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乙烯 (E) /乙烯醇 (V)共聚物 (EVOH)为结晶性高聚物 ,作为膜材料有着广泛的用途 .在该体系中 ,不仅存在复杂的化学和物理结构 ,如序列分布、立构规整性和共晶结构 ,还存在复杂的氢键相互作用 ,是研究化学结构、聚集态结构和氢键相互作用之间关系的代表性体系 .通过DSC[1 ] 、X 射线衍射[2 ] 、固体高分辨核磁共振碳谱 (1 3C CP/MAS NMR) [3~ 7] 等不同的研究方法 ,前人对EVOH体系及与之直接相关的乙烯醇均聚物(PVA)的熔融温度、结晶度以及结晶结构等问题进行了大量研究 .1 984年Terao等[6] 首先报道了在固… 相似文献
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淀粉-丙烯酸钠接枝共聚物的固体高分辨核磁共振研究 总被引:9,自引:0,他引:9
运用固体高分辨核磁共振技术,通过测量13C魔角旋转/交叉极化(CP/MAS)谱、1H自旋-晶格弛豫时间T1及旋转坐标系中的自旋-晶格弛豫时间T1ρ,对一系列淀粉-丙烯酸钠接枝共聚物的相结构进行了研究,并与淀粉、均聚丙烯酸钠及两者共混物的实验结果进行了比较.结果表明,接枝共聚导致了淀粉结晶度的明显降低;在共混物和接枝共聚物中,淀粉和聚丙烯酸钠组分都具有纳米尺度的相容性,由于接枝的效应,接枝共聚物中两个组分表现出比共混物更高的相容水平. 相似文献
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乙烯-乙烯醇共聚物氢键相互作用与链结构关系的变温溶液氢谱研究 总被引:2,自引:0,他引:2
用变温溶液核磁共振氢谱研究了不同组成的乙烯-乙烯醇共聚物在二甲亚砜溶液中的氢键相互作用.结果表明,乙烯醇单元中羟基的信号随温度升高而线性地向高场位移,且不同的三单元组中羟基信号的位移速率不同,表明羟基形成的氢键强度与链结构间存在相关性. 相似文献
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丙烯-乙烯共聚物/乙烯-1-辛烯共聚物层状复合材料的力学性能研究 总被引:3,自引:0,他引:3
利用自主设计的一套可进行微层共挤出的口模,分别制备了2层、16层、32层和64层丙烯-乙烯共聚物(PPE)/乙烯-1-辛烯共聚物(POE)交替层状复合材料。研究了制得的层状复合材料的应力-应变行为,利用等效盒子模型(equivalent box model)描述了层状复合材料与相应的常规PPE/POE共混材料力学行为的区别.通过对共挤出材料和共混材料的拉伸数据进行分析后发现,具有层状结构特别是多层结构的共挤出材料具有比共混材料更为优异的屈服和断裂伸长性能. 相似文献
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用固体高分辨核磁共振碳谱方法对不同拉伸比的聚醚酯嵌段共聚物的聚集态结构和分子运动进行了研究,发现共聚物中的聚四氢呋喃(PTMO)链段在拉伸比为2 0时开始就出现结晶,且结晶度和晶片厚度都随着拉伸比增加而明显增加,而样品中未结晶部分的高频分子运动随拉伸比的变化则不明显,拉伸导致的PTMO结晶主要发生在“纯”的PTMO非晶区.通过1 H自旋扩散实验,估算出在拉伸比为4 . 0倍时,PTMO非晶区与结晶区的界面层厚度为1 .1nm ,PTMO非晶区与硬段的结晶区的界面厚度约为3 .1nm . 相似文献
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热诱导相分离法制备亲水性乙烯-丙烯酸共聚物微孔膜 总被引:6,自引:0,他引:6
选择 3种不同丙烯酸含量的乙烯 丙烯酸共聚物 (EAA)为原材料 ,二苯醚 (DPE)为稀释剂 ,采用热诱导相分离法 (TIPS)制备了亲水性高分子微孔膜 .接触角实验证明 ,EAA为亲水性高分子材料 .利用熔点仪根据浊度的变化测绘出 3种不同EAA/DPE体系的双结点线以及通过DSC得出相应 3体系的结晶温度曲线 .实验结果还表明 ,随着乙烯 丙烯酸共聚物中丙烯酸含量的增加 ,结晶温度曲线向低温方向移动 ,相对应的膜孔直径也增加 .此外 ,随着EAA DPE体系中EAA初始浓度的逐渐增加 ,膜孔直径逐渐变小 ,当体系中EAA初始浓度高于 5 0 %时 ,不再出现微孔结构 相似文献
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单茂钛/MAO体系催化乙烯/丙烯共聚合研究:Ⅱ.乙烯/丙烯共聚物的核磁共振分 总被引:4,自引:2,他引:2
用13C-NMR测定了由单茂基钛化合物/mMAO催化体系制备的乙烯/丙烯共聚物大分子链的立体结构和单体序列分布,计算了单体的竞聚率r1=7.91±0.06,r2=0.135±0.03,其乘积r1r2≈1.Fineman-Ross计算得到的单体竞聚率与13C-NMR测定值相近,即r1=7.94,r2=0.134,其乘积r1r2=1.04.这表明共聚物是立构无规的.共聚物经溶剂萃取后,乙醚可溶和己烷可溶两个级分中单体的序列分布和竞聚率略有不同.乙醚可溶级分中丙烯链段稍长,而己烷可溶级分中乙烯链段稍长. 相似文献
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烷基甲基二烯丙基溴化铵共聚物是一种新型疏水改性的聚皂,应用多种核磁共振分析技术对其结构和共单体的组成进行了定量的讨论.研究结果表明,在测定化学结构和性质上比较接近的共单体组成时,核磁共振方法是一种有效的工具. 相似文献
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Qun Chen Takeyoshi Yamada Hiromichi Kurosu Isao Ando Takeshi Shiono Yoshiharu Doi 《Journal of Polymer Science.Polymer Physics》1992,30(6):591-601
The 13C spin-lattice relaxation times T1 of 13C-labeled polyethylene crystallized under different conditions were measured at temperatures from ?120 to 44°C by variable-temperature solid-state high-resolution 13C nuclear magnetic resonance (NMR) spectroscopy, in order to determine accurately the dynamics of the noncrystalline region of the polymer. From these results, it was found that the T1 minimum for the CH2 carbons in the noncrystalline region of solution-crystallized polyethylene with high crystallinity appears at higher temperature by about 20°C than that of melt-quenched polyethylene with low crystallinity. This means that the molecular motion of the CH2 carbons in the noncrystalline regions is more constrained at a given temperature in the material of higher crystallinity. Furthermore, dynamics of the noncrystalline region is discussed in terms of the 13C dipolar dephasing times. 相似文献
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The structure and the phase transition temperatures of [NH2(CH3)2]2ZnCl4 were determined using X-ray diffraction and DSC, respectively. The temperature dependence of chemical shifts and the spin–lattice relaxation time T1ρ in the rotating frame were measured for the 1H and 13C nuclei in [NH2(CH3)2]2ZnCl4. From these results, it was observed that the structural change by chemical shifts does not occur with temperature. However, T1ρ for 1H and 13C in [NH2(CH3)2]2ZnCl4 showed a minimum, and it is apparent that both T1ρ values are governed by the same tumbling motions. The activation energies of tumbling motions for 1H and 13C are nearly the same owing to the connection between CH3 and NH2 ions in the [NH2(CH3)2]+ group. 相似文献
