从溶胀平衡研究玻璃态高聚物的凝聚缠结网络

在13~15℃室温条件下对聚苯乙烯(PS)颗粒在二氧六环/水混合溶剂中的溶胀情况进行目视观察,可以看到,当减小混合溶剂二氧六环/水中的水含量时,PS颗粒从玻璃态到溶胀的玻璃态、溶胀的高弹态、流体态的转变,与PS颗粒升温时从玻璃态到高弹态、流体态的转变相对应.选定混合溶剂二氧六环/水(水6·8wt%)对一个单分散PS试样(Mw=1·68×105)在30℃进行分相平衡和溶胀平衡的测定.分相平衡是先将PS/二氧六环/水(混合溶剂水含量6·8wt%)体系加热到130℃使PS溶解成一均相溶液,然后在冷却过程中分相,在30℃达分相平衡(30天)时,浓相高分子体积浓度p″=0·304,稀相几乎为纯溶剂.从Flory-Huggins相平衡理论得出此体系的高分子-溶剂相互作用参数χ=0·63.本工作使用的单分散PS试样在选定的混合溶剂,即二氧六环/水(水6·8wt%)中,30℃时不能溶解只能溶胀,单分散PS颗粒淬冷试样(密度ρp=1·0451g/mL)到达溶胀平衡(80天)时浓相高分子体积浓度p″=0·308.而此淬冷试样经在80℃热处理100h后的老化试样(ρp=1·0470g/mL)达溶胀平衡(70天)时p″=0·312.从溶胀过程中浓相体积变化曲线可知试样经在80℃热处理过程中凝聚网络趋向于更均一,更接近热处理温度下的平衡态,试样密度增大,网络产生了新的链间凝聚,物理交联密度增大(凝聚点间分子量减小).从溶胀平衡理论并取χ=0·63(分相平衡)可得到淬冷试样的物理交联点间分子量Mc=11·6×104,老化试样的物理交联点间分子量Mc=6·9×104.实验结果说明溶胀过程及溶胀平衡的测定可以反映玻璃态高聚物中的凝聚网络结构的细节,而且非常敏感.     

Aspects of molecular design of conducting polymers

A review discussion of the facts and factors to be considered in the molecular design of conducting polymers is presented. Topics discussed are: molecular properties and solid state properties; towards high conductivity— conjugation length and chain orientation; counter ions and ion exchange; materials design—solubilization, processability and molecular composites.     

A novel memcapacitor and its application in a chaotic circuit

Nonlinear Dynamics - In this paper, a novel memcapacitor is designed by the SBT ( $$\hbox {Sr}_{0.95}\hbox {Ba}_{0.05}\hbox {TiO}_{{3}}$$ ) memristor and two capacitors. A fifth-order memcapacitor...     

The state of high global chain orientation but nearly random segmental orientation of amorphous polymers

In the rubbery state of amorphous polymers under uni-axial drawing the global chain orientation will relax in orders of magnitude slower than the relaxation of local segmental orientation. When this state of hot drawn sample is frozen at temperatures lower than its glass transition, T_g, an amorphous state with high global chain orientation but nearly random segmental orientation (GOLR) could result. Experimentally the GOLR state of amorphous polymers is easily realized by uni-axial drawing the polymer at temperatures 20–30°C above its T_g. The characteristic features of a GOLR state are i) large recovery of the elastic deformation of global chain on being heated to temperatures above T_g, ii) very small birefringence and IR dichroism, iii) nearly isotropic sonic and ultrasonic velocity of propagation, iv) nearly isotropic WAXD pattern, while it shows v) pronounced anisotropy in stress-strain behavior for large deformations and vi) appreciable anisotropy of thermal conductivity and of microwave dielectric properties. Concrete examples with detailed experimental results will be reviewed.     

