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 s...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 （Tg） 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）＂ 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 Tg of copolymers is 489 K, which is much higher than that of pure benzoxazine resin.展开更多
In this study, a novel bio-based thermosetting system has been developed from epoxy resin （EP）, with rosin-sourced anhydrides （maleopimaric acid, RAM） as curing agent and imidazole type latent catalyst （two amino...In this study, a novel bio-based thermosetting system has been developed from epoxy resin （EP）, with rosin-sourced anhydrides （maleopimaric acid, RAM） as curing agent and imidazole type latent catalyst （two amino imidazole salt complex, IMA）, to be used as matrix for hot-melt prepreg curing at mid-temperature. For comparison, the epoxy resin system with petroleum sourced hardener methylhexahydrophthalicanhydride （MHHPA） was also examined. The curing behaviour and mechanism were investigated by non-isothermal differential scanning calorimeter （DSC） analysis and Fourier transform infrared （FTIR） spectra. The results showed that the curing course of bio-based epoxy resin system containing RAM included two stages, which were the reaction between the free carboxyl group of RAM and oxirane ring under the acceleration of IMA, and the main reaction attributed to the reaction between anhydride and oxirane. According to Kissinger method, the reaction activation energy （E,） of two stages were 68.9 and 86.5kJmo1-1, respectively. The Eo of EP/MHHPA and EP/IMA resin system were 81.04 and 77.9kJmol-I. The processing property of EP/RAM/IMA system, i.e. the relationship between viscosity-temperature-time, was characterized by cone-plate viscometer aim to decide the processing parameter ofprepreg preparation. The effect of RAM content on mechanical performance and dynamic mechanical property was investigated. Noteworthily, compared with the laminates with EP/MHHPA as matrix, the laminates with RAM as hardeners achieved a 44%, 73% and 70℃ increase in bending strength, bending modulus and the glass transition temperature, respectively, due to the bulky hydrogenated phenanthrene ring structure incorporated into the cross-linking networks. When the fiber volume fraction reached 47%, the mechanical property of the laminates prepared with hot melt prepreg was superior or comparable to that of composites with pure petroleum sourced matrix. RAM as cross-linking agent of epoxy resin holds a great potential to satisfy the requirement of composites such as structure and secondary structure parts preparation.展开更多
基金Project (20050106) supported by the Key Science and Technology Item of Guangdong Province,China
文摘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 （Tg） 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）＂ 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 Tg of copolymers is 489 K, which is much higher than that of pure benzoxazine resin.
基金supported by the China-EU co-funded project ECO-COMPASS(Grant No.MJ2015-HG-103)
文摘In this study, a novel bio-based thermosetting system has been developed from epoxy resin （EP）, with rosin-sourced anhydrides （maleopimaric acid, RAM） as curing agent and imidazole type latent catalyst （two amino imidazole salt complex, IMA）, to be used as matrix for hot-melt prepreg curing at mid-temperature. For comparison, the epoxy resin system with petroleum sourced hardener methylhexahydrophthalicanhydride （MHHPA） was also examined. The curing behaviour and mechanism were investigated by non-isothermal differential scanning calorimeter （DSC） analysis and Fourier transform infrared （FTIR） spectra. The results showed that the curing course of bio-based epoxy resin system containing RAM included two stages, which were the reaction between the free carboxyl group of RAM and oxirane ring under the acceleration of IMA, and the main reaction attributed to the reaction between anhydride and oxirane. According to Kissinger method, the reaction activation energy （E,） of two stages were 68.9 and 86.5kJmo1-1, respectively. The Eo of EP/MHHPA and EP/IMA resin system were 81.04 and 77.9kJmol-I. The processing property of EP/RAM/IMA system, i.e. the relationship between viscosity-temperature-time, was characterized by cone-plate viscometer aim to decide the processing parameter ofprepreg preparation. The effect of RAM content on mechanical performance and dynamic mechanical property was investigated. Noteworthily, compared with the laminates with EP/MHHPA as matrix, the laminates with RAM as hardeners achieved a 44%, 73% and 70℃ increase in bending strength, bending modulus and the glass transition temperature, respectively, due to the bulky hydrogenated phenanthrene ring structure incorporated into the cross-linking networks. When the fiber volume fraction reached 47%, the mechanical property of the laminates prepared with hot melt prepreg was superior or comparable to that of composites with pure petroleum sourced matrix. RAM as cross-linking agent of epoxy resin holds a great potential to satisfy the requirement of composites such as structure and secondary structure parts preparation.
