新型侧链液晶聚甲基丙烯酸酯研究

以横向取代的液晶基元为侧基合成了聚甲基丙烯酸酯,并对此聚合物进行初步表征.在玻璃化温度(170℃)以上样品进入液晶态.样品较高的玻璃化温度以及能形成液晶态的特性被认为是棒状液晶基元使聚合物分子链刚性化的结果.     

溶致凝聚过程中分子链构象的演变

详细讨论了稀溶液、亚浓溶液、浓溶液和极浓溶液中分子链构象的演变,考察了在溶致凝聚过程中分子链的链间相互作用、关联作用和分子链尺寸的变化规律,给出了排除体积的严格定义,引入热关联效应、长程关联效应和全高斯链浓度等概念。指出在不同浓度溶液中,分子链在不同尺度上构象状态不同;在从孤立单链态(良溶液中)向多链聚集态的溶致凝聚过程中,单链的尺寸一直在收缩,由Flory尺寸RF缩小至无扰尺寸R0。这是大分子凝聚过程的一个特点。     

链分子的构象弹性理论

研究基于旋转异构态模型、用末端距与构象能描述的链构象分布函数、以及链构象态在体系形变中的消失规则,发展了一个链分子的构象弹性理论.用该理论描述的理想形变行为,支持天然橡胶在大形变时应力陡然上翘归因于链构象变化的观点在物理上的合理性.该理论能够区别不同化学结构高分子所具有的不同形变行为,能够预报高分子形变中熵项与内能项各自的贡献.预报了天然橡胶形变中内能的贡献约为13%, 与实验相符.     

氧化淀粉的氧化度对其交联海藻酸钠/明胶互穿网络膜性能的影响

以氧化淀粉为交联剂交联明胶、以氯化钙为交联剂交联海藻酸钠,采用分步交联的方法制备了海藻酸钠/明胶互穿网络膜.通过红外光谱仪表征了氧化淀粉、海藻酸钠/明胶互穿网络膜的结构;研究了氧化淀粉的氧化度对互穿网络膜力学性能、热稳定性能、微观形貌、交联度、吸水保水性能等各种性能的影响.结果表明,随着氧化淀粉氧化度的增加,互穿网络膜的拉伸强度、断裂伸长率、交联度呈现先增加后降低的趋势,氧化度为60%的氧化淀粉交联制备的互穿网络膜的以上性能达到最大值;吸水保水性能呈现先降低后增加的趋势,这主要是因为随着互穿网络膜交联度的增加,使两相间形成了均匀、致密的网络结构,两者分子链上大量的羟基和羧基受到束缚,导致互穿网络膜吸水率、保水率的下降.同时也说明了该体系的交联度并不是随着氧化淀粉氧化度的提高而逐渐提高,对于该体系氧化淀粉存在最佳氧化度.     

无定形1,2-聚丁二烯的分子链结构与分子链的相互作用

本工作用聚合物玻璃化转变温度,内聚能密度和分子链内旋转势垒及异构化能表征分子链的相互作用;提出了在混合溶剂中用特性粘数法测定内聚能密度,和从聚合物玻璃化转变时的自由体积及稀溶液性质计算分子链内旋转参数等方法。     

环形侧链聚合物刷的合成与表征

通过grafting-onto方法合成高侧链接枝密度的环形侧链聚合物刷并进行结构表征.先通过开环易位聚合(ROMP)制备带有炔基侧基的线形聚降冰片烯衍生物主链(l-PND),通过原子转移自由基聚合(ATRP)和铜催化的叠氮-炔环加成(Cu AAC)反应制备带有一个叠氮基的环形聚丙烯酸叔丁酯侧链(c-Pt BA),再利用Cu AAC反应将环形侧链高密度地接入主链,得到环形侧链聚合物刷.通过核磁氢谱(1H-NMR)、凝胶渗透色谱(GPC)和红外光谱(IR)对聚合物主/侧链及聚合物刷的结构和组成进行了表征.该聚合物刷主链聚合度为400,高接枝密度的环形侧链使主链构象伸展.聚合物刷在原子力显微镜(AFM)下呈单分子蠕虫形貌(柱状形貌),分子长度为200 nm,直径为30 nm.     

