A Novel Synthesis of Poly(styrene peroxide) with Controlled Peroxy Linkages at Room Temperature

Singh, R. P.; Desai, Shrojal M.; Sivaram, Swaminathan; Kishore, K.

doi:10.1002/1521-3935(200211)203:15<2163::aid-macp2163>3.0.co;2-h

Cited by 9 publications

(5 citation statements)

References 19 publications

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“…[1][2][3][4][5][6][7][8][9][10][11] The obtained PP includes a labile O-O bond in their main chain, differing from common vinyl and diene polymers. We have previously reported that PP can be conveniently produced by the radical copolymerization of alkyl sorbates (1) with oxygen under mild polymerization conditions, that is, ambient pressure and temperature in the presence of a radical initiator.…”

Section: Introductionsupporting

confidence: 91%

“…Molecular oxygen, having a triplet electronic structure in the ground state, reacts with various kinds of unsaturated compounds, such as diene monomers, to provide polyperoxides ( PP ) consisting of both 1,2- and 1,4-repeating structures. − The obtained PP includes a labile O−O bond in their main chain, differing from common vinyl and diene polymers. We have previously reported that PP can be conveniently produced by the radical copolymerization of alkyl sorbates ( 1 ) with oxygen under mild polymerization conditions, that is, ambient pressure and temperature in the presence of a radical initiator .…”

Section: Introductionmentioning

confidence: 99%

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Regiospecific Structure, Degradation, and Functionalization of Polyperoxides Prepared from Sorbic Acid Derivatives with Oxygen

et al. 2006

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We have fabricated degradable polyperoxides (PP) consisting of well-controlled 5,4-repeating units using various sorbic acid derivatives and molecular oxygen by an alternating radical copolymerization process. The PP obtained from the sorbic esters decompose via a radical chain reaction mechanism, leading to the formation of controlled low-molecular-weight products. In contrast, PP from some amide derivatives include an irregular chain structure, resulting in a more complicated degradation behavior. The theoretical calculations account for the selectivity in the two-step regiospecific propagation depending on the monomer structure. We have demonstrated the synthesis of functional PP based on two methods: one is the copolymerization of functional diene monomers with oxygen, and the other is the polymer reaction of PP including an azide group with a functional alcohol.

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Section: Introductionsupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Regiospecific Structure, Degradation, and Functionalization of Polyperoxides Prepared from Sorbic Acid Derivatives with Oxygen

et al. 2006

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“…In order to gain a deeper insight into how oxygen is operating during the Gilch polymerization, a further series of experiments was carried out. Here, the development of the PPVs' molar masses was analyzed during the reaction time: all above entries a-d were repeated exactly in the described way, but samples were taken from the reaction mixtures after 2, 4, 6, and 22 h. Since it is reliable to assume that all oxygen is first incorporated into the formed polymer chains as peroxy groups, [21,22] it can be concluded that subsequent cleavage of these peroxy groups is certainly a quite fast process, almost finished soon after the polymer chain-growth itself. This was exactly the missing information we needed to answer questions which were still open: acknowledging (i) the high lability of the peroxy moieties within the intermediately formed chains, (ii) the rather moderate overall decrease in the molar mass of the high-molecularweight PPV fractions -keeping in mind that up to 0.5 equiv.…”

Section: Resultsmentioning

confidence: 99%

“…[21,22] It is also well known that, depending on the constitution of the neighboring groups, these peroxy moieties decay under more or less mild conditions: for example, while comparably stable in polystyrene, [21] cleavage of these peroxy moieties already occurs under very mild conditions for poly(vinyl chloride) (PVC) [22] -a polymer in which the chemical surrounding of the peroxy moieties is quite similar to that expected in Gilch-PPVs. In the following, we present experimental evidence which proves that this strategy of using oxygen as a molar-mass regulating agent in Gilch polymerizations is indeed operating very nicely.…”

Section: Strategymentioning

confidence: 99%

Efficient Oxygen‐Induced Molar‐Mass Control of Poly(p‐phenylene vinylenes) Synthesized via the Gilch Route

Schwalm

Rehahn

2008

Macromol. Rapid Commun.

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Oxygen is shown to act as an efficient molar‐mass regulating agent in Gilch syntheses of PPV. As a scavenger, it undergoes instantaneous recombination with the initiating diradicals as soon as they appear in the system. Regular polymer formation can only start when all oxygen has been used, proceeding predominantly as chain‐growth polymerization of the p‐quinodimethane monomers. Since all radical species involved in this Gilch process are diradicals, some polyrecombination events occur in parallel. Therefore the initially formed peroxy diradicals are also incorporated into the resulting chains. Later, they break under very mild conditions, thereby causing a systematic decrease of the final molar mass of PPV.magnified image

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“…The pyrolysis of PSP has been studied experimentally by Kishore and co-workers as well. − ,− These authors used differential scanning calorimetry (DSC) to report an exothermic decomposition around 100 °C, which is a characteristic of peroxide bond breakage . Kishore and Ravindran calculated the heat of degradation as ca.…”

Section: Introductionmentioning

confidence: 99%

Distribution Changes during Thermal Degradation of Poly(styrene peroxide) by Pairing Tree-Based Kinetic Monte Carlo and Artificial Intelligence Tools

Dogu

Plehiers

Vijver

et al. 2021

Ind. Eng. Chem. Res.

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A tree-based kinetic Monte Carlo (kMC) model is presented that differentiates between 38 end-group pairs for isothermal degradation of poly(styrene peroxide) (PSP). The binary trees allow for fast and accurate calculation of reaction probabilities, with mass-weighted binary trees for the accurate sampling of peroxide bond fissions and hydrogen abstractions along chains. The kinetic parameters are tuned via artificial neural networks (ANNs) to successfully predict literature experimental data, among other lumped product yields. ANNs are also utilized for sensitivity analysis to unravel the effects of individual reactions on the time evolution of experimental responses and other simulation outputs, including the variations of the chain length distributions of the macrospecies. PSP degradation is characterized by three stages of degradation considering both instantaneous and time-averaged concentrations. The first stage features rapid unzipping and results in the fast production of major products benzaldehyde and formaldehyde, the second stage features the most significant level of hydrogen abstractions involving PSP and other macrospecies types, and the third stage exhibits the consumption of the remaining peroxide bonds toward oligomeric species in a wide time frame until the degradation process is finalized by the depletion of peroxide bonds. This proof-of-concept study based on unprecedentedly detailed analyses of the chemistry via kinetic Monte Carlo paves the way to further improve our understanding of chemical recycling of solid plastic waste.

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A Novel Synthesis of Poly(styrene peroxide) with Controlled Peroxy Linkages at Room Temperature

Cited by 9 publications

References 19 publications

Regiospecific Structure, Degradation, and Functionalization of Polyperoxides Prepared from Sorbic Acid Derivatives with Oxygen

Regiospecific Structure, Degradation, and Functionalization of Polyperoxides Prepared from Sorbic Acid Derivatives with Oxygen

Efficient Oxygen‐Induced Molar‐Mass Control of Poly(p‐phenylene vinylenes) Synthesized via the Gilch Route

Distribution Changes during Thermal Degradation of Poly(styrene peroxide) by Pairing Tree-Based Kinetic Monte Carlo and Artificial Intelligence Tools

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