不同比例的s-BPDA/i-BPDA型聚酰亚胺共聚结构与性能关系

由不同比例的二酐单体3,3′,4,4′-联苯四酸二酐(s-BPDA)/2,2′,3,3′-联苯四酸二酐(i-BPDA)与二胺单体4,4′-二氨基二苯醚(4,4′-ODA)制得了一系列共聚可溶聚酰亚胺. 采用DSC 、TGA和拉伸等测试方法对所得共聚聚酰亚胺进行了表征, 实验结果表明, 所得聚酰亚胺具有优异的力学性能和热稳定性, 并且随着i-BPDA含量的增加, 聚酰亚胺的溶解性提高, 玻璃化转变温度(Tg)升高, 中间体聚酰胺酸的固有黏度降低.     

1,6- And 1,7-Regioisomers of Perylene Tetracarboxylic Dianhydride and Diimide: The Effects of Neutral Bay Substituents on the Electrochemical and Structural Properties

Abstract

The electrochemical and structural properties of a series of 1,6- and 1,7-regioisomers of different sized bay-appended perylene diimides (PDIs) and perylene tetracarboxylic dianhydrides (PTCDs) were assessed. Steric effects by large bay substituents triphenylsilylacetylene and tritylacetylene play a major role in the geometry of the solid and solution states. New triphenylsilylacetyene and 1-pentynyl derivatives were prepared and characterized. Suitable crystals for X-ray analysis of tritylacetylene and n-hexyl compounds illustrated the structural alterations in the bay region. The bulky tritylacetylene appended PDI assumed a nearly planar π-configuration, equivalent to an unsubstituted PDI. In contrast, a slender and less bulky hexyl chain incorporated PDI underwent a significant twisting of the central core of PDI. Neutral and conjugated groups at the bay region of PDI enhanced its reductive capability. In contrast, incorporation of neutral and nonconjugated groups at the bay region slightly diminished the reductive capability of resulting PDI derivative. PTCDs consisting of both bulky and slender groups were reduced significantly more readily in relation to the respective PDIs. Electrochemical reductive properties of selected PDIs and PTCDs were obtained along with optical properties of 1,6- and 1,7-PDIs.     

新型手性联萘修饰的金属卟啉的合成及催化烯烃环氧化作用

合成了系列新型手性联萘化合物1～9和具有不同手性空腔的新型刚性联萘卟啉14～17.利用元素分析、UV-Vis,MS(HRMS),IR,1HNMR,13CNMR及旋光分析等手段进行了表征.由于卟啉配合物的手性空腔大小不同,不同金属(Fe,Zn,Mn)的取代反应表现出很大的差异.用1HNMR对其中代表性的联萘化合物6,8和手性卟啉14,16的结构特点进行了讨论.以亚碘酰苯为氧源,将手性铁卟啉15和17应用于苯乙烯衍生物环氧化反应,催化结果表明该类催化剂具有高的对映选择性和催化稳定性,拥有合适手性空腔尺寸的15对苯乙烯的对映选择性为e.e.93%,转化率96%,在转化数为10000时仍保持了e.e.82%值.     

Novel organosoluble and colorless poly(ether imide)s based on 3,3‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]phthalide dianhydride and aromatic bis(ether amine)s bearing pendent trifluoromethyl groups

A novel series of colorless and highly organosoluble poly(ether imide)s were prepared from 3,3‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]phthalide dianhydride with various fluorinated aromatic bis(ether amine)s via a conventional two‐stage process that included ring‐opening polyaddition to form the poly(amic acid)s followed by cyclodehydration to produce the polymer films. The poly(ether imide)s showed excellent solubility, with most of them dissoluble at a concentration of 10 wt % in amide polar solvents, in ether‐type solvents, and even in chlorinated solvents. Their films had a cutoff wavelength between 358 and 373 nm, and the yellowness index ranged from 3.1 to 9.5. The glass‐transition temperatures of the poly(ether imide) series were recorded between 237 and 297 °C, the decomposition temperatures at 10% weight loss were all above 494 °C, and the residue was more than 54% at 800 °C in nitrogen. These films showed high tensile strength and also were characterized by higher solubility, lighter color, and lower dielectric constants and moisture absorption than an analogous nonfluorinated polyimide series. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3140–3152, 2006     

Synthesis of an axially chiral Ir–NHC complex derived from BINAM

The Ir–NHC complex 6 was successfully synthesized from the reaction of axially chiral binaphthyl dibenzimidazolium salt 5 with [Ir(COD)Cl]₂ (COD = 1,5‐cyclooctadiene) in tetrahydrofuran in the presence of KO^tBu base under reflux. Its unique crystal structure is unambiguously disclosed by X‐ray diffraction. Complex 6 is orthorhombic, with space group P2₁2₁2₁, unit cell dimensions a = 12.1406(16) Å, b = 19.110(3) Å, c = 20.312(3) Å, α = β = γ = 90° and volume 4712.6(11) ų, Z = 4, D_calc = 1.930 Mg m^?3. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis,structure, and activity of (PhCH2NH2)2CuCl2 for oxidative coupling of 2‐naphthylamine

