Two-dimensional lattice Monte Carlo simulation of the compatibility of A/B/functionalized A ternary polymer mixtures coupled with chemical reaction

Compatibility of A/B and functionalized A ternary polymer mixtures was studied by Monte Carlo simulation in a two-dimensional lattice. Polymer A was a nonreactive polymer, whereas polymer B was a reactive polymer and immiscible with polymer A. Functionalized polymer A could react with the end group of polymer B, leading to the formation of block copolymers. Simulation results showed the phase domain sizes dropped considerably with increasing functionalized polymer A content, indicating that the compatibility between polymer A and B could be markedly improved with the introduction of functionalized polymer A. Moreover, it was shown that the resulting block copolymers tended to distribute at the phase interface between polymer A and B, and the block copolymer conformation depended on the structures of polymer B and functionalized polymer A. In case 1, i.e., both polymer B and functionalized polymer A were with single end group, it could be found that the block A and block B of resulting A–B copolymer inserted into polymer A and polymer B phase domains, respectively. In case 2, i.e., functionalized polymer A was with single end group and polymer B was with double end groups, it was found that the resulting A–B–A triblock copolymer tended to connect two neighbor separated polymer A phase domains. However, in case 3, namely functionalized polymer A was with double end groups and polymer B was with single end group, it was found that the resulting B–A–B triblock copolymer was likely to form a folding conformation. These lead to the different compatibilizing effects for different polymer structures. Comparing with case 1 and case 2, functionalized polymer A with double end groups (case 3) had less effective to compatibilize the A/B polymer blends. For the purpose of comparison, same simulations were carried out in a three-dimensional lattice. The results showed the compatibility behavior of the mixtures was similar to those in the two-dimensional lattice with the addition of functionalized polymer A. However, the conformation of the resulting block copolymers was different from that in the two-dimensional lattice.     

动态流变法在聚合物/聚合物界面分子链扩散研究中的应用

聚合物/聚合物界面的分子链扩散问题在塑料注塑、焊接、共混等领域普遍存在.动态流变法是研究聚合物/聚合物界面分子链扩散的一种有力手段,这种方法对于界面间分子链扩散的监测非常灵敏.本文简述了用动态流变法研究聚合物/聚合物界面扩散的原理、实验方法以及优点,着重讨论了采用该方法研究初始界面分子链末端分布对扩散机理的影响、对称聚合物/聚合物界面分子链扩散的量化,非对称聚合物/聚合物界面的相互扩散,分子量多分散性对聚合物/聚合物界面扩散的影响,聚合物/聚合物界面间的流动和扩散耦合以及近年来动态流变法在化学反应型聚合物/聚合物界面的应用进展.     

The effect of polymer chain length and surface density on the adhesiveness of functionalized polymersomes

Giant cell-like polymer vesicles, polymersomes, made from the diblock copolymer poly(ethylene oxide)-polybutadiene (PEO-PBD), have bilayer structures similar to the cell membrane but have superior and tunable properties for storage and stability. We have modified the terminal hydroxyl of the hydrophilic block with biotin-lysine (biocytin), a biologically derived group that imparts specific adhesiveness to a polymer colloid coated with avidin. The functionalized polymer will form vesicles, either on its own or when mixed with unmodified block copolymers that also form vesicles. The incorporation and mixing of the functionalized polymer into vesicle bilayers is measured using a fluorescent version ofbiocytin with confocal microscopy. The fluorescence signal associated with the vesicle is in proportion with the concentration of functional polymer added during vesicle construction. The adhesiveness of polymer vesicles containing functionalized biotinylated polymer to avidin coated microspheres is measured with micropipet aspiration. Two types of polymer vesicles were constructed: one where the functionalized polymer (molecular weight (MW), 10400 Da) was longer than the surrounding unfunctionalized polymer (MW, 3600 Da) and one where the functionalized polymer (MW, 10400 Da) was the same length as the unfunctionalized polymer. In all cases, the avidin-biotin bonds form kinetically trapped crossbridges that impart little tension as they form but require significantly more tension to break. The relative length of the functionalized polymer on the surface of the vesicle is an important determinant for the adhesion of a polymer vesicle but not for the adsorption of soluble avidin. Greater adhesion strengths are seen where the functionalized polymer is longer than the surrounding polymer. The concentration of functionalized polymer at which adhesion is maximal depends on the relative lengths of the polymers. When the functionalized polymer is the same length as the surface brush of the polymersome membrane, the critical tension is maximal at 10 mol % functionalized polymer concentration. However, when the biocytin groups are attached to a polymer which is larger than the surface brush, the critical tension is maximal at 55 mol % functionalized polymer. These results indicate that polymer mixing and length can control the interfacial adhesion of polymer brushes and must be understood to tune polymersome adhesiveness.     

