原子转移自由基聚合反应制备多种结构的聚合物

介绍了原子转移自由基聚合反应这一新型的活性自由基聚合方式,综述了利用这种聚合方法制备的多种结构的聚合物,包括嵌段共聚物,交替共聚物,接枝共聚物,星形聚合物,超支化聚合物,梳形聚合物等。     

Preparation of fluorescent hyperbranched polymer materials by end-capping approach

Two kinds of novel fluorescent hyperbranched polymers were synthesized by the end-capping approach. The fluorescent hyperbranched polyether (FPEOTM) was obtained by end capping the hyperbranched poly(hydroxyl ether) (PEOTM) with guest molecules N,N-dimethylaminobenzaldehyde (DMABA). In addition, in the presence of triethylamine, the hyperbranched polysulfone-amine with terminal double bonds (HPSA) was synthesized by polyaddition of a new AB₂ type monomer (SAP, sulfone amine piperazine) at 40°C for 60 h in chloroform solution. Then the fluorescent hyperbranched polysulfone-amine (FHPSA) was prepared by addition of guest molecules N, N-dimethylaminoanilines (DMAA) with the terminal double bonds of HPSA. The two resulting polymers fluoresce yellow-green color in both solid and solution states. The maximum emission wavelength is (460±10) nm and (470±10) nm, respectively. A novel “complex quenching effect” for hyperbranched polymer was observed. The fluorescence can be quenched by transition metal cations such as Ag⁺, cu²⁺ and Fe³⁺, while alkali and alkaline earth metal cations almost have no influence on the fluorescence intensity.     

聚对苯乙烯撑型超支化共轭聚合物的合成及荧光淬灭研究

通过Heck缩聚反应合成了2种以三苯胺为核的"A2 B3"聚对苯乙烯撑型超支化共轭聚合物.通过FT-IR,1HNMR,GPC和TGA等测试对聚合物进行了表征.此类超支化聚合物具有良好的溶解性和热稳定性.通过紫外吸收光谱,荧光发射光谱表征了聚合物的光化学性能,并首次对含硝基芳香烃淬灭其溶液荧光的能力进行了初步研究.此类聚合物不仅合成较为容易,检测的灵敏度也较高,是一类潜在的检测含硝基芳香烃爆炸物的荧光传感器材料.     

端丙烯酸酯基超支化聚酯的合成及固化反应性能

对超支化聚合物端基反应性能进行研究,可为其在热固性树脂中的应用提供指导。以丙烯酸为反应试剂,对端羟基脂肪型超支化聚酯进行端基改性,以高的收率及反应程度得到了端丙烯酸酯基超支化聚酯。研究了改性聚合物的紫外光固化反应性能。结果表明:由于空间位阻的影响,单独改性聚合物的端基反应程度很低;在其中加入活性稀释剂丙烯酸羟丙酯后,端基的反应能力得到很大改善。     

超支化聚己内酯的制备与表征

在Novozyme 435固定化脂肪酶催化下,甲基丙烯酸羟乙酯(HEMA)引发己内酯(ε-CL)开环聚合反应,得到分别以双键和羟基封端的直链聚己内酯(PCL)产物;利用α-溴代异丁酰溴与开环聚合产物的端羟基发生酯化反应,得到大分子型AB*单体;再以CuCl/bpy(联吡啶)为催化体系,令大分子型AB*单体通过自缩合乙烯基聚合反应(利用原子转移自由基聚合反应形式),成功合成了超支化聚己内酯目标产物。     

不同结构两亲性嵌段共聚物的合成、药物负载及释放行为研究

采用阴离子活性聚合(AROP)的方法分别合成3种不同结构的两亲性嵌段共聚物:线型共聚物聚乙氧基乙基缩水甘油醚-聚乙二醇(PEEGE-PEO-(OH))、星型聚合物PEEGE-PEO-(OH)_3以及类树枝状聚合物PEEGE-PEO-(OH)_(24).通过~1H-NMR及GPC等手段对聚合物的结构进行表征.采用透析法制备负载阿霉素的聚合物胶束,通过透射电镜(TEM)和动态光散射(DLS)对胶束的形貌及尺寸进行表征.结果表明:3种胶束均具有球形结构;与线型及星型聚合物相比,两亲性类树枝状聚合物具有最高的载药效率与载药量;体外药物释放结果显示3种聚合物均具有pH敏感释放特性,且类树枝状表面致密结构可降低药物在中性环境下的释放率.     

