Synthesis and characterization of well-defined end-chain functional macrophotoinitiators of polystyrene and polyacrylonitrile by RAFT/MADIX polymerization

Uyar, Zafer; Turgut, Ferhat; Arslan, Ulku; Durgun, Mustafa; Degirmenci, Mustafa

doi:10.1016/j.eurpolymj.2019.07.028

Cited by 17 publications

(15 citation statements)

References 42 publications

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“…The photoreactive benzoin functionalized RAFT/ MADIX agent, B-CTA (1), was prepared according to the procedure described in our previous study. 30 First, the reaction of benzoin with NaH and then CS 2 in THF yielded sodium O-(2-oxo-1,2-diphenylethyl)carbonodithioate at room temperature. Next, ethyl 2-bromo-2-phenylacetate was added to this mixture to obtain the target xanthate molecule, B-CTA (1) (Scheme 2).…”

Section: Synthesis Of Photofunctional Chain Transfer Agent [B-cta (1)]mentioning

confidence: 99%

“…15,28,29 In our pursuit to design a photoreactive CTA that allows both photopolymerization and RAFT polymerization with a wide range of monomers, we previously synthesized a xanthate-type CTA with benzoin as the photoreactive Z group and benzyl (−CH 2 −Ph) as the R group and used it in the RAFT/MADIX polymerization of St, MMA, AN, and VAc monomers. 30 Although this CTA gave excellent results in the RAFT polymerization of St and AN, it had shortcomings with MMA and VAc. The result with the VAc was particularly surprising because CTAs with xanthate Z groups are usually effective in the RAFT polymerization of less activated monomers such as VAc.…”

Section: ■ Introductionmentioning

confidence: 98%

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A Xanthate-Type Photofunctional Chain Transfer Agent for the Synthesis of Macrophotoinitiators

Uyar

Arslan

Boyraz

et al. 2022

ACS Appl. Polym. Mater.

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Polystyrene (PSt), poly(methyl methacrylate) (PMMA), and poly(vinyl acetate) (PVAc) macrophotoinitiators with well-defined structures comprising a photoreactive group, benzoin (B), at the chain end were successfully synthesized by RAFT/MADIX polymerization. First, a photofunctional xanthate-type chain transfer agent (B-CTA) was produced by an efficient two-step one-pot synthesis. Then, B-CTA was used in the RAFT/MADIX polymerization of styrene (St), methyl methacrylate (MMA), acrylonitrile (AN) (more activated monomers), and vinyl acetate (VAc) (a less activated monomer). Based on spectral and GPC data, the RAFT/MADIX polymerizations of St, MMA, and VAc monomers produced well-controlled macrophotoinitiators with narrow molecular weight distributions and compatible theoretical and experimental number-average molecular weights. The resulting well-defined macrophotoinitiators, B-PSt, B-PMMA, and B-PAVc, were used as precursors to obtain block copolymers PSt-b-PCHO, PMMA-b-PCHO, PVAc-b-PCHO from cyclohexene oxide (CHO) and PSt-b-PBVE, PMMA-b-PBVE, PVAc-b-PBVE from butyl vinyl ether (BVE) monomers, respectively, via photoinduced free radical promoted cationic polymerization. Various analyses such as elemental, spectroscopic, and GPC techniques were used to confirm the structures of the synthesized molecules.

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Section: Synthesis Of Photofunctional Chain Transfer Agent [B-cta (1)]mentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 98%

A Xanthate-Type Photofunctional Chain Transfer Agent for the Synthesis of Macrophotoinitiators

Uyar

Arslan

Boyraz

et al. 2022

ACS Appl. Polym. Mater.

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“…This technique has been successfully used for producing homopolymers and copolymers of AN with the desired MW, composition and monomer sequence distribution. 11,[46][47][48][49][50][51][52][53][54] In the present research we apply RAFT polymerization to the synthesis of copolymers of AN with MA, ethyl acrylate (EA), n-butyl acrylate (BA), 2-ethylhexyl acrylate (EHA) and lauryl acrylate (LA) in DMSO solution with monomer feed in the range 5-20 mol%. Here we report about the first comparative study of the thermal behavior of the resultant copolymers as a function of the length of the alkyl substituent in alkyl acrylate and the copolymer composition.…”