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The temperature dependences of the chemical shifts and intensities of 1H, 13C, and 14N nuclei in tetramethylammonium tetrabromozincate, [N(CH3)4]2ZnBr4, were investigated using single-crystal nuclear magnetic resonance (NMR) and magic angle spinning (MAS) NMR spectroscopy to elucidate the structural geometry near the phase transition temperature. Based on the analysis of the 13C cross-polarization (CP)/MAS NMR and 14N NMR spectra, the two chemically inequivalent N(1) (CH3)4 and N(2) (CH3)4 ions were distinguished. Furthermore, the 14N NMR spectrum at the phase transition temperature indicated the existence of the ferroelastic characteristics of the N(CH3)4 ions. 相似文献
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Kenji Masuda Hironori Kaji Fumitaka Horii 《Journal of Polymer Science.Polymer Physics》2000,38(1):1-9
The chain conformation and hydrogen bonding in the crystalline and noncrystalline regions have been characterized for atactic poly(vinyl alcohol) (PVA) films prepared under different conditions by CP/MAS 13C NMR analyses developed recently. The CH resonance lines of the crystalline and noncrystalline components split in different ways, depending significantly on casting solvents and annealing. These lines are found to be successfully resolved into 3–7 constituent lines by the least‐squares curve fitting. In this analysis, nine lines with different chemical shifts are prepared as elementary lines for the curve fitting by assuming the upfield shifts due to the γ‐gauche effect and the downfield shifts due to the formation of the intramolecular hydrogen bonds. The integrated intensities of the constituent lines thus obtained are also interpreted in terms of statistical calculations, assuming the random distribution of the trans and gauche conformations along PVA chains and the statistical distribution of the intramolecular and intermolecular hydrogen bonds between appropriate adjacent OH groups. On the basis of probabilities ft and fa for the trans conformation and the intramolecular hydrogen bond obtained through these analyses, the effects of casting solvents and annealing are discussed for both crystalline and noncrystalline components. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1–9, 2000 相似文献
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Z. Dega-Szafran G. Dutkiewicz Z. Kosturkiewicz M. Petryna 《Journal of Molecular Structure》2004,708(1-3):15
Crystals containing three kinds of molecules 1-piperidiniumacetate (II), 1-piperidiniumacetic acid (III) and 2,4,6-trinitrophenolate (picrate, TNP−), belong to the monoclinic system, space group P21/c and Z=4, a=12.831(3), b=26.093(5), c=7.157(1) Å, β=101.18(3)°, R=0.0758. The zwitterion molecule (II) is a double acceptor of protons from two molecules of 1-piperidiniumacetic acid (III) (N–HO, 2.735(5) Å and O–HO, 2.472(5) Å), and a donor of proton to the picrate molecule (N–HO, 2.747(5) Å). These three molecules, which have three donor centers and several acceptor groups, form hydrogen-bonded chains parallel to the z axis. The oxygen atoms inactive in these hydrogen bonds, are engaged in the C–HO short contacts, which can be treated as weak hydrogen bonds, and join the chains into a three-dimensional network. The presence of protonated 1-piperidineacetic acid (III) and its zwitterion (II) in the crystal has been confirmed by 13C CP MAS NMR and solid state FTIR spectra. 相似文献
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无水SnCl4及SbCl5是典型的Lewis酸,是有机反应中常用的催化剂。它们的溶剂化热效应早已受到人们的关注,然而用NMR方法来研究它们的溶剂化作用至今未见报道。本工作用119Sn、121Sb及(13)C NMR考察了典型Lewis酸无水SnCl4、SnCl5与二十几种Lewis碱的相互作用,直接证实了Lewis酸碱反应为电子的授受过程。 相似文献