Aa—Bb,Cc,Dd缩聚反应的固化理论

本文讨论了A_a-B_b,C_c,D_d缩聚反应.给出了溶胶-凝胶分配公式、凝胶化条件、分布函数和适合固化全过程的高分子矩的循环公式,以及k次矩的解析表示式.     

含内环化A_a－B_b，C_c缩聚反应的溶胶－凝胶分配

结合Ａａ－Ｂｂ，Ｃｃ型缩聚反应，给出了溶胶中含内环化的溶胶－凝胶分配公式及凝胶化条件。     

含内环化A—Bb,Cc缩聚反应的溶胶—凝胶分配

结合Ａａ－Ｂｂ，Ｃｃ型缩聚反应，给出了溶胶中含内环化的溶胶－凝胶分配公式及凝胶化条件。     

一般的A_aB_b缩聚反应的固化理论——Ⅰ.溶胶分数和凝胶化条件

本文讨论了最一般的A_aB_b缩聚反应,包括A基和A基、B基和B基、以及A基和B基的反应,给出了溶胶-凝胶分配公式和相应的凝胶化条件。     

乙二醇与顺丁烯二酸及邻苯二甲酸酐聚酯化反应动力学的研究

<正> 聚酯化反应是逐步增级的缩聚过程。是由氢离子催化的反应,总的动力学方程为     

缩聚反应中体系反应程度与数均聚合度关系的推导

从反应程度和聚合度的定义出发,推导出了反应体系的反应程度ps和数均聚合度Xn之间简单的函数关系式:Xn=1/(1-ps),并给出了非过量官能团的反应程度ps和体系反应程度ps之间的关系:ps=2rpa/(1+r),深化了对反应程度概念以及反应程度与数均聚合度关系的理解和认识。     

A_(a_1)B_(b_1)—A_(a_2)B_(b_2)缩聚反应的分布函数和高分子矩

本文用概率统计方法,得到了A_(a1)B_(b1)—A_(a2)B_(b2)缩聚反应的分布函数。应用分布函数定义了高分子各类矩。用直接微商法,得到了计算矩的循环公式。解决了用矩表征这类反应的问题。本文也得到了凝胶化条件。     

St-DVB凝胶化反应动力学机理的模型理论研究

高分子凝胶化反应对功能高分子骨架结构有重要影响，它经历溶胶一凝胶的不可逆转变（sol－geltransition）；导致高分子网络结构及分子尺寸的突变，动力学过程和机理十分复杂，因此，人们对这一领域的研究始终贯注了巨大兴趣．追溯过去，人们对高分子凝胶化过程的研究经历了由未考虑环化、搭环的Flory－stockmayer理论问；静态渗流理论［’］到动态凝胶化模型＊三个发展阶段·后者除克报了前两种的不足外，还引入了与几何形状密切相关的动态标度处理方法．近年来，分形概念的产生更激励了动态标度的发展，这种增长模型的研究方法考虑了增长…     

杂多酸为催化剂的丙烯与醋酸气-液酯合成的反应模型初探

杂多酸对有机羧酸与低级烯烃的直接加成反应具有催化作用,但一般需在高压下进行。作者研究了较低压力(0.5～2.0 MPa)下的醋酸与丙烯、丁烯的加成酯化反应,结果较令人满意。本文初步探讨了醋酸与丙烯加成反应模型,为预测最佳反应条件提供了证据。     

顺酐加氢制备丁二酸酐催化剂的研究进展

顺酐催化加氢是目前制备丁二酸酐最有效的途径。本文概述了铜系、镍系和贵金属催化剂在顺酐加氢制备丁二酸酐反应中的应用,并重点介绍了近几年来合成丁二酸酐催化剂的研究进展,提出了现在存在的问题,以为今后工业化生产提供有益的参考。     

用原位红外光谱研究氧化镁上甲醛与乙醛合成双季戊四醇反应的机理

 以甲醛和乙醛为原料，研究了在碱性催化剂存在下合成双季戊四醇反应的机理和工艺．结果表明，与液体碱NaOH的碱催化作用相比，固体碱MgO上的产物季戊四醇、双季戊四醇和三季戊四醇在收率方面水平相当．用原位红外光谱研究了在MgO上甲醛和乙醛各自的吸附物种及甲醛－乙醛混合物的吸附物种，考察了这些吸附物种随温度的变化．结果发现，吸附作用削弱了甲醛和乙醛分子中的C＝O双键；甲醛与乙醛原位反应后表明有α，β不饱和醛吸附物种生成，说明由甲醛与乙醛合成双季戊四醇的反应经历了丙烯醛中间物．     

Synthesis and Insecticidal Evaluation of Novel Phthalic Diamides Containing 1,2,3‐Triazoles via Click Reaction

A series of novel phthalic diamide derivatives containing 1,2,3‐triazole moiety were synthesized using one‐pot click chemistry approach and characterized by ¹H NMR and HRMS. The insecticidal activity against armyworm (Mythimna separata), Tetranychu scinnabarinus and cowpea aphid (Aphis craccivora) was evaluated. Compounds 4II‐a and 4II‐i showed 50% insecticidal activity against armyworm (Mythimna separata) at the concentration of 4 mg/L and one‐third of the compounds had moderate activity against Tetranychus cinnabarinus at 500 mg/L.     

