Determination of Polymer Compatibility by Viscometric Measurements on Ternary Solutions of the Two Polymers

Results on the intrinsic viscosity [η] are reported for the system solvent(1)/polymer(2)/polymer(3) in which the solvent was benzene, polymer(2) was polystyrene (PS), and polymer(3) was poly(dimethylsiloxane) PDMS. The values of [η] were then used to determine the likely compatibility of polymer blends of PS and PDMS. Initial focus was on the traditional interaction parameter b ₂₃ ⁽¹⁾ used by several authors to predict compatibilities, it but depends on the molar mass, weight fractions, and concentrations of each polymer. A new interaction parameter b ₂₃ ⁽²⁾ that is independent of polymer(3) concentration and molar mass was evaluated for determinations of polymer compatibility.     

Preparation of Ultrafine Water-soluble Polymers Nanofiber Mats via Electrospinning

A series of water-soluble polymers such as poly(ethylene oxide)(PEO),polyacrylamide(PAM) and poly(vinyl pyrrilidone)(PVP) was successfully prepared via the electrospinning of their aqueous solutions without the use of a surfactant.The effects of solution properties on the electrospinning of PEO,PAM and PVP solutions were investigated.The viscosity of the solution,charge density carried by the jet,and the surface tension of the solution are the key factors that influence the morphology and diameter size of t...     

光通讯波段聚合物光波导材料的研究进展

光学聚合物由于其在光通讯领域的集成光电器件与光互连应用方面有经济和实用价值而备受关注。本文介绍了光通讯波段有机聚合物光波导材料的特点和研究进展。     

Friedel-Crafts Polymers. 8. Friedel-Crafts Polycondensation of β-Resorcylic Acid or Resorcinol with p-Xylylene Dichloride,p,p′-Dichloromethyldiphenyl Ether,and p,p′-Dichloroacetyldiphenyl Ether

Friedel-Crafts polycondensation of β-resorcylic acid (BRA) with p-xylylene dichloride (PXDC) or 4,4′-dichloromethyldiphenyl ether (DDE) in dioxane could be effected without simultaneous decarboxylation of BRA. The similar polycondensation of BRA with PXDC, DDE, or 4,4′-dichloroacetyldiphenyl ether (DADE) in nitrobenzene or in the absence of solvent at 150°C was associated with decarboxylation of BRA. Polymers having structures isomeric with those of the polycondensation product of BRA formed with subsequent in situ decarboxylation were prepared by Friedel-Crafts polycondensation of resorcinol with the above dichlorides. All the polymer samples were characterized, and those with related structures were compared. The ion-exchange properties of the polymer sample prepared from BRA and DDE in dioxane were studied.     

Effect of Macromolecular Crowding on the Conformation of Confined Chain Polymers

Summary: The conformational behavior of flexible linear chain polymers confined in cylindrical pores and slab pores has been studied, employing a hard‐bead chain model and a modification of a recently proposed recoil‐growth bias Monte Carlo methodology, which improves the sampling efficiency in confined environments. It is found that the scaling law that correlates the unconstrained component of the radius of gyration of the polymer with the pore diameter in cylindrical pores is close but neatly different than the de Gennes mean‐field value. The results also indicate that the addition of spherical particles with sizes within the protein limit may be employed to tune the folding of the confined polymer, since in this case the depletion constraints work against the effective stretching forces induced by confinement. Remarkably, the presence of the depleting particles at sufficiently high concentration leads to appreciable changes in the exponents of the conformational scaling laws with respect to the uncrowded system.

Conformational behavior of flexible hard‐bead chain polymers confined in narrow pores.     

基于稀土金属离子配位超分子聚合物的荧光微囊

以基于金属配位作用的聚合物材料Eu-L₂EO₄为带负电的聚电解质, 利用静电相互作用通过层层组装的方法制备了自发光的聚合物荧光微囊. 该微囊壁孔径很小, 对小分子负载具有良好的封闭性, 且在盐浓度高达500 mmol·L^-1时依然稳定, 表现出良好的耐盐性质. 以Eu³⁺-Tb³⁺混合离子取代Eu³⁺, 可以制备多色荧光微囊.     

