Irregular polystyrene peroxides – a promising macroinitiators synthesized by radical polymerization under oxygen inflow

Silant'ev, Mikhail A.; Perepelitsina, E. O.; Grachev, V. P.; Kurochkin, S. A.

doi:10.1016/j.eurpolymj.2017.02.010

Cited by 9 publications

(9 citation statements)

References 83 publications

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“…Recently, the synthesis of polyperoxides has been carried out by the polymerization of diene monomer and oxygen using liquid marble as an efficient macro‐reactor with neither stirring the reaction media nor oxygen bubbling during the course of a reaction . A macroinitiator from styrene having different peroxide groups was synthesized in presence of oxygen via radical polymerization . Very recently, alternating copolymerization of cyclic conjugated diene monomers (furan and cyclopentadiene) with molecular oxygen have been carried out to prepare degradable polyperoxides …”

Section: Introductionmentioning

confidence: 99%

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

Mete

Goswami

2020

Journal of Polymer Science

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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.

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Section: Introductionmentioning

confidence: 99%

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

Mete

Goswami

2020

Journal of Polymer Science

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“…reported the perspectives of polyperoxides use as additives for jet fuel due to the high exothermicity of the decomposition . Vinyl polyperoxides also used for the preparation of organic coatings, adhesives, regulating supplements in the synthesis of block and graft copolymers, interpenetrating networks . Due to their high solubility in the vinyl monomers, possibility of sequentially and gradually radicals generating, and the ability to incorporate into the polymer chain, polyperoxides are actively used as the macromolecular initiators of radical polymerization, − including “pseudo‐living” RAFT polymerization…”

Section: Introductionmentioning

confidence: 99%

The Oxidative Polymerization of Vinyl Monomers in the Presence of N‐Hydroxyphthalimide

et al. 2019

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The oxidation of vinyl compounds such as styrene, α‐methylstyrene, methyl methacrylate, acrylonitrile with molecular oxygen in the presence of N‐hydroxyphthalimide have been studied. It was shown that the N‐hydroxyphthalimide is efficient in initiation of the oxidative polymerization of vinyl monomers. The products of the monomer oxidation at 66 °C and 1 atm of O2 are corresponding polyperoxides and low molecular carbonyl compounds. IR‐ and 1H NMR spectroscopy confirm the alternating copolymer structure of polyperoxides with –O–O– bonds in the main chain. In the oxidative polymerization of vinyl monomers initiated with the mixtures of N‐hydroxyphthalimide and 2,2′‐azobisisobutyronitrile or benzoyl peroxide it was observed a synergistic effect of initiators’ action. N‐hydroxyphthalimide reacts with molecular oxygen, initiator radicals or monomer to form the phthalimide‐N‐oxyl radical, which participates in the chain initiation stage and does not participate in the termination stages, which leads to a synergistic effect.

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“…Solid state copolymerizations of dibenzofulvene, 7,7,8,8-tetrakis(ethoxycarbonyl)quinodimethane, and related monomers with oxygen were used to prepare alternating copolymers having repeating peroxy units in the polymer main chain. Polymerization of 1,3-diene monomers has been extensively studied, and various polyperoxides were readily synthesized by the radical copolymerization process using sorbic derivatives and molecular oxygen as the starting materials. , Liquid marbles were also used as an efficient microreactor for the synthesis of polyperoxides in a good yield by the radical alternating copolymerization of 1,3-diene monomers with oxygen. , Very recently, polystyrenes with various contents of peroxide units (a small content of peroxy groups to an alternating copolymer of styrene with oxygen) have been synthesized . Although fatty acids (FA) and their derivatives are important biorenewable resources with numerous applications in diverse fields, they have never been used in polyperoxide synthesis.…”

Section: Introductionmentioning

confidence: 99%

“…20,21 Very recently, polystyrenes with various contents of peroxide units (a small content of peroxy groups to an alternating copolymer of styrene with oxygen) have been synthesized. 22 Although fatty acids (FA) and their derivatives are important biorenewable resources with numerous applications in diverse fields, 23 they have never been used in polyperoxide synthesis. Their easy availability, inexpensiveness, and biocompatible nature prompted us to use various FAs to the polyperoxide synthesis.…”

Section: ■ Introductionmentioning

confidence: 99%

Degradable Crystalline Polyperoxides from Fatty Acid Containing Styrenic Monomers

et al. 2018

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Vinyl polyperoxides, alternating copolymers of vinyl monomers and molecular oxygen, are highly viscous amorphous materials because of the flexible peroxy (−O− O−) bonds in the main chain. In this study, crystalline polyperoxides have been synthesized by oxidative radical polymerization of styrenic monomers having fatty acid moieties attached to the phenyl ring using molecular oxygen at 100 psi pressure. Determination of active oxygen contents in polyperoxides, 13 C NMR spectroscopy, and electron impact mass spectroscopy (EI-MS) confirmed alternating placement of −O−O− bonds after every styrenic monomer unit in the copolymer main chain. Thermal stability was studied by thermogravimetric analysis (TGA). Exothermic degradation of these polyperoxides was observed by differential scanning calorimetry (DSC), and degradation products have been identified from EI-MS study. DSC and powder X-ray diffraction (PXRD) studies revealed crystallinity in the polyperoxides with fatty acids having 12 carbon atoms or longer. This crystalline behavior was further supported by polarized optical microscopy (POM), where a birefringence texture which is characteristic of semicrystalline polymer was formed for polyperoxides with C ≥ 12 of the side-chain alkyl carbons. Transmission electron microscopy (TEM) was used to define the thickness and crystal structure of the polymers. Theoretical studies have been performed using density functional theory (DFT) to support the experimental interlamellar distance from X-ray diffraction studies.

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Irregular polystyrene peroxides – a promising macroinitiators synthesized by radical polymerization under oxygen inflow

Cited by 9 publications

References 83 publications

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

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

The Oxidative Polymerization of Vinyl Monomers in the Presence of N‐Hydroxyphthalimide

Degradable Crystalline Polyperoxides from Fatty Acid Containing Styrenic Monomers

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