聚醚醚酮链结构与反应的模型化合物的量子化学研究

利用ＡＭ１方法对聚醚醚酮模型化合物全优化，结果为：芳环平均相互扭转角为３３．０度，桥键角１１７．０－１１８．０度，其分子结构拓扑图形表明：所有苯环（核）为平面构型，但其内角扭曲；其氢原子对苯环构型无实质性贡献，在更长链的计算中，冻结苯核与氢原子也得出满意结果，根据Ｍｕｌｌｉｋｅｎ键序与电荷讨论了醚交换与磺化反应。     

聚醚醚酮酮和含联苯聚醚醚酮酮共聚物的熔融热

根据Ｆｌｏｒｙ热力学统计理论和比容－熔融热作国法，由ＤＳＣ结果得到了不同联苯含量的聚醚醚酮酮－含联苯聚醚醚酮酮（ＰＥＥＫＫ－ＰＥＢＥＫＫ）共聚物的熔融热，两种方法获得的结果吻合。在此基础上给出了ＰＥＥＫＫ－ＰＥＢＥＫＫ共聚物不同联苯含量的熔点计算表达式。结果还表明，随着联苯含量ｎＢ，的变化，明显改变；当ｎＢ＝０．３５时，ＰＥＥＫＫＰＥＢＥＫＫ共聚物的值最小。     

Synthesis and Characterization of Two Binuclear Macrocyclic Zinc(Ⅱ) Complexes by Anion Exchange

Two macrocyclic zinc(II) complexes {[ZnL(VO3)2]·0.33H2O}n(1) and [ZnL(H2O)2][Ni(CN)4](2)(L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) have been obtained from the reactions of [ZnL](ClO4)2 with NH4VO3 and K2[Ni(CN)4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn(II) atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2+, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL(H2O)2]2+ and [Ni(CN)4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.     

Study on the cationic modification and dyeing of ramie fiber

A modification procedure for ramie fiber using 3-chloro-2-hydroxypropyltrimethyl ammonium chloride (CHPTAC) as a cationic agent and NaOH as a catalyst was developed in this paper. The morphological and structural transformations of the fiber induced by modification were determined by XRD (XRD), differential scanning calorimetry (DSC), and thermogravimetry analysis (TGA). XRD results show that the crystal structure of the modified fiber was still preserved although its crystallinity was decreased, which was confirmed from the TGA results. The mechanisms for the modification and dyeing of ramie fiber were analyzed, and the optimum modification conditions were determined to be the CHPTAC concentration of 30 g L⁻¹, the NaOH concentration of 15 g L⁻¹, the reaction temperature of 50 °C, and the reaction time of 60 min. The raw and the modified fibers were dyed with C.I. reactive red 2. The K/S values for the cationic modified fiber increased to be three times as high as the unmodified fiber. The dye uptakes increased greatly with an increase in the nitrogen contents up to 0.4% on the modified fibers.     

热塑性聚酰亚胺与聚醚醚酮共混物的等温结晶动力学

采用熔融共混方法制备了热塑性聚酰亚胺(TPI)与聚醚醚酮(PEEK)的共混物; 用示差扫描量热分析(DSC)研究了共混物的等温结晶动力学. 分别采用Avrami方程和Hoffman-Lauritzen方程分析共混物的等温结晶动力学、端表面自由能(σe)和分子链折叠功(q). 结果表明, 加入TPI后PEEK的结晶速率降低, 结晶活化能、σe和q均增加. 但这些数值的变化与TPI含量不呈线性关系, 并从共混物的相容性和表面形貌给出了可能的解释.     

含间苯基聚芳醚酮的合成与性能研究

含间苯基聚芳醚酮的合成与性能研究林权，张万金，吴忠文，尹玖梅（吉林大学化学系，长春，１３００２１）（中国科学院长春应用化学研究所）关键词聚芳醚酮，间苯基，熔点，结晶度聚芳醚酮作为一类耐高温特种工程塑料，由于具有优异的热、电、机械性能，已被广泛应用于电...     

Catalytic asymmetric construction of spirocyclopentaneoxindoles by a combined Ru-catalyzed cross-metathesis/double Michael addition sequence

Biologically important and synthetically challenging spirocyclopentaneoxindoles with four contiguous stereocenters including one spiroquaternary stereocenter have been constructed in good yields (72-87%) with excellent diastereoselectivity (16:1→30:1 dr) and enantioselectivity (93→99% ee) by a combined Ru-catalyzed cross-metathesis/organocatalyzed asymmetric double-Michael addition sequence.     

CO和CH_30N0在Al_20_3负载钯铜合金催化剂上合成草酸二甲酯的原位红外光谱研究

利用原位红外光谱技术研究了常压下CO和CH3ONO多相催化合成草酸二甲酯的反应．发现在草酸二甲酯生成的同时还存在副反应，副产物NO继续与CO反应生成CO2和N2O．铜在合金催化剂中起辅助作用，铜分散把，使CO桥式吸附减少，线式吸附增多．主反应与CO桥式吸附无关，而副反应却依赖于CO的桥式吸附．CO线式吸附具有更高的反应活性．     

芳香聚醚酮酮晶体结构及其晶型变化的研究（Ⅰ）

利用Ｘ射线及热分析技术研究了聚醚酮酮（ＰＥＫＫ）的溶剂诱导结晶及从玻璃态结晶和从熔融态结晶的行为。发现ＰＥＫＫ有两种晶型结构（Ⅰ和Ⅱ），晶型Ⅱ的形成与热历史和溶剂诱导有关，其熔点始终低于Ⅰ型１０℃左右。ＰＥＫＫ的低温熔融峰与其分子链极化有关，而与热历史无关，此低温熔融峰热焓占总热焓２％～１０％，其平衡熔点为４０９℃。     

聚芳醚酮在溶液中的分子构象与分子极化

经从头计算,得到4,4'-二氟苯酮二面角为44°,MES₃二面角为51°;用UV光谱法研究了单分散齐聚物在H₂SO₄中的分子构象与极化,结果表明:H₂SO₄使碳基质子化是产生极化的主要因素之一,由此产生的新吸收峰在λ=400nm左右;极化作用产生的平面构象经重叠后在λ=500nm左右产生另一新的吸收峰.由质子化模型并考虑组态相互作用的计算结果与文献一致.证明了聚芳醚酮高聚物在H₂SO₄中,于400nm左右处产生的峰(UV)为羰基极化的结果,指明在H₂SO₄中测其分子量时应按羰基含量校正.