利用薄膜去润湿行为研究线形和环形聚苯乙烯及共混薄膜的黏度

研究了线形聚苯乙烯(LPS)薄膜,环形聚苯乙烯(RPS)薄膜以及不同配比的共混薄膜在聚二甲基硅氧烷(PDMS)高分子刷上的去润湿动力学行为.研究发现,LPS薄膜的去润湿速度要快于RPS薄膜的去润湿速度,共混薄膜的去润湿速度介于LPS薄膜和RPS薄膜之间,且共混薄膜的去润湿速度随着RPS在共混薄膜中含量的增加而降低.利用水和乙二醇在薄膜表面的接触角计算得到LPS薄膜,RPS薄膜及共混薄膜的表面张力.结果发现,共混薄膜的表面张力均小于LPS薄膜和RPS薄膜的表面张力,且当RPS含量为70%时,共混薄膜的表面张力达到最小值.通过对薄膜在去润湿过程中的孔半径、去润湿速度、边宽以及后退接触角的研究,获得了LPS薄膜、RPS薄膜及共混薄膜的黏度.结果表明,LPS薄膜的黏度要低于RPS薄膜的黏度,实验得到的不同比例共混薄膜的黏度介于LPS薄膜和RPS薄膜的黏度之间,且其低于LPS和RPS的质量权重平均值.     

Analysis of structure transition and compatibility of PTT/PC blend without transesterification

Poly(trimethylene terephthalate)/polycarbonate (PTT/PC) blends were prepared by solvent mixing to avoid transesterification during high temperature blending. The influences of compositions on the thermal behavior, crystallization morphology and structure of the blends were studied. FTIR results indicated that there was no COO linking to two phenyl groups on each side chain and DSC results supported no transesterification reaction. DSC curves showed that T _c and T _mc increased to maximum range when PC contents were between 7 wt%-15 wt%, however, T _m decreased constantly with the increase of PC contents. It was observed from POM that PTT spherulitic morphology and crystallization kinetics were obviously influenced by the change of PC contents. Structural evolutions during cooling were investigated by SAXS which showed L _c of PTT remained a constant with different PC contents and also fixed during crystallization, nevertheless, it revealed a maximum value of L _nc for sample PTT₉₃. It was concluded that PC chains could be permeated into not only amorphous crystallite structure but also amorphous lamellae structure and 7 wt% PC content was supposed to be the “proper” penetration amount into PTT lamellae structure which led to a maximum capacity of amorphous lamellar layer. Fringedmicelle crystal model was adopted to illustrate semi-crystalline physical structures of the blend in two kinds of component aggregation states.     

Confined crystallization behaviors of cross-linked comb-like copolymers

Cross-linked PEG-based copolymers were obtained via synthesis of polyethylene glycol (PEG) and methoxy polyethylene glycol (MPEG) by the bridging and/or cross-linking agent of 2,4-tolylene diisocyanate (TDI) and/or hexamethylene-1,6-diisocyanate homopolymer (HDI trimer). The effects on the crystallization behaviors of the samples could be found with the changes in molecular weight of MC-PEG and molecular weight of SC-PEG in certain cross-linked density. It is revealed that the samples appear not to crystallize when the molecular weight of MC-PEG and SC-PEG are 1000 g/mol or less than that. The samples begin to crystallize when the molecular weight of either MC-PEG or SC-PEG reaches 2000 g/mol. The crystallinity of crystallized MC-PEG decreases with the increasing molecular weight of uncrystallized SC-PEG and the crystallinity of crystallized SC-PEG declines with the rise of molecular weight of uncrystallizable MC-PEG. The chains of SC-PEG (M _n = 2000 g/mol) can fold and align easilier than those of MC-PEG (M _n = 2000 g/mol), when the content of PEG is the same.     

聚己内酯在有机/无机杂化体系中的受限结晶行为

通过Sol Gel技术合成了聚己内酯 (PCL) /二氧化硅 (SiO2 )杂化材料 ,并对杂化样品进行了DSC和WAXD测试 .实验结果表明杂化样品中PCL的结晶度随二氧化硅含量增加而减小 ,当样品中二氧化硅含量达到 60 %时 ,PCL为非晶态 ;含有PCL结晶的杂化样品中PCL熔融温度基本相同 ,但是比纯PCL的熔融温度低 .杂化样品中结晶PCL的结晶结构和微晶尺寸和纯PCL的一致 .这说明杂化材料中PCL的结晶行为和结晶度受到了限制 ,含PCL结晶的样品中PCL的结晶结构和微晶尺寸并没有受到影响 .     

具有最高共溶温度高分子共混体系的压力诱导相容性热力学研究

根据具有最高共溶温度高分子共混体系的压力诱导相容实验结果, 结合Sanchez-Lacombe格子流体理论和文中给出的关于嵌段共聚物标度参数组合规则, 对高分子体系在压力作用下的混合焓、混合组合熵、混合空位熵和Gibbs混合自由能等热力学性质进行了研究. 研究结果表明Sanchez-Lacombe格子流体理论和新的关于嵌段共聚物标度参数组合规则可以用来描述压力作用下的具有最高共溶温度高分子共混体系的压力诱导相容性.     

剪切条件下等规聚丙烯的结晶行为

聚丙烯是工业中应用最广泛的聚合物。聚丙烯在静态结晶时生成球晶，剪切后会生成排核，最终长成柱晶或纤维晶；在强剪切条件下会生成串晶。聚丙烯是一种存在多种晶型的聚合物，α型晶是热动力学最稳定的晶型，在一般实验条件下很难得到其他晶型；在剪切条件下聚丙烯会生成β晶-热动力学亚稳晶型。剪切会显著影响聚丙烯的结晶动力学：增加球晶的生长速率，缩短结晶诱导时间，增加活化晶核密度。人们提出了许多模型来解释剪切加速结晶动力学的实验现象，但是都有不足之处。     

Confined lamella formation in crystalline-crystalline poly(ethylene oxide)-b-poly(ɛ-caprolactone) diblock copolymers

The real time and in situ investigation of the crystallization process and structure transitions of asymmetric crystalline-crystalline diblock copolymers from the melt was performed with synchrotron simultaneous SAXS/WAXS. The asymmetric poly(ethylene oxide)-b-poly(ε-caprolactone) diblock copolymers were chosen for the present study. It was shown that the short blocks crystallized later than the long blocks and final lamellar structure was formed in all of the asymmetric diblock copolymers. The final lamellar structure was confirmed by AFM observation. The SAXS data were analyzed with different methods for the early stage of the crystallization. The Guinier plots indicated that there were no isolated domains formed before the formation of lamellae in the asymmetric diblock copolymers during the crystallization process. Debye-Bueche plots implied the formation of correlated domains during crystallization.     

高分子结晶理论的新概念与新进展

回顾了传统的高分子结晶成核与生长模型,指出了该模型在应用中遇到的一些问题;同时总结了Strobl根据近年小角X射线散射结果提出的高分子结晶新机理-中介相机理.介绍了Strobl等构建的热动力学图解对熔体、中介相和片晶的转变过程,阐述了各相间的平衡转变温度、潜在的转变热以及表面自由能,说明了处于熔体和晶体之间的中介相的热动力学性质是理解高分子结晶过程的重要依据.