Solid-State 13C-NMR spectral evidence for charge transfer complex formation in aromatic diimides and dianhydrides

Solution and solid-state proton decoupled ¹³C-NMR spectra were determined on two diimides derived from 4, 4′-oxydiphthalic anhydride. Comparison of the individual diimide spectra to that of a mixture of the two diimides indicates that ordering of these materials occurs in the solid state via charge transfer complex formation. A similar study was conducted using two isomeric dianhydrides, 4, 4′-isophthaloyldiphthalic anhydride (IDPA) and 4, 4′-terephthaloyldiphthalic anhydride (TDPA). The solution spectra of these compounds are similar and are those which would be expected for these compounds. However, their solid state spectra differ from each other. The solid-state spectrum of TDPA resembles its solution spectrum, whereas, that of IDPA differs greatly from its solution spectrum and indicates charge transfer complex formation occurs with this molecule. This difference is explained in terms of the stereochemistry of the two isomeric dianhydrides.     

AVM/蒙脱石复合材料的制备及吸水保水性能的研究

通过乙酸乙烯酯／顺丁烯二酸酐（ＶＭ）共聚树脂的碱解，制备了水溶性的碱解ＶＭ树脂（ＡＶＭ）．用ＣａＣｌ２将ＡＶＭ水溶与蒙脱石水悬浮体共凝胶，制备了ＡＶＭ／蒙脱石复合材料．吸水性和保水性测试结果证示：当ＣａＣｌ２用量为１０％，蒙脱石用量为１５％时，复合材料的吸水性和保水性最好．粒度测试结果表示蒙脱石在水中的粒径为０．７５μｍ，属于超微细分散．ＳＥＭ照片显示，ＡＶＭ／蒙脱石复合材料具有疏松的凝胶结构．     

马来酸酐接枝稀土异戊橡胶接枝率的测试方法

以马来酸酐(MAH)和稀土异戊橡胶(IR)聚合液为主要原料,采用溶液接枝改性反应制备了马来酸酐接枝稀土异戊橡胶(IR-g-MAH)。以IR-g-MAH接枝率的测试方法为研究对象,对比直接滴定法和返滴法,并进一步优化直接滴定法的测试条件。实验结果表明,直接滴定法测试的结果准确度高、重复性好,且测试过程简单。其较优的测试条件为:水解试剂为乙醇,样品用量为0.2~0.5g,KOH-乙醇标准溶液浓度为0.02~0.06mol/L。     

二氧化碳/环氧丙烷/马来酸酐三元共聚物对PPC/PHB共混物力学性能的影响

采用稀土三元催化剂制备了二氧化碳-环氧丙烷-马来酸酐三元共聚物(PPCMA).用红外和核磁谱图确定了PPCMA的结构及马来酸酐单元的含量,3 wt％马来酸酐投料量的PPCMA(共聚物中马来酸酐单元含量4.1％)的玻璃化转变温度(Tg)和起始热分解温度(Td-5％)分别为13.4℃和217℃,拉伸强度为2.88 MPa,断裂伸长率为1669％,与二氧化碳-环氧丙烷共聚物(PPC)相比,引入少量马来酸酐的PPCMA有望成为一种韧性材料,并可对PPC和聚3-羟基丁酸酯(PHB)共混体系进行改性.当在PPC/PHB共混体系中添加10 wt％的PPCMA时,所得共混材料的拉伸强度为18.2 MPa,断裂伸长率则提高到85％,较没有添加PPCMA的样品提高了4.25倍,因此PPCMA的加入能有效提高PPC/PHB共混体系的韧性,改善PPC/PHB共混体系的力学性能.偏光显微镜的研究表明PPC/PHB共混体系加入PPCMA后,很快形成大量尺寸小的PHB球晶,且结晶速度大幅度提高,因此PPCMA在一定意义上可视为一种特殊的“成核剂”.     

