固体1H-NMR表征玻璃态高分子链的缠结、互穿及链间邻近度

系统回顾了缠结定义的演化及对其表征的各种方法,比较了这些方法的特点和不足.在以往研究的基础上,发展了一套在分子尺度上表征玻璃态高分子链互穿的方法.该方法结合高速魔角和偶极滤波,用固体1H-NMR探测互穿区域的质子信号,表征了玻璃态聚苯乙烯的链互穿程度.该方法在0.5 nm尺度范围内测定了分子链间的距离,且与以往方法相比,该方法具有耗时短、需要样品量少、灵敏度和信噪比高等优点.     

聚苯乙烯/聚异戊二烯嵌段共聚物相态结构的固体核磁研究

本文将固体核磁中的交叉极化与魔角旋转(CP/MS)技术与Goldman-Shen脉冲序列相结合,研究了不同分子量的单分散聚苯乙烯/聚异戊二烯嵌段共聚物(SAI)中磁化矢量的自旋扩散速度。以一个均匀分布的相结构模型为基础,求解了扩散方程和样品中的微区尺寸。     

聚苯乙烯-聚(4-乙烯基吡啶)嵌段共聚物LB膜结构形态的研究

采用氯仿作为铺展溶剂,将嵌段共聚物聚苯乙烯-聚(4-乙烯基吡啶)(PS-b-P4VP)稀溶液铺展于空气与水界面上,利用Langmuir-Blodgett(LB)膜技术转移至固体基底.研究了不同的嵌段比、表面压和小分子1-芘丁酸(PBA)的加入对嵌段共聚物气液界面聚集组装的影响.研究发现随着亲水段(P4VP)的增加,聚集组装结构由纳米片状、带状转变成纳米条状、纳米点状结构.表面压对纯PS-b-P4VP聚集组装产生影响,表面压增大,组装体排列紧密;随着表面压的继续增大,单层聚集结构遭到破坏,发生堆叠.加入PBA小分子后,PBA与PS-b-P4VP形成氢键,形态发生明显变化,原来的片状结构转变为条状或点状结构.     

由特殊相互作用导致的高分子间的络合Ⅸ.聚(苯乙烯-co-4-乙烯基苯酚)/聚(苯乙烯-co-4-乙烯基吡啶)在本体中的相容-络合行为

采用结合物理老化技术的示差扫描量热法（ Ｄ Ｓ Ｃ） 以及非辐射能量转移荧光光谱法（ Ｎ Ｒ Ｅ Ｔ） 研究了聚（ 苯乙烯 ｃｏ ４ 乙烯基苯酚） （ Ｓ Ｔ Ｖ Ｐｈ） 与聚（ 苯乙烯 ｃｏ ４ 乙烯基吡啶）（ Ｓ Ｔ Ｖ Ｐｙ） 共混体系在本体中的相容与络合行为．当 Ｓ Ｔ Ｖ Ｐｈ 中 Ｏ Ｈ 含量为３ ,６ ,９ ｍ ｏｌ ％ 时,可以分别与吡啶基含量是２５ ,５０ ,７５ ｍｏｌ ％ 的 Ｓ Ｔ Ｖ Ｐｙ 实现相容, Ｏ Ｈ 含量更高时还可进一步形成络合,表现为远较 Ｆｏｘ 方程预示值高的 Ｔｇ 和窄的转变温度区间．此外,还讨论了浇膜溶剂对相容与络合的影响     

酚氧树脂/聚(4-乙烯基吡啶)高分子复合物的制备及表征

采用元素分析、DSC、FTIR、紫外光谱及XPS等手段对酚氧树脂和聚(4-乙烯基吡啶)在氯仿中溶液共混形成的高分子复合物的组成及结构进行了研究,并与相应的共混物作了比较。结果表明,所得的各复合物的组成相同,其值与组分分子中的链节等摩尔比一致;而共混物也为相容体系,其组成与两高分子组分的投料比对应。基于实验结果,揭示了复合物的形成过程。     

