乙烯、丙烯中微量水含量的分析

采用便携式微量水分析仪和库仑法微量水分析仪测定了乙烯、丙烯试样中的微量水含量,对试样的传输系统、进样量的控制、液体试样的气化和水标准气体的制备方法进行了改进,优化了测试条件。以低吸附惰性管线和小死体积单进单出的不锈钢减压器为试样传输系统,缩短了测试时间。采用液态烃闪蒸气化取样进样器气化液体试样并准确控制试样的进样量,可避免液体试样渐次气化对水含量测定结果的影响及对采样钢瓶大小的限制。采用渗透管发生器制备水标准气体,可验证分析结果的准确度。采用库仑法微量水分析仪测定水含量时,试样流量选择600 m L/min较适宜,开封保存15 d之内的卡尔·费休试剂对测定结果无影响。采用便携式微量水分析仪测定水含量时,选择试样流量在400~800 m L/min之间较适宜。两种仪器的测量结果相近,稳定性好,准确度高,回收率在102%~107%之间,相对偏差小于10%。     

The Interplay of Modulus,Strength, and Ductility in Adhesive Design Using Biomimetic Polymer Chemistry

High‐performance adhesives require mechanical properties tuned to demands of the surroundings. A mismatch in stiffness between substrate and adhesive leads to stress concentrations and fracture when the bonding is subjected to mechanical load. Balancing material strength versus ductility, as well as considering the relationship between adhesive modulus and substrate modulus, creates stronger joints. However, a detailed understanding of how these properties interplay is lacking. Here, a biomimetic terpolymer is altered systematically to identify regions of optimal bonding. Mechanical properties of these terpolymers are tailored by controlling the amount of a methyl methacrylate stiff monomer versus a similar monomer containing flexible poly(ethylene glycol) chains. Dopamine methacrylamide, the cross‐linking monomer, is a catechol moiety analogous to 3,4‐dihydroxyphenylalanine, a key component in the adhesive proteins of marine mussels. Bulk adhesion of this family of terpolymers is tested on metal and plastic substrates. Incorporating higher amounts of poly(ethylene glycol) into the terpolymer introduces flexibility and ductility. By taking a systematic approach to polymer design, the region in which material strength and ductility are balanced in relation to the substrate modulus is found, thereby yielding the most robust joints.     

Performance and Commercial Application of the Promoter LCC-A for Maximization of Propylene Yield

1 Introduction Propylene as an important feedstock for organic chemicals is mainly originated from steam cracking and catalytic cracking processes. During the FCC process the propylene content varies with the FCC catalyst and process technology adopted, resulting in significant difference in propylene concentration in the cracked product——LPG. The conventional FCC pro- cess generally gives a propylene yield of around 4%, while the FCC process with maximization of propylene yield can in…     

外源乙烯对黄瓜幼苗根系生长及内源多胺含量的影响

精确控制营养液溶氧浓度和外源乙烯浓度,研究了黄瓜幼苗根系在低氧水培时的生长情况以及PAs含量的变化。结果表明,外源乙烯对根际低氧逆境下黄瓜幼苗根系的生长有抑制作用,虽然根径增粗,含水量增加,但根系的总根数、总表面积、总体积、干重和鲜重都有所减少,随着乙烯浓度的增加,抑制作用增强;外源乙烯对根际低氧逆境下黄瓜幼苗根系PAs含量有着明显的拮抗作用,外源乙烯使根际低氧逆境下黄瓜幼苗根系的伤害症状加重。     

Segmented polymer networks containing amino‐dendrimers

Polymer networks in which poly(propylene imine) dendrimers (Astramol?) are connected to each other by linear polytetrahydrofuran (polyTHF) segments, were prepared by two methods. The first method was a one‐step procedure in which bifunctionally living polyTHF, obtained by initiation of the THF polymerization with trifluoromethane sulfonic anhydride (triflic anhydride), was reacted with an amino‐dendrimer. This reaction was very fast but did not allow formation of the end products. The second method was a two‐step procedure. In a first step, living polyTHF, prepared with acryloyloxybutyl triflate as initiator, was grafted on an amino‐dendrimer, to form a star‐like, acrylate‐terminated polyTHF multi‐macromonomer with the dendrimer as core. In a second step, networks were obtained by Michael addition between the acrylate end‐groups and unreacted amino‐groups of the dendrimer. This cross‐linking reaction occurred spontaneously upon heating of the solution of the multi‐macromonomer with gelation times varying from a few minutes to a few hours, depending on the temperature and the composition of the prepolymers. With this method it was possible to prepare networks in the form of coatings or films. © 2003 Society of Chemical Industry     

Dynamical considerations of network properties

Elasticity is discussed as an aspect of viscoelasticity, which is described by the tube model. The effects of both crosslinks and entanglements contribute to this model and a discussion of how these effects can be quantified is given. At high enough concentration, entanglements ensure the existence of elastic effects even without crosslinks, and a theory is presented on how this dynamical phase change comes about.     

Network topology and the theory of rubber elasticity

The earliest investigations on rubber elasticity, commencing in the 19th century, were necessarily limited to phenomenological interpretations. The realisation that polymers consist of very long molecular chains. commencing c. 1930, gave impetus to the molecular theory of rubber elasticity (1932-). according to which the high deformability of an elastomer, and the elastic force generated by deformation, stem from the configurations accessible to long molecular chains. Theories of rubber elasticity put forward from 1934-1946 relied on the assumption that the junctions of the rubber network undergo displacements that are affine in macroscopic strain. The theory of James and Guth (1947) dispensed with this premise, and demonstrated instead that the mean positions of the junctions of a ‘phantom’ network consisting of Gaussian chains devoid of material properties are affine in the strain. The vital significance of the distinction between the actual distribution of chain vectors in a network and their distribution if the junctions would be fixed at their mean positions went unnoticed for nearly 30 years. Experimental investigations, commencing with the incisive work of Gee in 1946. revealed large departures from the relationship of stress to strain predicted by the theories cited. This discrepancy prompted extensive studies, theoretical and experimental, during succeeding years. Inquiry into the fundamentals of polymer networks, formed for example by interlinking very long polymer molecules, exposed the need to take account of network imperfections, typically consisting of chains attached at only one end to a network junction. Various means were advocated to make corrections for these imperfections. The cycle rank ζ of the network has been shown (1976) to be the fundamental measure of its connectivity, regardless of the junction functionality and pattern of imperfections. Often overlooked is the copious interpenetration of the chains comprising typical elastomeric networks. Theories that attempt to represent such networks on a lattice are incompatible with this universal feature. Moreover, the dense interpenetration of chains may limit the ability of junctions in real networks to accommodate the fluctuations envisaged in the theory of phantom networks. It was suggested in 1975 that departures from the form predicted for the elastic equation of state are due to constraints on the fluctuations of junctions whose effect diminishes with deformation and with dilation. Formulation of a self-consistent theory based on this suggestion required recognition of the non-affine connection between the chain vector distribution function and the macroscopic strain in a real network, which may partake of characteristics of a phantom network in some degree. Implementation of the idea was achieved through postulation of domains of constraint affecting the equilibrium distribution of fluctuations of network junctions from their mean positions. This led in due course to a theory that accounts for the relationship of stress to strain virtually throughout the ranges of strain accessible to measurement. The theory establishes connections between structure and elastic properties. This is achieved with utmost frugality in arbitrary parameters.     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.