基于乙炔基-苯并噁嗪单元双重交联反应的聚酰亚胺树脂的制备与性能

为开发可低温固化的聚酰亚胺树脂, 通过分子结构设计将苯并噁嗪单元引入聚酰亚胺树脂中, 合成了含苯并噁嗪单元及乙炔基封端的双官能化新型聚酰亚胺预聚体(PIBzA). 经高温处理, 苯并噁嗪单元发生开环交联, 同时, 乙炔基端基发生三聚成环反应, 从而在固化树脂中形成双重交联网络结构. 苯并噁嗪单元的引入使聚酰亚胺树脂最快固化反应温度降低约32 ℃, 有效降低了固化温度. 同时, 苯并噁嗪单元的引入未大幅度降低树脂的耐热稳定性, 其玻璃化转变温度(T_g)介于266~290 ℃之间, 5%热失重温度(T_d,5%)接近500 ℃, 依然可以满足耐高温复合材料的应用需求. 此外, PIBzA固化树脂具有低介电特性, 其介电常数k介于2.3~3.0, 介电损耗介于0.002~0.008, 可满足透波复合材料及先进微电子封装材料的应用需求.     

Effect of methoxy position on dynamic mechanical and shape memory properties of methoxyphenol-based polybenzoxazines

Abstract

Two series of benzoxazines were synthesized from o-, m-, and p-methoxyphenols, two polyetheramines with different molecular weights, and formaldehyde. The glass transition temperatures (T _gs) of m-methoxyphenol-based polybenzoxazines are respectively higher than those of o- and p-methoxyphenol-based counterparts. The polybenzoxazines exhibit thermally induced one-way dual-shape memory behavior based on T _g, and the o- and p-methoxyphenol-based polybenzoxazines exhibit higher shape memory performance than m-methoxyphenol-based counterparts under motion constraints.     

Studies on thermal and flame retardant behaviour of mixtures of bis(m-aminophenyl)methylphosphine oxide based benzoxazine and glycidylether or benzoxazine of Bisphenol A

The curing of mixtures of bis(m-aminophenyl)methylphosphine oxide based benzoxazine and glycidylether or benzoxazine of Bisphenol A has been studied. In all samples the molar ratio of benzoxazine monomers or the benzoxazine-epoxy system was varied to achieve different phosphorus content. The phosphorus-containing polybenzoxazines have been characterized by dynamic mechanical and thermogravimetric analysis. Limiting oxygen index values indicate good flame retardant properties.     

Efficient synthesis of 2,3-dihydro-1,4-benzoxazines via intramolecular copper-catalyzed O-arylation

A highly efficient synthetic approach to 2,3-dihydro-1,4-benzoxazines is described. The method involves a mild intramolecular copper-catalyzed O-arylation of β aminoalcohol, which works well without N-protection.     

Chemorheology and Curing Kinetics of a New RTM Benzoxazine Resin

The chemorheology and curing kinetics of a new high performance resin transfer molding benzoxazine resin was investigated. A chemorheological model based on a modified Arrhenius equation that describes the resin viscosity as a function of temperature and time was proposed. The model, which agreed well with the experimental data, can provide theoretical support for the mold-filling stage in the resin transfer molding process. The average activation energies of the polymerization reaction were obtained by means of gelation times at different temperatures based on the Arrhenius equation and from dynamic differential scanning calorimetry (DSC) results based on the Kissinger and Ozawa methods; the values were 96.0,84.0 and 87.8 KJ/mol, respectively. A plot of activation energy vs. conversion in the curing process was obtained using the Flynn-Wall-Ozawa model. The reaction orders were estimated from isothermal DSC based on a modified Kamal kinetics model which can describe both the autocatalytic and diffusion-controlled curing mechanism.     

Gelation study of high processability and high reliability ternary systems based on benzoxazine, epoxy, and phenolic resins for an application as electronic packaging materials

 Fourier transform mechanical spectroscopy technique (FTMS) is utilized as a powerful tool to study the sol-gel transition of covalent bonded polymeric network. Winter and Chambon criteria resulting from the fractal-geometry characteristic of the gel networks allow the determination of the gel point with only single experiment using this technique. The gelation behaviors of low melt viscosity ternary systems of benzoxazine, epoxy, and phenolic resins are investigated and analyzed by the technique in order to study the effect of epoxy diluent on the rheological property development before and after the gel points. The gel time at 140 °C ranges from 5 min to 30 min and less than 5 min at 180 °C for all tested ternary system compositions. The gelation of the ternary mixture shows an Arrhenius-type behavior and the gel time can be well-predicted by the Arrhenius equation. Received: 23 November 1999 Accepted: 2 January 2001     

Reaction of Primary Alkylamines,Heterocumulenes, and Isatoic Anhydride,Catalyzed by Magnetic Fe3O4 Nanoparticles in H2O

An efficient protocol for the one‐pot reaction of isatoic anhydride (=1,2‐dihydro‐4H‐3,1‐benzoxazine‐2,4‐dione), primary alkylamines, and heterocumulenes (isothiocyanates and isocyanates) in H₂O catalyzed by magnetically recoverable Fe₃O₄ nanoparticles is described.     

Acid-mediated four-component tandem cyclization: Access to multifused 1,3-benzoxazine frameworks

An acid-mediated multicomponent reaction has been developed for the direct synthesis of multifused 1,3-benzoxazine derivatives from simple and readily available arylglyoxal monohydrates and 2-aminobenzyl alcohols under mild conditions. This novel protocol is proposed to proceed through intramolecular poly-heterocyclizations, thus leading to the formation of three new rings and six new chemical bonds, including four CN and two CO bonds.     

Ambient Preparation of Benzoxazine-based Phenolic Resins Enables Long-term Sustainable Photosynthesis of Hydrogen Peroxide

Rational design of polymer structures at the molecular level promotes the iteration of high-performance photocatalyst for sustainable photocatalytic hydrogen peroxide (H₂O₂) production from oxygen and water, which also lays the basis for revealing the reaction mechanism. Here we report a benzoxazine-based m-aminophenol-formaldehyde resin (APFac) polymerized at ambient conditions, exhibiting superior H₂O₂ yield and long-term stability to most polymeric photocatalysts. Benzoxazine structure was identified as the crucial photocatalytic active segment in APFac. Favorable adsorption of oxygen/intermediates on benzoxazine structure and commendable product selectivity accelerated the reaction kinetically in stepwise single-electron oxygen reduction reaction. The proposed benzoxazine-based phenolic resin provides the possibility of production in batches and industrial application, and sheds light on the de novo design and analysis of metal-free polymeric photocatalysts.