High-efficiency synthesis of well-defined cyclic poly(N-vinylcaprolactam) and its solution properties

Yang, Yaozong; Tang, Gang; Hu, Minqi; Shao, Li; Li, Jie; Yun-mei, BI

doi:10.1016/j.polymer.2015.05.027

Cited by 17 publications

(20 citation statements)

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“…27 Despite the interest of poly(vinyl esters) and poly(vinyl amides) for a range of applications, the controlled radical polymerization of unconjugated monomers has long been recognized as a challenge due to the difficulty in controlling the equilibrium between the unstabilized radical and the dormant species. 5,14 In the recent years, improvements in RAFT/MADIX polymerization, 9,[28][29][30][31][32][33][34] OMRP, 13,[35][36][37] RITP 38 and ATRP, 39,40 offered opportunities to control the polymerization of the so-called less activated monomers (LAM) such as vinyl acetate, Nvinylcaprolactam (VCL) or N-vinylpyrrolidone (VP). RAFT/MADIX polymerization afforded the possibility to synthesize various LAM-based copolymers such as block copolymers (PVAcb-PVCL, 30 , PVCL-b-PVP 41 ) or statistical copolymers (P(VP-stat-VCL) 12,42 ).…”

Section: Introductionmentioning

confidence: 99%

“…The most developed CRP techniques are nitroxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP), copper(0)-mediated radical polymerization, , reversible addition–fragmentation chain transfer (RAFT) , including macromolecular design via the interchange of xanthates (MADIX), reversible iodine transfer polymerization (RITP), and organometallic-mediated radical polymerization (OMRP) . Despite the interest of poly(vinyl esters) and poly(vinyl amides) for a broad range of applications, the controlled radical polymerization of unconjugated monomers has long been recognized as a challenge due to the difficulty in controlling the equilibrium between the unstabilized radical and the dormant species. , In the recent years, improvements in RAFT/MADIX polymerization, ,− OMRP, ,− RITP and ATRP, , offered opportunities to control the polymerization of the so-called less activated monomers (LAM) such as vinyl acetate, N -vinylcaprolactam, or N -vinylpyrrolidone (VP). RAFT/MADIX polymerization afforded the possibility to synthesize various LAM-based copolymers such as block copolymers (PVAc- b -PVCL, PVCL- b -PVP) or statistical copolymers (P(VP- stat -VCL) , ).…”

Section: Introductionmentioning

confidence: 99%

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RAFT Copolymerization of Vinyl Acetate and N-Vinylcaprolactam: Kinetics, Control, Copolymer Composition, and Thermoresponsive Self-Assembly

et al. 2016

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Well-defined thermoresponsive amphiphilic statistical copolymers based on Nvinylcaprolactam (VCL) and vinyl acetate (VAc) were successfully synthesized by RAFT/MADIX polymerization mediated by O-ethyl-S-(1ethoxycarbonyl)ethyldithiocarbonate chain transfer agent at 65°C. We achieved the synthesis of a series of copolymers with controlled molar masses and low dispersities over a wide range of monomer feed ratios (0 < fVac,0 < 1). Both conventional linearization methods and a nonlinear least square methods (NLLS) were applied to estimate reliable values of reactivity ratios for VAc and VCL radical polymerization in regards to the disparate values previously reported in the literature. The highest measurement precision was observed for the NLLS method based on the integrated form of the copolymerization equation developed by Skeist. The calculated values of the reactivity ratios (rVAc = 0.33  0.10 and rVCL = 0.29  0.15) perfectly fitted the drift in monomer feed ratio versus conversion. The VCL and VAc monomer units are distributed homogeneously along the copolymer chains. Both the cloud point temperatures and glass transition temperatures evolve linearly with the copolymer composition. Analyses of the aqueous solutions of the amphiphilic copolymers by means of dynamic and static light scattering show that P(VAc-co-VCL) copolymers undergo a reversible temperature-induced conformational change between large aggregates (T > Tcloud point) and either unimers for FVAc inferior to 0.3 (Nagg = 1, Dh  7 nm) or small aggregates for FVAc = 0.53 (Nagg = 3, Dh  14 nm).

