双酚A为基础的双苯并噁嗪中间体的合成与表征

双酚A为基础的双苯并噁嗪中间体（BPAALF）是以双酚A、苯胺和甲醛为原料合成的六元杂环化合物．是聚苯并噁嗪树脂的一类单体。聚苯并噁嗪树脂在固化过程没有小分子放出，成型收率缩小，尤其适用于制造低孔隙率高性能、低成本的纤维增强树脂基复合材料。目前，苯并噁嗪中间体的合成方法主要是溶剂法和以水反应介质的悬浮法，     

丁胺-芴基苯并噁嗪/环氧共混树脂的性能研究

以双酚芴、正丁胺和多聚甲醛为原料,二氧六环为溶剂,通过Mannich缩合反应,合成了高纯度丁胺-芴基苯并噁嗪单体（BF-n-b）。以差式扫描量热仪（DSC）研究了苯并噁嗪单体/E-51环氧共混树脂的固化行为,通过动态热机械分析（DMA）和热重分析（TGA）研究了共混树脂的热机械和热稳定性能。结果表明,采用改进的制备方法简化了苯并噁嗪单体的合成过程,单体收率和纯度显著提高;苯并噁嗪/环氧共聚物的玻璃化转变温度（Tg）达到165~178℃,初始热分解温度（热失重5%）达312~342℃,800℃时残碳率最高达22.4%。     

硅氧烷改性苯并噁嗪材料的合成及研究进展

苯并噁嗪树脂存在脆性大、成膜性低、开环温度过高以及与复合材料的相容性差等缺点,可用硅氧烷对其进行改性。概括了硅氧烷改性苯并噁嗪的方法及硅氧烷的引入对苯并噁嗪性能的影响;综述了硅氧烷改性苯并噁嗪的研究进展(作为紫外光固化、热致性形状记忆及人体运动检测材料),并展望了未来硅氧烷改性苯并噁嗪的发展方向。     

苯并噁嗪分子内杂化树脂的研究进展

综述了近年来利用分子设计方法,简述了通过在苯并噁嗪单体中引入磷、硼、溴、硅和硫等杂原子以提高苯并噁嗪树脂的耐热性能及力学性能的研究进展,并指出了其未来的研究方向,即合成工艺设计及单体结构设计,同时还展望了其应用前景。     

全生物基苯并噁嗪树脂的合成及聚合研究

为降低苯并噁嗪的聚合温度,采用焦性没食子酸、糠胺和多聚甲醛等原料通过溶剂法成功合成了一种含有酚羟基的新型全生物基苯并噁嗪单体,并探讨了其耐热性和热稳定性等特征。研究结果表明:该苯并噁嗪单体具有高开环聚合活性,放热峰值温度(T_p)仅为176℃,明显低于传统苯并噁嗪单体;其初始热分解温度为150℃,高温时具有很高的残炭率,在氮气氛围下800℃时的残炭率为55%。     

苯并噁嗪树脂耐热和增韧改性的研究进展

介绍了国内外对新型热固性树脂苯并噁嗪的改性研究。并分别通过从分子结构设计、无机粒子改性、共混或共聚改性对苯并噁嗪树脂进行改性;通过合成具有特殊结构的新型苯并噁嗪树脂来进一步提高其性能,并对其进行了概述,进而对苯并噁嗪树脂的研究进行了展望。     

酚酞乙二胺型苯并噁嗪树脂的合成与性能研究

用酚酞、乙二胺和甲醛为原料,通过缩聚反应制备了酚酞乙二胺型苯并噁嗪聚合物（PTBZO）,并通过热聚合法制备了酚酞乙二胺型苯并噁嗪树脂（PPTBZO）。采用1H-NMR对聚合物及树脂的结构进行了表征。借助TG-DTG技术,运用模型拟合法和非模型拟合法研究了PPTBZO的热分解行为及热分解机理,并测试了其介电性能。结果表明,在低失重率（10~50%）下,PPTBZO分解主要是Mannich桥键的断裂,分解过程符合随机成核和随后生长机理;酚酞基团的引入极大地提高了树脂的热稳定性;树脂的复介电常数实部和虚部分别为2.65和0.05,介电损耗角正切值在0.02~0.14,具有良好的介电性能。     

二甲苯型苯并噁嗪的合成及其固化行为的研究

本文以甲苯为溶剂,采用苯酚、苯胺、甲醛和二甲苯甲醛树脂(XF)为原料,通过mannich反应合成了一种二甲苯型苯并噁嗪.运用傅立叶红外光谱表征苯并噁嗪单体及其固化产物的结构,利用GPC表征单体分子量以及分子量分布,并采用DSC对单体的固化行为进行了研究,运用热重法对其固化产物热性能进行了分析.结果表明,此苯并噁嗪分子量分布较窄,在加热条件下可开环聚合,其固化温度区间为145～230℃,此笨并噁嗪固化产物(聚苯并噁嗪)具有优良的热性能,其耐热指数为197℃.     

