Synthesis and characterization of poly(ϵ‐caprolactone)‐b‐poly(ethylene glycol) block copolymers prepared by a salicylaldimine‐aluminum complex

A series of poly(?‐caprolactone)‐b‐poly(ethylene glycol) (PCL‐b‐PEG) block copolymers with different molecular weights were synthesized with a salicylaldimine‐aluminum complex in the presence of monomethoxy poly(ethylene glycol). The block copolymers were characterized by ¹H NMR, GPC, WAXD, and DSC. The ¹H NMR and GPC results verify the block structure and narrow molecular weight distribution of the block copolymers. WAXD and DSC results show that crystallization behavior of the block copolymers varies with the composition. When the PCL block is extremely short, only the PEG block is crystallizable. With further increase in the length of the PCL block, both blocks can crystallize. The PCL crystallizes prior to the PEG block and has a stronger suppression effect on crystallization of the PEG block, while the PEG block only exerts a relatively weak adverse effect on crystallization of the PCL block. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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。     

Correlation between crystallization kinetics and melt phase behavior of crystalline-amorphous block copolymer/homopolymer blends

We show that the phase behavior of the strongly segregated blend consisting of a crystalline-amorphous diblock copolymer (C-b-A) and an amorphous homopolymer (h-A), which depends on the degree of wetting of A blocks by h-A, can be probed by the crystallization kinetics of the C block. A lamellae-forming poly(ethylene oxide)-block-polybutadiene (PEO-b-PB) was blended with PB homopolymers (h-PB) of different molecular weights to yield the blends exhibiting ‘wet brush’, ‘partially dry brush’, and ‘dry brush’ phase behavior in the melt state. The crystallization rate of the PEO blocks upon subsequent cooling, as manifested by the freezing (crystallization) temperature (T_f), was highly sensitive to the morphology and spatial connectivity of the microdomains governed by the degree of wetting of PB blocks. As the weight fraction of h-PB reached 0.48, for instance, T_f experienced an abrupt rise as the system entered from the wet-brush to the dry-brush regime, because the crystallization in the PEO cylindrical domains in the former required very large undercooling due to a homogeneous nucleation-controlled mechanism while the process could occur at the normal undercooling in the latter since PEO domains retained lamellar identity with extended spatial connectivity. Our results demonstrate that as long as the C block is present as the minor constituent the melt phase behavior of C-b-A/h-A blends can also be probed using a simple cooling experiment operated under differential scanning calorimetry (DSC).     

聚氨酯-丙烯酸酯的前端自由基聚合

由甲苯二异氰酸酯（TDI）、聚醚二元醇（N210、220）、丙烯酸-2-羟丙酯（HPA）制得端烯基聚氨酯-丙烯酸酯大分子;然后通过前端自由基聚合;制备了聚氨酯-丙烯酸酯共聚物。研究了引发剂浓度对前端速度和温度分布的影响。FTIR显示前端聚合产物与间歇聚合产物有相似的红外吸收;TGA分析表明;前端聚合产物具有更好的热稳定性。     

三元乙丙橡胶－甲基丙烯酸甲酯溶胀机械接枝共聚研究

采用直接溶胀法，在叶片混合器中以不同条件制备了三元乙丙橡胶－甲基丙烯酸甲酯接枝共聚物。通过动态力学粘弹谱表征，该接枝共聚物具有稳定的双相体系相态。在适宜条件下，可以制得较好综合性能的接枝共聚物。     

双亲性氯化聚乙烯接枝共聚物的吸水膨胀性能

采用反相悬浮法制备了颗粒状接枝共聚物———氯化聚乙烯接枝丙烯酸(CPE-g-AA)、氯化聚乙烯接枝丙烯酰胺(CPE-g-AM)和氯化聚乙烯接枝混合单体丙烯酸、丙烯酰胺[CPE-g-(AA-AM)],并通过热压法制得接枝共聚物片材。考察了颗粒状接枝共聚物和接枝共聚物片材的吸水膨胀性能。结果表明,接枝共聚物的吸水性能与接枝单体的种类及其接枝率有关,相同接枝率的CPE-g-AA的吸水量比CPE-g-AM的大。当混和单体丙烯酸/丙烯酰胺的质量比为2/2时,所得接枝共聚物的抗盐性能最好。接枝共聚物片材可反复吸水膨胀,接枝率为62%的CPE-g-AA片材的二次吸水达到平衡时的吸水率和膨胀率分别为120%和41%。通过测定接枝共聚物的接触角表明,CPE-g-AA对水的润湿作用比CPE-g-AM明显。     

导静电乳液胶粘剂的研制

用多元乳液共聚法制备了用于粘贴导静电PVC地板胶粘剂,加入乙炔碳黑赋予乳液胶粘剂导静电性能。研究了影响胶接强度和初粘力的主要因素,确定m(VAc)/m(BA+VAc)较合适比为1∶3;研究了乳化剂和交联单体对乳液性能的影响,研究得出,适量加入AA和HMAM可以减少乳化剂的用量,提高乳液的性能;考查了影响导静电性能的因素,研究表明,导静电性能由乙炔碳黑决定,其加入量越大,导静电性能越好。得到的导静电乳液胶粘剂胶接强度达到0.51MPa以上,导静电可达到7.2×103Ω,两项指标均超过国家标准。     

阳离子改性苯乙烯-马来酸酐共聚物的制备与表征及应用

以2,3-环氧丙基三甲基氯化铵(ETA)为阳离子化试剂,对苯乙烯-马来酸酐共聚物(SMA)进行阳离子化改性,制备出一种阳离子性高分子分散剂(SMG)。通过红外光谱、含氮量、表面张力以及溶解性等的测定,研究了SMG的结构与性质;通过对颜料黄14的分散性考察,研究了SMG的分散性能。结果表明,SMA在阳离子化过程中,酸酐基团全部开环,部分形成酯键,阳离子化度达到7.5%左右;SMG的表面活性较低,但对颜料黄14的分散稳定性较好,在pH=7.0条件下,可以使颜料的Zeta电位提高至 35.4 mV。     

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。     

PP-R管材料熔融挤出过程MFR控制研究

分析了PP-R（无规共聚聚丙烯）管材料MFR（熔体流动速率）的变化对力学性能的影响，着重通过双螺杆挤出机研究了PP—R管材料熔融挤出过程中影响MFR变化的因素。结果表明，合适的加工工艺控制和优良的抗氧体系是保证PP-R管材料加工过程中MFR稳定的前提。