Preparation of nanocomposites of thermosetting resin from benzoxazine and bisoxazoline with montmorillonite

The thermosetting resin from 2,2′‐(1,3‐phenylene)‐bis(4,5‐dihydro‐oxazoles) (PBO) and bis(3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine)isopropane (BZ) was prepared, and it was found that the thermal property of the final resin was affected greatly by the content of PBO. The nanocomposite from the thermosetting resin from BZ and PBO (molar ratio of PBO to BZ, 0.8 : 1) (PBZ–PBO) and organically modified montmorillonite (OMMT) was prepared by melt method. Differential scanning calorimetry showed that on the introduction of OMMT, the onset curing temperature of the copolymerization of BZ and PBO decreased. The X‐ray diffractometer and transmission electron micrograph characterization of the dispersion of OMMT in the PBZ–PBO matrix suggested that exfoliation structure of OMMT was achieved. Dynamic mechanical analyses indicated that the nanocomposites exhibited much higher T_g values than the PBZ–PBO resin and pristine polybenzoxazine, and storage modulus of the nanocomposites was maintained up to higher temperature with the increasing OMMT content. Dynamic thermogravimetric analysis showed that the dispersion of clay nanolayers in the PBZ–PBO copolymer gave better thermal stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4741–4747, 2006     

Non-isothermal curing kinetics and thermal properties of benzoxazine-phenolic copolymers

Using novolac phenolic resin, aniline and formaldehyde as raw materials, benzoxazine-phenolic copolymers with different percentages of benzoxazine rings were prepared. FT-IR was adopted to characterize the molecular structure of the novolac-type phenolic resin and the benzoxazine-phenolic copolymer BP31. In order to understand the curing process of the copolymers, the curing behavior and curing kinetic characteristics were studied by differential scanning calorimetry (DSC), and the catalytical effect of phenolic hydroxyl on the curing behavior of copolymers was investigated. To investigate the thermal properties of this resin, the thermal degradation behaviors of the cured samples were studied by thermal gravimetric (TG) method, and glass-transition temperatures (T _g) of the cured copolymers were also evaluated by DSC. The dynamic Ozawa method was adopted to determine the kinetic parameters of the curing process as well. The activation energy is 78.8 kJ/mol and the reaction rate constant is in the range from 40.0 to 5.2 (K/min) ⁿ according to reaction temperatures. The Ozawa exponent decreases from 2.4 to 0.7 with the increase of reaction temperature, and curing mechanism is expounded briefly according to the results. TG result shows that the highest char yield of copolymers is 50.3%. The highest T _g of copolymers is 489 K, which is much higher than that of pure benzoxazine resin. Foundation item: Project (20050106) supported by the Key Science and Technology Item of Guangdong Province, China     

Study on the volumetric expansion of benzoxazine curing with different catalysts

A systematic investigation on the volumetric expansion of four benzoxazine systems, which are benzoxazine, benzoxazine/tertiary amine, benzoxazine/organic acid, and benzoxazine/epoxy resin/tertiary amine, was done. By using gravitometric and dilatometric methods, etc., studies on volumetric shrinkage, isothermal cure shrinkage, and density versus cure time plots were done. The cure reactions of these benzoxazines were carried out at 140 and 160°C. The results show that all benzoxazine systems exhibit apparent volumetric expansion after polymerization, that is, the densities of monomers are larger than are those of polymers at room temperature. But, meanwhile, they exhibit volumetric shrinkage while curing isothermally. The results also show that the higher the cure temperature is, the larger the cure shrinkage of the benzoxazines will be and that the extent of the cure shrinkage of the benzoxazines with the aid of catalysts is larger than is that of thermal polymerization systems. The reason for this is that, accelerated by catalysts, the polymerization rate become faster and the extent of polymerizatiom becomes larger. It is obvious that catalysts can make a notable impact on the cure reaction of benzoxazines. Therefore, the dimension of the volumetric expansion of benzoxazine is associated with its polymerization mechanism, molecular structure, and extent of polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1107–1113, 2002; DOI 10.1002/app.10267     

Synthesis of linear polymers containing benzoxazine moieties in the main chain with high molecular design versatility via click reaction

Linear polymers with benzoxazine rings in the main chain have been synthesized applying click chemistry approach. These polymers possess molecular weights significantly higher than the benzoxazine polymers which have been chain extended via Mannich reaction. The number average molecular weight is estimated from size exclusion chromatography (SEC) to be between 20,000 and 40,000 Da. The structure of the polymers is confirmed by ¹H and ¹³C nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FTIR). Differential scanning calorimetry (DSC) is used to study crosslinking behavior of the polymers. The nature of the low temperature exotherm DSC peak observed in this work and the previous work of other authors is studied by model reactions. It is due to thermal coupling of the residual propargyl and azide end groups in the absence of active catalyst. In addition, a novel diazide-functional benzoxazine monomer has been prepared, showing a tremendous flexibility for applying click reaction to obtain various polymer architectures. Three types of polymers have been prepared from dipropargyl- and diazide-functional benzoxazine monomers. These polymers have been characterized by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA).     

