Addition−Fragmentation Chain Transfer in Allyl Polymerization at Elevated Temperatures

Inoue, Satoshi; Tamezawa, Hajime; Aota, Hiroyuki; Matsumoto, Akira; Yokoyama, Katsutoshi; Matoba, Yasuo; Shibano, Michirou

doi:10.1021/ma1029423

Cited by 6 publications

(6 citation statements)

References 29 publications

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“…Our first investigation was thus the homopolymerization of these five monomers using 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile, V-70) as the initiator at 40 °C, at a concentration of 3 mg/mL in DMC (Table S4). In line with previous literature reports, no homopolymers were obtained. − Next, the feasibility of copolymerizing the above-mentioned renewable monomers with vinyl acetate was investigated using V-70 at 40 °C in the bulk and targeting a 10 mol % feed of renewable monomer (entries 6–9, Table S4). For each copolymerization, an increase in molecular weights was observed and conversions above 23% were obtained (Table S4).…”

Section: Resultssupporting

confidence: 67%

Plant-Based Nonactivated Olefins: A New Class of Renewable Monomers for Controlled Radical Polymerization

Scholten

Detrembleur

Meier

2018

ACS Sustainable Chem. Eng.

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In light of fossil fuel depletion and a general necessity for sustainable development, the synthesis of polymers from renewable resources is gaining more and more importance, yet industrially relevant radical polymerizations still struggle with the incorporation of renewable resources as the number of natural molecules containing suitable double bonds is limited. Herein, we present the sustainable synthesis of nonactivated allylic and olefinic carbonate monomers from renewable resources in a solventless one-pot transesterification reaction. We subsequently confirm the first controlled radical copolymerization of such challenging nonactivated monomers with vinyl acetate, in which molecular weights above 10 000 g·mol–1 were reached. The controlled nature of the copolymerizations was verified by the low dispersities obtained and the linear increase in molecular weights with conversion. The so-prepared copolymers were purified using sustainable extractions by supercritical carbon dioxide (scCO2), which allowed recovery of up to 58% of unused monomer. Using FT-IR and NMR spectroscopy, the incorporation of the renewable monomers into the copolymer in up to 49 mol % was confirmed, which is the highest reported to date. The combination of a sustainable double bond functionalization pathway with controlled radical polymerizations highlights the potential of radical polymerizations in the quest for renewable polymers and introduces a new set of monomers for this technique.

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Section: Resultssupporting

confidence: 67%

Plant-Based Nonactivated Olefins: A New Class of Renewable Monomers for Controlled Radical Polymerization

Scholten

Detrembleur

Meier

2018

ACS Sustainable Chem. Eng.

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“…To reassess the allyl polymerization mechanism, the resulting oligomers were characterized by MALDI‐TOF‐MS spectrometry; we have proposed an improvement of the well‐known reaction scheme for the free‐radical polymerization of allyl monomers 10. On the course of a series of our studies concerned with the elucidation of allyl polymerization mechanism,10, 13–15 we used azo‐initiators such as AIBN and DMAIB in place of BPO as a most typical peroxide initiator in allyl polymerization. Incidentally, we found that the initial rate of polymerization initiated by DMAIB was more than two times higher than that by AIBN, although the decomposition rate constants of AIBN and DMAIB are almost same at 80 °C.…”

Section: Discussionmentioning

confidence: 99%

“…On the course of a series of our studies concerned with the elucidation of allyl polymerization mechanism,10, 13–15 we used azo‐initiators such as 2,2′‐azobis(isobutyronitrile) (AIBN) and dimethyl 2,2′‐azobis(isobutyrate) (DMAIB) (Fig. 1) in place of BPO as a most typical peroxide initiator.…”

Section: Introductionmentioning

confidence: 99%

Peculiar initiation behavior of azo‐initiators in allyl polymerization

Tamezawa

Kumagai

Aota

et al. 2012

J. Polym. Sci. A Polym. Chem.

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On the course of a series of studies concerned with the elucidation of the allyl polymerization mechanism, the bulk polymerization of allyl benzoate was carried out using a large amount of 2,2′‐azobis(isobutyronitrile) (AIBN) and dimethyl 2,2′‐azobis (isobutyrate) (DMAIB). Incidentally, the initial rate of polymerization initiated by DMAIB was more than two times higher than that by AIBN, although the decomposition rate constants of AIBN and DMAIB are almost same at 80 °C. This peculiar initiation behavior of azo‐initiators is discussed to clarify the initiation mechanism in allyl polymerization, especially focused on the competitive contribution to the initiation and termination reactions by primary radicals.

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“…We also showed that, depending on both the reaction conditions and of the R substituent, the resulting polymeric species could have either hyperbranched (with high M w values) or linear structure (with low M w values). Indeed, it is well‐known that the radical homopolymerization of allyl monomers usually results in low M w oligomers, mainly due to degradative chain transfer 13–15. The weakness of the allyl CH bond arises from the high resonance stability of the allyl radical, which is too stable to reinitiate polymerization and undergoes termination by reaction with a propagating radical 11…”

Section: Introductionmentioning

confidence: 99%

Synthesis of novel copolymers obtained from acceptor/donor radical copolymerization of phosphonated allyl monomers and maleic anhydride

Negrell-Guirao

David

Boutevin

et al. 2011

J. Polym. Sci. A Polym. Chem.

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A series of four phosphonated‐bearing allyl monomers, that is, diethyl‐1‐allylphosphonate (AP), dimethyl‐1‐allyloxymethylphosphonate (AOP), 5‐ethyl‐5‐(allyloxymethyl)‐2‐oxo‐1,3,2‐dioxaphosphorinane (AEDPH), and 2‐benzyl‐5‐ethyl‐5‐(allyloxymethyl)‐2‐oxo‐1,3,2‐dioxaphosphorinane (AEDPBn) were synthesized. These monomers were then copolymerized by free radical polymerization in the presence of maleic anhydride, thus leading to alternated copolymers with phosphonate moieties. It was shown that both monomer conversion and reaction rate were dependent on the phosphonate moieties carried out by the allyl monomer: the bulkier the phosphonate group, the higher the polymerization rate. Thermogravimetric analysis of the copolymers revealed a high content of residue, also varying with the nature of the phosphonate moieties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

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Addition−Fragmentation Chain Transfer in Allyl Polymerization at Elevated Temperatures

Cited by 6 publications

References 29 publications

Plant-Based Nonactivated Olefins: A New Class of Renewable Monomers for Controlled Radical Polymerization

Plant-Based Nonactivated Olefins: A New Class of Renewable Monomers for Controlled Radical Polymerization

Peculiar initiation behavior of azo‐initiators in allyl polymerization

Synthesis of novel copolymers obtained from acceptor/donor radical copolymerization of phosphonated allyl monomers and maleic anhydride

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