苯并噁嗪树脂合成、耐热及增韧改性研究进展

介绍了苯并噁嗪(BZ)树脂的合成方法(溶剂法和非溶剂法),特别综述了BZ耐热、增韧改性在单体的分子结构设计、引入其他可聚合官能团、形成共混或共聚物以及加入纳米粒子等方面的研究进展。最后对BZ树脂的发展方向进行了展望。     

含苯磷苯并噁嗪的合成与表征

以含磷中间体(BPPP)、苯胺和甲醛溶液为原料合成了一种新型含苯磷苯并噁嗪单体,通过H谱(1H-NMR)和傅里叶红外光谱(FT-IR)对其化学结构进行了表征,利用差示扫描量热仪和热重分析仪分别研究了其热固化行为及聚合物的热稳定性.结果表明:含苯磷苯并噁嗪的固化过程从135℃开始放热,到261℃放热结束,固化峰值温度为226.5℃;含苯磷苯并噁嗪在不添加任何催化剂的情况下能完全聚合,而且该聚合物具有很好的热稳定性.     

2008年我国热固性工程塑料进展

根据2008年国内公开发表的文献,综述了我国热固性树脂及塑料的开发研究状况。2008年我国热固性工程塑料的研究重点是大品种树脂的高性能化改性和新型结构热固性树脂的开发。利用纳米粒子、液晶聚合物等对传统热固性材料的改性取得了较多的成果,对互穿网络聚合物、梯度材料、特种功能材料的研究也有逐渐增多的趋势。     

Thermally curable main-chain benzoxazine prepolymers via polycondensation route

Polybenzoxazines are addition-cure thermosetting polymers exhibiting versatility in a wide range of applications due to their good mechanical properties, dimensional stability, chemical resistivity, flame resistance property phenolic or epoxy resins have myriad applications in diverse fields starting from commodity materials to high technology aerospace industries. In this paper, we present synthetic strategies to incorporate thermally curable benzoxazine functionality into polymers as main-chain fashion in order to further improve various properties. The strategies successfully employed including monomer synthesis and polycondensation routes like Mannich reaction, click chemistry, hydrosilylations, and coupling reactions. The structure–property relationships of the cured materials have also been presented and discussed.     

Development of low‐viscosity benzoxazine resins and their polymers

With unsubstituted phenol, formaldehyde, and primary aromatic amines as the starting materials, a series of monofunctional benzoxazine resins with low viscosities at room temperature were developed. The polymerization behavior of these resins into thermosetting materials was monitored by differential scanning calorimetry. Stress relaxation of the obtained polybenzoxazines revealed these polymers to be chemically crosslinked networks. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2953–2966, 2002     

2007 年我国热固性工程塑料进展

根据2007年国内公开发表的文献,综述了我国热固性树脂及塑料的开发研究状况。2007年我国热固性工程塑料的研究重点是大品种树脂的高性能化改性和新型结构热固性树脂的开发。利用纳米粒子、液晶聚合物等对传统热固性材料的改性取得了较多的成果,对互穿网络聚合物、梯度材料、特种功能材料的研究也有逐渐增多的趋势。     

High-Performance Vitrimeric Benzoxazines for Sustainable Advanced Materials: Design,Synthesis, and Applications

Polybenzoxazines are high-performance materials capable of replacing conventional thermosets such as phenolics, epoxies, and bismaleimides in composites manufacturing due to their excellent thermomechanical and chemical behavior. Their versatility and compatibility with biobased precursors make them an attractive option as composite matrices. Like other thermosets, polybenzoxazines are not recyclable and cannot be reprocessed. Incorporating dynamic bonds in benzoxazine monomers can produce vitrimeric polybenzoxazines, which can potentially overcome this limitation and can be tuned to exhibit smart functionalities such as self-healing and shape memory. Dynamic bond exchange mechanisms for vitrimer development such as transesterification, imine bond, disulfide exchange, transamination, transcarbamoylation, transalkylation, olefin metathesis, transcarbonation, siloxane-silanol exchange, boronic ester, silyl ether exchange, and dioxaborolane metathesis are potentially applicable to benzoxazine chemistry, with disulfide bond and transesterification having successfully vitrimerized benzoxazines with topological transitions at −8.5 and 88 °C, respectively. Benzoxazine vitrimers featuring glass transitions of 193, 224, and 222–236 °C are now known. These place polybenzoxazines at the forefront of the development of reprocessable and recyclable thermosetting polymers and composite matrices.     

