Living radical polymerization of methylstyrenes by a stable nitroxyl radical, and stability of the aminoxy chain end

Yoshida, Eri; Fujii, Takamasa

doi:10.1002/(sici)1099-0518(19980130)36:2<269::aid-pola9>3.0.co;2-m

Cited by 24 publications

(16 citation statements)

References 7 publications

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“…That is, with respect to the stereocontrol of polymerization, the RTCP of MiPDO is identical to nonliving polymerization insofar as the ee value of charged monomer is not changed. Such a comparable tendency has been reported in NMP of 2‐methylstyrene, RAFT polymerization of MMA, and living cationic polymerization of iso ‐butyl vinyl ether, in which the stereoregularity of resulting polymers is little changed by living or nonliving polymerization. As shown in Table and Figure , Đ is all less than 1.3 and the M n is close to M n,theo .…”

Section: Resultssupporting

confidence: 80%

“…In the case of MiPDO in Figure , lower R p in the isospecific polymerization will be ascribed to the stability of the dormant. It has been reported that the steric hindrance of monomers and capping agents significantly affects the stability of the dormant and large steric hindrance around the propagating chain end enhances the polymerization rate. Furthermore, the ceiling temperature ( T c ) has been known to be higher in an isospecific polymerization rather than an atactic polymerization because of a smaller steric hindrance of the isospecific propagation of acrylates .…”

Section: Resultsmentioning

confidence: 99%

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Stereospecific reversible deactivation radical polymerization of biomass‐based acrylates for precise control of tacticity and molecular weight

Tanaka

Kibayashi

Okuda

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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Reversible deactivation radical polymerization (RDRP) of biomass-based acrylates, (S)-and (R)-2-isopropyl-5methylene-1,3-dioxolan-4-ones (S-MiPDO and R-MiPDO), was successfully performed to produce a well-defined polymer with simultaneously controlled tacticity and molecular weight, and low dispersity ( -D < 1.3). In particular, meso triad (mm) of the polymer was continuously controlled as designed from 28.1% to about 100% by changing the molar ratio of S-MiPDO/R-MiPDO in feed. In kinetic studies, the rate of RDRP was strongly influenced by the stereostructures of the propagating radical, and it was much lower in isospecific RDRP than atactic one in reversible chain transfer catalyzed polymerization (RTCP) in contrast to atom transfer radical polymerization (ATRP) where the rate would not change regardless of the tacticity. Increase of molecular weight and low -D of the polymer were also observed in reversible addition-fragmentation chain transfer (RAFT) polymerization of MiPDO. In addition, block copolymers including stereoblock copolymers were feasibly synthesized by RTCP of styrene and methyl methacrylate using poly(MiPDO) prepolymer. V C 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 445-456

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Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 99%

Stereospecific reversible deactivation radical polymerization of biomass‐based acrylates for precise control of tacticity and molecular weight

Tanaka

Kibayashi

Okuda

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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“…[34,52] Similarly, the polymerisation of methylstyrene isomers with 4-MeO-TEMPO was fastest with the ortho isomer. [30] Consequently, it is feasible that the rate enhancement with 9 is due the greater steric bulk of the nitroxide moiety compared to either TEMPO or PROXYL. However, this does not explain the behaviour of 11 which should be at least as bulky as 9.…”

Section: Alkoxyamine Synthesis and Use In Polymerisationsmentioning

confidence: 99%

“…[29] A study on CRP of methylstyrenes in the presence of MTEMPO indicated that polymerisation of the o-isomer was the most rapid due to steric hindrance. [30] Perhaps more significantly, several nitroxides have been found to mediate effectively the CRP of acrylates. Listigovers et al [31] obtained homopolymers of t-and nbutyl acrylate with molar masses up to ca.…”

Section: Introductionmentioning

confidence: 99%

Studies on controlled radical polymerisation using 5-membered cyclic PROXYL nitroxides and corresponding alkoxyamines

Cameron¹,

Reid²,

Span³

et al. 2000

Macromol. Chem. Phys.

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“…Yoshida and Fujii13 performed radical polymerization of methyl styrene by using BPO in the presence of 4‐methoxy‐2,2′, 6, 6′‐tetramethyl‐1‐piperidinyl‐1‐oxy (MTEMPO). The tetramethyl protons from MTEMO on the polymer exhibited their 1 H‐NMR peaks at 0.30, 0.45, 1.00, and 1.15 ppm.…”

Section: Resultsmentioning

confidence: 99%

Grafting of polystyrene branches to polyethylene and polypropylene

Park¹,

Jin²,

Lee³

et al. 2001

J of Applied Polymer Sci

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Polyethylene (PE) and polypropylene (PP) were reacted with benzoyl peroxide (BPO) and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) to prepare PE-TEMPO and PP-TEMPO macroinitiators, respectively. Molecular weight of PP decreased, whereas that of PE increased during the reaction with the BPO/TEMPO system. Polystyrene (PS) branches were grafted to PE and PP backbone chains as a result of bulk polymerization of styrene with the PE-TEMPO and PP-TEMPO macroinitiators. A significant amount of PS homopolymer was produced as a byproduct. Weight of the resulting PE-g-PS and PP-g-PS increased with the polymerization time up to 20 h and then leveled off. Melting point of PE and PP domains in PE-g-PS and PP-g-PS, respectively, lowered as the content of PS in the copolymers increased. However, glass transition of the copolymers was almost identical with that of PS homopolymer, indicating that the constituents in the copolymers were all phase-separated from each other. In scanning electron microscopy of the incompatible PE/PS, PP/PS, and PE/ PP/PS compounded with PE-g-PS and PP-g-PS, any clear indication of enhanced adhesion between the phases was not observed. However, phase domains in the blends were, nevertheless, reduced significantly to raise mechanical properties such as maximum stress and elongation at break by 20 -75%.

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Living radical polymerization of methylstyrenes by a stable nitroxyl radical, and stability of the aminoxy chain end

Cited by 24 publications

References 7 publications

Stereospecific reversible deactivation radical polymerization of biomass‐based acrylates for precise control of tacticity and molecular weight

Stereospecific reversible deactivation radical polymerization of biomass‐based acrylates for precise control of tacticity and molecular weight

Studies on controlled radical polymerisation using 5-membered cyclic PROXYL nitroxides and corresponding alkoxyamines

Grafting of polystyrene branches to polyethylene and polypropylene

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