高聚物从高弹态到流体态的转变

将高聚物由高弹态转变为流体态的转变温度命名为流动温度Tf,该转变温度与高聚物分子量密切相关.在高聚物从高弹态转变为流体态的研究中,由于T1.1的概念忽视对高聚物分子量的依赖性,因此采用Tf的概念更为合理.本文对高聚物的流动温度Tf的讨论涉及高聚物温度-形变曲线、高弹态温区、高聚物熔体剪切粘度.从高聚物凝聚态观点来看,高聚物熔体中凝聚缠结网络中的凝聚结点是分子链的局部向列相互作用使链单元间产生平行凝聚而形成的,而高聚物从高弹态到流体态的转变正是反映了高聚物熔体中凝聚缠结网络的物理交联点,即凝聚结点状态的变化.高聚物熔体可以流动,说明熔体中凝聚网络中的凝聚结点至少是可以在瞬间内打开的,升温使凝聚结点的解凝聚状态存在的时间加长,凝聚状态存在时间减短,当升高到某一温度时,在凝聚结点解凝聚状态的时间内,分子链通过内旋转使质量中心在外加力的方向上可以发生位移,此时高聚物从高弹态转变为流体态,而此时的温度就是流动温度Tf.对高聚物流体弛豫网络的研究,是一个很有前景的研究课题.     

The study of structure formation in a polymer-containing ionic liquid in terms of the integral equation theory

The structural properties of a polymer-containing ionic liquid under the conditions of good solubility of a flexible polymer are studied theoretically. Two systems are discussed: In one, polymer solubility is due to the presence of specific interaction between polymer chains and solvent cations; in the other, polymer solubility is due to the presence of specific interactions between the polymer and solvent anions. The dependences of the structural characteristics of a solution on the polymer concentration and the energy of attraction between polymer chains and solvent ions are calculated. In a semidilute polymer solution, long-range correlations of polymer chains with a power dependence of the characteristic scale of ordering on the polymer density appear. The conditions under which, along with the intermediate ordering typical of a pure ionic liquid, the long-range ordering of the solvent cations and anions occur after addition of a polymer to the ionic liquid are studied.     

聚烯烃／极性聚合物界面的分子状态

为了克服高分子共混物界面不易表征的缺点，提出用溶剂选择性溶解方法使界面暴露．结合Ｘ－射线光电子能谱（ＸＰＳ）表征手段，研究了官能化聚合物，接枝型共聚物及带有反应性基团的聚合物作为共混物增容剂时在界面区域的分子状态．实验结果表明，作增容剂时，官能化聚合物在界面区内采取最有利的分子构象，充分发挥增容作用；接枝型共聚物主链、侧链向相应本体聚合物内扩散；而带有反应性基团的聚合物与某个本体聚合物发生反应之前存在反应基团在界面富集的过程     

聚合物科学进展

本文对2011~2013年我国高分子科学重要研究进展进行了综述。全文分为高分子化学、响应性高分子、高分子物理、高分子组装、超分子聚合物、光电功能聚合物、生物医用高分子、石墨烯/聚合物复合体系、聚合物杂化体系和高分子工程等10部分。近年我国内地学者发表的高分子领域研究论文总量跃居世界第一,论文引用数跃居第二,在诸多分支领域中学科发展水平大幅提高,达到或接近国际水平的研究成果快速增多,国际影响力逐年提高。我国高分子学者通过基础研究,为高分子工业技术水平提升和创新也做出了许多贡献。本文还对本学科前沿、发展趋势进行了介绍与展望。文中共引用了227篇参考文献。     