Modification of epoxy resins with functional silanes,polysiloxanes, silsesquioxanes,silica and silicates

Epoxy resins are very important and widely used thermosetting polymers that find many practical applications. Very often their properties can be effectively modified by an addition of reactive silanes, polysiloxanes, silsesquioxanes, silica, montmorillonite, and other fillers. This review considers the literature concerning: (a) synthesis of carbofunctional silanes (CFS), polysiloxanes (CFPS) and polyhedral silsesquioxanes (POSS); (b) properties of neat epoxy resins and their composites and nanocomposites, obtained by modifications with reactive silanes, silicon containing monomers and polymers, and silica based fillers, enabling improvement of their mechanical properties, thermal and flame resistance as well as providing corrosion and antimicrobial protection.     

Time–temperature–transformation (TTT) and TTT–viscosity diagrams of a typical benzoxazine resin

Benzoxazine resins have attracted much attention because of their excellent properties. As a new kind of thermosetting resin, their gelation and vitrification behaviors during the curing process are worth studying for promoting their development, but few research works have been done on this subject. In this work, an ordinary diamine-type benzoxazine resin (PH-ddm) was chosen as a research object. Its curing kinetics were studied by differential scanning calorimetry (DSC) and a phenomenological model was used to get equal curing degree curves reflecting the relationship among curing degree, curing temperature and time. Moreover, a gelation curve and a vitrification curve of PH-ddm based on an Arrhenius equation and a DiBenedetto equation were obtained by parallel plate rheometer and modulated DSC (MDSC), respectively. Then, a well-known time–temperature–transformation (TTT) diagram was plotted. Besides, the rheological behavior of PH-ddm was analyzed through rotatory viscometer testing and modified double Arrhenius equation to obtain the equal viscosity curves. A TTT–viscosity diagram was obtained through combining the equal viscosity curves with the TTT diagram. This is the first time for using the TTT diagram to investigate the curing process of benzoxazine resins. Our results provide an effective method to optimizing molding conditions of the benzoxazine resins.     

超支化聚酯在环氧树脂改性中的应用

超支化聚合物是一类具有三维树形结构的高度支化的大分子。由于其独特的结构和性能以及可实现工业化生产的潜力,超支化聚合物已经成为高分子材料领域研究的热点之一,并且得到了越来越多的关注。作为一类非常重要的超支化聚合物,超支化聚酯(HBPE)引起了研究人员的极大兴趣。目前,HBPE已经在众多领域获得应用,特别是在环氧树脂改性中的研究发展迅速。综述了HBPE作为改性剂在环氧树脂中的应用研究进展,同时对HBPE在环氧树脂和其他热固性树脂改性中的应用研究方向作了展望。     

苯并恶嗪树脂的耐热改性研究进展

分别从分子结构设计、无机粒子改性、共混或共聚改性以及新型苯并恶嗪的合成等方面介绍了近年来国内外对新型热固性树脂苯并恶嗪在耐热改性方面取得的研究性进展,预测了苯并恶嗪树脂的未来发展趋势。分子结构设计是利用苯并恶嗪分子的灵活性,将反应性基团或刚性基团引入到苯并恶嗪中。研究表明,各种改性方法均从不同方面显著地提高了苯并恶嗪树脂的耐热性能。     

A renewable approach to thermosetting resins

This is a review of recent developments of thermostable resins derived basically from vegetable oils. Natural vegetable oils have been transformed in polymers following three main routes. The first is the direct polymerization through the double bonds of the fatty acid chain. The cationic copolymerization of soybean oil with styrene, divinylbenzene and different amounts of styrenic monomers containing Si, B and P has been used to produce materials with improved flame retardant properties. The second route is the functionalization of the triglyceride double bonds to introduce readily polymerizable groups: The singlet oxygen photoperoxidation of the allylic positions of high oleic sunflower oil has been used to produce hydroperoxide-containing triglycerides that were dehydrated or reduced to produce respectively enone- and hydroxyl-containing triglycerides. The enone containing derivative has been chemically crosslinked with aromatic diamines through aza-Michael reactions leading to quinoline containing thermosets. The hydroxyl-containing triglycerides have been crosslinked radically prior the introduction of acrylate groups to produce conventional and flame retardant acrylate resins. The third route explored consists of using plant oil-derived chemicals like 10-undecenoic and oleic acids to produce tailor made monomers. Acyclic diene metathesis (ADMET) polymerization has been applied to prepare a set of thermosetting polyesters with flame retardant properties. Moreover thiol-ene “click” coupling has been used to prepare carboxylic monomers that have been explored to produce thermosetting polyanhydrides for fast drug delivery systems. A set of tailored polyols from the products of coordinative polymerization of the methyl epoxyoleate and the cationic ring opening polymerization of fatty acid-derived 2-oxazolines were also prepared. These polyols have been used to produce different thermosetting polyuretanes with a wide range of properties and characteristics.Finally, some recent research in producing benzoxazine thermosetting resins applying this renewable approach is presented. The benzoxazines based on diphenolic acid, a derivative of levulinic acid, are studied.