β-二酮钛配合物/甲基铝氧烷催化体系用于苯乙烯的间规聚合

β 二酮钛配合物／甲基铝氧烷催化体系用于苯乙烯的间规聚合许学翔谢光华（中国科学院化学研究所北京１０００８０）关键词β 二酮钛配合物，苯乙烯，甲基铝氧烷，间规聚合苯乙烯聚合物可分为无规聚苯乙烯（ａ ＰＳ），等规聚苯乙烯（ｉ ＰＳ），间规聚苯乙烯（ｓ?..     

单茂钛化合物/MAO/AlR_3均相催化体系合成sPS与aPP研究

先考察部分水解三甲基铝（ＴＭＡ）制备固体改性甲基铝氧烷（ｍ ＭＡＯ）时，反应物Ｈ２Ｏ和ＴＭＡ的摩尔比对固体产物ｍ ＭＡＯ中ＴＭＡ含量的影响；然后考察不同的钛化合物特别是茂钛化合物（ＬｎＴｉＸｎ′，ｎ＝１，２，ｎ′＝２，３）和ｍ ＭＡＯ组成的均相催化体系分别进行苯乙烯间规聚合和丙烯无规聚合的效果作比较．在此基础上分析以茂基三正丙氧基钛［ＣｐＴｉ（ＯＰｒｎ）３］为主催化剂，不同ＴＭＡ含量的ｍ ＭＡＯ为助催化剂，及外加各种烷基铝（ＡｌＲ３）所组成的催化体系中钛的氧化数，同时对苯乙烯间规聚合和丙烯无规聚合进行比较研究，从中发现活性中心钛的氧化数以Ｔｉ（Ⅲ）为主时有利于苯乙烯间规聚合，不利于丙烯无规聚合；而氧化数以Ｔｉ（Ⅳ）为主时则对丙烯无规聚合有利．苯乙烯间规聚合时，外加烷基铝可节省ＭＡＯ用量．     

β-二酮-茂基二氯化钛/MAO催化体系用于苯乙烯间规聚合

制备了 β 二酮类配体 [O ,O]的茂基二氯化钛配合物CpTi(dbm)Cl2 .实验证明 ,这类配合物在助催化剂甲基铝氧烷MAO作用下 ,可催化苯乙烯间规聚合 .显示较高的活性 (10 7× 10 5gPS molTi·h) .所得聚合物具有较高的间规度 .CpTi(dbm)Cl2 MAO体系催化活性随铝 钛比的增加呈上升而后衰减 ,当铝 钛比为 5 0 0左右时活性最高 ;聚合温度较高时会导致催化活性下降 .对聚合物进行了1 3C NMR表征     

杯芳烃钛化合物的合成及用于乙烯和苯乙烯聚合的研究

杯芳烃钛化合物的合成及用于乙烯和苯乙烯聚合的研究李勇郑炎松谢光华（中国科学院化学研究所北京１０００８０）关键词杯芳烃，钛化合物，聚乙烯，间规聚苯乙烯在茂金属／甲基铝氧烷（ＭＡＯ）均相催化体系中，催化剂的结构起着至关重要的作用，配体的空间效应、电...     

茂钛催化剂的苯乙烯间规聚合

比较了几种庞钛化合物/甲基铝氧烷/三甲基铝均相催化剂的苯乙烯间规聚合,认为茂基三正丙氧基钛[CpTi(O－n－Pr)₃]是苯乙烯间规聚合的良好催化剂[催化效率：ω_ps·ω_Ti^-1=4×10⁴g·g^-1]．探索了催化剂浓度、单体浓度、聚合温度和时间对苯乙烯聚合的影响．聚合反应产物用佛丁酮萃取,沸丁酮不可溶级分大于95％,经¹³CNMR分析该级分为间规聚苯乙烯．     

单茂钛催化剂的苯乙烯间规聚合和乙烯聚合的比较

考察三甲基铝（ＴＭＡ） 部分水解法制备固体改性甲基铝氧烷（ｍ ＭＡＯ） 时,反应物Ｈ２Ｏ 和ＴＭＡ 的摩尔比对ｍ ＭＡＯ 的产量及ｍ ＭＡＯ 中ＴＭＡ 含量的影响;以五甲基茂基三苄氧基钛［Ｃｐ ＊ Ｔｉ（ＯＢｚ）３］／ｍ ＭＡＯ 组成的均相催化体系,分别考察ｍ ＭＡＯ 的用量［ 即Ａｌ／Ｔｉ 摩尔比］ 及ｍ ＭＡＯ 中ＴＭＡ 含量对苯乙烯间规聚合和乙烯聚合的影响．通过分析Ｃｐ ＊ Ｔｉ（ＯＢｚ）３／ｍ ＭＡＯ 催化体系钛氧化态的分布,发现Ｔｉ（ Ⅲ） 活性中心有利于合成间规聚苯乙烯;而Ｔｉ（ Ⅳ） 活性中心有利于合成聚乙烯．苯乙烯间规聚合时,外加三异丁基铝（ＴＩＢＡ） ,将提高催化活性,同时可节省ＭＡＯ 用量．     