聚合物的静电纺丝

静电纺丝法是聚合物溶液或熔体在静电作用下进行喷射拉伸而获得纳米级纤维的纺丝方法.由纳米纤维制得的无纺布,具有孔隙率高、比表面积大、纤维精细程度与均一性高、长径比大等优点,从而赋予了静电纺丝纤维广泛的应用前景,它已在国内外引起了广泛的关注.本文介绍了静电纺丝的装置、基本原理及静电纺丝制备纳米纤维的研究进展,同时也叙述了其在各个领域的应用,最后展望了静电纺丝制备纳米纤维的发展方向及前景.     

Simulation of Chain Organization in Encapsulated Polymers

Summary : The dimensional and structural properties of polymers confined into a cavity are computed by the Monte Carlo method as a function of the chain stiffness. The reduction of the size ratio <R² > / < R> close to 2, distinctive of compact spheres, is observed at squeezing of chains into a capsule. The plots of the static structure factor S(q) computed for stiff chains show characteristic humps attributed to the toroidal structure. The orientation correlation function is found to be a very sensitive indicator of the globule – toroid transition in encapsulated chains. Evidence is presented that the toroidal morphology is formed in stiff polymers when the capsule radius approaches the chain persistence length (D ∼ P).     

共轭高分子链构象和溶液聚集结构研究进展

共轭高分子具有优异的光电性质和可加工性,被广泛用于有机光电器件的制备。共轭单元的存在使得此类高分子具有更刚性的主链结构。由于较强的分子间相互作用,共轭高分子容易在溶液中形成组装结构。共轭高分子的链构象、组装体结构、薄膜形貌和光电性能之间的联系研究成为了本领域的研究热点。然而,共轭高分子在可见光区存在较强的吸收效应,用传统的光散射技术对共轭高分子溶液的研究充满挑战。本文总结了近年来对于共轭高分子链刚性的研究,并从分子尺度上讨论了链结构与光学、电学性能间可能存在的关联;进一步阐述了共轭高分子溶液聚集的形成和演化,总结了溶液聚集与成膜过程中影响场效应迁移率的因素。试图在不同尺度上讨论共轭高分子的微观结构与宏观性能之间的关系。     

两种异金属链状配位聚合物的合成和晶体结构

在甲醇溶液中,将K2NiL·H2O和M(OAC)2(M = Co,Zn)按1:1的摩尔比进行组装反应,得到了镍、钴和镍、锌两种异金属一维链状配位聚合物,其化学组成分别为{[Ni2Co2L2(H2O)2]·CH3OH·3H2O}n（1）和{[Ni2Zn2L2 (H2O)2]·2CH3OH·H2O}n（2）,（H4L=2-羟基-3-[(E)-({2-(2-羟基苯甲酰胺基)乙基}亚氨基)甲基]苯甲酸,OAC- = CH3COO-）。通过IR谱,元素分析的方法对其进行了表征,利用X-射线单晶衍射方法对其晶体结构进行了测定,结构分析表明：它们都是由不对称四核单元组成链状配位聚合物。     

Highly sensitive detection of nitroaromatic explosives using an electrospun nanofibrous sensor based on a novel fluorescent conjugated polymer

An electrospun nanofibrous explosive sensor was first constructed based on a newly developed fluorescent conjugated polymer P containing heteroatom polycyclic units. Electrospinning by doping polymer P as a fluorescent probe in a polystyrene supporting matrix afforded a fluorescence nanofibrous film with unique porous structures, and effectively avoided the aggregation of polymer P. The novel explosive sensor exhibited stable fluorescence property, satisfactory reversibility with less than 5% loss of signal intensity after four quenching–regeneration cycles, and good reproducibility among three batches with a relative standard deviation of 2.8%. Such fabricated sensor also showed remarkable sensitivity toward a series of trace nitroaromatic explosive vapors, including picric acid (parts-per-trillion level) and 2,4,6-trinitrotoluene vapor (parts-per-billion level), as well as good selectivity with less than 10% response to typical interferents. Therefore, the present strategy extends the application of different kinds of conjugated polymers for the construction of optical chemosensors.     