超支化聚(胺-酯)增韧环氧树脂

采用一步法合成超支化聚(胺-酯)(HBP),并测试不同温度下的粘度变化情况;以所合成的超支化聚(胺-酯)作为增韧剂,增韧环氧树脂,测试其冲击强度与弯曲性能,并采用扫描电镜对冲击断口进行了观察。结果表明:所合成的超支化聚(胺-酯)的粘度随温度升高而下降,超支化聚(胺-酯)作为增韧剂与环氧树脂相容性好,使环氧树脂的冲击强度从9.8 kJ/m2提高到22.4 kJ/m2,弯曲强度和弯曲模量有一定程度提高,冲击断口表现出明显的韧性断裂的特征。     

超支化高分子的理论研究进展

以ABb型缩聚反应体系为主从理论角度较为系统地对超支化高分子近年来的理论研究进行了总结,重点指出了统计力学、热力学、微分动力学方程、反应动力学和分子模拟等一些理论方法在相关研究中的应用.这些理论研究工作有助于更好地研究超支化高分子结构和性能的关系,为合成具有指定性能的超支化高分子提供了有意义的线索,从而可为全面研究超支化高分子的结构特征提供必要的支持.     

富勒醇聚醚聚氨酯的热性能

通过水溶性多羟基化合物C60(OH)n和聚醚聚氨酯(PEO—PU)预聚体反应合成了一系列新型的C60星形聚醚聚氨酯，并用傅里叶红外分析(FTIR)、差式扫描量热分析(DSC)、热重分析(TGA)等手段对其性能进行了表征．结果表明，C60星形聚醚聚氨酯比线性的聚醚聚免酯具有更高的柔顺性和热稳定性；随着聚氧化乙烯数均分子量Mn的增加，C60星形聚醚聚氨酯的玻璃化转变温度(Tg)降低，热分解温度(td)提高．     

Synthesis of Hyperbranched Polymers and Its Effect on Water Vapor Permeability of Microfiber Synthetic Leather

A series of hyperbranched poly(amine-ester)polyols were synthesized by the polycondensation of N,N-diethylol-3-amine-methylpropionate(prepared by Michael addition reaction of methyl acrylate with diethanolamine)as an AB2-type monomer with trimethylol propane as the core moiety,proceeding in one-step procedure in the melt with p-toluenesulfonic acid as catalyst.The obtained monomer and polymers were characterized by FTIR and 1H-NMR spectroscopy.The solubility and surface activity in aqueous solution of the polymers were also examined.The gas permeability,water vapor permeability,and moisture absorption of microfiber synthetic leather treated by hyperbranched polymer were studied.The optimum conditions were that the dosage of dye and hyperbranched polymer was 5% and 10%,respectively.The water vapor permeability and moisture absorption of microfiber synthetic leather reached to 0.525 4 mg/(10 cm2·24 h)and 0.046 7 mg/(10 cm2·24 h).Compared with blank samples,they increased by 15% and 35%,respectively.However,the dosage of hyperbranched polymer has little influence on gas permeability of microfiber synthetic leather.SEM results show that the fiber of microfiber synthetic leather treated by hyperbranched polymer is incompact.     

A Novel Calixarene-containing Hyperbranched Aliphatic Polyester Incorporated with Pendant Europium Complexes

1 Results Hyperbranched polymers can be easily functionalized,while the calixarene-rare earth complexes enjoy the advantages of narrow emission bands.It is expected that materials combining their advantages can possess good luminescence properties[1-2].For this reason,in this paper,a novel calixarene-containing hyperbranched aliphatic polyester incorporated with pendant europium complexes (H2O-Cal-Eu) was synthesized and characterized by FTIR,UV and element analysis.DSC measurement shows that the glass-...     

Synthesis and photophysical properties of linear and hyperbranched conjugated polymer

A novel light-emitting alternating copolymer, known as hyperbranched conjugated polymer (HPV), has been designed and synthesized by Wittig reaction, and so have its linear counterparts, including MPV and PPV. FTIR, 1H NMR, 13C NMR and GPC were combined to characterize these polymers. Their photophysical properties were investigated both in solution and in solid film. Interestingly, almost the same maxima of absorption and emission wavelengths were observed for the solution of HPV and MPV in CH2Cl2 respectively, located at the shorter wavelength region related to PPV. In addition, the absorption peak of HPV film blue shifted while its emission peak red shifted as MPV compared with the case of its CH2Cl2 solution. However, both the absorption and emission spectra of the PPV film showed red shift, which resulted from a special electronic structure.     