茂钛化合物／改性MAO催化剂制备聚丙烯—b—间规聚苯乙烯嵌 …

以五甲基环戊二烯基三苄氧基钛化合物「Ｃｐ＊Ｔｉ（ＯＢｚ）３」为主催化剂，改性甲基铝氧烷作助催化剂，采用单体顺序投入法，合成了聚丙烯－ｂ－间规聚苯乙烯嵌段共聚物。外加三异丁基铝可以使活性中心的氧化态由Ｔｉ（Ⅳ）还原为Ｔｉ（Ⅲ），从而提高苯乙烯共聚单体的转化率。实验表明此催化体系对共聚物的合成具有较高活性，适宜的茂钛化合物浓度可阻止活性中心被丙烯预聚物包埋。抽除残余丙烯气也可促进苯乙烯的共聚合。对聚合     

茂金属催化剂催化苯乙烯间规聚合 Ⅱ.Cp Ti(CH_2SiMe_3)_3/B(C_6F_5)_3的结构与活性中心

茂金属催化剂催化苯乙烯间规聚合＊Ⅱ．Ｃｐ＊Ｔｉ（ＣＨ２ＳｉＭｅ３）３／Ｂ（Ｃ６Ｆ５）３的结构与活性中心许光学（中山大学高分子研究所，广州５１０２７５）关键词阳离子配合物，茂金属化合物，均相催化剂，苯乙烯，间规聚合分类号Ｏ６４３／ＴＱ３２有关茂钛催化体...     

三个新茂钛催化剂的合成及苯乙烯间规聚合

合成了三个新茂钛催化剂:茂基三呋喃甲氧基钛,茂基三(四氢呋喃甲氧基)钛,茂基三苄氧基钛,其结构均经元素分析、^1HNMR、^1^3CNMR、IR及MS确证。它们与甲基铝氧烷(MAO)组成的催化体系对苯乙烯间规均聚合有良好的催化活性。     

合成高分子量无规聚丙烯的研究

用合成得到的五甲基环戊二烯基三苄氧基钛「ＣｐＴｉ（ＯＢｚ）３」与甲基铝氧烷（ＭＡＯ）组成新型催化体系进行丙烯的均聚合，研究了影响聚合活性及产物分子的各种因素，结果表明，用甲基取代钛化全物基环上的氢可使聚合产物分子是一增大一个数量级，所制得的聚丙烯为无规聚丙烯，具有高分子量。     

Luminescent Tungsten(VI) Complexes: Photophysics and Applicability to Organic Light‐Emitting Diodes and Photocatalysis

The synthesis, excited‐state dynamics, and applications of two series of air‐stable luminescent tungsten(VI) complexes are described. These tungsten(VI) complexes show phosphorescence in the solid state and in solutions with emission quantum yields up to 22 % in thin film (5 % in mCP) at room temperature. Complex 2 c , containing a 5,7‐diphenyl‐8‐hydroxyquinolinate ligand, displays prompt fluorescence (blue–green) and phosphorescence (red) of comparable intensity, which could be used for ratiometric luminescent sensing. Solution‐processed organic light‐emitting diodes (OLEDs) based on 1 d showed a stable yellow emission with an external quantum efficiency (EQE) and luminance up to 4.79 % and 1400 cd m⁻² respectively. These tungsten(VI) complexes were also applied in light‐induced aerobic oxidation reactions.     

Supramolecular polymeric complexes of calix[8]arenes

Formation of ionic complexes of calix[8]arenes with polymers of various basicities was studied, and previously unknown ternary polymeric complexes of calix[8]arenes of the ion-ion (polymer-calixarene-uranyl ion) and ion-hydrophilic molecule-hydrophobic molecule (polymer-calixarene-fullerene) types were prepared.     

O hyperfine structure in ESR spectra of Cu(II) hydroxyquinolinate: phthalimide

ESR spectra of ¹⁷O isotopic modifications of the Cu(II) hydroxyquinolinate complex substituted in phthalimide single crystals are reported and used to derive principal values and orientation of the hyperfine interaction tensors of the unpaired electron with the ¹⁴N and ¹⁷O nuclear magnetic moment.     

