N-(口恶)唑啉苯基马来酰亚胺的合成

以靛红酸酐、2-氨基醇和马来酸酐为原料合成了一类N-嚼唑啉苯基取代马来酰亚胺衍生物。考察了催化剂种类、原料配比、反应时间和温度等反应条件对酰胺酸环化反应的影响,发现ZnCl2／HMDS二组分体系是比较有效的催化剂,确定了最佳反应条件,产物收率可达到60％以上。应用核磁共振、红外光谱及元素分析等方法对产物进行了表征。     

含柔性酯基的N-取代马来酰亚胺的合成及溶液聚合

以马来酸酐(MA)、氨基丙酸(Aln)、直链醇为原料,选择合适的溶剂、催化剂,通过三步两釜法合成了侧链含柔性酯基的N-取代马来酰亚胺单体(RAM);以自由基溶液聚合法进行了均聚和共聚;利用IR、TG、DTA对产物(PRAM)进行了表征;并讨论了侧链长度对均聚物溶解性能、热性能的影响,结果表明柔性链长度对溶解性、起始热分解温度影响不大,但玻璃化温度(Tg)随柔性链增长而明显下降。     

Copolymerization of N‐substituted maleimide with alkyl acrylate and its industrial applications

A series of new copolymers with desired thermal stability and mechanical properties for applications in leather industry were synthesized from various substituted maleimides and alkyl acrylates. Polymerization was carried out by a free‐radical polymerization using benzoyl peroxide (BPO) as initiator. The monomers and polymers synthesized were characterized by elemental analysis, IR, and nuclear magnetic resonance (NMR). Interestingly, these polymers were soluble in common organic solvents. Copolymer composition and reactivity ratios were determined by ¹H‐NMR spectra. The molecular weights of the polymers were determined by gel permeation chromatography. The homo‐ and copolymer of maleimide showed single‐stage decomposition (ranging from 300–580°C). The initial decomposition temperatures of poly[N‐(phenyl)maleimide] [poly(PM)], poly[N‐4‐(methylphenyl)maleimide] [poly(MPM)] and poly[N‐3‐(chlorophenyl)maleimide] [poly(CPM)] were higher compared to those of the copolymers. Heat‐resistant adhesives such as blends of epoxy resin with phenyl‐substituted maleimide‐co‐glycidyl methacrylate copolymers with improved adhesion property were developed. Different adhesive formulations of these copolymaleimides were prepared by curing with diethanolamine at two different temperatures (30°C and 60°C). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1870–1879, 2001     

Synthesis and characterization of optically active star‐shaped poly (N‐phenylmaleimide)s with a calixarene core

Two N‐phenylmaleimide derivatives bearing a chiral oxazoline group, N‐[o‐(4‐phenyl‐4,5‐dihydro‐1,3‐oxazol‐2‐yl)phenyl]maleimide [(R)‐PhOPMI] and N‐[o‐(4‐isopropyl‐4,5‐dihydro‐1,3‐oxazol‐2‐yl)phenyl]maleimide [(S)‐PrⁱOPMI], were polymerized using in situ generated calixarene‐based phenates as initiators to yield optically active polymers. The formation of star‐shaped architectures was strongly dependent on both polymerization conditions and calixarene moieties. In the case of polymerization conducted in toluene at 80–100 °C, the arm‐chain numbers achieved their respective maxima for the polymers with these multifunctional initiators. In contrast, the polymers obtained in polymerizations at lower temperature possessed fewer arm chains. The structure and chiroptical properties were investigated on the basis of ¹³C NMR, multiangular laser light scattering, gel permeation chromatography, and circular dichroism for the macromolecules with calixarene cores. Copyright © 2006 Society of Chemical Industry     

Methyl methacrylate–N-chlorophenyl maleimide copolymers: Effect of structure on properties

The article describes the preparation of cast acrylic sheets by copolymerizing methyl methacrylate (MMA) with varying mole fractions of N-o-chlorophenyl maleimide (OC), N-m-chlorophenyl maleimide (MC), and N-p-chlorophenyl maleimide (PC) using benzoyl peroxide as an initiator. The effect of incorporation of varying mole fraction of N-chlorophenyl maleimides in poly(methyl methacrylate) backbone on the optical, physicomechanical, and thermal properties of cast acrylic sheets were evaluated. Vicat softening temperature, glass transition temperature (T_g) and thermal stability of the copolymers increased with an increase in the maleimide content. The solar transmittance and percentage of transmittance of the copolymer sheets having low mole fractions of N-chlorophenyl maleimides (i.e., 0.025–0.085) were found to be comparable with that of PMMA. Further increase in the comonomer content resulted in a decrease in the percentage of transmittance. Copolymer sheets having low mole fractions of N-chlorophenyl maleimides (0.025–0.108) have tensile strength comparable to that of PMMA, whereas the percentage of elongation decreased. Tensile modulus increased with increasing mole fraction of N-chlorophenyl maleimides. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 527–534, 1998     

N-邻位取代苯基马来酰亚胺的研究概述

介绍了N-苯基取代马来酰亚胺的主要应用和制备方法，叙述了邻位苯基取代马来酰亚胺的国内外研究概况，提出应对这类具有特殊性质的单体和聚合物进行更深入的研究。     

Michael Addition of Ketones and Aldehydes to Maleimides Catalyzed by Modularly Designed Organocatalysts

Modularly designed organocatalysts (MDOs) formed in situ from the self‐assembly of primary α‐amino acids and Cinchona alkaloid thioureas were found to be excellent catalysts for the stereoselective Michael addition of enolizable ketones and aldehydes to maleimides. Using an MDO formed from quinidine thiourea and L ‐2‐chlorophenylglycine, the corresponding Michael addition products, 3‐substituted succinimides, may be obtained in excellent yields and high enantio‐ and diastereoselectivities.     

呋喃/马来酰亚胺Diels-Alder反应在聚合物复合材料自愈合的应用

呋喃(双烯体)/马来酰亚胺(亲双烯体)Diels-Alder环加成反应(DA反应)是应用于聚合物复合材料自愈合的最重要的DA反应之一。总结了呋喃/马来酰亚胺DA反应的六种类型,包括各种呋喃衍生物与马来酰亚胺衍生物之间的线性聚合、支化和交联DA反应,含呋喃聚合物与含马来酰亚胺聚合物之间、主链含呋喃衍生物聚合物与马来酰亚胺衍生物之间、侧链含呋喃衍生物聚合物与马来酰亚胺衍生物之间和多种呋喃衍生物与马来酰亚胺衍生物之间共聚合的DA反应,综述了呋喃/马来酰亚胺DA反应在聚合物复合材料本体自愈合应用的微胶囊、中空纤维、微管道技术和聚合物/纤维、聚合物/纳米材料(纳米二氧化硅、层状硅酸盐、石墨烯)界面自愈合的研究进展。     

Thiourea‐Catalyzed Highly Diastereo‐ and Enantioselective Conjugate Additions of α‐Substituted Cyanoacetates to Maleimides: Efficient Construction of Vicinal Quaternary‐ Tertiary Stereocenters

A highly diastereo‐ and enantioselective conjugate addition of α‐substituted cyanoacetates to maleimides in the presence of a chiral bifunctional thiourea‐tertiary amine catalyst has been investigated for the first time. The procedure was capable of tolerating a relatively wide range of substrates with respect to α‐substituted cyanoacetates and maleimides, providing a series of substituted succinimidates bearing two vicinal quaternary‐tertiary stereocenters in excellent yields (up to 97%) with excellent diastereo‐ (up to 98:2) and enantioselectivities (up to 98%) under mild reaction conditions.