二苯并[b,f][1,5]二氮杂芳辛四烯衍生物的合成及拆分

以邻氨基二苯甲酮为原料,经自身缩合环化合成了3种二苯并[1,5]二氮杂芳辛四烯衍生物(1a~1c);以邻苯二甲酸酐和溴苯为原料经傅-克反应制得中间体2-(4-溴苯甲酰溴)苯甲酸(M1);M1经叠氮化后自缩合制得6,12-二(4-溴苯基)二苯并[b,f][1,5]二氮杂环辛四烯(1d);以邻氨基苯甲酸甲酯为原料,经自身缩合环化制得中间体二苯并[b,f][1,5]二氮杂环辛四烯-6,12(5H,11H)-二酮(M2);M2经氯化合成6,12-二氯二苯并[b,f][1,5]二氮杂环辛四烯(1e),化合物1a~1e的结构经~1H NMR,~(13)C NMR和ESI-MS表征,其中化合物1c为新化合物。利用超临界色谱(SFC)技术对化合物1a~1e实现了手性拆分,获得5对具有高旋光度的光学活性异构体(ee99%)。     

Improving the water resistance of epoxy–anhydride matrices by the incorporation of bentonite

Epoxy–anhydride‐based polymers are commonly used as a matrix in pipeline systems exposed to water during their in‐service life. Water absorption at moderate temperatures and/or at long exposure times could lead to irreversible hydrolysis reaction decreasing considerably the polymer overall performance. A strategy to enhance the barrier properties of epoxy resins is to add nanofillers to traditional matrices. In this work, we added bentonite and chemically modified bentonite to this purpose. Water absorption of the resulting materials at three different temperatures (22°C, 80°C, and 93°C) was studied, and simultaneously, the evolution during the immersion tests of glass transition temperature and flexural modulus was recorded. Long‐term gravimetric results showed that composites with chemically modified bentonite produce a delay on the hydrolysis of epoxy–anhydride matrix, which is a relevant result, because of the tough application and uses of the system, from the technological point of view. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis of 3-Substituted Pyrazole Derivatives by Mixed Anhydride Method and Study of Their Antibacterial Activities

A convenient synthesis of 3-substituted pyrazole derivatives by a mixed anhydride method using i-butylchloroformate and N-methylmorpholine at ?20 °C in tetrahydrofuran and study of in vitro antibacterial activities of the prepared compounds against Staphylococcus epidermidis, Bacillus subtilis, Pseudomonas aeruginosa, and Proteus valguris by agar-diffusion method were carried out. The results suggested that the products 4a, 4b, and 4c exhibited moderate to feeble inhibition against all test bacteria at greater concentration but 4d was best against Staphylococcus epidermidis (22 mm) and worst against Pseudomonas aeruginosa (16 mm) at the greatest concentration (2.5 mg/ml), and the activities decreased with decrease in concentration.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Vilsmeier Reagent: An Efficient Reagent for the Transformation of 2-Aminobenzamides into Quinazolin-4(3H)-one Derivatives

Clean and easy preparation of quinazolin-4(3H)-one derivatives using 2-aminobenzamides and Vilsmeier reagent is described. 2-Aminobenzamides were converted into the corresponding quinazolinones under mild and efficient conditions, in good yields without undesirable by-products.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Triflic Anhydride: A Mild Reagent for Highly Efficient Synthesis of 1,2-Benzisoxazoles,Isoxazolo, and Isothiazolo Quinolines Without Additive or Base

The synthetic utility of trifluoromethanesulphonic anhydride (triflic anhydride, TA) without additive or base for the high-yielding synthesis of a wide variety of 1,2-benzisoxazoles from 2-hydroxyaryl aldoximes and ketoximes under mild conditions has been carried out for the first time. As a continuation of our study, syntheses of isoxazolo and isothiazolo quinolones have also been demonstrated using triflic anhydride under similar conditions. This method is simple and has benefits from the easy way to isolate the products in excellent yields.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

紫外光固化超支化聚酯的合成及性能

以季戊四醇为核,2,2-羟甲基丙酸为臂,采用熔融缩聚法合成并表征了末端含大量羟基的超支化聚酯,其支化度高,黏度低,具有良好的热稳定性.以甲基丙烯酸酐改性超支化聚酯,得到链末端含有C=C的超支化甲基丙烯酸酯,在最佳反应条件下改性反应的转化率可达89%以上.改性后的超支化聚酯表现出更低的黏度,热失重曲线呈现为两段,玻璃态转...