Composition‐dependent crystallization behavior of copolyperoxides from methyl methacrylate and 4‐vinylbenzyl stearate

Abstract

To study the composition‐dependent crystallization behavior of copolyperoxides, herein a series of copolymers were prepared by varying the ratios of methyl methacrylate (MMA) and 4‐vinylbenzyl stearate (VBS) under 100 psi oxygen pressure using AIBN as an initiator at 50°C in toluene. Both 13C NMR and electron impact mass spectroscopy (EI‐MS) approved an alternative placement of either of the monomer and peroxy (–O–O–) links throughout the polymer chain. Thermal stability of the resulting copolyperoxides was investigated by thermogravimetric analysis (TGA) and the degradation fragments have been recognized from EI‐MS study. In addition, differential scanning calorimetry (DSC) displayed an endothermic peak as well as an exotherm associated with the melting of the side chain crystalline domains and degradation of –O–O– links in the polymer main chain, respectively. Furthermore, DSC thermograms unveiled a systematic decrease of the crystalline melting temperature (Tm) with the enhancement of MMA content in the copolymers. Small angle X‐ray scattering (SAXS) revealed the existence of lamellar morphology (depends on VBS content in the copolyperoxide) in the synthesized polyperoxide materials, further supported by atomic force microscopy (AFM) analysis showing a layered fibrillar assembly with multiple heights of the lamella. The significant crystalline nature of the polyperoxides was further evidenced from the appearance of lattice fringes in the transmission electron microscope (TEM) micrographs. The crystalline morphology with birefringent texture was further evidenced from the polarized optical microscopy (POM) study. Thus, the present study reported the effective variation of crystalline behavior in copolyperoxide materials with the incorporation of MMA units in the copolyperoxide chains.

Methyl Methacrylate-Based Copolymers: Recent Developments in the Areas of Transparent and Stretchable Active Matrices

“…Methyl methacrylate (MMA), also known as methacrylic acid methyl ester is the key monomer that is involved in the synthesis of a wide array of acrylics and plastics . MMA is a popular monomer choice in polymer chemistry owing to its contribution toward durability, thermal stability, optical clarity, impact strength, and scratch/abrasion resistance in the polymers . It is an acrid smelling liquid that is prone to undergo self-polymerization, generating considerable amounts of heat.…”

“…Hence, continuous efforts have been directed toward controlling the polymer structures to tune the molecular weights, surface packing, composition of the polymer, etc. PMMA possess a high resistivity value (∼10 15 Ω cm), appropriate dielectric constant (at low frequencies), and impressive film processability. However, the dielectric constant of PMMA is found to be lacking at high frequencies (∼3 at 1 MHz), which limit the more practical applications of pure PMMA as a dielectric material.…”

“… 14 MMA is a popular monomer choice in polymer chemistry owing to its contribution toward durability, thermal stability, optical clarity, impact strength, and scratch/abrasion resistance in the polymers. 15 It is an acrid smelling liquid that is prone to undergo self-polymerization, generating considerable amounts of heat. Hence, the commercially available MMA contains a small amount of inhibitor (∼0.1%) to allow for its safe storage.…”