Synthesis and Application of Tetracycline Imprinted Polymer

Molecular imprinted polymer was synthesized by polymerization of methacrylate and ethylene glycol dimethacrylate in presence of tetracycline. The prepared polymer exhibited selectivity of 1.8 to 3.9 over non-imprinted polymer depending on nature of solvent. In water, 3.45 mg of tetracycline bind to 1 g of imprinted polymer. Non-covalent interactions between tetracycline and polymer provided selectivity to imprinted polymer. The polymer was evaluated in column chromatography and the bound tetracycline can be eluted with acetonitrile. Ciprofloxacin interacted with imprinted polymer, whereas amoxicillin did not. The feasibility of using MIP for concentrating tetracycline from milk has been demonstrated.     

端基功能化聚合物的表面性能

综述了端基功能化聚合物表面结构与性能的最新研究进展.聚合物端基功能化是实现聚合物表面改性的一种有效技术.通过端基功能化可以精确控制聚合物表面功能基团的种类和数量,从而影响聚合物表面的化学结构与性能.重点论述了功能化端基在聚合物表面的离析现象和产生这一现象的原因,以及功能化端基对聚合物表面分子运动能力的影响.本文还介绍了近年来用于研究端基功能化聚合物表面的表征新技术,如SFG、NR、SSIMS等.对端基功能化聚合物表面的环境响应性也进行了阐述.指出了利用不同功能化端基可以有效地控制聚合物表面的亲疏水性.并对端基功能化聚合物的应用进行了展望.     

高分子单链的研究进展

随着纳米科技在高分子领域的不断升温,高分子单链凝聚态的研究引起了人们的广泛重视。高分子单链以纳米尺度的微粒孤立存在,不存在分子链之间的几何缠结。本文综述了近年来国内外高分子单链的研究进展。首先介绍了高分子单链的主要制备方法如喷雾法、冷冻干燥法、微乳液聚合法、反向沉淀法以及表面扩展膜法,接着详细介绍了高分子单链的表征技术及高分子链构象的计算机模拟技术,最后介绍了高分子单链及单分子胶束在制备金属纳米粒子领域的应用,并展望了高分子单链的研究领域和方向。     

剪切作用对功能聚合物微观结构性能的影响研究

梳型聚合物和活性聚合物是目前常用驱油聚合物,其增黏性和黏弹性是评价其驱油能力的重要指标.为考察剪切作用对两种聚合物溶液性能的影响,分别研究了梳型聚合物和活性聚合物溶液经过模拟炮眼剪切前后的宏观和微观性能变化.结果表明,在高速剪切、拉伸应力作用下,梳型聚合物黏度损失率为40.73%,活性聚合物黏度损失率为70.10%;当剪切频率为0.02 Hz时,梳型聚合物界面扩张弹性降低了19.03%,而活性聚合物界面扩张弹性降低了68.03%;相比活性聚合物,梳型聚合物紧密的空间网状结构虽被部分破坏,但仍有疏松的网络结构,且以聚集体的形式紧密地分散在溶液中,通过DLS及AFM测定表明其粒径尺寸稍有变小;可见梳型聚合物抗剪切能力较活性聚合物强.     

