基团转移聚合反应中的有机硅引发剂

评述了近年来基团转移聚合反应中几种常用的有机硅引发剂(如单官能团引发剂、双官能团引发剂、其它乙烯酮硅烷缩醛引发剂、大分子引发剂及其它含硅引发剂)的研究进展,并展望了基团转移聚合反应在高分子合成中的重要作用及应用前景。     

石蜡聚苯乙烯微球的制备

通过悬浮聚合技术合成了石蜡聚苯乙烯微球，研究了合成过程中引发剂浓度及交联剂用量对微球粒径及其分布的影响。     

改性淀粉与丙烯酸接枝共聚物的合成及应用性能

研究经过热处理的改性淀粉与丙烯酸的接枝共聚反应。接枝共聚产物在 790cm-1、85 0cm-1(物理改性淀粉的特征吸收峰 )和 172 0cm-1(聚丙烯酸的特征吸收峰 )处的红外光谱验证了接枝共聚反应的发生。探讨了引发剂过硫酸铵浓度、丙烯酸浓度、反应温度和反应时间等因素对接枝率和接枝效率的影响。当 ρ(淀粉 ) =70 g/L、t =6 0℃、反应时间为 3h、c〔(NH4) 2 S2 O8〕 =3 0× 10 -3 mol/L、c(丙烯酸 ) =0 4 2mol/L时 ,合成胶粘剂的初粘力为 10 0 % ,吸水率为 15 0 14 % ,吸油率为 2 0 6 % ,其压制的纸板冲击强度为 3 2 5kN/m ,拉伸强度为 3 75MPa ,与纯淀粉粘接剂相比较 ,所压制纸板的应用性能得到较大的改善。     

在位分散聚合制备聚甲基丙烯酸甲酯/二氧化硅复合材料研究

采用在位分散聚合方法制备聚甲基丙烯酸甲酯 /二氧化硅微米级复合材料 ,讨论了不同表面性质的二氧化硅对材料拉伸性能、热性能、耐溶剂性能的影响 ,并用SEM、TG等手段研究了材料性能。结果表明 :由WD -70硅烷偶联剂处理过的二氧化硅微粒子填充的材料的各方面性能较好 ,由WD -10硅烷偶联剂处理过的二氧化硅填充的材料的拉伸性能次之 ,未经表面处理二氧化硅填充的材料的拉伸性能最差 ,后两者的热性能以及耐溶剂性能无明显差异     

氯丁橡胶在向高性能发展

市场需求特别是汽车工业的需求对氮丁橡胶(CR)的性能提出了更高的要求。固外CR制造商通过改进聚合工艺,已开发出在耐热性、耐寒性及抗疲劳性方面有突出改进的新品级、新牌号;传统的黄原二硫化物衍生物调节型CR的性能得到了全面提高,出现了CR同特种橡胶结合的新动向;粘接型CR的性能更加完善。羧基化CR的缺点得到克服,一种便于使用的接枝型CR已经问世。国内CR生产厂应重视科技投入,加紧研究、开发高性能CR,特别要突破传统的聚合工艺,开发分子链线形程度高的CR。     

高固含量的苯乙烯/丙烯酸丁酯/丙烯酸共聚物乳液的制备

利用预乳化半连续乳液聚合方法,合成了固含量高达65%的苯乙烯/丙烯酸丁酯/丙烯酸(St/BA/AA)聚合物乳液,并系统研究了固含量、单体配比、乳化剂含量、引发剂浓度、聚合反应温度及功能单体浓度对聚合物乳液主要性能的影响,利用透射电子显微镜对乳胶粒子的微观形态进行了表征。     

原子转移自由基聚合法制备聚乳酸三嵌段共聚物的研究

以自制的双端羟基聚乳酸与α-溴代丙酰溴反应而制得的含溴端基的聚乳酸为大分子引发剂,溴化亚铜/2,2′-联吡啶为催化体系,研究了N-乙烯基吡咯烷酮的原子转移自由基聚合行为,制得了具有两亲性聚乳酸嵌段共聚物。随单体/引发剂摩尔比的增大、聚合温度的升高,共聚物溶液的特性黏度增大,共聚物薄膜的吸水率增加;共聚物在不同降解介质中的降解规律相似,均随降解时间的延长,共聚物薄膜的失重增加,且在不同介质中呈现的降解速率表现为碱液>酸液>水>缓冲液。对聚合物进行了结构表征。     

活性自由基乳液聚合的研究进展

活性自由基乳液聚合是一个非常新的研究领域。介绍了目前活性自由基乳液聚合领域的3种常用的方法及应用这些方法进行乳液聚合的研究进展,包括:原子转移自由基聚合(ATRP),氮氧调节自由基聚合(NMP)和可逆加成-断裂链转移自由基聚合(RAFT)。     

Characterization of ramie yarn treated with sodium hydroxide and crosslinked by 1,2,3,4‐butanetetracarboxylic acid

Ramie yarns were treated with various concentrations of NaOH at room temperature and subsequently crosslinked with 1,2,3,4‐butanetetracarboxylic acid (BTCA). The microstructure and tensile properties of the treated yarns were characterized. X‐ray diffraction (XRD) and FTIR were used to study the crystalline structure of the resultant ramie yarns. The results showed that the maximum change in the structure of the alkali‐modified ramie took place at 16% NaOH, which would completely transform cellulose I to cellulose II. At the same time, the crystallinity index and fiber orientation decreased to the minimum value while the absorption properties were enhanced. The average degree of polymerization (DP ) of the treated ramie yarns slightly decreased after NaOH treatment. Tensile properties including tenacity, breaking elongation, and modulus of the treated yarns were also investigated. Scanning electron microscopy (SEM) was used to investigate the breakage of the treated yarns. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1857–1864, 2004     

Reaction kinetics modeling and thermal properties of epoxy–amines as measured by modulated‐temperature DSC. II. Network‐forming DGEBA + MDA

Reaction‐induced vitrification takes place in the network‐forming epoxy–amine system diglycidyl ether of bisphenol A (DGEBA) + methylenedianiline (MDA) when the glass‐transition temperature (T_g) rises above the cure temperature (T_cure). This chemorheological transition results in diffusion‐controlled reaction and can be followed simultaneously with the reaction rate in modulated‐temperature DSC (MTDSC). To predict the effect of T_cure and the NH/epoxy molar mixing ratio (r) on the reaction rate in chemically controlled conditions, a mechanistic approach was used based on the nonreversing heat flow and heat capacity MTDSC signals, in which the reaction steps of primary (E_1OH = 44 kJ mol^?1) and secondary amine (E_2OH = 48 kJ mol^?1) with the epoxy–hydroxyl complex predominating. The diffusion factor DF as defined by the Rabinowitch approach expresses whether the chemical reaction rate or the diffusion rate determines the overall reaction rate. A model based on the free volume theory together with an Arrhenius temperature dependency was used to calculate the diffusion rate constant in DF as a function of conversion (x) and T_cure. The relation between x, r, and T_g, needed in this model, can be predicted with the Couchman equation. An experimental approximation for DF is the mobility factor DF* obtained from the heat capacity signal at a modulation frequency of 1/60 Hz, normalized for the effect of the reaction heat capacity in the liquid state and the change in C_p in the glassy region with x and T_cure. In this way, an optimized set of diffusion parameters was obtained that, together with the optimized kinetic parameters set, can predict the reaction rate for different cure schedules and for stoichiometric and off‐stoichiometric mixtures. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2814–2833, 2004