The effect of initiators and oxidants on the morphology of poly [(±)‐2‐(sec‐butyl) aniline] a chiral bulky substituted polyaniline derivative

The nano and micro sphere synthesis of chiral bulky substituted polyaniline from monomer (±)‐2‐sec‐butylaniline in bulk and template‐free method (rapid mixing) was done successfully using ammonium peroxydisulfate (APS) and FeCl₃·6H₂O as oxidants. The effect of initiators such as p‐phenylendiamine and 1,4‐benzenediamine, temperature and concentration of monomer on morphology is demonstrated by scanning electron microscopy (SEM) images. The nano and micro sphere morphology was obtained using initiators. Smallest particles were achieved when 1,4‐benzenediamine was used as initiator in the presence of FeCl₃·6H₂O as oxidant. By increasing the concentration of monomer more uniform spheres were obtained. Characterization was made via FT‐IR, UV–Vis, ¹H and ¹³C‐NMR spectroscopy. Elemental analysis and electrical conductivity of products are also presented. All analysis data are in good agreement with nigraniline oxidation state of polyaniline. Copyright © 2015 John Wiley & Sons, Ltd.     

基于双锂法的炔基功能化热塑性弹性体的合成

苯乙烯-异戊二烯-苯乙烯三嵌段聚合物(SIS)是目前广泛使用的一种热塑性弹性体(TPE)材料, 建立高效、 精准、 普适的SIS功能化方法一直是提高TPE材料性能的关键. 首先, 利用双烯单体与单官能度引发剂的反应合成了双官能度的双锂引发剂; 然后采用双锂引发法, 以炔基功能化单体封端, 高效合成了α,ω-端炔基官能化SIS聚合物. 采用叔丁醇锂作为异戊二烯聚合段的调节剂, 叔丁醇钾作为苯乙烯聚合段的调节剂, 合成了低乙烯基结构含量(5.8%)、 窄分子量分布(<1.17)的SIS三嵌段聚合物; 再向SIS三嵌段聚合物中一步加入炔基官能化的1,1-二苯基乙烯(DPE)衍生物进行封端, 以高于90%的收率高效合成了α,ω-端炔基官能化SIS三嵌段模块聚合物, 借助炔基的高效点击反应, 实现了功能化及拓扑化TPE材料的制备.     

Preparation of multifunctional organolithium initiator in cyclohexane solutions

Multifunctional organolithium initiator was prepared in cyclohexane solvent.The process started with adding the cyclohexane solution of butadiene to naphthalene-lithium in batches to produce butadiene oligomer dilithium with 4-8 butadiene repeating units.In the first feeding,the maximum loading of cyclohexane and the minimum concentration of butadiene cyclohexane solution must be controlled under V_cyclohexane≤1.33V_THFand p≥40.6C_N.Then,SnCl₄ was added and eventually the multifunctional organolithium initiator containing Sn atom was synthesized through coupling reaction. Experiment results showed that adding the cyclohexane solution in batches was effective in overcoming some difficulties, such as insolubility of naphthalene-lithium in cyclohexane,low efficiency of naphthalene-lithium in initiating butadiene.In practice,benzene can be replaced by cyclohexane completely,which can not only reduce environmental pollution from benzene,but also overcome the difficulty of solvent recovery caused by similar boiling point between benzene and cyclohexane.Prepared with multifunctional organolithium containing Sn atom as initiator,the star-shaped solution polymerized styrene-butadiene rubber（star S-SBR）with better vulcanization performances,lower rolling resistance and higher wet-skid resistance was obtained.     

咪唑型阳离子聚丙烯酰胺P(AM/MAPD)的合成

以丙烯酰胺(AM)、自制的1-(2-甲基丙烯酰氧丙基)-3-癸基咪唑盐酸盐(MAPD-Cl)为原料,通过自由基共聚合,得到了咪唑型阳离子聚丙烯酰胺P(AM/MAPD)。 红外光谱表征结果证明其为目标产物。 采用单因素考察和响应面分析法相结合,对聚合工艺条件进行了优化。 优化聚合条件为：单体总质量分数25.41%,反应温度26 ℃,引发剂(NaHSO3-(NH4)2S2O4)质量分数0.03%,反应时间10 h。 所得聚合物的特性粘数可达到12.56 dL/g。     