含pH敏感聚(4-乙烯基吡啶)的嵌段共聚物成核胶束化过程的NMR研究

利用NMR技术研究了聚乙二醇-b-聚(4-乙烯基吡啶)(PEG114-b-P4VP107)和聚(N-异丙烯基丙烯酰胺)-b-聚(4-乙烯基吡啶)(PNIPAM53-b-P4VP260)在逐步降低聚(4-乙烯基吡啶)链段质子化程度时嵌段共聚物的胶束化过程.在开始形成胶束时,吡啶环上氢原子的自旋-晶格弛豫时间(T1)急剧减小.结果表明,PEG114-b-P4VP107在质子化程度降为0.54时已有胶束生成;PNIPAM53-b-P4VP260在质子化程度降为0.58时也能观测到胶束生成的信号.将两个嵌段共聚物各自制得胶束的溶液相混合,观测到了发生在高分子链间的2DNOE信号,这表明所制得溶液中胶束与高分子链间有链交换的动态平衡.     

4-乙烯基吡啶与丙烯酰胺共聚合的研究

以过硫酸钾为引发剂 ,采用溶液自由基共聚合方法 ,实现了丙烯酰胺 (AM)与 4 乙烯基吡啶 (4 VP)的共聚合 .通过详细研究共溶剂体系、单体总浓度、反应温度、反应时间及引发剂量对共聚合过程中转化率和分子量的影响 ,从而确定了适宜的共溶剂体系和最佳的工艺条件 .用紫外分光光度法测得了共聚物的组成 .用Kelen Tudos方法 ,求得 4 乙烯基吡啶 (4 VP)和丙烯酰胺 (AM)单体的竞聚率 ,r4 VP =0 6 4 4 ,rAM =0 371.最后通过FTIR和1 3C NMR表征共聚物的结构并验证了共聚物的组成 .     

4-乙烯基吡啶 - 苯乙烯共聚物正离子与十二基烷基硫酸钠相互作用研究

４ 乙烯基吡啶 苯乙烯共聚物正离子与十二基烷基硫酸钠相互作用研究郑晓亮曹维孝（北京大学化学与分子工程学院北京１００８７１）关键词４ 乙烯基吡啶 苯乙烯共聚物正离子，十二烷基硫酸钠，疏水相互作用，胶束交联水溶性聚合体尤其是聚电解质与表面活性剂相互...     

纳米CdSe与聚4-乙烯基吡啶盐的复合与表征

用巯基乙酸作稳定剂在水相中合成了CdSe纳米颗粒. 聚4-乙烯基吡啶季铵盐(PVPNI)通过静电作用与CdSe纳米颗粒复合形成了纳米复合材料.该复合材料通过红外光谱数据（IR）、电感耦合等离子发射光谱（ICP-AES）、透射电镜（TEM）等方法进行了表征,并通过紫外可见吸收光谱(UV-Vis)和荧光光谱(PL)对其光学性质进行了研究.结果表明,复合材料的形成,改善了纳米CdSe的分散性,并提高了纳米CdSe的荧光强度.     

聚(苯乙烯-4-乙烯基吡啶)钕配合物的研究

含氮聚合物是一类很有意义的配位体,它在某些反应的催化过程中起载体作用。在含氮聚合物中,聚(苯乙烯-4-乙烯基吡啶)(PS4VPY)也是一种很重要的配体,因其杂环氮原子有一定的反应能力和配位能力。聚(4VPY)过渡金属(如Co、Ni、Cu和Zn)配合物已有报道。但PS4VPY的稀土配合物未见报道。本文报道NdCl_3·PS4VPY的合成和表征,及催化活性。     

超分子体系中次层相互作用对59Co NMR谱的影响

用＾５０Ｃｏ固体静态ＮＭＲ对〔Ｃｏ（ＣＮ６〕＾３－离子与质子化的大环聚胺阳离子形成的超分子络合物的次层相互作用进行研究,结果表明,氢键的形成对该超分子结构的稳定性起了重要的作用。与仅有静电作用存在的Ｋ３〔ＣｏＣＮ）６〕分子相比,＾５９Ｃｏ的三个化学位移张量的主值差值在超分子体系中明显增大。氢键作用的结果使〔Ｃｏ（ＣＮ６〕３－的对称性发生了改变,导致＾１Ｔ１ｇ三重简并态发生分裂。分裂的大小反映了相互     

