Synthesis of poly(vinyl acetate) by degenerative transfer polymerization in the presence of iodine

Xu, Wenjing; Zhang, Wensheng; Li, Wei; Yan, Jin-Long; Guoyu, Shen; Li, Jun

doi:10.1002/app.36664

Cited by 18 publications

(6 citation statements)

References 23 publications

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“…Highly efficient living radical polymerization (LRP) of vinyl acetate (VAc) is a major polymer science objective since poly-(vinyl acetate) (PVAc) has a wide range of applications in materials science 1,2 and PVAc is the precursor for poly(vinyl alcohol) which is a water soluble biocompatible polymer material. [3][4][5] Exhaustive efforts to control radical polymerization of VAc have been attempted using atom transfer radical polymerization, [6][7][8][9] degenerative transfer through alkyl iodide, 10,11 organo-tellurium, 12,13 trithiocarbonate, [14][15][16] xanthate, [17][18][19][20] and cobalt transfer agents. [21][22][23][24][25] Cobalt(II) bis-acetylacetonate (Co II (acac) 2 , Fig.…”

Section: Introductionmentioning

confidence: 99%

Vinyl acetate living radical polymerization mediated by cobalt porphyrins: kinetic–mechanistic studies

2014

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Section: Introductionmentioning

confidence: 99%

Vinyl acetate living radical polymerization mediated by cobalt porphyrins: kinetic–mechanistic studies

2014

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“…The results show that the polymerization of VBz proceeds to high conversions. The free radical homopolymerization of VAc in the presence of AIBN as initiator at 75 °C with initial molar ratio [VAc] 0 :[AIBN] 0 of 10:1 has been carried out and conversion of 66% in 10 min has been observed . Therefore, one can conclude that the rate of conventional free radical bulk homopolymerization of VAc is higher than that of VBz.…”

Section: Resultsmentioning

confidence: 99%

Reverse iodine transfer polymerization of vinyl acetate and vinyl benzoate: synthesis and characterization of homo- and copolymers

Abdollahi

Bigdeli

Hemmati³

et al. 2015

Polym. Int.

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Homo-and copolymers of vinyl esters including vinyl acetate (VAc) and vinyl benzoate (VBz) were synthesized via the reverse iodine transfer radical polymerization technique. Polymerization was carried out in the presence of iodine as the in situ generator of the transfer agent and 2,2 ′ -azobis(isobutyronitrile) as the initiator at 70 ∘ C. Reverse iodine transfer radical homopolymerization of VAc and VBz led to conversions of 76 and 57%, number-average molecular weights of 8266 and 9814 g mol −1 and molecular weight distributions of 1.58 and 1.49, respectively. The microstructure of the synthesized polymers was investigated in detail using gel permeation chromatography, 1 H NMR, 13 C NMR and distortionless enhancement of polarization transfer (135 ∘ decoupler pulse) techniques. Relatively narrow molecular weight distribution and controlled and predictable trend of molecular weight versus conversion were observed for the synthesized polymers, showing that reverse iodine transfer radical homo-and copolymerization of VAc and VBz proceeded with controlled characteristics. Results of molecular weight and its distribution along with the 1 H NMR spectra recorded for homo-and copolymers indicated that side reactions can occur during the course of polymerization with a significant contribution when VAc, even in a small amount, was present in the reaction mixture. This can result in polymer chains with aldehyde dead end and broadening of the molecular weight distribution.

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“…Thermal radical initiator is necessary to supply sufficient radical flux during the polymerization. Iodine DT can be used for polymerization of most of the monomers [37][38][39][40]. Iodide-mediated radical polymerization has successfully been used in the homogeneous or heterogeneous mediums [37][38][39][40][41][42].…”

Section: Introductionmentioning

confidence: 99%

“…Iodine DT can be used for polymerization of most of the monomers [37][38][39][40]. Iodide-mediated radical polymerization has successfully been used in the homogeneous or heterogeneous mediums [37][38][39][40][41][42]. These techniques (ITP and RITP) are performed under catalyst-free condition; resulting in easy purification of product [42].…”

Section: Introductionmentioning

confidence: 99%

Radical polymerization of butadiene mediated by molecular iodine: a kinetic study of solution homopolymerization

Abdollahi

Hajiataloo

2021

J Polym Res

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Homopolymerization of butadiene (Bu) in 1,4-dioxane (Dox) was performed at 70 °C using molecular iodine (I 2 ) in the presence of 4,4'-azobis(4-cyanovaleric acid) (ACVA), resulting in α-carboxyl ω-iodine heterotelechelic polybutadiene. Effect of Dox concentration, molar ratio of ACVA to I 2 and initiator type on the Bu conversion was studied. Inhibition of the reaction by molecular I 2 was observed until complete consumption of the I 2 (induction period). Then, polymerization initiated by carboxyl-functionalized alkyl iodides in situ generated during induction period. ACVA decomposition rate constant (k d ), induction time t ind and k 2 p ∕k t ratio were calculated using Bu conversion as a function of time data. A good agreement between the theoretical and experimental changes in the conversion versus time was observed, indicating accuracy of the kinetic parameters estimated in this work. Experimental t ind was always less that theoretical one. It was attributed to reaction between Bu and I 2 , resulting in butadiene diiodide (I-Bu-I) compound. Formation of I-Bu-I species was further confirmed by 1 H-NMR analysis of end functional groups (i.e. alkyl iodide and allyl iodide) of polybutadiene chains. Based on the 1 H-NMR analysis, [I-Bu-I]/[I 2 ] 0 ratio was obtained for reaction B4 to be 0.235. It was found that among 1,2 and 1,4 additions, 1,2 addition of I 2 to Bu is the dominant reaction. Exchange constant between the growing and dormant species (C ex ) was estimated using GPC and conversion data to be in the range of 3.20-3.94. Then, M n and D evolution with conversion was investigated theoretically. Fraction of − carboxyl, − iodide heterotelechelic PBu chains f HOOC−PBu−I relative to all chains was estimated from 1 H-NMR data to be 87% for reaction B4.

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Synthesis of poly(vinyl acetate) by degenerative transfer polymerization in the presence of iodine

Cited by 18 publications

References 23 publications

Vinyl acetate living radical polymerization mediated by cobalt porphyrins: kinetic–mechanistic studies

Vinyl acetate living radical polymerization mediated by cobalt porphyrins: kinetic–mechanistic studies

Reverse iodine transfer polymerization of vinyl acetate and vinyl benzoate: synthesis and characterization of homo- and copolymers

Radical polymerization of butadiene mediated by molecular iodine: a kinetic study of solution homopolymerization

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