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     

Principal component analysis of carbon-13 substituent-induced chemical shifts of some unsaturated compounds

Principal component analysis (PCA) is applied to 32 disubstituted unsaturated compounds (Y–CH₂–X): cyanides, oximes and propenes; bearing 12 -substituents: F, Cl, Br, I, OMe, OEt, SMe, SEt, NMe₂, NEt₂, Me, and Et. The experimental ¹³C chemical shifts for the -carbon and functional carbon atoms are correlated with theoretically derived molecular properties, i.e. partial charges, electronegativity, hardness, dipole moments and the nuclear repulsion energies. In the first PCA, the clustering of these three classes of organic compounds occurred mostly because of the chemical shifts and partial charges, and also of the dipole moments, hardness and electronegativity parameters as confirmed by loading graph. A strong grouping is observed in the second PCA, showing the chemical shift dependence on the type of heteroatom substituents. Therefore, sulfur, nitrogen, oxygen and neutral groups exhibit four types of C-13 SCS influences, indicating that the heteroatom (Y) properties play a significant role on the effects on chemical shifts. The -halogenated compounds represent a very heterogeneous group due to possible orbital interactions between the functional group and the substituent. The third PCA shows the grouping of F, Cl, Br and I derivatives, confirming the second PCA results that same halogen presents the same or very similar effects on the chemical shifts.     

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．     

聚酯聚醚嵌段共聚物与1,4-二咔唑环丁烷在激发态及基态的相互作用

<正> 聚酯聚醚嵌段共聚物具有十分良好的物理和机械性能,能加工成橡胶、纤维、塑料胶粘剂等,近年来也有作为医用高分子材料的报道。所以对聚酯聚醚嵌段共聚物的研究十分活跃。然而,有关其光物理性质的研究还很少见。本文报道了混合聚醚-聚酯嵌段共聚物(MPEE)与反式1,4-二咔唑环丁烷(1,4-DCC)在激发态和基态下的相互络合作用。结果表明,MPEE可以猝灭1,4-DCC的荧光,同时形成激基复合物。在分散     

Synthesis and characterization of segmented liquid crystal poly(azoxy polyester-co-polyoxypropylene)

In this study a series of a segmented copolyester, poly(4,4′-dioxy-2,2′-dimethyl-azoxybenzene dodecanedioyl) (PMABD)-co-polyoxypropylene 400 (POP), was prepared. The chain length of PMABD studied (n) was varied from 7.8-18.2, and that of POP was unchanged. The intrinsic viscosity of the segmented copolyesters was 1.04-1.30, and the number average molecular weight obtained was 2.53 × 10⁴?3.49 × 10⁴ g/mol. The mesophase texture and thermal properties of the segmented copolyesters were measured as functions of n. It was found that the insert of flexible POP between those liquid crystalline domains of PMABD did affect thermotropic properties of PMABD. As the n value was 9.0 and 7.8 (or 7.4 and 8.6% by weight POP) the texture appeared as cholesteric-like oily streaks. The effect could not be attained by simply copolymerizing a mesogenic moiety with a pair of spacers of different lengths. The fluidity and domain structure of the flexible dodecanedioyl-POP-dodcanedioyl segments are taken into account for the obtained results. © 1995 John Wiley & Sons, Inc.     

主链含硅聚芳酯的合成及气体透过性能的研究

以双［对－酰氯苯基］二甲基硅烷和酚酞、四溴酚酞以及双酚Ａ为原料，合成了三种主链含硅聚芳酯，并对聚合物相关的物理性质进行了表征，制成了均质透明的薄膜．采用低真空法测定这些聚合物对Ｈ２、Ｏ２、Ｎ２、ＣＯ２、ＣＨ４的气体透过速率，并计算出气体透过系数、扩散系数、溶解系数、分离系数．从气体透过性能与聚合物分子结构关系的角度，按照气体透过的溶解－扩散机制，对聚合物的气体透过性能进行了研究，而且着重讨论了聚合物的堆积密度对气体扩散系数的影响，以及聚合物主链中极性链段的百分含量对气体溶解系数和溶解选择性的影响。     

A novel hyperbranched polyester acrylate used for microfabrications

A novel hyperbranched polyester acrylate (HPEA) was synthesized based upon ethylenediamine tetraacetic acid as a “core” molecule, 5‐hydroxyisophthalic acid as an AB₂ monomer, and 2‐hydroxyethyl acrylate as an endcapping reagent. The obtained oligomer has an unsaturation concentration of 4.10 mmol_C?C g^?1 measured by nuclear magnetic resonance and a wide molecular weight distribution of 1.64 measured by gel permeation chromatography. The two‐photon absorption (TPA) photopolymerization of HPEA under the exposure of a Ti : sapphire femtosecond laser with a wavelength of 800 nm was investigated through laser exposure dose‐dependant spatial resolutions of its resins. The TPA photopolymerization thresholds at the range 1.6–4.3 × 10⁷ mJ cm^?2, and exposure dose windows at the range 3.4–4.3 for three formulations were determined. A spatial resolution of 0.85 μm was obtained through the TPA photopolymerization of the formulation containing 1 wt% photoinitiator and 0.3 wt% photoinhibitor. A diffraction grating and real three‐dimensional coupled gear wheel created by TPA photopolymerization were described to demonstrate the unique capability of HPEA in microfabrications. Copyright © 2004 John Wiley & Sons, Ltd.