啉嵌段共聚物，并用ＩＲ，ＧＰＣ对开环产物进行了表征。     

异丁烯-co-对甲基苯乙烯的合成研究

以二枯基氯(DCC)、四氯化钛(Ti Cl4)、2,6-二叔丁基吡啶(Dt BP)为合成原料,通过活性正离子聚合成功地合成了不同异丁烯和对甲基苯乙烯进料比、不同聚合时间下的聚(异丁烯-co-对甲基苯乙烯)无规共聚物。通过TG以及DSC对产物进行表征。结果表明,无规共聚物的单体转化率与分子量呈线性关系,分子量分布窄,具有活性聚合的特征。     

两亲性三嵌段共聚物PLA-PEG-PLA的合成及其自组装行为的研究

采用阴离子开环聚合方法合成了两亲性嵌段共聚物PLA-PEG-PLA。用1H-NMR和GPC对聚合物的结构进行了表征,通过透射电子显微镜(TEM)观察了聚合物在离子液体中自组装的形貌,发现PLA-PEG-PLA在离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIM][PF6])中形成了胶束。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。     

借助UV光聚合制备热塑性聚氨酯–聚苯乙烯嵌段共聚物

采用端羟基的光引发剂2–羟基–2–甲基–1–苯基–1–丙酮(HMPP)封端聚氨酯预聚物,合成PUPI(一种聚氨酯大分子光引发剂),在紫外(UV)光照射下引发苯乙烯制备了聚氨酯–聚苯乙烯(PUPS)嵌段共聚物。采用实时红外、核磁共振和凝胶渗透色谱(GPC)对共聚物进行表征。通过考察苯乙烯转化率随时间的变化,发现UV光聚合可以在室温下进行。对PUPS嵌段共聚物的热力学性能和耐水性进行了研究,结果表明:聚苯乙烯链段的引入提高了聚氨酯的使用温度、拉伸强度,同时也提高了其耐水性能。     

BMIMBF_4/P(MMA-VBIMBr)凝胶型离子液体聚合物电解质的合成与性能

以甲基丙烯酸甲酯(MMA)和1-乙烯基-3-丁基咪唑溴盐(VBIMBr)为单体,通过自由基溶液聚合制备了无规共聚物聚(甲基丙烯酸甲酯-1-乙烯基-3-丁基咪唑溴盐)[P(MMA-VBIMBr)],并以此聚合物为基体,离子液体1-丁基-3-甲基咪唑四氟硼酸盐(BMIMBF4)为增塑剂,制备了BMIMBF4/P(MMA-VBIMBr)凝胶型离子液体聚合物电解质,采用红外光谱(FTIR)、X射线衍射(XRD)、扫描电镜(SEM)、热重分析(TG)和电化学交流阻抗(EIS)等方法对聚合物和聚合物电解质的性质进行了研究。结果表明,聚合物电解质膜具有优良的热稳定性和机械强度;当BMIMBF4/P(MMA-VBIMBr)质量配比为2时,离子电导率高达2.77×10-3S/cm(20℃),且离子电导率随着温度的升高而迅速增加,电导率-温度曲线符合Arrhenius方程。     

Polymerized ionic liquids with guanidinium cations as host for gel polymer electrolytes in lithium metal batteries

Polymerized ionic liquids (PILs) having guanidinium cations with different counter‐anions, such as PF₆^? and N(CF₃SO₂)₂^? (TFSI^?), were synthesized by copolymerization of a guanidinium ionic liquid monomer with methyl acrylate followed by an anion exchange reaction. Furthermore, incorporating a guanidinium ionic liquid, LiTFSI salt and nano‐size SiO₂, a quaternary gel polymer electrolyte based on one of the PILs as the polymer host was prepared. The quaternary gel polymer electrolyte was chemically stable even at a higher temperature of 80 °C in contact with the lithium anode. In particular, the electrolyte exhibited high lithium ion conductivity, wide electrochemical stability window and good lithium stripping/plating performance. Li/LiFePO₄ batteries with the quaternary gel polymer electrolyte at 80 °C had capacities of 140 and 130 mA h g^?1 respectively at 0.1 and 0.2 C current rates. Copyright © 2011 Society of Chemical Industry     

离子膜鼓泡的原因及预防措施

介绍了离子膜的特性，分析了引起离子膜鼓泡的原因，并提出了相应的预防措施。     

Separation Performance and Stability of PVDF-co-HFP/Alkylphosphonium Dicyanamide Ionic Liquid Gel-Based Membrane in Pervaporative Separation of 1-Butanol

In this study, a membrane prepared by gelling trihexyl(tetradecyl)phosphonium dicyanamide ionic liquid (IL) with poly(vinylidene fluoride-co-hexafluoropropylene) copolymer is tested for performance and stability in pervaporative separation of 1-butanol. Feed concentration and temperature affected separation performance mainly through plasticizing and swelling effects in the membrane which promoted liquid-like transport behavior. Microscale IL-in-polymer networks formed within the gel matrix where the neat IL possibly functioned as conventional liquid membrane. IL gelling has significantly improved the membrane operational lifetime to ～80 h, a significant improvement on the ～10 h shown by a simple supported IL membrane counterpart. The instability was consequent to polymer-IL incompatibility and so further investigations are underway to resolve this issue.     