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

RAFT Copolymerization of Vinyl Acetate and N-Vinylcaprolactam: Kinetics, Control, Copolymer Composition, and Thermoresponsive Self-Assembly

et al. 2016

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“…Their LCST values increased with decreasing the linear‐dendritic copolymer concentration, and the lower the polymer concentration were, the broader the temperature range exhibited by the decrease in transmittance. Such a phenomenon is known to be a general trend in the concentration effect on the LCST of PNVCL‐containing block copolymers …”

Section: Resultsmentioning

confidence: 90%

“…The linearly PNVCL‐based block copolymers have gained much impetus in recent years due to the enhanced boost of the so‐called controlled free radical polymerization methods, such as atom transfer free radical polymerization (ATRP), reversible addition fragmentation chain transfer (RAFT) polymerization, or organometallic‐mediated radical polymerization . However, only six recent articles were concerned on nonlinear block copolymers containing the PNVCL moiety . Recently, star‐shaped copolymers with four and six poly(ε‐caprolactone)‐block‐poly( N ‐vinylcaprolactam) S(PCL‐ b ‐PNVCL) arms were successfully synthesized by combining ring opening polymerization of ε‐caprolactone (CL) and RAFT polymerization of N ‐vinylcaprolactam (NVCL) .…”

Section: Introductionmentioning

confidence: 99%

Dendritic poly(benzyl ether)‐b‐poly(N‐vinylcaprolactam) block copolymers: Self‐organization in aqueous media, thermoresponsiveness and biocompatibility

Tang

et al. 2017

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

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Four generations of new amphiphilic thermoresponsive linear‐dendritic block copolymers (LDBCs) with a linear poly(N‐vinylcaprolactam) (PNVCL) block and a dendritic poly(benzyl ether) block are synthesized by atom transfer radical polymerization (ATRP) of N‐vinylcaprolactam (NVCL) using dendritic poly(benzyl ether) chlorides as initiators. The copolymers have been characterized by 1H NMR, FTIR, and GPC showing controlled molecular weight and narrow molecular weight distribution (PDI ≤ 1.25). Their self‐organization in aqueous media and thermoresponsive property are highly dependent on the generation of dendritic poly(benzyl ether) block. It is observed for the LDBCs that the self‐assembled morphology changes from irregularly spherical micelles, vesicles, rod‐like large compound vesicles (LCVs), to the coexistence of spherical micelles and rod‐like LCVs, as the generation of the dendritic poly(benzyl ether) increases. The results of a cytotoxicity study using an MTT assay method with L929 cells show that the LDBCs are biocompatible. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 300–308

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“…When the higher the polymer concentration was, the narrower the temperature range exhibited by the increase in transmittance. This phenomenon is due to the concentration effect on the LCST of PNVCL‐containing block copolymers 40 …”

Section: Resultsmentioning

confidence: 99%

Thermal and enzymatic dual‐stimuli responsive linear‐dendritic block copolymers based on poly(N‐vinylcaprolactam)

Qian

Wei

Wang

et al. 2020

Polymers for Advanced Techs

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The first‐ and second‐generation well‐defined thermal and enzymatic dual‐stimuli responsive amphiphilic linear‐dendritic block copolymers (LDBCs) based on hydrophilic linear poly(N‐vinylcaprolactam) (PNVCL) and a hydrophobic Fmoc‐terminated dendron derived from an aliphatic polyester of 2, 2′‐dimethylolpropionic acid (bis‐MPA) have been synthesized via a combination of reversible addition fragmentation chain transfer (RAFT) polymerization of N‐vinylcaprolactam (NVCL) and “chain‐first” strategy. The copolymers were characterized by 1H NMR spectra and gel permeation chromatograph (GPC) analyses, showing controlled molecular weight and narrow molecular weight distribution (PDI ≤1.27). They self‐assemble in water into vesicles that are able to disrupt and release encapsulated cargos upon papain treatment. Their thermal‐responsive property was highly dependent on the generation and concentration of copolymers, and enzyme‐responsive behavior was affected by the generation of dendritic aliphatic polyester block. Moreover, papain influenced the thermal‐responsive behavior of the copolymers. Such smart copolymers could be efficiently used in drug delivery systems or biosensors.

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High-efficiency synthesis of well-defined cyclic poly(N-vinylcaprolactam) and its solution properties

Cited by 17 publications

References 50 publications

RAFT Copolymerization of Vinyl Acetate and N-Vinylcaprolactam: Kinetics, Control, Copolymer Composition, and Thermoresponsive Self-Assembly

RAFT Copolymerization of Vinyl Acetate and N-Vinylcaprolactam: Kinetics, Control, Copolymer Composition, and Thermoresponsive Self-Assembly

Dendritic poly(benzyl ether)‐b‐poly(N‐vinylcaprolactam) block copolymers: Self‐organization in aqueous media, thermoresponsiveness and biocompatibility

Thermal and enzymatic dual‐stimuli responsive linear‐dendritic block copolymers based on poly(N‐vinylcaprolactam)

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