Distinct Antifouling Mechanisms on Different Chain Densities of Zwitterionic Polymers

Antifouling polymer coating surfaces are used in widespread industries applications. Zwitterionic polymers have been identified as promising materials in developing polymer coating surfaces. Importantly, the density of the polymer chains is crucial for acquiring superior antifouling performance. This study introduces two different zwitterionic polymer density surfaces by applying molecular modeling tools. To assess the antifouling performance, we mimic static adsorption test, by placing the foulant model bovine serum albumin (BSA) on the surfaces. Our findings show that not only the density of the polymer chain affect antifouling performance, but also the initial orientation of the BSA on the surface. Moreover, at a high-density surface, the foulant either detaches from the surface or anchor on the surface. At low-density surface, the foulant does not detach from the surface, but either penetrates or anchors on the surface. The anchoring and the penetrating mechanisms are elucidated by the electrostatic interactions between the foulant and the surface. While the positively charged ammonium groups of the polymer play major role in the interactions with the negatively charged amino acids of the BSA, in the penetrating mechanism the ammonium groups play minor role in the interactions with the contact with the foulant. The sulfonate groups of the polymer pull the foulant in the penetrating mechanism. Our work supports the design of a high-density polymer chain surface coating to prevent fouling phenomenon. Our study provides for the first-time insights into the molecular mechanism by probing the interactions between BSA and the zwitterion surface, while testing high- and low-densities polymer chains.     

晶态非极性聚合物内聚能密度的估算

有关凝聚态结构对聚合物内聚能密度的影响,在高分子物理学界一直未被关注。本文首次提出了利用结晶熔融热估算晶态非极性聚合物内聚能密度的方法,并对结晶态的聚四氟乙烯、聚乙烯和聚丙烯的内聚能密度进行了估算。估算值较好地解释了上述聚合物用作塑料但内聚能密度较小的理由。结晶熔融热本质上反映了非极性聚合物的晶态与非晶态分子间色散力相...     

由聚合物结构预测气体的透过性能

本文利用基团加和法,对20多种常见聚合物的自由体积和内聚能进行了计算。发现氧气和氮气在聚合物膜中的透过率与自由体积和内聚能的比值有直接关系。此比值越大,气体的透过率越大,透过率的对数与自由体积和内聚能的比值基本呈线性关系。据此,对未知聚合物可根据其化学结构,从已有的基团数据计算该比值,从而预测它对氧气和氮气的透过性能。     

A Modified Method for Estimating Unperturbed Dimensions of Macromolecules from Viscosity Data

Abstract

A new empirical equation is presented which modifies the Krigbaum equation for calculating Kθ values from measurements of intrinsic viscosity in good solvents. This is found to fit the molecular weight data better for the polymer systems investigated.     

Origin of Bends in Unperturbed Vinyl Polymers: An Illustration with Polystyrene

Previous experimental works have shown that dendronized vinyl polymers exhibit bends when adsorbed onto a surface. Two different mechanisms are believed to be responsible for the formation of these bends. These mechanisms are the temperature dependent random fluctuations of torsional bond states on one hand, and the intramolecular interactions due to the randomness in the stereochemical sequence of side chains on the other hand. Investigation of the amplitude and scope of the above mechanisms has been made by studying the conformational space of PS chains via RIS based Monte Carlo sampling. It was found that at low temperature bend formation is due to tacticity, whereas it was thermally driven at high temperature. The existence of a transition temperature between these two bend formation modes was demonstrated. It was also shown that for atactic chains, the maximum of bend formation occurs at P_m ≈ 0.7.