全氟端基超支化聚缩水甘油的合成与表征

合成了以超支化聚缩水甘油为核、氟碳链为臂的超支化聚合物，并利用红外光谱、核磁共振、元素分析、凝胶渗透色谱、差热分析等手段对其进行了初步表征．作为核的超支化聚缩水甘油是以丙三醇为起始剂、缩水甘油为单体，在三氟化硼乙醚引发下阳离子开环聚合得到的．全氟辛酸酰氯由全氟辛酸与亚硫酰氯在DMF的催化下反应得到．利用聚缩水甘油的大量端羟基，将氟碳链接入聚缩水甘油中，得到了全氟端基超支化聚合物．这种全氟端基超支化聚合物其合成方法简单，结构独特：内核为亲水性，外臂疏水疏油，而且具有良好的成膜性能，有利于其在实际中的应用．     

1，1，1－三羟甲基丙烷为核的三臂星形聚甲基丙烯酸甲酯的控制合成及表征

通过三羟甲基丙烷和2－溴异丁酰氯反应合成了三臂星型聚合物引发剂,利用原子转移自由基聚合合成了三臂星型的聚甲基丙烯酸甲酯,并对引发剂和聚合物的结构进行了^1HNMR和GPC的表征,合成了聚合物分子量分布较窄的端基含溴原子的三臂星状聚合物．     

超支化聚合物的合成及应用

介绍了超支化聚合物合成方法及其应用前景，旨在加深人们对该领域的了解，从而加速该领域的发展。     

新型核-多臂星形聚合物电解质

采用傅里叶转换红外光谱法(FT-IR)、微分扫描量热分析(DSC)、离子阻抗谱等测试手段对以超支化聚缩水甘油(HPG)为核，线型聚氨酯(PEU)为臂的核-多臂星形聚合物进行了表征，对其分子结构与电导性能之间的关系进行了初步探索．结果表明，星形聚合物比线型聚合物有更强的溶盐能力和离子传输能力．氧锂比(氧化乙烯单元与锂离子的摩尔比)为4，共混比(质量)为30％时，体系的最高电导率可达0．2mS／cm．当星形聚合物的臂数为5时，体系的电导率高于相同条件下的其他臂数的聚合物体系．体系的电导率随温度的升高而升高，其变化规律符合Arrhcnius方程．     

Synthesis and Characterization of Aliphatic-Aromatic Hyperbranched Polyesters

IntroductionHyperbranched polymers have gained muchresearch interest in the last ten years.They aremainly prepared by polycondensation of AB2monomers at high temperature under reducedpressure.Compared with their linearanalogs,theyshow lower viscosity and higher solubility,and con-tain more end- groups.These unique chemophysicalproperties make them useful candidates forviscosity modificators,ultraviolet spectroscopy( UV ) - radiation coatings,membranes,etc.[115]Recently,all- aromatic hyperbra…     

超支化聚合物HP-NH2的合成及防塌机理研究

井壁稳定是当前水基钻井液钻深层页岩气的技术难点。以二乙烯三胺和N，N-亚甲基双丙烯酰胺为原料，通过迈克尔加成反应合成了超支化聚合物HP-NH₂。采用红外光谱法、液相色谱-质谱联用法、凝胶色谱法、粒度分析法和热失重分析法表征了HP-NH₂的结构和特征。研究发现，HP-NH₂的数均分子量为3 371 g/mol，多分散指数为2.7，分子量分布较宽，粒径280～1 900 nm，抗温能力达到280℃。通过线性膨胀实验、回收率实验、泥饼分散实验和“人造泥饼”法分析了HP-NH₂作为防塌剂的防塌性能。研究表明，随着HP-NH₂浓度的增加，膨润土的线性膨胀率逐渐降低（最低为19.11%），岩屑的滚动回收率逐渐升高（最高为75.18%），人造泥饼的渗透率逐渐下降。小分子HP NH₂能够插入蒙脱石的晶层间，交换出层间易水化的阳离子，拉紧基底间距，抑制蒙脱石的水化分散；大分子HP-NH₂能有效封堵泥饼的微纳米孔缝，起到一剂多用的功效。因此，HP-NH₂可作为一种潜在的一剂多用防塌剂应用于水基钻井液体系。     

FeCl2/IDA催化体系制备两亲性超支化星状聚合物

采用氯化亚铁(FeCl2)/亚胺基二乙酸(IDA)催化体系引发对氯甲基苯乙烯的原子转移自由基聚合,获得端基和线性单元上含有多个氯原子的超支化聚对氯甲基苯乙烯(PCMS).并以此为大分子引发剂再次引发甲基丙烯酸特丁酯(tBMA)进行原子转移自由基聚合,制得了具有超支化核的星状接枝共聚物P(CMS-g-tBMA),所得产物在酸性条件下水解后得到两亲性超支化星状共聚物P(CMS-g-MAA).     

超支化聚(胺-酯)的合成、表征及其改性研究

以氯乙酸乙酯和二乙醇胺为原料,利用先低温后高温的"二步法"制得新型的超支化聚(胺-酯).元素分析、FTIR和MS分析结果表明,在低温反应阶段合成了预想的单体,高温聚合反应制备出超支化聚(胺-酯),合成反应过程中没有凝胶产生.进一步研究了聚(胺-酯)上端羟基与马来酸酐、丙烯酰氯的功能化反应,FTIR结果表明在超支化聚合物末端成功引入了双键.