Hydrogen Bonding Complexes of Poly(styrene-co-2-hydroxyethyl acrylate) and Poly (styrene-co-4-vinylpyridine)

Summary: Random copolymers of poly(styrene-co-4-vinylpyridine) (S4VP) and poly (styrene-co-2-hydroxyethyl acrylate) (SHEA) of different compositions were prepared and characterized. An investigation of the effects of solvent and densities of the interacting species incorporated within these copolymers showed that novel and various hydrogen bonding interpolymer complexes of different structures were elaborated when these copolymers are mixed together. The specific interactions that occurred within the SHEA copolymers and the elaborated complexes were evidenced by FTIR qualitatively from the appearance of a new band at 1604 cm⁻¹ and quantitatively using appropriate spectral curve fitting in the carbonyl and pyridine regions. The intermolecular hydrogen bonding interactions that occurred between the hydroxyl groups of the SHEA and the nitrogen atom of the pyridine groups in the S4VP are stronger than the self-associations within the SHEA. In the solid state, a DSC analysis showed that the variation of the glass transition temperatures of these materials with the composition behaved differently with the densities of interacting species and were analyzed quantitatively. A thermal stability study of the synthesized copolymers and of their different mixtures carried by thermogravimetry confirmed a similar behaviour.     

Study on crystallographically inequivalent protons in RbH2AsO4 using static NMR and MAS NMR

Two inequivalent protons from ¹H NMR spectra of RbH₂AsO₄ in the paraelectric phase were distinguished using static NMR and MAS NMR. From the ¹H spin–lattice relaxation times in the laboratory frame, T₁, and rotating frame, T_1ρ, of the two crystallographically inequivalent hydrogen sites, i.e., H(1) and H(2), the temperature dependences of T₁ and T_1ρ for H(1) were related to the reorientational motion. The shorter H(1) bonds give rise to stronger H-bonds, and protons involved in stronger H-bonds have long relaxation times. Consequently, the RbH₂AsO₄ structure has two crystallographically inequivalent sites with two different hydrogen-bond lengths.     

12-磷钨酸及其铯盐的酸位可接近性:固体核磁共振探针分子研究

 固体酸催化剂的酸位可接近性是影响催化剂性能的重要性质. 使用与反应分子大小接近的碱性探针分子三甲基膦和固体核磁共振技术,定量研究了磷钨酸及其铯盐的酸位可接近性. 结果表明,磷钨酸具有“假液相性”,三甲基膦可以接近磷钨酸体相中的酸位,在无水的磷钨酸中,有大约2/5的酸位可以被三甲基膦所接近. 磷钨酸的铯盐没有“假液相性”,探针分子只能接近催化剂表面的酸位,在无水的Cs1.5H1.5PW12O40中,只有大约5%的酸位能够被三甲基膦所接近.     

Fabrication of Poly（4-vinylpyridine） Nanofiber and Fluorescent Poly（4-vinylpyridine）/Porphyrin Nanofiber by Electrospinning

Poly（4-vinylpyridine）（P4-VP） nanofiber and fluoresent poly（4-vinylpyridine）/porphyrin（P4-VP/TPPA） nanofiber were respectively prepared by electrospinning. The effect of the concentration of P4-VP/dimethylformamide （DMF） electrospinning solutions on the morphology of P4-VP nanofiber was investigated and it was found that the average diameter of the nanofiber of P4-VP/DMF increased with the increase of the concentration of the spinning solution. After the addition of TPPA to the P4-VP/DMF spinning solution, the diameter of P4-VP/TPPA nanofiber became even due to the increase of the conductivity of the P4-VP/DMF-TPPA solution. The photoluminescent（PL） spectral analysis indicates that the emission peak position of P4-VP/TPPA nanofiber is almost the same as that of pure TPPA at about 650 nm without peak shift, and when it was stored for 20 days, the emission peak of P4-VP/TPPA nanofiber is also at 650 nm, indicating that the fluorescent property of P4-VP/TPPA nanofiber is stable. Fourier-transform iufrared（FTIR） spectrum confirms the chemical composition of the resulting P4-VP/TPPA composite nanofiber.     