Section: Introductionmentioning

confidence: 99%

“…To minimize this factor and to form copolymers with a narrow molecular weight distribution (MWD) a reversible addition–fragmentation chain transfer (RAFT) polymerization can be applied. This technique has been successfully used for producing homopolymers and copolymers of AN with the desired MW, composition and monomer sequence distribution 11,46–54 …”

Section: Introductionmentioning

confidence: 99%

Reversible addition–fragmentation chain transferbased copolymers of acrylonitrile and alkyl acrylates as possible precursors for carbon fibers: synthesis and thermal behavior during stabilization

Томс

Balashov

Gervald

et al. 2021

Polymer International

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Copolymers of acrylonitrile and alkyl acrylates with various alkyl substituents (methyl, ethyl, butyl, 2‐ethylhexyl and lauryl) were synthesized via reversible addition–fragmentation chain transfer polymerization in dimethylsulfoxide. It is demonstrated that reactivity of alkyl acrylate in copolymerization decreases with increase of the length of the alkyl substituent. The molar fractions of homodiads and homotriads of acrylonitrile and the number‐average sequence length of acrylonitrile units decreases with a decrease in the acrylate content in the copolymer or with an increase in the length of the alkyl substituent in the acrylate. The copolymer composition was held constant throughout copolymerization in all the studied systems resulting in the formation of copolymers with high compositional homogeneity. Additionally the reversible addition–fragmentation chain transfer mechanism provides low dispersity of the copolymers. Both factors enable the effect of the alkyl substituent in alkyl acrylate on the thermal behavior of acrylonitrile copolymers to be carefully revealed. Being inert in the cyclization reaction, alkyl acrylates have no effect on the activation energy of the reaction. However, increase of the length of the alkyl substituent is followed by a slower evolution of the ladder structure. In contrast, in conditions of oxidative stabilization, the stabilization index increases in the order of increase of the number‐average sequence length of the acrylonitrile units in the copolymers. Thus, the use of alkyl acrylates with longer alkyl substituents provides an increase of chain flexibility and the formation of an enhanced ladder structure during oxidative stabilization which is profitable for carbon fiber production. © 2021 Society of Industrial Chemistry.

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“…xanthates (MADIX) polymerizations [25][26][27][28][29][30]. More distinct and specific results are obtained by combining CRP mechanisms with certain other processes [31,32].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, spectral characterization and DFT calculations of novel macro MADIX agent: mechanism of addition-fragmentation reaction of xanthate compound

2020

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In this study, the macromolecular design was performed via interchange of xanthates (MADIX) polymerization. The macro RAFT/MADIX agent containing the structure of polytetrahydrofuran (PTHF) (average Mn ~ 1000 g/mol) was synthesized to use in the polymerization. PS-b-PTHF-b-PS triblock copolymer was obtained by styrene-controlled radical polymerization using the RAFT/MADIX agent. The plot of ln [M] o /[M] versus monomer concentration versus polymerization time exhibits first-order kinetic behavior. Block copolymer formation has a controlled character. The formation of the narrow molecular weight polymer controlled by the styrene's RAFT/MADIX polymerization is confirmed by the increase in the polymerization time of the molecular weight. The results are in good agreement with theoretical values. Block copolymers having a narrow molecular weight distribution and a predetermined average molecular weight have been obtained using this polymerization process. The synthesized RAFT/MADIX agents, polymer, and copolymers were characterized by NMR and FT-IR spectroscopy, GPC, and differential scanning calorimetry. Based on the vibration analysis, the thermodynamic properties of the compound were also calculated. Optimized structure, frontier molecular orbitals (HOMO and LUMO) and global reactivity descriptors were analyzed by DFT calculations. As a result of the DFT study with trimer and hexamer; although the chain length is increased, the energy parameters obtained are very proximate to each other.

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Synthesis and characterization of well-defined end-chain functional macrophotoinitiators of polystyrene and polyacrylonitrile by RAFT/MADIX polymerization

Cited by 17 publications

References 42 publications

A Xanthate-Type Photofunctional Chain Transfer Agent for the Synthesis of Macrophotoinitiators

A Xanthate-Type Photofunctional Chain Transfer Agent for the Synthesis of Macrophotoinitiators

Reversible addition–fragmentation chain transferbased copolymers of acrylonitrile and alkyl acrylates as possible precursors for carbon fibers: synthesis and thermal behavior during stabilization

Synthesis, spectral characterization and DFT calculations of novel macro MADIX agent: mechanism of addition-fragmentation reaction of xanthate compound

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