ON THE ORIGIN OF STRESS PEAK IN UNI-AXIAL STRETCHING OF AMORPHOUS POLYMERS

Rubber of high molar mass, like cis-polybutadiene, shows a stress peak on theenineering stress-strain curve during stretching at room temperature. In this work cis-polybutadiene samples were swollen in a poor solvent, CHCl_3/EtOH (1/1 v/v), for differenttimes. It was found that both the initial modulus and the stress peak on stretching de-creased in magnitude with increasing swelling time and the peak disappeared entirely after1 hour of swelling. On further swelling the initial modulus increased somewhat and a smallstress peak re-appeared after swelling for 2 h. The disappearance of the stress peak afterswelling is interpreted as the result of disruption of cohesional entanglements present in theinitial rubber sample. The re-appearance of a small stress peak and the increase of modu-lus on further swelling are interpreted as being of the same nature as the phenomenon ofanti-plasticization. It is the result of forming some new cohesional entanglements of largerbinding energies through longer range chain segmental motions excited after the disruptionof the previously existing cohesional entanglements in the rubber. Thus an understand-ing of the stress peak on stretching a high molar mass rubber and the phenomenon ofanti-plasticization on molecular level has been put forward.     

高分子液晶向列相的向错结构

高分子液晶态向错结构在正交偏振片下呈现出具有不同数目黑刷子的纹影织构，是由于分子指向矢取向排列上的不连续性所引起的一种光学效应。近年来，高分子液晶态向错结构的研究已取得了较大进展，发展和应用片晶装饰、条带织构装饰和表面裂纹装饰等技术可以在电镜和偏光显微镜下直接观察各种向错结构。本文简要介绍高分子液晶态向列相的向错和反转壁结构的几何学、高强度向错以及近年在实验上观察各类型向错形态的研究进展。     

以MCM-22为原料合成高水热稳定性的介孔材料

以合成的微孔分子筛MCM-22为原料,将其与表面活性剂及氢氧化钠一起回流溶解,再调节溶液的pH值至7～9, 使MCM-22转化为高水热稳定性的介孔材料. 所得介孔材料具有蠕虫状的均匀孔道,骨架中不含有MCM-22的微观结构单元. 该介孔材料至少含有18%的表面活性剂,经823 K焙烧脱除表面活性剂后,其孔径为2 2 nm, 比表面积为 1 038 m2/g, 孔容为0 97 cm3/g. 焙烧后的介孔材料具有非常高的水热稳定性,经沸水回流100 h后其比表面积为896 m2/g, 孔容为0 90 cm3/g, 孔径为2 1 nm, 即使经过300 h的回流,该材料仍能保持698 m2/g的比表面积和0 90 cm3/g的孔容. 固体 29Si MAS NMR结果表明,该介孔材料的高水热稳定性与其高表面缩合度有关.     

STUDIES ON POLY(ETHYLENE TEREPHTHA LATE)-POLY(TETRAMETHYLENE ETHER) MULTIBLOCK COPOLYMER.Ⅰ.COMPOSITIONAL HOMOGENEITY

The compositional homogeneity of a poly (ethylene terephthalate)-poly (tetramethylene ether) multiblock copolymer sample with low content of hard segment was examined by GPC, TLC, and solubility method. The copolymer sample was found to have a uniform composition as a function of elution volume over the major portion of sample from GPC method. However within one elution fraction, the copolymer chains, although having the same hydrodynamic volume, may have some difference in composition. Two fractions with different composition were obtained by precipitation in ethanol. Some low molar mass copolymers were also separated by a TLC technique from the copolymer sample.     

STUDIES ON POLY(ETHYLENE TEREPHTHALATE)-POLY(TETRAMETHYLENE ETHER) MULTIBLOCK COPOLYMER.Ⅱ.THE MOLAR SEGMENT MASS AND MOLAR MASS

The molar segment mass, weight-average molar mass, and molar mass distribution of a poly-(ethylene terephthalate)-poly (tetramethylene ether) multiblock copolymer sample were determined by the methods of proton nuclear magnetic resonance, low angle laser light scattering, and gel permeation chromatography.