原子转移自由基聚合的近期研究进展

对原子转移自由基聚合(ATRP)的引发体系、催化体系及反应介质进行了全面的综述。介绍了四种不同催化剂脱除技术;结合最新的研究成果,介绍了ATRP在进行聚合物分子设计尤其是在制备嵌段共聚物方面的进展。     

新型聚氨酯微球制备及其药物释放规律的研究

以低相对分子质量生物可降解DL-聚乳酸二醇和六亚甲基二异氰酸酯为原料,通过悬浮聚合法合成了一种新型聚氨酯微球(PUMS),考察了扩链剂1,4-丁二醇(BDO)的含量对微球表面形态和药物包封率的影响。用傅立叶变换红外光谱(FFIR)、扫描电子显微镜(SEM)以及激光粒度分析仪对微球的化学结构、表面形态、粒径及其分布进行了表征,并以溴百里酚兰为亲水性模型药物,初步研究了微球的药物释放行为。结果表明,合成的微球的平均粒径47um,粒径分布在10～90um之间;微球表面有孔,但随着BDO含量的增加,微球表面变得相对粗糙,孔数减少,孔径减小,直至孔消失;BDO含量的增加也使模型药物的包封率减小,释放速率变慢;药物释放初期出现程度不同的“暴释”现象,但随后近似于零级释放。     

Neutral Pd(II) and Ni(II) Acetylide Initiators for Polymerization of (Dimethylamino)ethyl Methacrylate

A series of air-stable, late transition, metal-based initiators with the structures ML₂(CCR)₂ (M=Pd and Ni; L=PPh₃ and Pn-Bu₃; R=Ph and CH₂OH) for the polymerization of (dimethylamino)ethyl methylate (DMAEMA) were developed. Transition metal, phosphine, alkynyl, as well as solvents exhibited significant influence on the polymerization. Among them, Pd(CCPh)₂(PPh₃)₂ (PPP) shows the highest activity in CHCl₃ for DMAEMA polymerization. The PDMAEMA obtained is a syndiotactic polymer with high number-average molecular weight (M_n) of 20.2 × 10⁴. A free radical polymerization mechanism with some ATRP characteristics was proposed for the present polymerization.     

烯烃聚合过程的分形演化及其生长模型

The surface morphology of Ti-Mg supported catalyst and the polyethylene particles are studied using scanning electron microscope(SEM) technology.The results show that either the catalyst‘s surface or polymer particle‘s surface is irregular and has fractal characteristics,which can be described by fractal parameter.The more interesting discovery is that the surface fractal dimension values of the polymer particles vary periodically with the polymerization time.We call this phenomenon fractal evolution,which can be divided into the “revolution“ stage and the “evolution“ stage,And then we present polymerization fractal growing model(PFGM),and successfully describe and /or predict the whole evolving process of the polyethylene particle morphology under the different slurry polymerization(including pre-polymerization) conditions without H2.     

无皂乳液聚合的进展

本文介绍了无皂乳液聚合的反应机理（包括成核机理和核增长机理）、反应动力学，着重介绍了影响无皂乳液稳定性的因素以及提高无皂胶乳稳定性和固含量的方法，包括引发剂碎片法、引入亲水性或表面活性单体性、调整聚合反应的分散介质法和选择适当的聚合工艺法。并概括了当今无皂乳液聚合的研究动态、应用和发展前景。     

Preparation and Performance Evaluation of Fatty Amine Polyoxyethylene Ether Diethyl Disulfonate for Enhanced Oil Recovery in High‐Temperature and High‐Salinity Reservoirs

To enhance oil recovery in high‐temperature and high‐salinity reservoirs, a novel fatty amine polyoxyethylene ether diethyl disulfonate (FPDD) surfactant with excellent interfacial properties was synthesized. The interfacial tension (IFT) and contact angle at high temperature and high salinity were systematically investigated using an interface tension meter and a contact angle meter. According to the experimental results, the IFT between crude oil and high‐salinity brine water could reach an ultra‐low value of 10^?3 mN m^?1 without the aid of extra alkali at 90°C after aging. The FPDD surfactant has strong wettability alternation ability that shifts wettability from oil‐wet to water‐wet. The FPDD surfactant with a high concentration also has good emulsion ability under high‐temperature and high‐salinity conditions. Through this research work, we expect to fill the lack of surfactants for high‐temperature and high‐salinity reservoirs and broaden its great potential application area in enhanced oil recovery.     

Recent Advances in Reactive Extrusion Processing of Biodegradable Polymer‐Based Compositions

This review reports on recent advances in the design of biodegradable polymers built from petroleum and renewable resources using reactive extrusion processing. Reactive extrusion represents a unique tool to manufacture biodegradable polymers upon different types of reactive modification in a cost‐effective way. Partially based on our ongoing research, ring‐opening polymerization of biodegradable polyesters will be approached as well as the chemical modification of biodegradable polymers, particularly natural polymers. The development of environmentally friendly polymer blends as well as (nano)composites from natural polymers, including natural fibers and nanoclays, through reactive extrusion, as an efficient way to improve the interfacial adhesion between these components, will be also discussed.

     

PET连续聚合工艺流程优化改造

采用将五釜流程改为四釜流程的方法,即以酯化预聚塔一个反应器取代五条工艺流程的第二酯化釜和第一预缩聚釜两个反应器,对PET聚合工艺流程优化,改造后的PET单线生产能力由160t/d提高到200 t/d,其单耗PTA由改造前的865 kg/t降至863 kg/t,EG由338 kg/t降至334 kg/t,降低了成本,提高了产品质量。     

阻聚剂对自由基聚合的活性化影响

研究了阻聚剂对自由基聚合活性化的影响,用1H NM R表征了聚合物的结构。发现在甲基丙烯酸甲酯(MM A)自由基聚合体系中加入少量的加成型阻聚剂2,4,6-三硝基苯酚(TNP)或1,4-苯醌(BQ)时,体系转化率降低,引发效率降低,呈现出一定的缓聚性质;同时得到的聚合物分子量变小,分子量分布变窄,具有一定的“活性”/可控的特征。链转移型阻聚剂如对羟基苯甲醚(4-M P)和对苯二酚(HQ)则不能起到类似的效果。     

PVC的升级换代产品--纳米PVC复合树脂

在杭州华纳化工有限公司开发的纳米CaCO3微乳液存在下采用原位聚合方法制备纳米PVC复合树脂,在云南盐化股份天塑分公司30m^3聚合釜上实现了产业化。该项目研究了纳米CaCO3团聚体的解离技术及原位聚合过程中的继续分散情况。透射电子显微镜(TEM)图像显示：纳米CaCO3在PVC基体内呈微胶束结构和微曝炸崩解结构,聚合过程崩解后的纳米CaCO3颗粒直径为5～10nm,呈良好的分散分布。在剪切速率为50rad/s的剪切流变实验中,纳米PVC比普通PVC切变黏度降低了一个数量级。在ThennoHaake上进行塑化实验,实验温度185℃、转速50r／min,纳米PVC的塑化时间为2.5min,普通PVC的塑化时间则需要6min。