纤维素醋酸酯接枝己内酯的聚合研究

以冰醋酸为溶剂,浓硫酸为催化剂,将取代度为2 4的二醋酸纤维素水解为取代度为1 4的醋酸纤维素(CA)。以此醋酸纤维素为接枝骨架,ε 己内酯(ε CL)为接枝单体,在辛酸亚锡的引发下,合成了醋酸纤维素/聚己内酯接枝共聚物(CA g PCL)。研究了反应物纯度、原料配比、引发剂与单体摩尔比、反应时间、反应温度对单体转化率(C%)、接枝率(G%)、接枝效率(GE%)的影响。结果表明,当反应温度为140℃,单体ε 己内酯与醋酸纤维素的质量比为4∶1,引发剂辛酸亚锡与单体ε 己内酯的摩尔比为0 005,反应时间为16h,C%,GE%和G%分别为46 8%,65 2%和122 1%。     

核壳型乳液聚合研究进展

综述了近年来核/壳结构聚合物乳液的聚合工艺、性能及核/壳结构的表征方法进行,讨论了影响核/壳结构聚合物乳胶粒子形态的各种因素。     

Poly(p-tert-butoxycarbonyloxystyrene): a convenient precursor to p-hydroxystyrene resins

An efficient synthetic route to pure, high molecular weight poly(p-hydroxystyrene) is reported. The route involves synthesis of a new monomer, p-tert-butoxycarbonyloxystyrene, polymerization by radical initiation or by cationic initiation in liquid SO₂, followed by thermolysis or acidolysis of the tert-butoxycarbonyl protecting group. Porous, crosslinked resin beads containing the nucleophilic, phenol pendant group have been prepared in a similar fashion from the precursor terpolymer of p-tert-butoxycarbonyloxystyrene, styrene and divinylbenzene. The utility of this resin for solid-phase synthesis has been demonstrated.     

Aggregation behaviour of well defined amphiphilic diblock copolymers with poly(N-isopropylacrylamide) and hydrophobic blocks

Series of amphiphilic diblock copolymers with poly(N-isopropylacrylamide) as a hydrophilic block and a hydrophobic block consisting of either polystyrene or poly(tert-butyl methacrylate) were synthesised using RAFT polymerisations. Differential scanning calorimetry showed the chemically different blocks being phase separated in dry polymers. Light scattering and microcalorimetry studies were performed on aqueous solutions to investigate the phase behavior of the diblock copolymers. By carefully transferring the polymers from an organic solvent to water, either micellar particles or large aggregates were obtained depending on the relative lengths of the blocks. Large aggregates collapsed upon heating, whereas collapse occurred slowly within a broad temperature range in the case of micelle like structures. However, microcalorimetrically the collapse of the PNIPAM chains was observed to take place in all samples, suggesting that the shells of the micellar particles are crowded in a way which hinders the compression of the poly(N-isopropylacrylamide) chains.     

Syndiotactic Polystyrene/Organoclay Nanocomposites: Synthesis via In Situ Coordination‐Insertion Polymerization and Preliminary Characterization

Summary: Syndiotactic polystyrene (sPS)/organophilic clay nanocomposites were obtained by in situ coordination‐insertion polymerization of styrene. Two cationic surfactants (alkylammonium and alkylphosphonium) were used for the intercalation of montmorillonite (MMT). For each organically modified clay, three protocols were performed using an MAO‐activated hemi‐metallocene catalyst, in order to compare the influence of experimental conditions on the composite microstructure and on its thermal stability. The microstructures of nanocomposites were investigated by wide angle X‐ray scattering and DSC. Partially exfoliated or intercalated materials were obtained in all cases and a decrease of crystallinity is observed. Thermal properties were also studied by DSC and thermogravimetric analysis. The presence of clay does not have a strong influence on the sPS thermal transitions but the thermal decomposition process of the material was slowed down in the presence of few organoclay percents, particularly in the degradation beginning. The influence of these two organically modified clays on the thermal stability of the material is discussed.

Gel and suspension formed from the combination of cloisite with toluene (left) and styrene (right), respectively.     

工业聚合反应装置—Ⅶ.悬浮聚合反应器（下）

讨论了悬浮聚合反应器的放大问题及计算机控制技术，介绍了具有预分散器的悬浮聚合反应器和连续悬浮聚合反应器。     

Polymer reaction engineering: From reaction kinetics to polymer reactor control

Polymer reaction engineering is a relatively “young”, very broad, multidisciplinary, rapidly developing field. It is the combination of polymer science, chemistry and technology with process engineering principles. The outcome of this high degree of synergism has evolved over the last fifteen or so years towards an area that includes any or all of the following: polymerization and post-polymerization (chemical modification) reaction kinetics; mathematical modelling and process simulation; polymer reactor design and scale-up; sensor development and process monitoring; and polymer reactor optimization, state estimation and computer control. This article will attempt to give an overview of the results obtained in our laboratory over the last seven years from systematic studies of polymer reaction engineering and polymer production technology problems. These problems cover all aspects of polymer reaction engineering mentioned above. Going from fundamentals to practice, the basic premise of the article is that only by adopting a holistic approach can one devise effective strategies in order to achieve the final objective of more efficient polymer reactor design and control, and hence improved production systems of polymeric materials.     

高聚合度聚氯乙烯的加工性能

本文对高聚合度聚氯乙烯(H-PVC)的发展及其优异的物理机械性能作了简要介绍;着重分析了H-PVC的加工性能和表征方法,并讨论了分子特性和颗料特性及加工组成、加工条件对加工性能的影响,提出了改进H-PVC加工性能的方法。     

Resins containing amino and carboxylic acid groups. Synthesis,characterization, and metal ion retention properties

The crosslinked poly[3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonium hydroxide], P(MAPDSA), and poly[3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonium hydroxide‐co‐acrylic acid], P(MAPDSA‐co‐AA), were synthesized by radical polymerization. The resins were completely insoluble in water. Due to the lower metal ion retention of P(MAPDSA), the metal ions investigated under competitive and noncompetitive conditions for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), and Cr(III) ions by batch and column equilibrium procedures were carried out only for P(MAPDA‐co‐AA), particularly for Hg(II). The resin–Hg(II) ion equilibrium was achieved before 15 min. The resin showed a maximum retention capacity value for Hg(II) at pH 2 of 1.89 meq/g. The resin showed a high selectivity to Hg(II) ions. The recovery of the resin was investigated at 25°C with different concentrations of HNO₃ and HClO₄. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 525–530, 2005     

Interfacial polymerization of pyrrole and in situ synthesis of polypyrrole/silver nanocomposites

We present a new synthetic approach leading to the formation of polypyrrole architectures in submicron level and to silver/polypyrrole nanocomposites via an interfacial polymerization in a water/chloroform interface. The oxidizing agent was either Ag(I) or Fe(III). In the first case, silver nanoparticles resulted. The mean diameter of the polypyrrole structures is in the range of 200-300 nm according to the addition or not of various surfactants. The progress of the reaction was studied by UV-visible spectroscopy, which also revealed the formation of a polaron band during the growth of the oligomers. The crystal structure of the polymers was examined by X ray diffractometry and all samples appeared to be amorphous, while the samples were further characterized by thermogravimetric analysis and FT-IR spectroscopy.