Catalyzing the inverse vulcanization reaction via 1,3-benzoxazines

Abstract

High-performance polymers take a vital role in our daily life by their commercial manufacturing and extensive range of applications in various areas like structural materials, aerospace, electronics, printed circuit boards, coatings and adhesives. Polymeric materials can be categorized as thermosets and thermoplastics according to their behavior against temperature. Thermoplastics are a resin which is solid at the room temperature, but becomes softer by increasing the heat and showing fluid behavior or properties due to the melting point or passing the glass transition temperature. Some of thermoset polymers can be consider as a high-performance polymers because of their unique features such as flame resistance, decent mechanical strength, dimensional stability and durability against many solvents. Although these remarkable advantages, they have some disadvantages like shorth shelf life, being brittle, water adsortion and etc. The common members of thermoset resins are phenol-formaldehyde, urea-formaldehyde, melamine-formaldehyde and etc. Phenol-formaldehyde resins are well-known, the most and wide produced in the thermoset resins family. In the 20th century it has been found that the drawbacks of phenolic resins can overcome by polybenzoxazines via their excellent properties: high char yield, high thermal resistance and stability, zero volumetric change and low toxic substance releasing during curing, cost-effective, low moisture absorption, without any requirement for catalyst and etc. Additionally, the easy synthesis procedure of polybenzoxazines is also one of their striking advantages. Because there are corresponding monomers as a polybenzoxazine precursors which can be prepared from cost-effective raw materials such as primary amines, formaldehyde and phenols. In this study, it is aimed to catalyze the reaction of vinylic monomers with sulfur, known as reverse vulcanization. In general, for reverse vulcanization to occur, elemental sulfur must be heated up to the homolytic bond breaking temperature of 160 °C. The resulting sulfur radicals react with the double bond and trigger the polymerization from there. Although the required temperature for reverse curing is high, side reactions increase at this temperature. Therefore, it is important that inverse vulcanization can be catalyzed at more reasonable temperatures. In this study, benzoxazines with different functionalities will be used as catalysts. All the benzoxaiznes acted as catalyst to reduce inverse vulcanization. Among the benzoxazine monomers pyridine containing benzoxazine reduced inverse vulcation temperature better compared to other benzoxazines. It is known that pyridine-type systems contribute to the homolytic decomposition of sulfur, and that sulfur generates radicals by removing hydrogen from benzoxazines. An effective catalytic system was designed by combining these two approaches in a single structure. In this thesis, the development of benzoxazine-based high-performance catalysts by utilizing the flexibility of benzoxazine chemistry is described. The designed benzoxazine will contain the pyridine structure on it. Thus, it is thought that the catalytic performance for reverse vulcanization will increase. With a design benzoxazine catalyst, an attempt will be made to reduce the required minimum temperature of 160 oC to 130 oC for inverse vulcanization.