再谈“高分子物理”本科阶段教学内容

高分子的特殊性在于其长链结构,特殊的长链结构带来运动的特殊性。本文从"高分子物理"的定义是运动着的高分子物质和高分子物质的运动出发,确定高分子物理的定位是高分子物质的结构、结构演变和各层次结构单元的运动,围绕"高分子物理"的核心本质是长链状结构、长链状结构的演变及各层次长链结构的运动规律,针对本科阶段的任务和特点,阐述教学主要内容是结构和运动,附带相关性能,提出对现行教材内容和编排顺序的建议和想法。     

Potential distribution theorem for the polymer-induced depletion between colloidal particles

The authors investigated the polymer-mediated colloidal interactions in a good solvent wherein the particle size varies from that much smaller than the polymer radius of gyration up to macroscopic and the polymer concentration varies from that corresponding to a dilute solution to that close to a melt. At conditions directly accessible to molecular simulations, the theoretical predictions agree favorably with the simulation results for the distributions of polymer segments and for the polymer-mediated colloidal interactions. The theoretical methods were then exploited to examine the polymer structure and colloidal interactions when the particle/polymer size ratio changes from the "protein" limit to the "colloid" limit at different regimes of the polymer concentration (i.e., dilute, semidilute, and concentrated). The authors found that the surface curvature plays a significant role on the distribution of polymer segments near the particle surface at low polymer concentration, but this effect diminishes as the polymer concentration increases. The Derjaguin approximation works reasonably well at high polymer concentration even in the protein limit, but it may fail qualitatively at low polymer concentration where the polymer-induced colloidal force becomes long range.     

环糊精包合作用诱导聚合物自组装的研究进展

将主客体识别与聚合物自组装相结合,利用环糊精对聚合物的包合作用在溶液中诱导聚合物组装形成结构可控的纳米粒子,形成有别于基于环糊精/聚合物包合作用形成的结晶粉末和超分子水凝胶的新型材料.本文介绍了这种诱导组装方案的研究背景及最新的研究成果,综述了诱导组装的原理、特点及影响因素.研究表明,由这种方案制备的聚合物纳米粒子具有超分子动态可逆的特征,进而显示出对温度和pH等敏感的性质.该类环糊精包合作用诱导组装的聚合物超分子聚集体在生物医学材料方面具有潜在的应用价值,如用作药物和基因的可控传递释放载体.     

《高分子近代史》本科课程教学的探索与思考

为了培养学生对高分子科学技术的专业兴趣,激发学习热情,浙江大学从2004年开始面向高分子材料专业本科生开设《高分子近代史》专业选修课。通过让同学们了解高分子科学和高分子工业的建立和发展历程,建立和加深学生对高分子科学和学科知识整体性、结构性的理解。以世界高分子发展和中国高分子发展的两条线索向同学们介绍高分子科学技术发展中的重要历史事件、涌现的著名高分子科学家、产生的具有历史性意义的研究成果与材料,给同学们展现高分子科学与技术发展的波澜壮阔的历史画卷。经过十多年的尝试和努力,《高分子近代史》课程在教学内容、授课方式和考核方式上均形成了自己的教学特色,受到了本科生的欢迎,对激发和培养同学们学习高分子的兴趣和热情,起到了积极的作用。     

Synthesis and characterization of monodisperse porous polymer particles

Monodisperse porous polymer particles in the size range of 10 μm in diameter were prepared via seeded emulsion polymerization. Linear polymer (polystyrene seed) or a mixture of linear polymer and solvent or nonsolvent were used as inert diluents. The pore diameters of these porous polymer particles were on the order of 1000 Å with pore volumes up to 0.9 mL/g and specific surface areas up to 200 m²/g. The physical features of the porous polymer particles depended on the diluent type and the crosslinker content, as well as the molecular weight of polymer seed particles. By varying the molecular weight of the linear polymer, monodisperse porous polymer particles with different pore size distribution could be synthesized. Polymer seed with a low degree of crosslinking instead of linear polymer could also be used to prepare monodisperse porous polymer particles with smaller pore volume and pore size.     