普通离子液体和功能化离子液体的合成研究进展

离子液体是在室温下为液体、具有离子特性的新型绿色溶剂,作为一类环境友好型的反应介质,在诸多领域有其独特的性质.综述了普通离子液体和功能化离子液体的合成研究进展,并对其前景进行了展望.     

负载型离子液体催化剂在催化反应中的应用

负载型离子液体催化剂具有高催化活性、易于分离和环境友好型等特点。综述不同种类负载型离子液体催化剂在不同催化反应中的应用,并展望负载型离子液体催化剂在催化领域的发展方向。     

Ionic Liquids and Cellulose: Dissolution,Chemical Modification and Preparation of New Cellulosic Materials

Due to its abundance and a wide range of beneficial physical and chemical properties, cellulose has become very popular in order to produce materials for various applications. This review summarizes the recent advances in the development of new cellulose materials and technologies using ionic liquids. Dissolution of cellulose in ionic liquids has been used to develop new processing technologies, cellulose functionalization methods and new cellulose materials including blends, composites, fibers and ion gels.     

离子强度和溶质浓度对蛋白质在Q Sepharose FF中吸附动力学的影响

采用孔扩散模型, 模拟不同盐浓度和不同蛋白质初始浓度条件下,吸附牛血清白蛋白(BSA)的动态吸附曲线并获得孔扩散系数;考察了离子强度和溶质浓度对蛋白质在阴离子交换剂Q Sepharose FF中吸附动力学的影响.结果表明,蛋白质的孔扩散系数随初始浓度的增大而下降;在氯化钠浓度小于0.10 mol•L^-1的范围内,蛋白质的孔扩散系数随着盐浓度的增加而增大,但当盐浓度增大到0.15 mol•L^-1时又有所降低,表明存在着一个最佳的离子强度,使蛋白质的孔扩散系数最大.     

Structural and ion transport properties of [(AgI)x(AgBr)0.4−x](LiPO3)0.6 and (AgBr)x(LiPO3)(1−x) solid electrolytes

The (AgBr)_x(LiPO₃)_(1−x) (x=0.4 and 0.5) and [(AgI)_x(AgBr)_0.4−x](LiPO₃)_0.6 (x=0.1, 0.2, and 0.3) superionic electrolytes have been prepared by conventional melt quenching using a twin roller. These electrolytes are characterized by X-ray diffraction, SEM, and energy dispersive X-ray analysis (EDAX) for structural investigation. Electrical characterizations have been carried out by the AC impedance analysis. The conductivity of LiPO₃ glassy system at room temperature is improved by doping with the silver bromide (AgBr)_x(LiPO₃)_(1−x) and the mixture of silver iodide, silver bromide (AgI-AgBr-LiPO₃ system) up to 10⁻⁵ and 10⁻³ Ω⁻¹ cm⁻¹, respectively (improvements by four or five orders of magnitude). The frequency response of ionic conductivity has been analyzed by universal dynamic response model (Jonscher's law) and AC conductivity data are fitted using the Jonscher's power law. The conductivity values obtained by the power law and impedance plots are comparable. The frequency exponent (n) has a value between 0 and 1. The AgI-AgBr-LiPO₃ system shows the mixed alkali effect. Summerfield scaling master curve is temperature dependent, which may be due to the contribution of the both lithium and silver ions to ionic conduction.     

Protic and aprotic anionic oligomeric ionic liquids

We report on synthesis of linear and hyperbranched protic and aprotic anionic oligomeric ionic liquids (OILs). α,ω-Dicarboxy- and α,ω-disulfooligo(ethylene oxide)s, α-carboxy- and α-sulfooligo(ethylene oxide monomethyl ether)s, and di[(α-carboxyoligo(ethylene oxide monomethyl ether)] were synthesized using reaction of oligo(ethylene oxide diol) (MW 1000) and its monomethyl ether (MW 750) with phthalic-, 2-sulfobenzoic anhydride and pyromellitic dianhydride. Di- and mono-substituted anionic OILs were prepared by neutralizing these compounds with N-methylimidazole. Aprotic anionic OILs were synthesized by reaction of sodium salts of the prepared oligomeric di- and monoacids with 1,3-dimethyl imidazolium iodide. Hyperbranched protic and aprotic anionic OILs were prepared in a similar manner. The structure, thermal stability and ionic conductivity of the synthesized compounds in the range of 20–120 °C in anhydrous conditions is governed by the molecular architecture of the oligomeric chains and the type of the cation/anion moieties. OILs under study are amorphous at room temperature but some protic and aprotic linear-chain OILs prone to form a low melting temperature crystalline phase. The ionic conductivity of the synthesized OILs can be varied in broad range reaching 10⁻³ S/cm value at temperatures over 100 °C under anhydrous conditions.