高聚物高压下的状态方程

本文从高分子体系内分子链间相互作用能出发,得到了一个描述高聚物高压下的等温状态方程 从实验中发现n、m为普适常数,n=6.14,m=1,16.在不存在转变的情况下,该方程对处于玻璃态、结晶态及液态高聚物体系均适用.     

菌类多糖链构象及其表征方法研究进展

概述了菌类多糖在溶液中链构象及其表征方法的研究进展.主要报道从各种真菌(香菇、茯苓、灵芝、木耳、黄单胞菌、裂褶菌等)中提取的多糖在溶液中的分子量、分子形态和尺寸,即链构象.同时介绍多糖链构象对生物活性的影响,并且指出多糖刚性链带电基团及适量分子量有利于促进它与免疫细胞上受体结合,从而抑制肿瘤细胞增殖.由此表明,多糖链构象的研究对弄清其生物功能和推动生命科学发展十分重要.多糖在溶液中主要以无规线团、双螺旋、三螺旋、蠕虫状、棒状链以及聚集体构象存在,它取决于单糖组成、糖苷键、支链结构以及分子内和分子间作用力.测定链构象的方法主要包括光散射、黏度、显微技术(透射电镜,扫描电镜以及原子力显微镜)、微量热法和小角X-射线散射等.此外,介绍了多糖溶液理论以及计算链构象参数的表达式.     

一种侧链液晶高分子的合成与表征

合成了一种主链为甲基丙烯酸酯 ,侧链是三个苯环以酯键相连的介晶基元 ,柔性间隔段为两个亚甲基的新的侧链液晶高分子 .聚合物和单体的化学结构、液晶相转变和液晶态织构采用红外光谱、核磁共振、偏光显微镜、差热分析和广角X光衍射进行了表征 .研究表明 ,单体呈现近晶相和向列相两个液晶相 ,聚合物在很宽的温度范围内呈向列相 .该单体和聚合物在一定条件下可形成固化诱导条带织构     

一种新的侧链型液晶高分子的光谱研究

本工作使用FTIR、FT-RAMAN、~1H-NMR和~(13)C-NMR等方法,对一新型的侧链型液晶高分子聚-2,5-双(4-甲氧基苯甲酰氧基)苯乙烯的结构进行了表征,并对形成液晶态的分子间相互作用力作了讨论。实验结果表明,这种侧链型液晶高分子的相互作用主要发生在作为侧基的液晶基元之间。聚合物的核磁谱表现异常,其原固有待进一步研究。     

MEASUREMENTS OF CHAIN INTERPENETRATION OF POLYMER GLASSES

The concept of entanglement provides the basis of our current understanding of the flow behavior of polymer melts, Current techniques developed to investigate the degree of interpenetration of polymer chains only provide indirectly the information of the degree of entanglement in a relatively large scale （several to tens of nanometer）. In this article, we report ^1H-NMR spectroscopy with dipolar filters under fast magic angle spinning for probing chain interpenetration of polymer glasses at the molecular level.     

Entanglement and phase separation in hyperbranched polymer/linear polymer/solvent ternary blends

Hyperbranched polyethylene (HBPE)/linear polystyrene (PS)/chloroform (CF) solution was selected as a model system to investigate the effect of branching structure on entanglement and phase separation behavior in semi-dilute ternary polymer solutions. All the HBPE materials in this work were found to have similar chain architectures and the critical molecular weight was estimated to be 81.2 kDa. The results obtained by elastic light scattering and intrinsic fluorescence methods suggested that all ternary solutions exhibited UCST transition behavior upon cooling. Also, it was found that the increase in the molecular weight of PS led to increase in the phase separation rate, consistent with de Gennes prediction. However, the increase of molecular weight of HBPE did not monotonously reduce the compatibility of polymer components and the phase separation rate in ternary blends is as follows: medium molecular weight HBPE (HBPE-M) > high molecular weight HBPE (HBPE-H) > low molecular weight HBPE (HBPE-L). This abnormal behavior can be explained by the fact that, (i) for HBPE-L, no entanglements between HBPE chains occurred and the branching effect can be ignored, and (ii) for HBPE-M and HBPE-H, entanglement of HBPE chains can be formed, and the dilution of branches on entanglement of backbones should be taken into consideration, that is, the shorter the branches of HBPE, the higher the possibility of interpenetration of HBPE backbones between neighboring molecules and, consequently, the faster aggregation of HBPE during phase separation. Furthermore, a simple model based on decomposition reaction was proposed to quantitatively describe the phase separation kinetics and the apparent activation energies of phase separation were calculated to be −150.3 and −52.3 kJ/mol for HBPE-M/PS/CF and HBPE-H/PS/CF systems, respectively.     