非高分子专业《高分子化学与物理》教学中的几点体会

高分子科学已渗透于各个领域与学科,形成了一个无法替代的交叉学科,因此,工科化学或材料相关专业纷纷开设高分子相关课程。《高分子化学与物理》作为哈尔滨工程大学材料化学专业的主干课之一,包括高分子化学和高分子物理两个侧面,其中高分子化学部分侧重高分子合成的基本理论知识,高分子物理部分则侧重于高分子的结构与性能。本文分析了高分子化学与物理的课程特点,总结了在课堂教学中采取的行之有效的措施和教学尝试,介绍了在课堂教学过程中,如何导入心理教育,提高学生的学习兴趣。     

Electrochemical oxidation of 2,5-di-(-2-thienyl)-pyrrole in acetonitrile: cathodic stripping of the electrogenerated conducting polymer

The electrochemical behaviour of 2,5-di-(-2-thienyl)-pyrrole was studied by cyclic voltammetry, chronoamperometry and chronopotentiometry. The monomer oxidation—polymerization takes place on platinum at potentials more positive than 0.3 V vs SCE. At higher potentials, the oxidation processes in the polymer layer seem to control the generation of the polymer and the polymer properties. Polymer films electrogenerated at potentials lower than 0.7 V are insoluble in LiClO₄ + acetonitrile solutions. When the polymer film is reduced electrochemically, it becomes soluble. The solubility is a faradaic process: the weight of electrochemically solubilized polymer is proportional to the cathodic electrical charge consumed. The linearity of the process was proved using different cathodic current densities. The polymer oxidation at potentials more positive than 1 V promotes the insolubility of the polymer, probably by a crosslinking process. The reduction of the polymer at potentials below 0.2 V promotes stripping of the polymer from the electrode. The polymer structure was studied by Fourier transform IR reflectance. The UV—Vis study of the oxidized and reduced polymer in solution led to the band structure and showed the self-reduction of the dissolved polymer.     

Analysis of the roles of nitrogen and oxygen in the synthesis of an alcohol polymer during plasma-induced reactions

This paper investigates the roles of nitrogen and oxygen in forming a 1-butanol polymer. The analyses show that nitrogen is the key species for forming a stable 1-butanol polymer, and the viscosity of the polymer is increased as the ratio of nitrogen in the polymer is increased. In contrast, oxygen does not contribute to forming the polymer but rather prevents formation of the polymer instead. This article also analyzes the origin of C=O bonding in the 1-butanol polymer. IR analysis demonstrates that oxygen in the atmosphere is fixed in the polymer as C=O bonds, instead oxidizing the O-H group in 1-butanol.     

On the origin of mesoscopic inhomogeneity of conducting polymers

The mesoscopic inhomogeneity of conducting polymer films obtained by electropolymerization and spin-coating was studied using Kelvin probe force microscopy (KFM) and current-sensing atomic-force microscopy (CS-AFM). A well-pronounced correlation was established between the polymer morphology, on the one hand, and its local work function (which is related to the polymer oxidation degree) as well as polymer conductivity, on the other. The most conducting regions were associated with the tops of the polymer grains and showed Ohmic behavior. They were surrounded first by semiconducting and then by insulating polymer. The conductivity of the grain periphery could be lower by as much as 2 orders of magnitude. The grain cores also showed consistently higher values of the local work function as compared to the grain periphery. This fact suggested that the grain cores were more oxidized and/or more ordered as compared to the grain periphery, which is in good agreement with the local conductivity data. More uniform morphology corresponded to less variability in the other properties of the polymer. A model is proposed that relates the observed inhomogeneity to preferential deposition of polymer molecules with higher molecular weight at the early stages of the polymer phase formation. The polymer deposition in either electropolymerization or various solution-casting techniques involves the nucleation of a new phase from a solution containing polymer fractions of different molecular weights. The driving force of the nucleation process depends on the solubility of the polymer fractions, which decreases with an increase in the molecular weight. This gives rise to preferential deposition of more crystalline, higher molecular weight polymer at the early stages of the polymer deposition to form the cores of the polymer grains. The fractions with lower molecular weights are deposited later and form less ordered/less conducting grain periphery. On the basis of this model, we conclude that, to ensure the formation of materials with low inhomogeneity and high quality, one should use the starting polymer with as narrow molecular weight distribution as possible. Yet another possibility is to use solvents which would reduce the differences in the solubilities of polymer fractions with different molecular weight.