Specific Polymerization Mechanism Involving β-Scission of Mid-Chain Radical Yielding Oligomers in the Free-Radical Polymerization of Vinyl Ethers

Kumagai, Takeo; Kagawa, Chihiro; Aota, Hiroyuki; Takeda, Yoshiaki; Kawasaki, Hideya; Arakawa, Ryuichi; Matsumoto, Akira

doi:10.1021/ma800949q

Cited by 27 publications

(28 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…When Kumagai et al analyzed the produced oligomer by MALDI-TOF mass spectrometry, a peak series was identified that could be assigned to aldehyde end-group-functional PBVE. 122 This was in accordance with an addition fragmentation mechanism proposed by the authors, in which the expulsion of a butyl radical from the macroradical chain-end by bscission led to chain transfer and formation of the aldehyde endgroup. However, 1 H-NMR revealed the major species carried an intra-chain ketone instead of an aldehyde end-group.…”

Section: Branchingsupporting

confidence: 89%

Mass spectrometry in polymer chemistry: a state-of-the-art up-date

et al. 2010

View full text Add to dashboard Cite

Section: Branchingsupporting

confidence: 89%

Mass spectrometry in polymer chemistry: a state-of-the-art up-date

et al. 2010

View full text Add to dashboard Cite

“…We first attempted the reaction with cyanomethyl substituted thiocarbonylthio compounds as chain transfer agents (CTAs) ( 1 a – 1 e , Figure 1 C, Figures S3‐S4 and Scheme S1). When CTAs from 1 a to 1 d were employed, polymers of low molecular weights ( M n , entries 1–4 in Table 1) were obtained at moderate to high conversions of M1 and M2 , which could be attributed to the oligomerization of VEs [18] . Although CTA 1 e has shown good control in the copolymerization of chlorotrifluoroethylene, [19] the employment of 1 e in the terpolymerization of FM1 resulted in poor VE conversion (entry 5).…”

Section: Resultsmentioning

confidence: 99%

Visible‐Light‐Enabled Organocatalyzed Controlled Alternating Terpolymerization of Perfluorinated Vinyl Ethers

Quan

Wang

et al. 2021

Angewandte Chemie

View full text Add to dashboard Cite

Polymerizations of perfluorinated vinyl ethers (PFVEs) providea ni mportant category of fluoropolymers that have received considerable interests in applications.Inthis work, we report the development of an organocatalyzed controlled radical alternating terpolymerization of PFVEs and vinyl ethers (VEs) under visible-light irradiation. This method not only enables the synthesis of ab road scope of fluorinated terpolymers of lowdispersities and high chain-end fidelity,f acilitating tuning the chemical compositions by rationally choosing the type and/or ratio of comonomers,b ut also allows temporal control of chain-growth, as well as the preparation of avariety of novel fluorinated blockcopolymers. To showcase the versatility of this method, fluorinated alternating terpolymers have been synthesized and customized to simultaneously displayav ariety of desirable properties for solid polymer electrolyte design, creating new opportunities in high-performance energy storage devices.

show abstract

“…The first employment of MS to prove the formation of macromonomers in acrylate systems comes from Grady and coworkers [85,97]. A recent MS study even shows that backbiting followed by b-scission seems to occur in RP of butyl vinyl ether, resulting in a carbonyl group being incorporated into the polymer backbone [98]. However, it is Barner-Kowollik and colleagues who have made far the greatest effort to study the consequences of b-scission in acrylate polymerization, using MS as their scalpel.…”

Section: Acrylate Systemsmentioning

confidence: 99%

Elucidation of Reaction Mechanisms: Conventional Radical Polymerization

Buback

Russell

Vana

2011

Mass Spectrometry in Polymer Chemistry

View full text Add to dashboard Cite

It is often remarked that the molar mass distribution (MMD) of a polymer contains the entire history of its synthesis. It is because of this truism that those interested in the kinetics of polymerization are driven to understand polymer MMDs. As will be seen in this chapter, in the case of (conventional) radical polymerization (RP), this quest has been enormously advanced by the advent of large-molecule mass spectrometry (MS), for it is a characterization technique that furnishes hitherto unimaginable detail about the MMD of a polymer, and thus it may be used to elucidate or confirm the mechanisms of RP in many ways that simply were not previously possible.What is it that is so special about an MMD yielded by MS? It is not the distribution amount, for size exclusion chromatography (SEC) already makes a superior fist of measuring that, mostly through the use of refractive-index (RI) detection. Admittedly there can be issues with this, for example, that RI is molar mass dependent for oligomers [1]. However, such issues apply only in particular circumstances, and they pale beside the general uncertainty one must attach to polymer amounts as returned via MS: there is no doubt that SEC is a vastly superior technique in this respect. Rather, what is so special about MS is its delivery of the MMD variable, namely molar mass, M. The two important aspects here are mass accuracy and mass resolving powerFor many large-molecule studies, it is the mass accuracy of MS that is revolutionary. Indeed, the knee-jerk reaction of most RP workers would be that this is also the case in their field. In fact, the matter is not so straightforward. A good illustrative example of this is the pulsed-laser polymerization (PLP) method for measuring propagation rate coefficients, k p [3, 4], which requires knowledge of absolute values of M. By now an enormous quantity of accurate k p data has been yielded by this method, almost all of it through the use of SEC [5,6]. This evidences that for the study of RP kinetics and mechanisms, accurate SEC calibration is commonly possible, either directly through the use of standards, or indirectly through the additional use of Mark-Houwink parameters (so-called universal calibration). So, it is not this aspect alone that makes MS so useful.In fact what is so groundbreaking about MS for the study of RP mechanisms is its mass resolving power, that is, the ability of mass analyzers to separate and measure small differences in M, by now to well under 1-Dalton level with most instruments. As Barner-Kowollik et al. expressed it, this gives the power to visualize the individual polymer chains present in a given sample [7]. Thus, for example, polymer chains of identical degree of polymerization but with a different end group can be resolved, something of which SEC will never (in general) be capable. Because of the accurate determination of the M of the resolved species, their precise chemical composition may be deduced, and from this the mechanism of polymer formation can be inferred. Numerous examples of this ge...

show abstract

Specific Polymerization Mechanism Involving β-Scission of Mid-Chain Radical Yielding Oligomers in the Free-Radical Polymerization of Vinyl Ethers

Cited by 27 publications

References 35 publications

Mass spectrometry in polymer chemistry: a state-of-the-art up-date

Mass spectrometry in polymer chemistry: a state-of-the-art up-date

Visible‐Light‐Enabled Organocatalyzed Controlled Alternating Terpolymerization of Perfluorinated Vinyl Ethers

Elucidation of Reaction Mechanisms: Conventional Radical Polymerization

Contact Info

Product

Resources

About