Proton magnetic shielding in H2O and (H2O)2

The proton magnetic shielding constants in the water molecule and its linear perpendicular dimer are computed from SCF-MO-LCGO wave functions by using the uncoupled Hartree-Fock variation-perturbation procedure due to Karplus and Kolker. The convergence of the calculated shielding constants as well as their gauge dependence is studied. The final results for 17-term polynomial variation function indicate that the best choice for the gauge origin corresponds to the molecular electronic centroid.The calculated proton magnetic shielding constant in the water molecule is in remarkable agreement with experimental data and favourably compares with the best coupled Hartree-Fock results. It follows from the calculations for the water dimer that the H-bond NMR-shift amounts in this case —1.0 ppm and qualitatively agrees with the experimental data for the liquid water.     

The Polymerization of Propargyl Chloride Activated by Interaction with Poly(4-vinylpyridine)

The reaction between poly (4-vinylpyridine) and propargyl chloride was studied in methanol. It was shown that, independently of the ratio of reactants to each other, the end products of the reaction are polymers with conjugated bond systems formed by the opening of the propargyl triple bond which was activated by interaction with poly (4-vinylpyridine). It was shown that “normal” quarternization of poly (4-vinylpyridine) by propargyl chloride precedes accelerated polymerization of propargyl chloride which begins at 6 to 8% alkylation. It was established that the solution becomes structured before accelerated polymerization begins. A possible mechanism for this reaction has been proposed.     

Supramolecular Complex of Poly(styrene)-b-Poly(4-vinylpyridine) and 1-Pyrenebutyric Acid in Thin Film

Summary: Here, we have described a novel supramolecular complex (SMC) between poly(styrene)-b-poly(4-vinylpyridine) (PS-b-P4VP) and 1-pyrenebutyric acid (PBA) and studied of its self assembly in thin film. PBA will make supramolecular complex with the P4VP block due to strong hydrogen bonding between the carboxylic group of 1-pyrenebutyric acid and pyridine ring of P4VP. The formation of supramolecular complex between PS-P4VP and PBA through hydrogen bonding is investigated through FTIR study. The supramolecular complex of PS-b-P4VP and 1-pyrenebutyric acid changed the block copolymer morphology from cylindrical to lamella in thin film due to the increase of the volume fraction of P4VP (PBA). In both cases (parent block copolymer and SMC), the microdomains are oriented normal to the substrate after annealing in a selective solvent. Pure block copolymer shows cylindrical morphology with a periodicity of ∼26 nm, whereas the SMC shows lamellar morphology with a periodicity of ∼ 29 nm. After fabricating the thin film from SMC, 1-pyrenebutyric acid can be easily removed by dissolving the thin film in ethanol to transform the block copolymer thin film into nanotemplate or membrane.     

Interpolymer complexation in hydrolysed poly(styrene-co-maleic anhydride)/poly(styrene-co-4-vinylpyridine)

Complexation between hydrolysed poly(styrene-co-maleic anhydride) (HSMA) copolymers containing 28% and 50% maleic anhydride and a poly(styrene-co-4-vinylpyridine), St4VP32 copolymer with 32% of 4-vinylpyridine content has been investigated. Formation of interpolymer complexes from 1,4-dioxane solutions is observed, over the entire composition range and the stoichiometry of these complexes has been determined from elemental analysis.Quantitative FTIR study of the system HSMA50/StV4Py32 shows that the ideal complex composition leads to 2:1 unit mole ratio of interacting component. FTIR results are in good agreement with DSC and TGA ones, since this complex composition gives the maximum value of the glass transition temperature and the best thermic stability.For the systems investigated, the T_g versus composition curve do not follow any of the commonly accepted models proposed for polymer blends. A new model proposed by Cowie [Cowie JMG, Garay MT, Lath D, McEwen IJ. Br Poly J 1989;21:81] is used to fit the T_g data and found to reproduce the experimental results more closely.