Preparation of Nitroxide Polymer Brushes and Their Applications in the Synthesis of an Epoxidized Soybean Oil Acrylate as an Inhibitor

Abstract

With polystyrene (PS) microspheres as the matrix and glycidyl methacrylate (GMA) and methyl methacrylate (MMA) as monomers, two polymer brushes including a homopolymer brush of PS–PGMA and a block copolymer brush of PS–P­(MMA-b-GMA) were synthesized via surface-initiated activators regenerated by electron-transfer atom-transfer radical polymerization. Furthermore, a ring-opening reaction between epoxy groups in these brushes and hydroxyl groups in 4-hydroxy-2,2,6,6-tetramethylpiperidinooxy (4-OH-TEMPO) was carried out, consequently obtaining nitroxide polymer brushes of PS–PGMA–TEMPO and PS–P­(MMA-b-GMA)–TEMPO. The obtained nitroxide polymer brushes were characterized using a variety of analytical techniques. The nitroxide polymer brush as a supported inhibitor was successfully applied in the synthesis of epoxidized soybean oil acrylate (AESO), showing a good inhibiting effect and easy recyclability. Then the supported TEMPO inhibitor (nitroxide polymer brush) and free TEMPO inhibitor (4-OH-TEMPO) were combined as a compound-inhibiting system to synthesize AESO. After synthesis, the supported inhibitor was recovered by filtration and the free inhibitor was reserved in AESO to prevent it from gelling in the storage process. AESO with excellent performance and low inhibitor residual was obtained through use of this combined inhibitor.

Development of acrylated soybean oil‐based UV‐curable coatings with high impact strength from low viscosity oligomer

“…Hydrochloric acid (37%), acetone, ethyl acetate, sodium bicarbonate, anhydrous magnesium sulfate, petroleum ether, butanone, triethylamine (TEA), and dichloromethane were provided by Shijiazhuang Jingu Renewable Resources Co., Ltd., and used as received. The nitroxide polymer brush of polystyrene (PS)–poly(methyl methacrylate) (PMMA)–poly(glycidyl methacrylate) (PGMA)–2,2,6,6‐tetramethylpiperidinooxy (TEMPO) as a recoverable inhibitor was from our previous work . The preparation process is illustrated in Figure (a).…”

“…AESO could also be used as a complete replacement of toxic and volatile St in the unsaturated polyester resins . Furthermore, UV‐curable coatings with excellent properties have been prepared with AESO as oligomer through UV‐irradiated free radical polymerization in the presence of an initiator . The oligomers with similar structure could also be obtained from high oleic sunflower oil and castor oil …”

“…Then SOL was reacted with acryloyl chloride (AC) to obtain ACSO. For comparison, AESO with low inhibitor residual was prepared . The structural characteristics of ACSO and AESO were analyzed by Fourier transform infrared spectroscopy (FT‐IR) and nuclear magnetic resonance (NMR).…”

POSS-based glycidyl methacrylate copolymer for transparent and permeable coatings

“…, poly(MDO-co-GMA) (20), P(NiPAAm-co-GMA-co-DBA-co-AA) (22), and aminated PGMA vectors (23,31) or grafted P(GMA-co-EGDMA) nanoparticle (32). On the other hand, it has proved that adding the POSS copolymer into an epoxy resin could obviously enhance the toughening and thermal properties of epoxy resin (33), due to nano-scale effect of the POSS structure and the formation of anchor structure in the cured network.…”

“…In order to obtain the well-defined POSS-based copolymer with excellent thermostability and adhesive property, glycidyl methacrylate (GMA) is favorable candidate (21)(22)(23)(24) A c c e p t e d M a n u s c r i p t feature, in which an unsaturated group is suitable for free radical grafting and an epoxy group is capable of interacting with numerous reactive groups of hydroxyl, carbonyl, and amine (25).…”