Malononitrile-involved Michael addition polymerization: An efficient and facile route for cyano-rich polyesters with programmable thermal and mechanical properties

An efficient, atom-economic, oxygen-tolerant, and water-tolerant strategy has been established to synthesize cyano-rich polyesters. Four kinds of organic bases, 1,1,3,3-tetramethylguanidine (TMG), 4-dimethylaminopyridine, triethylamine, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were explored for accelerating Michael addition polymerization of malononitrile and 1,4-butandiol diacrylate. TMG can promote the polymerization efficiently under mild conditions to quantitatively afford polyester with high-molecular weight and moderate polydispersity. The comparison of the kinetic studies of TMG and TBD reveals that TMG shows better catalytic performance, while the catalysis of TBD brings about oligomers in spite of the higher efficiency at early age of the polymerization. Moreover, other diacrylate compounds could also be quantitatively polymerized to afford polyesters with high molecular weight. When dimethacrylate is chose as the monomer, the polymerization becomes sluggish. All the afforded polyesters display programmable thermal and mechanical properties that are closely related to their chemical structures.     

Effects of Moisture and Stresses on the Structure and Properties of Polyester Resin

The results of a complex study of structural changes in a cured Norpol 440 polyester resin under the action of damp environment and mechanical loading are presented. A considerable effect of absorbed moisture on the structure and some characteristics of the material is revealed by using thermophysical methods and X-ray diffractometry. The joint effect of moisture and mechanical stress is estimated by investigating the creep in stationary and nonstationary moisture conditions. The anisotropy of the material structure formed during creep is evaluated from the results of dilatometric measurements. It is found that the degree of anisotropy of the material after creep accompanied by moisture sorption is higher than that after creep in the conditions of moisture equilibrium with atmosphere. It is established that the aftercure and relaxation of the residual creep deformation come to an end at heating to 80-85°C. At a further rise in temperature and repeated heating, changes in the material structure are not observed.     

Synthesis of unsaturated polyester resins for large sized composites

A series of unsaturated polyesters based on phthalic anhydride (PHA), maleic anhydride (MA), ethylene glycol (EG), diethylene glycol (DG), triethylene glycol (TG), propylene glycol (PG), styrene (Sty) and acrylonitrile (AN) were prepared. The molecular weights of the prepared polyesters were determined by end-group analysis. The effect of the structure of the resin on its curing behavior has been investigated. On the basis of the experimental study, the following were concluded: (1) The maximum curing temperature (T_max) is related to the molecular weight of the glycol incorporated in these castings. In this context the T_max was found to decrease with increasing the molecular weight. Meanwhile the time to peak temperature t_max was increasing. (2) The higher the percentage of AN in the crosslinking monomer system, the slower a resin cures. (3) The values of T_max were found to be influenced to a large extent by the percentage of AN.     

The effect of crystallinity on chain mobility and free volume in the amorphous regions of a miscible polycarbonate/polyester blend

Homopolymers and blends of polycarbonate/ThermX have been investigated by differential scanning calorimetry, dynamic mechanical analysis, density measurements, and positron annihilation lifetime spectroscopy. The study focuses on the chain mobility and free volume in the amorphous miscible regions of the blends and how this mobility and free volume are affected by increasing crystallinity. It is proposed that judicious annealing, which results in increasing crystallinity (while avoiding ageing or transesterification), induces a constraint on the amorphous region leading to an increase in T_g and coalescence of free volume sites. © 1994 John Wiley & Sons, Inc.     

INFLUENCE OF COMPOSITIONAL HETEROGENEITY ON MORPHOLOGY AND PROPERTIES OF SEGMENTED COPOLYMERS

Polyethylene terephthalate(PET)/polycaprolactone(PCL) segmented copolymers with different hard segment contents and a blend of two of them were studied by using DSC, WAXS, TEM and IR techniques and dynamic mechanical, stress-strain and isothermal crystallization measurements. Emphasis was laid on the studies of influence of compositional heterogeneity on the morphology and properties of these segmented copolymers. It was found that the solution cast specimens of the more heterogeneous sample exhibit better segregation of segments, high crystallinity and melting temperature. They have higher thermal stability of mechanical properties at small deformations. However, they are less stable against large deformations and may become softer than the more homogeneous ones.     

