End-group analysis of vinyl polyperoxides by MALDI-TOF-MS, FT-IR technique and thermochemical calculations

Nanda, Ajaya K.; Ganesh, Kannan; Kishore, K.; Surinarayanan, M

doi:10.1016/s0032-3861(00)00112-9

Cited by 34 publications

(30 citation statements)

References 18 publications

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“…4. The spectra unanimously showed broad absorption at 3200-3500 cm -1 , which was ascribed to the vibration of -OH or -OOH at the end of PMMAP [34,35]. The results from 1 H NMR and FT-IR confirmed sufficiently the initiating behavior of PMMAP in the polymerization.…”

Section: Resultsmentioning

confidence: 57%

Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization of Vinyl Monomers Initiated by Poly(methyl methacrylate) Peroxide

Zhang

Zhu

et al. 2007

E-Polymers

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Poly(methyl methacrylate) peroxide (PMMAP) was synthesized and used as the initiator in the reversible addition-fragmentation chain transfer (RAFT) polymerization. Methyl methacrylate (MMA) as the monomer and 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as the chain transfer agent was used in the polymerization system. The polymerization was successfully initiated by PMMAP while maintaining features of "living"/controlled radical polymerization such as the number-average molecular weights (M n ) increasing linearly with the monomer conversions and low polydispersity index (PDI) values. The results of 1 H NMR and IR spectra confirmed that a small quantity of polymer chains were derived from the PMMAP moieties. The PMMAP can also initiate the RAFT polymerization of styrene (St) and methyl acrylate (MA), and the polymerization proceeded in a "living"/controlled fashion.

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Section: Resultsmentioning

confidence: 57%

Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization of Vinyl Monomers Initiated by Poly(methyl methacrylate) Peroxide

Zhang

Zhu

et al. 2007

E-Polymers

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“…The PSP obtained from AIBN‐initiated polymerization (Figure A) shows weak bands near 1739–1747, 1604 and 3400–3500 cm −1 due to the presence of chain ends such as carbonyl groups (CO), double bonds (CC), and hydroxyl (OH)/hydroperoxide (OOH) end groups, respectively. These end groups are formed by various chain transfer mechanisms . The FTIR spectra of PSP obtained from NHPI‐AIBN (Figure B) and only NHPI (Figure C) system are similar except for an additional intense peak at 1735 cm −1 , which is assigned to the carbonyl groups from phthalimide ring coming from the PINO radical‐initiated chain ends (vide infra).…”

Section: Resultsmentioning

confidence: 90%

N‐Hydroxyphthalimide‐Mediated Oxidation of Styrene by Molecular Oxygen

Khan

Pal

2013

Macro Chemistry & Physics

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In this work, the N‐hydroxyphthalimide (NHPI) is used for the oxidative polymerization of styrene at 25–100 psi oxygen pressure at 35–55 °C to obtain a faster rate of polymerization than in 2,2′‐azobisisobutyronitrile (AIBN)‐initiated polymerizations. The rates for oxidative polymerization are determined from the oxygen consumption (Δp) against time plots and NHPI shows a reaction rate increased several fold compared with AIBN. The kinetics of the oxidative polymerization reactions are studied at various concentrations of oxygen, NHPI, AIBN, and monomer. The polymerization rate of styrene is almost the same when the NHPI analogue, N‐hydroxysuccinimide (NHSI), is employed. A mechanism of oxidative polymerization in the presence of NHPI is suggested on the basis of the kinetic data and characterization results of poly(styrene peroxide) (PSP). The NHPI is efficient in initiation of the oxidative radical polymerization of styrene.

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“…The carbonyl moieties in the copolymers showed a strong absorption at 1,732–1,747 cm −1 , the intensity of the peak increased with increasing the MMA content in the copolymer . Additionally, a broad absorption peak was also seen which is due to the stretching of the hydroxyl (–OH) and hydroperoxide (–OOH) end groups, generated during polymer formation through numerous chain transfer process …”

Section: Resultsmentioning

confidence: 98%

“…It was observed that the polymers have low molecular weight (Figure S1), in the range of 3,200–4,700 g/mol. This is due to the facile degradation reaction of the propagating macro‐peroxy radicals, leading to the formation of several chain transfer agents for example alcohols, aldehyde, ketone, etc., and subsequent chain transfer reactions with the macro‐radicals causing lesser molecular weight polymers. To prove the existence of ‐O‐O‐ bonds in the backbone, FT‐IR spectra of CPVBM2 and CPVBM3 were recorded (Figure S2), which exhibited the –O–O– bond stretching frequency at 1,013–1,028 cm −1 .…”

Section: Resultsmentioning

confidence: 99%

“…All the carbon atoms in the inverse gated 13 C NMR spectra of polymers are assigned in Figure (right side) (also see Figure S4). Resonance signals at δ 75.3 and 82.5 ppm correspond to the respective methylene and methine carbons of PVBSP attached with the electron withdrawing peroxy groups in the main chain . As a result, these carbons also show a significant downfield shift.…”

Section: Resultsmentioning

confidence: 99%

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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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End-group analysis of vinyl polyperoxides by MALDI-TOF-MS, FT-IR technique and thermochemical calculations

Cited by 34 publications

References 18 publications

Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization of Vinyl Monomers Initiated by Poly(methyl methacrylate) Peroxide

Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization of Vinyl Monomers Initiated by Poly(methyl methacrylate) Peroxide

N‐Hydroxyphthalimide‐Mediated Oxidation of Styrene by Molecular Oxygen

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

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