超高分子量聚乙烯烧结制品的链缠结调控及其对性能影响

利用新的单中心Ziegler-Natta(Z-N)催化剂,通过干预分子链的生长与聚集行为,可获得低缠结的超高分子量聚乙烯(UHMWPE)初生树脂.本研究利用这类低缠结UHMWPE,通过设置不同的烧结温度(Ts)来改变熔体缠结状态,并探讨了链缠结程度对烧结制品结构与性能的影响.实验结果表明TS=220℃下,UHMWPE样品发生显著的复缠,造成高缠结度;而Ts=170℃下,初始低缠结状态能够得以充分保留,从而获得了缠结度具有明显差别的不同样品.示差扫描量热法(DSC)测试表明,在Ts=170℃下,低缠结度有利于在随后等温及冷却结晶过程中生成高熔点(最高达141℃)晶体与高的结晶度(最高达65%).力学测试表明低缠结度制品的综合力学性能显著提升,其中屈服强度提高72%,拉伸断裂强度提升139%,弹性模量提升162%以及断裂伸长率提升36%,实现了同时增强增韧.这就提供了一种从调节链缠结温度实现UHMWPE烧结制品高性能化的新思路.     

穿插程度对高分子链结晶初始阶段的影响

用分子动力学方法模拟了具有不同穿插程度的寡链凝聚体系结晶初始阶段的有序化过程. 链间穿插程度通过径向分布函数的统计进行表征. 模拟计算结果表明, 链间的穿插程度对体系的有序化过程具有明显的影响, 穿插程度越小的体系有序化越快, 形成的有序结构也更完整. 与实验结果的比较表明, 在聚合物粒子结晶的初始阶段, 体系由穿插引起的缠结就已经起到了作用.     

A Langevin dynamics simulation study of the tribology of polymer loop brushes

The tribology of surfaces modified with doubly bound polymer chains (loops) has been investigated in good solvent conditions using Langevin dynamics simulations. The density profiles, brush interpenetration, chain inclination, normal forces, and shear forces for two flat substrates modified by doubly bound bead-necklace polymers and equivalent singly bound polymers (twice as many polymer chains of 12 the molecular weight of the loop chains) were determined and compared as a function of surface separation, grafting density, and shear velocity. The doubly bound polymer layers showed less interpenetration with decreasing separation than the equivalent singly bound layers. Surprisingly, this difference in interpenetration between doubly bound polymer and singly bound polymer did not result in decreased friction at high shear velocity possibly due to the decreased ability of the doubly bound chains to deform in response to the applied shear. However, at lower shear velocity, where deformation of the chains in the flow direction is less pronounced and the difference in interpenetration is greater between the doubly bound and singly bound chains, some reduction in friction was observed.     

Mesoscale simulations of the behavior of charged polymer brushes under normal compression and lateral shear forces

Dissipative particle dynamics (DPD) was used to investigate the behavior of two opposing end-grafted charged polymer brushes in aqueous media under normal compression and lateral shear. The effect of polymer molecular weight, degree of ionization, grafting density, ionic strength, and compression on the polymer conformation and the resulting shear force between the opposing polymer layers were investigated. The simulations were carried out for the poly(tert-butyl methacrylate)-block-poly(sodium sulfonate glycidyl methacrylate) copolymer, referred as PtBMA-b-PGMAS, end-attached to a hydrophobic surface for comparison with previous experimental data. Mutual interpenetration of the opposing end-grafted chains upon compression is negligible for highly charged polymer brushes for compression ratios ranging from 2.5 to 0.25. Under electrostatic screening effects or for weakly charged polymer brushes, a significant mutual interpenetration was measured. The variation of interpenetration thickness with separation distance, grafting density, and polymer size follows the same scaling law as the one observed for two opposing grafted neutral brushes in good solvent. However, compression between two opposing charged brushes results in less interpenetration relative to neutral brushes when considering equivalent grafting density and molecular weight. The friction coefficient between two opposing polymer-coated surfaces sliding past each other is shown to be directly correlated with the interpenetration thickness and more specifically to the number of polymer segments within the interpenetration layer.     