(PhCH₂NH₂)₂CuCl₂ ( 2 ), an effective oxidation reagent for oxidative coupling of 2‐naphthylamine ( 1 ) to form 2,2′‐diamino‐1,1′‐binaphthyl ( 4 ), is studied. Oxidative coupling of 2‐naphthylamine ( 1 ) is carried out at room temperature in methanol by (PhCH₂NH₂)₂CuCl₂ ( 2 ), which is prepared from CuCl₂·2H₂O and benzylamine in methanol, to give a novel copper complex, [{1,1′‐(C₁₀H₆)₂‐2,2′‐(NH₂)₂}₂CuCl]Cl·CH₃OH·3H₂O ( 3 ), in good yield. Treatment of 3 with aqueous HCl (37%), followed by addition of NH₃·H₂O (25%), gives 2,2′‐diamino‐1,1′‐binaphthyl ( 4 ) in a moderate yield (total yield from 1 : > 70%). Both 2 and 3 have been characterized by various techniques, such as infrared spectroscopy, elemental analyses and X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.     

花二酸酐与嘧啶衍生物的氢键组装(英文)

用半经验AM1方法对苝二酸酐与嘧啶衍生物的1∶1及1∶2氢键复合物进行理论研究,表明随着氢键数目增多,弱相互作用能变大,主体上的供电基和客体上的吸电基有利于氢键相互作用,氢键导致电子从主体流向客体。用INDO／SCI方法计算配合物的电子光谱,表明其长波吸收峰与主体相比发生兰移,各配合物的长波吸收峰位置相差不大,与实验一致。讨论吸收峰兰移的原因并对电子跃迁进行理论指认,同时得到了配合物的双质子转移势能曲线,给出了相对于N-H键的过渡态和活化能。     

Synthesis of Rigid and Optically Active Bis(binaphthyl) Cyclic Compounds

Optically active cyclic bis(binaphthyl)s (4a–d), which are composed of aromatics, ethers, and ketonic carbonyls, were synthesized through a two‐step nucleophilic aromatic substitution reaction. Bis(binaphthyl) cyclic compounds (4a and 4b) were obtained in moderate yields when difluoride 3a and 3b were employed. On the other hand, bis(binaphthyl)s 4c and 4d were scarcely obtained when 3c and 3d were employed.     

Preparation and properties of high‐pretilt‐angle polyimides based on an alicyclic dianhydride and long alkyloxy side‐group‐containing diamines

A series of polyimides were prepared by a solution polycondensation reaction between 3‐carboxylmethylcyclopentane‐1,2,4‐tricarboxylic dianhydride and 4‐alkyloxybenzene‐1,3‐diamines in N‐methyl‐2‐pyrrolidone and chemical imidization with triethylamine and acetic anhydride. These polyimides possess great organo‐solubility, high optical transparency, and high pretilt angles. They are soluble not only in strong polar aprotic organic solvents such as N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, m‐cresol, and 1,4‐butyrolactone but also in common low‐boiling‐point solvents such as chloroform and tetrahydrofuran, and some are even soluble in acetone. They exhibit high transparency at wavelengths greater than 320 nm. They can generate pretilt angles greater than 5°, and some can even achieve pretilt angles greater than 10°. The pretilt angle of a polyimide increases with the increasing length of the alkyloxy side group. The polyimides possess glass‐transition temperatures between 180 and 230 °C and thermal decomposition temperatures (onset temperatures) of about 435 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1943–1950, 2000     

PMDA-6FHP-DR1/SiO2杂化纳米材料的结构设计和合成

以含氟的二胺5,5′ (六氟异丙基) 二 (2 氨基苯酚)及均苯四甲酸酐(PMDA)为单体,首先合成了经酰胺化的主链上带有活性羟基的含氟聚酰亚胺,再通过Mitsunobu反应将活性生色分子分散红1(DR1)共价链接到聚酰亚胺的侧链骨架上,合成了含氟聚酰亚胺.采用溶胶 凝胶(Sol Gel)技术,并利用偶联剂γ 氨丙基三乙氧基硅烷(APTES)制备带有发色团的和含有硅氧烷端分子的聚酰胺酸,其中的Si(OR)3基经水解、缩合后,与正硅酸乙酯(TEOS)在催化剂作用下反应,经杂化、凝胶后,得到光学透明且热稳定性高的有机/无机杂化材料.将制得的含氟聚酰亚胺/SiO2杂化材料,采用红外光谱(FT IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、示差扫描量热法(DSC),对材料的结构、表面形貌、热性能进行了表征.