KCD/MDEA/TA三元引发剂引发丙烯酸酯/液晶复合体系光聚合动力学

采用配有441.6 nm滤光片的光差示扫描量热仪研究了3,3'-羰基双(7-二乙胺香豆素)(KCD)/N-甲基二乙醇胺(MDEA)/2-(4-甲氧苯基)-4,6-双(三氯甲基)-1,3,5-三嗪(TA)三元引发剂引发丙烯酸酯/液晶复合体系光聚合动力学行为. 结果表明, 在KCD/MDEA复合引发剂中添加TA, 显著提高了丙烯酸酯/液晶复合体系的最大光聚合速率[R_p(max)]和单体转化率, 当TA质量分数为0.5%时, 体系的R_p(max)和单体转化率分别提高了100%和69%. 同时, 随着光照强度的增加, 该体系的R_p(max)和单体转化率呈增大的趋势, 当光强从1.5 mW/cm⁺²提高到35.2 mW/cm⁺²时, 其R_p(max)和最终单体转化率分别提高了2.5和2.8倍.     

大分子光引发剂的研究进展

综述了大分子光引发剂的研究现状和进展。简要叙述了大分子光引发剂的制备方法、引发机理。对小分子光引发剂和大分子光引发剂进行了对比,着重讨论了分子结构因素对引发性能的影响。     

Stable free radical polymerization of n-butyl acrylate in the presence of high-temperature initiators

Living radical polymerizations of acrylate are known to be difficult to achieve using TEMPO as a mediator. The stable free radical polymerization (SFRP) of acrylate tends to stop at low monomer conversion due to the accumulation of TEMPO in the medium as a result of unavoidable bimolecular termination. Rather than solving this problem by destroying the excess nitroxide using ascorbic acid or glyceraldehyde associated with pyridine as reported recently, high temperature initiators were used to slowly and continuously generate new radicals throughout the polymerization to consume the excess TEMPO molecules. Polymerizations of n-butyl acrylate initiated by the alkoxyamine unimer (1-benzoyloxy)-2-phenyl-2-(2′,2′,6′,6′-tetramethyl-1′-piperidinyloxy)ethane (BST) were performed between 130 °C and 134 °C in the presence of a series of high temperature peroxide and azo initiators. The best results in this study were obtained by the continuous addition of small amounts of di-tert-amyl peroxide throughout the polymerization. Under these conditions, the acrylate polymerizations fulfilled the criteria of a controlled polymerization process although the molecular weight distributions were slightly broad (M_w/M_n ∼ 1.5).     

Poly(2-oxazoline)-Containing Triblock Copolymers: Synthesis and Applications

This review focuses on poly(2-oxazoline) containing triblock copolymers and their applications. A detailed overview of the synthetic techniques is provided. Triblock copolymers solely based on poly(2-oxazoline)s can be synthesized by sequential monomer addition utilizing mono- as well as bifunctional initiators for the cationic ring-opening polymerization of 2-oxazolines. Crossover and coupling techniques enable access to triblock copolymers comprising, e.g., polyesters, poly(dimethylsiloxane)s, or polyacrylates in combination with poly(2-oxazoline) based segments. Besides systematic studies to develop structure property relationships, these polymers have been applied, e.g., in drug delivery, as (functionalized) vesicles, in segmented networks or as nanoreactors.     

一种新的富勒烯封端聚L-谷氨酸苄酯的合成

首次利用富勒烯谷氨酸苄酯的游离氨基引发谷氨酸苄酯-NCA开环聚合,得到了一种新的富勒烯封端的聚谷氨酸苄酯.利用核磁共振（1HNMR）、红外光谱、紫外可见光谱、基质辅助激光解吸电离飞行时间质谱（MALDI-TOF-MS）和热重分析等对产物进行了表征.     

聚能装药的多点环形起爆器性能测试及其应用

对聚能装药用多点环形起爆器的同步性能和环形起爆的聚能装药侵彻钢筋混凝土的侵彻威力进 行了研究。应用高速摄影技术和光纤探针技术测量了多点环形起爆器各点输出的同步性,结果表明环形起爆 器各点输出同步性好,时间差最大不超过0.1s;聚能装药对钢筋混凝土的侵彻威力实验结果表明,采用多点 环形起爆器的聚能装药对钢筋混凝土的侵彻威力比点起爆的有较大提高。