超高分子量聚苯乙烯的流变性能

以毛细管流变仪和Hakke转矩流变仪对稀土催化合成的超高分子量聚苯乙烯 (UHMWPS)的流变与加工性能进行了研究 .结果表明 ,UHMWPS最显著的流变特征为超高的熔体粘度和低剪切速率下出现不稳定流动 .不稳定流动与超高分子量聚合物长的松弛时间有关 ,并提出了临界剪切速率与分子量和温度的定量关系式 .较低的分子量和较高的温度有利于提高临界剪切速率 ,改善挤出物外观质量和降低熔体粘度 .分子链极度缠结不仅导致超高的熔体粘度 ,也使UHMWPS链解缠加快 ,导致更高的剪切速率敏感性 .UHMWPS塑化时熔体粘度高 ,转矩大 ,加工性能劣于通用聚苯乙烯 (GPPS)     

Effect of chain interpenetration on polymer–polymer interaction in solution

Two series of monodisperse polystyrenes have been prepared with a molecular weight range of 3,000 to 300,000. One series was lightly substituted with dimethylbenzylamine groups, the other with 2,6 dinitro-4-benzoyloxyphenol groups. Members of each series were dissolved together in benzene solution in the range of 0.1–30%, and the equilibrium constant for the formation of the ammonium phenolate ion pair measured. Also measured was the corresponding equilibrium constant between comparable small molecular weight analogs, and between these analogs and the substituted polymers. The degree of association found between the models and between the models and the polymers was independent of molecular weight, but deviations were found in the polymer–polymer interaction. Normal equilibrium constants were found at high polymer concentrations indicating that chain interpenetration occurred freely. At low concentrations of polymer, if several links per chain were possible it was found an excess of linkages were formed. If only one link per chain was possible, low degrees of association were found for high molecular weight polymers, but the effect was not as large as a consideration of excluded volumes on a spherical model would predict.     

Effect of ultrasound on the microstructure of polystyrene in cyclohexane: a synchrotron small-angle X-ray scattering study

Synchrotron small-angle X-ray scattering technique has been used to study the effect of ultrasound on the microstructure of polystyrene (PS) in cyclohexane solutions. The results show that the intramolecular radius of gyration (R _g) decreases with ultrasound, indicating the shrinkage and collapse of PS chains. There is an exponential relationship between R _g and the molecular weight of PS (M _w), and the exponent changes from 0.5 to 0.417, as the ultrasound time is increased. This means that the shape of PS chain changes from random coil to shrunken form. The Kratky plots also confirm the shape transformation of PS chains induced by ultrasound. Moreover, the intermolecular correlation length increases with the ultrasound time, which is indicative of the entanglement of PS chains.     

Monitoring Diffusion of Reptating Polymer Chains by a Direct Energy Transfer Method: A Monte Carlo Simulation

A kinetic Monte Carlo method was used to simulate the diffusion of reptating polymer chains across an interface. A time‐resolved fluorescence technique in conjunction with a direct energy transfer method was used to measure the extent of diffusion of dye‐labeled reptating polymer chains. The diffusion of donor‐ and acceptor‐labeled polymer chains between adjacent compartments was randomly generated. The fluorescence decay profiles of donor molecules were simulated at several diffusion steps to produce mixing of the polymer chains. Mixing ratios of donor‐ and acceptor‐labeled polymer chains in compartments were measured at various stages (snapshots) of diffusion. It was observed that for a given molecular weight, the average interpenetration contour length was found to be proportional to the mixing ratio. Monte Carlo analysis showed that the curvilinear diffusion coefficient is inversely proportional to the weight of polymer chains during diffusion.