     

Novel Conjugated Side Chain Fluorinated Polymers Based on Fluorene for Light-Emitting and Ternary Flash Memory Devices

Three novel conjugated polymers based on 9,9′-dioctylfluorene unit and isoindolo[2,1-a]benzimidazol-11-one with different fluorine substituents (0, 2 and 4) were synthesized. PLED and resistive memory devices based on these polymers were prepared consequently. PLED based on four-fluorinated polymer showed the highest maximum brightness of 3192 cd m⁻² with almost 5-fold increase of current efficiency 8-fold increase of external quantum efficiency compared to that of the other two, and all the PLEDs exhibited good emission stability with no noticeable change of electroluminescence even under high voltage of 10 V. The memory device of doubly-fluorinated polymer exhibited ternary flash behavior with threshold voltages below −2.5 V, while device of four-fluorinated polymer possessed ON/OFF current ratio above 10⁴. Impact of fluorine substitutions on the performance of devices were briefly investigated. The results revealed that the improvement of device performance might not scale with the increasing number of fluorine substitutions, and the four-fluorine-substituted polymer and doubly-fluorinated polymer could be encouraging materials for applications of PLED and resistive memory device and worth of further design of other new polymer systems.     

Nucleotide/Tb coordination polymer nanoparticles as luminescent sensor and scavenger for nitrite ion

Newly emerged metal organic coordination polymers have aroused the great interest in designing tailored functional materials. In this study, multiple functional components, luminescent Tb³⁺ ion, nucleobase and antenna molecule, were integrated in a single material and prepared into a responsive nanoparticle for nitrite. The terbium coordination polymer nanoparticles made of this kind of material have the dual functions of recognition and transduction and obey a preset sensing mechanism without a post-functionalization of common materials. As the result of the tailored, the terbium coordination polymer nanoparticles are highly sensitive and selective to nitrite by means of Dexter energy transfer between Tb³⁺ ion and nitrite, and can be used for the scavenger for nitrite in aqueous solution. The detection limit, dynamic range and removal capacity of U–Tb–OBBA CPNPs for nitrite are 0.3 µM, 0.3–470 µM and 4.44 mg per gram of particles, respectively. Metal organic coordination polymers show an attractive potential in constructing smart sensing materials.     

Viscometric properties of dilute polystyrene/dioctyl phthalate solutions

We report viscometric data collected in a Couette rheometry on dilute, single‐solvent polystyrene (PS)/dioctyl phthalate (DOP) solutions over a variety of polymer molecular weights (5.5 × 10⁵ ≤ M_w ≤ 3.0 × 10⁶ Da) and system temperatures (288 K ≤ T ≤ 318 K). In view of the essential viscometric features, the current data may be classified into three categories: The first concerns all the investigated solutions at low shear rates, where the solution properties are found to agree excellently with the Zimm model predictions. The second includes all sample solutions, except for high‐molecular‐weight PS samples (M_w ≥ 2.0 × 10⁶ Da), where excellent time–temperature superposition is observed for the steady‐state polymer viscosity at constant polymer molecular weights. No similar superposition applies at a constant temperature but varied polymer molecular weights, however. The third appears to be characteristic of dilute high‐molecular‐weight polymer solutions, for which the effects of temperature on the viscosity curve are further complicated at high shear rates. The implications concerning the relative importance of hydrodynamic interactions, segmental interactions, and chain extensibility with increasing polymer molecular weight, system temperature, and shear rate are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 787–794, 2006     

可逆加成-断裂链转移(RAFT)聚合在星形聚合物合成中的应用

可逆加成-断裂链转移(RAFT)聚合作为一种新型活性自由基聚合,由于其具有单体适用面广、操作条件温和、实施聚合的方法多--本体、溶液、乳液、悬浮聚合均可的优点已经在分子设计方面取得了广泛的应用.星形聚合物作为一种特殊结构的聚合物,由于其具有较低的结晶度、较小的流体动力学体积等独特的性质,越来越引起研究者的重视.本文综述了近几年来采用RAFT法合成星形聚合物的研究进展.根据合成星形聚合物所用的RAFT多官能团试剂种类,对RAFT法合成星形聚合物的反应进行了分类.