Moisture absorption by cyanate ester modified epoxy resin matrices. Part I. Effect of spiking parameters

The moisture absorption of cyanate ester modified epoxy resin matrices has been studied under thermal spiking conditions. Enhanced moisture absorption has been observed at spike-temperatures above 120 °C. The results of the desorption studies on both control specimens and the spiked specimens showed that some of the water molecules remained entrained in the polymer. It is postulated that this water could be associated with that which is hydrogen bonded or from the hydrolysis of isolated residual cyanate ester groups because the concentration of entrained water remains constant at spike-temperatures below 180 °C. Above 180 °C a thermally activated process, leading to chain scission as indicated by a reduced recoverability of the glass transition temperature (T_g) on drying.On isothermal resorption, the moisture concentration was found to be similar to that achieved through thermal spiking, showing that the entrained water at the lower spike-temperatures can also be achieved under mild conditions. The T_g is reversibly recovered to within 5 °C, which indicates a degree of relaxation rather than degradation. The moisture diffusion coefficient estimated from the resorption curves is lower than those estimated from the absorption and desorption curves. The isothermal resorption diffusion coefficient also decreased with increasing spike temperature. It is proposed that thermal spiking induced a relaxation of the network but as the spike-temperature approaches the transition region of the wet polymer, further hydrolytically induced relaxation events become feasible.     

阳离子交换树脂催化合成十三碳二元酸二乙酯

以强酸性阳离子交换树脂为催化剂,十三碳二元酸与乙醇为原料合成十三碳二元酸二乙酯,考察了影响反应的因素。结果表明:醇酸摩尔比为4∶1,催化剂用量为酸质量的2%,在3分子筛脱水的情况下反应7 h,酯化率达98.4%,并且催化剂可重复使用3次。     

Synthesis and characterization of poly(urethane‐ester)s based on calcium salt of mono(hydroxybutyl)phthalate

Calcium‐containing poly(urethane‐ester)s (PUEs) were prepared by reacting diisocyanate (HMDI or TDI) with a mixture of calcium salt of mono(hydroxybutyl)phthalate [Ca(HBP)₂] and hydroxyl‐terminated poly(1,4‐butylene glutarate) [HTPBG₁₀₀₀], using di‐n‐butyltin‐dilaurate as catalyst. About six calcium‐containing PUEs having different composition were synthesized by taking the mole ratio of Ca(HBP)₂:HTPBG₁₀₀₀:diisocyanate (HMDI or TDI) as 3:1:4, 2:2:4, and 1:3:4. Two blank PUEs were synthesized by the reaction of HTPBG₁₀₀₀ with diisocyanate (HMDI or TDI). The polymers were characterized by IR, ¹H NMR, Solid state ¹³C‐CP‐MAS NMR, TGA, DSC, XRD, solubility, and viscosity studies. The T_g value of PUEs increases with increase in the calcium content and decreases with increase in soft segment content. The viscosity of the calcium‐containing PUEs increases with increase in the soft segment content and decreases with increase in the calcium content. X‐ray diffraction patterns of the polymers show that the HMDI‐based polymers are partially crystalline and TDI‐based polymers are amorphous in nature. The dynamic mechanical analysis of the calcium‐containing PUEs based on HMDI shows that with increase in the calcium content of polymer, modulus (g′ and g″) increases at any given temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1720–1727, 2006     

Kinetics and mechanism of ?-caprolactone and l,l-lactide polymerization coinitiated with zinc octoate or aluminum acetylacetonate: The next proofs for the general alkoxide mechanism and synthetic applications

Following our previous papers on mechanism of cyclic esters' polymerization coinitiated by tin(II) octoate [tin(II) bis-(2-ethylhexanoate), (Sn(Oct)₂)] in the presence of either the low molar mass coinitiator (an alcohol, hydroxy acid, or H₂O) or a macromolecule fitted with a hydroxy end group (ROH), the present work deals with ?-caprolactone (CL) and l,l-lactide (LA) polymerizations coinitiated with zinc octoate (Zn(Oct)₂) or aluminum acetylacetonate (Al(Acac)₃). A series of kinetic measurements revealed that similarly as in the Sn(Oct)₂ coinitiated process, these polymerizations proceed by simple monomer insertion into the …Mt-OR bond, reversibly formed in the reaction -Mt-L + ROH ? …-Mt-OR + LH (where Mt = Sn, Zn or Al; L = Oct or Acac), taking place throughout the whole polymerization process. MtL_n itself does not play an active role in the polymerization. Applicability of the commercially available Zn(Oct)₂ or Al(Acac)₃ for the aliphatic polyester (10³ ≤ M_n ≤ 4 × 10⁵) synthesis is also discussed.     

环氧乙烯基酯树脂 (Ⅲ)环氧乙烯基酯树脂在有机溶剂中的稳定性

对环氧乙烯基酯树脂在有机溶剂中的稳定性作了理论上的探讨,并提供了3种环氧乙烯基酯树脂的溶解度参数实验数据。     

全水发泡硬质聚氨酯泡沫塑料技术研究进展

对CFC 11发泡替代技术中全水发泡技术路线进行了分析 ,指出水作为发泡剂存在的优点与不足。着重阐述了全水发泡中几种主要因素如水的用量、聚醚多元醇性质和结构以及异氰酸酯指数对泡沫性能的影响 ,并对国外近些年来全水发泡用聚醚多元醇研究现状进行了详细论述     

大型尿素造粒塔新型的腐蚀防护

详细阐述了尿素造粒塔的腐蚀机理，就其中的内外侧的防腐蚀形态进行了总结，并就此针对性的进行了防腐蚀材料的推荐及设计，尤其是玻璃鳞片胶泥。     

胶凝时间、pH值变化和水玻璃有机酯目硬砂性能的关系

将水玻璃混合液的胶凝时间、pH值变化与水玻璃有机酯自硬砂性能相比较表明：胶凝时间、pH值变化可间接反映自硬砂的性能。     

货车摇枕侧架脂硬化水玻璃自硬砂生产线的设计和应用

酯硬化水玻璃自硬砂生产线在铸造工业中已经有很长的历史，随着铸连工业的高速发展，其生产线的更新也比较频繁。本文从货车摇枕侧架酯硬化水玻璃自硬砂生产线的背景和设计应用出发，结合其设计的原则、方案、工艺参数的确定、高速造型图的构成、浇注工艺以及热法再生线的设置来简要的阐述了这套生产线的作用和应用价值。     

酯硬化水玻璃再生砂循环使用后的性能变化及应对策略

分析了酯硬化水玻璃砂多次再生使用后,其Na2O含量较大升高、溃散性显著下降、生产厚大铸型(芯)时硬透性变差并出现蠕变现象的原因,探讨了再生砂性能变化后的应对策略。认为:研究开发适于干法再生水玻璃砂的改性水玻璃、对再生砂实施表面处理、对旧砂进行高脱膜率的再生等,应是解决酯硬化水玻璃砂多次再生使用后溃散性恶化问题的主要措施;而控制再生砂的含水量、适当增加有机酯的加入量、CO2气体补充硬化等,是增加型(芯)硬透性和克服蠕变现象的主要方法。