Hydrothermal synthesis, crystal structure and properties of Ni(II)-4f complexes based on 1H-benzimidazole-5,6-dicarboxylic acid

Nine novel heterometallic coordination polymers [Ln(2)Ni(Hbidc)(2)(SO(4))(2)(H(2)O)(8)](n) (Ln = Pr (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6), Ho (7), Er (8), Yb (9), H(3)bidc = 1H-benzimidazole-5,6-dicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, FT-IR, TG analysis and single crystal X-ray diffraction. X-ray analysis revealed that all complexes present almost identical three-dimensional (3D) structures with PtS-type topology. Complexes 1-7 are all isomorphous, and the structure variation of polymers 8 and 9 is induced by the lanthanide contraction effect. In additional, the luminescence properties of complexes 2, 3 and 5-7, and the magnetic properties of complexes 4 and 6-8 were investigated.     

Hydrogenation of heterocyclic compounds using polymer-containing catalysts

The hydrogenation of a series of oxygen- and nitrogen-containing compounds: furan, sylvan, benzofuran, certain dioxa-compounds, and pyridine, was investigated under mild conditions in the presence of polymer-containing catalysts based on metals of group VIII. The catalysts used were soluble complexes of Pt, Pd, and Rh with various polymers and copolymers. The greatest activity was exhibited by rhodium complexes with carboxyl-containing polymers.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1032–1034, August, 1984.     

Electrically conducting polymers based on <Emphasis Type="Italic">trans</Emphasis>-[Pt(qol)<Subscript>2</Subscript>] complex

Oxidative electrochemical synthesis and formation kinetics of electrically conducting polymeric platinum(II) complexes with 8-quinolinol was studied. Spectroscopic and electrochemical properties of the polymers were characterized.     

8-羟基喹啉的高分子化及其Eu(Ⅲ)配合物的制备和表征

在合成含有8-羟基喹啉(8HOQ)配位基单体的基础上,将其与甲基丙烯酸甲酯(MMA)共聚得到含有8-羟基喹啉侧基的聚甲基丙烯酸甲酯(PMMA8q),实现了8-羟基喹啉的高分子化;通过PMMA8q和小分子协同配体与稀土离子Eu(Ⅲ)的配位反应,制备了两个稀土高分子发光配合物:Eu(PMMA8q)(8HOQ)2(H2O)3和Eu(PMMA8q)2(TTA)(H2O)3(TTA:噻吩甲酰三氟丙酮)。利用元素分析、红外光谱方法对各阶段产物进行了表征,用荧光光谱研究了两个稀土高分子配合物的荧光特性及发光机理。     

脂肪酸铕配合物聚合物材料的合成及发光性质

以一定比例正辛酸和月桂酸为第一配体,通过皂化法合成了脂肪酸铕配合物,并溶于甲基丙烯酸甲酯（MMA）单体通过本体聚合得到了含脂肪酸铕的PMMA光致发光聚合物材料AxByEu/PMMA（其中A=正辛酸根,B=月桂酸根,x、y分别表示正辛酸和月桂酸的比例）。考察了不同的第二配体（咔唑、二甲基-联吡啶、邻菲罗啉、噻吩甲酰三氟丙酮HTTA）对脂肪酸铕聚合物发光性能的影响,选择出合适的第二配体HTTA,进而合成了A3Eu/HTTA/PMMA聚合物。通过红外光谱、紫外光谱及荧光光谱对脂肪酸铕配合物及聚合物的结构和荧光性能进行表征。结果表明：合成的脂肪酸铕配合物及其聚合物均具有很好的光致发光性能,紫外激发能发射Eu3+离子的特征红光。当HTTA的质量分数减小至0.02%时,仍能很好地促进体系的发光,且不影响聚合物本身的透明性。     

Synthesis of metallosupramolecular polymers incorporating cage silsesquioxanes in the main chains

We first time prepared main‐chain type cage octasilsesquioxane (T₈) containing coordination polymers based on transition metal complexes with a bis‐Schiff base T₈ ligand ( bis‐SA‐T ₈ ), which was prepared from para‐bis(3‐aminopropyl)hexaisobutyl‐substituted T₈ cage ( bis‐T ₈ ) with salicylaldehyde. A mono‐Schiff base T₈ ligand ( SA‐T ₈ ) was prepared from 3‐aminopropylheptaisobutyl‐substituted T₈ cage ( mono‐T ₈ ) with salicylaldehyde. Coordination of bis‐SA‐T ₈ with Cu²⁺ and Zn²⁺ in a solution as well as the film state was confirmed by the d–d transition appearing as broad shoulder on the longer wavelength at around 600 nm and the fluorescence at around 440–470 nm, respectively. The resulting metallosupramolecular polymers gave optically transparent films in the visible region by a casting method. However, opaque green and whitish films were obtained in the case of the Cu²⁺ and Zn²⁺ complexes with SA‐T ₈ , respectively. The thermal stabilities of the metallosupramolecular polymers were higher than those of the corresponding metal complexes of SA‐T ₈ . © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2260–2266