Synthesis and Insecticidal Activities of Novel Phthalic Acid Diamides

In order to discover novel insecticides with the new action mode on ryanodine receptor (RyR), a series of novel phthalic acid diamide derivatives were designed and synthesized. All compounds were characterized by ¹H NMR spectra and HRMS. The preliminary results of biological activity assessment indicated that some title compounds exhibited excellent insecticidal activities against Mythimna separata, Spodoptera exigua, and Plutella xylostella. The title compound 3‐nitro‐N‐cyclopropyl‐N′‐[2‐methyl‐4‐(perfluoropropan‐2‐yl)phenyl]phthalamide ( 4a ) was more efficient against diamondback moths than the control (chlorantraniliprole). The effects of some title compounds on intracellular calcium of neurons from the Spodoptera exigua proved that the title compounds were RyR activators.     

Evaluation of the Removal of Selected Phthalic Acid Esters (PAEs) in Municipal Wastewater Treatment Plants Supported by Constructed Wetlands

Phthalic acid esters (PAEs) have a negative impact on living organisms in the environment, therefore, are among the group of Endocrine Disrupting Compounds (ECDs). Unfortunately, conventional methods used in municipal wastewater treatment plants (MWWTPs) are not designed to eliminate PAEs. For this reason, the development of cheap and simple but very effective techniques for the removal of such residues from wastewater is crucial. The main aim of this study was the evaluation of the removal of six selected PAEs: diethyl phthalate (DEP), di-n-octyl phthalate (DOP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis(2-ethylhexyl) phthalate (DEHP) and dimethyl phthalate (DMP), in real MWWTPs supported by constructed wetlands (MWWTP–CW system). For the first time, the possibility of using three new plants for this purpose, Cyperus papyrus (papyrus), Lysimachia nemorum (yellow pimpernel) and Euonymus europaeus (European spindle), has been presented. For determining the target PAEs in wastewater samples, a method of SPE (Solid-Phase Extraction)–GC–MS(SIM) was developed and validated, and for plant materials, a method of UAE (Ultrasound-Assisted Extraction)–SPE–GC–MS(SIM) was proposed. The obtained data showed that the application of the MWWTP–CW system allows a significant increase in the removal of DEP, DBP, BBP and DEHP from the wastewater stream. Euonymus europaeus was the most effective among the tested plant species for the uptake of analytes (8938 ng × g⁻¹ dry weight), thus, this plant was found to be optimal for supporting conventional MWWTPs.     

水溶性聚合物与硬石膏晶体相互作用的分子动力学模拟

用分子动力学(MD)方法, 模拟计算了6种水溶性聚合物阻垢剂{聚丙烯酸(PAA)、聚甲基丙烯酸(PMAA)、丙烯酸-丙烯酸甲酯共聚物[P(AA-co-MAE)]、丙烯酸-丙烯酸羟丙酯共聚物[P(AA-co-HPA)]、聚马来酸(HPMA)、丙烯酸-马来酸共聚物[P(AA-co-MA)]}与硬石膏晶体的相互作用. 结果发现, 聚合物与硬石膏晶体结合能的大小排序为P(AA-co-MA)＞HPMA＞P(AA-co-HPA)＞P(AA-co-MAE)＞PMAA＞PAA, 同种聚合物阻垢剂对硬石膏两晶面生长的抑制能力相差不大. 对体系各种相互作用以及对关联函数g(r)的分析表明, 体系结合能主要由库仑作用提供. 与硬石膏晶体结合的聚合物发生明显形变, 但形变能远小于体系的非键作用能. 聚合物中不同位置羧基的动力学行为差别很大, 链端羧基的运动翻转比链中部羧基剧烈得多, 因后者与硬石膏晶体的结合比前者牢固而能更有效地抑制垢晶体生长.     

甲基丙烯酸甲酯自由基聚合反应的统计理论研究

在自由基聚合反应中,每个聚合物分子都是经历成百上千次加成聚合形成。由于聚合次数不完全相同造成实际链长的不等性,故由稳态近似法所获得的结果只是一个平均的概念,对反应未达平衡态时不适用。本文运用统计的方法,克服了非稳态方法的限制。通过从任意时间微元扩展至反应结束,获得了甲基丙烯酸甲酯聚合反应相应的统计关系式,如聚合物的数量、重量分布及聚合物的平均分子量等,对深入了解高分子化学反应的本质具有重要的价值和意义。     

由邻苯二甲酸和Medpq配体构筑的锌的配合物的水热合成及晶体测定

A metal-organic coordination polymer [Zn(Pht)(Medpq)]_n (Pht=phthalic acid, Medpq=2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline) (1) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and X-ray single-crystal structure analysis. Title complex crystallizes in the monoclinic system, space group Cc, with a=1.027 4(4) nm, b=2.955 7(11) nm, c=0.685 2(3) nm, β=112.941°, V=1.916 3(13) nm³, C₂₃H₁₄N₄O₄Zn, M_r=475.75, D_c=1.649 g·cm^-3, μ(Mo Kα)=1.324 mm^-1, F(000)=968, Z=4, the final R=0.038 8 and wR=0.071 7 for 2 697 observed reflections (I>2σ(I)). In the crystal structure, the Zinc atom is six-coordinated with four carboxylate oxygen atoms from two different carboxylate groups and two nitrogen atoms from Medpq ligand, showing a slightly distorted octahedral geometry. Furthermore, it exhibits a one-dimensional structure with Pht-Zn-Medpq as building units. CCDC: 716600.