水溶性聚酯的结构和性能

由对苯二甲酸二甲酯、间苯二甲酸、间苯二甲酸二甲酯５－磺酸钠与乙二醇等共缩聚合成的ＰＥＴ型水溶性聚酯（ＷＳＰ）是一种新型的水溶性聚合物，在化纤、纺织、涂料、粘合剂、电子、油墨等领域有着广泛的应用前景．化纤领域超细纤维新材料的研究、开发和生产，迫切需要一...     

Mass spectrometric analysis of low molecular mass polyesters by laser desorption/ionization on porous silicon

A low molecular mass polyester was analyzed by desorption/ionization on porous silicon (DIOS) mass spectrometry. The results were compared with those of matrix-assisted laser desorption ionization (MALDI) mass spectrometry using matrixes of alpha-cyano-4-hydroxycinnamic acid (CHCA) and 10,15,20-tetrakis(pentafluorophenyl)porphyrin (F20TPP). The CHCA matrix was not suitable for characterization of low molecular mass components of the polyester because the matrix-related ions interfered with the component ions. On the other hand, the F20TPP matrix showed no interference because no matrix-related ions appeared below m/z 822. However, the solvent selection for determining optimal conditions of sample preparation was limited, because F20TPP does not dissolve readily in any of the available organic solvents. In the DIOS spectra, the polymer ions were observed at high sensitivity without a contaminating ion. No matrix is needed for DIOS spectra of low molecular mass polyesters, facilitating sample preparation and selectivity of a precursor ion in post-source decay measurements.     

聚十二烷二元酸酯及其共聚酯的合成

通过直接熔融缩聚法合成了一系列聚十二烷二元酸酯，用GPC、^1H—NMR、FTIR对产物进行了表征，并讨论了预聚酯合成时催化剂浓度和种类、预聚反应温度、预聚初始醇酸摩尔比对聚合反应的影响。结果表明，在所选的三个催化剂体系中，氮化亚锡二水合物与对甲苯磺酸复合催化剂的催化效果最好；最佳反应条件：n对甲苯横酯／n二元酸=0．0021～0．0032，反应温度为160～180℃，醇酸摩尔比范围为1．05—1.10。     

3，19－二羟基－1－硫杂－5，8，11，14，17－五氧杂环二十烷的醚化与缩聚反应

３，１９－二羟基－１－硫杂－５，８，１１，１４，１７－五氧杂环二十烷（简称二羟基硫杂２０－冠－６）在一缩二乙二醇二甲醚和氢化钠存在下可与卤代烷顺利地进行醚化反应，得到双己氧基、双十二烷氧基、双十六烷氧基、双节氧基和双烯丙氧基硫杂２０－冠－６，同时也得到了单己氧基、单十二烷氧基、单十六烷氧基和单辛氧基单羟基疏杂２０－冠－６副产物。二羟基硫杂冠醚可顺利地与丁二酰氯缩聚，得到主链含硫杂冠醚基团的聚酯     

热致型液晶聚合物的等温和非等温晶化动力学

利用等温和非等温方法详细研究了芳香族聚酯──热致型聚合物对，对’－联苯二甲酸二辛酯的结晶相和液晶相形成机理，并计算了相变过程中的表面自由能与温度系数，研究结果表明：从介晶相开始的结晶过程是二维异相成核、三维线性增长的，而从各向同性液相开始的液晶相形成过程则是二维异相成核二维线性增长的．对两个晶化过程的表面自由能的研究表明，该聚合物液晶相形成过程的相转变表面自由能比结晶过程小得多，预示了它将具有更大的晶化速率．研究还发现，该聚合物的液晶相形成过程具有比结晶过程大得多的温度敏感性．