苯并噁嗪及其在制备C/C复合材料领域的研究进展

综述了国内外新型热固性树脂苯并噁嗪聚合物的固化机理、固化体积变化、热分解机理及其复合材料的研究进展,并通过分析树脂体系的黏度、浸润性及其固化物的残炭率和炭的形貌,初步判断了苯并噁嗪树脂在制备C/C复合材料领域的应用前景。     

Investigation of polymerization of benzoxazines and thermal degradation characteristics of polybenzoxazines via direct pyrolysis mass spectrometry

Polymerization of benzoxazines and thermal degradation mechanisms of polybenzoxazines were investigated using the direct pyrolysis mass spectrometry (DP‐MS) technique. The benzoxazine structures were based on phenol and aniline and on bisphenol‐A and methylamine or aniline. Polymerizations of the benzoxazines were carried out by curing them at elevated temperatures without addition of initiator or catalyst. DP‐MS data showed the presence of chains generated by opposing polymerization reaction pathways indicating quite complex structures for the polybenzoxazines under investigation. Thermal decomposition of polybenzoxazines was started by the cleavage of methylamine or aniline linkages. It was determined that polybenzoxazines based on phenol were more stable than the corresponding bisphenol‐A‐based polybenzoxazines, while those based on methylamine were more stable than the corresponding polybenzoxazines incorporating aniline. Thus, it can be concluded that the presence of bulky groups decreased the extent of crosslinking which in return decreased the thermal stability. Copyright © 2012 Society of Chemical Industry     

New thermosetting resin from bisphenol A‐based benzoxazine and bisoxazoline

Bisphenol A‐based benzoxazine was prepared from bisphenol A, formaline, and aniline. Curing reaction of bisphenol A‐based benzoxazine with bisoxazoline and the properties of the cured resin were investigated. Consequently, using triphenylphosphite as a catalyst, for the first time the ring‐opening reaction of benzoxazine ring occurred at 170°C, and then the phenolic hydroxyl group generated by the ring‐opening reaction of the benzoxazine ring reacted with the oxazoline ring at 200°C. The melt viscosity of the molding compound was kept 0.1–1 Pa · s at 140°C even after 1.5 h, and increased rapidly at 180°C. It was realized that the molding compound showed good flowability below 140°C, curing reaction proceeded above 180°C rapidly. The cured resin from bisphenol A‐based benzoxazine and bisoxazoline showed good heat resistance, water resistance, electrical insulation, and mechanical properties, compared with the cured resin from bisphenol A‐type novolac and bisoxazoline. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1551–1558, 1999     

开环聚合酚醛树脂研究进展

介绍了苯并恶嗪中间体的国内外研究概况。着重介绍了国内近年来在苯并恶嗪中间体合成、树脂固化反应研究和产品应用开发等方面取得的进展。     

Gelation behavior of near‐zero shrinkage polybenzoxazines

A new class of phenolic thermosetting resins is developed that is based on the ring‐opening polymerization of a benzoxazine precursor. These new materials seek to combine the thermal properties and flame retardance of phenolics with the mechanical performance and molecular design flexibility of advanced epoxy systems. These materials overcome many of the traditional shortcomings of conventional novolac and resole‐type phenolic resins, while retaining their benefits. The viscoelastic behavior of the polybenzoxazines during isothermal cure is monitored by dynamic mechanical analysis. Isochronic measurements show that although the aniline‐based benzoxazine has a lower activation energy for the gelation process than the methylamine‐based resin, it has a slower rate of reaction. The purified monomer and as‐synthesized precursor for each benzoxazine are found to polymerize by the same mechanism, despite the absence of an initiating species in the purified resins. The chemical gelation phenomenon of the methylamine‐based resin is probed by a multifrequency dynamic cure analysis that allows determination of the instant of chemical gelation, as well as the network relaxation exponent, n. The constant value of the exponent regardless of cure temperature demonstrates that chemical gelation is, in fact, an isoconversion event for the methylamine‐based benzoxazine. The multifrequency and isochronic analyses are shown to produce very similar gel times and activation energies for the gelation process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 406–417, 2001     

Two novel halogen-free,phosphorus-free,and intrinsically flame-retardant benzoxazine thermosets containing electron-withdrawing bridge groups

Two novel furfurylamine type benzoxazine prepolymers are firstly synthesized from 4,4′-bishydroxydeoxybenzoin (BHDB) and 4,4′-dihydroxybenzophenone (DHBP). Both BHDB- and DHBP-based polybenzoxazines present accelerated curing behaviors, high glass transition temperatures, and very low heat release capacity values, resulting from the introduction of electron-withdrawing groups and furan rings. It is especially noteworthy that the flame retardancy of DHBP-based polybenzoxazine is classified as UL-94 V-1 grade, whereas that of BHDB-based polybenzoxazine is evaluated to be UL-94 V-2 grade. Hence, DHBP is considered as an alternative to BHDB for benzoxazine preparation because of its similar chemical structure, competitive price, high efficiency preparation, and outstanding flame resistance. Therefore, this work not only provides an economical and effective strategy for the preparation of halogen-free, phosphorus-free, and intrinsically flame-retardant benzoxazine resins but also provides important insight into the effects of electron-withdrawing bridge groups on the curing behavior and thermal and flame-retardant properties of benzoxazine resins.