Smart morpholine-functional statistical copolymers synthesized by nitroxide mediated polymerization

Lessard, Benoît H.; Savelyeva, Xeniya; Marić, Milan

doi:10.1016/j.polymer.2012.10.020

Cited by 31 publications

(43 citation statements)

References 59 publications

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“…The kinetics of phase separation in ILs was found to be extremely slow compared to that in aqueous solutions, mainly resulting from the much higher viscosity of ILs compared to that of water . In aqueous solutions, it is known that both the transition temperature and sharpness of the LCST transitions were dependent on heating rate . As heating rate increased, the CPT tended to increase and phase transition became more diffuse as the polymer chains had less time to react to the environmental change.…”

Section: Resultsmentioning

confidence: 99%

Fluorescent, thermoresponsive copolymers via nitroxide-mediated polymerization: Synthesis and effect of fluorescent groups on phase transitions in an ionic liquid

Zhang

Marić

2013

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

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Synthesis of poly(benzyl methacrylate) (PBzMA) by nitroxide‐mediated polymerization with a small fraction of fluorescent, controlling comonomer, 9‐(4‐vinylbenzyl)‐9H‐carbazole (VBK, 2–11 mol % in the feed), was studied along with the resulting copolymers' LCST phase behavior in the ionic liquid (IL) 1‐ethyl‐3‐methylimidazolium bis(trifluoromethane sulfone)imide. The effectiveness of VBK as a controlling comonomer was demonstrated by a dramatic decrease in the product of average propagation rate constant and average equilibrium constant, , compared to BzMA polymerizations with styrene as comonomer. Linear molecular weight increase with conversion (up to ∼40% conversion), with polydispersities of about 1.34–1.42, and successful chain extensions indicated the copolymerizations were relatively well controlled. The incorporation of fluorescent and solvatophobic VBK units in the BzMA/VBK copolymers not only affected transition temperature and reversibility of the LCST‐type phase separation in the IL, but also led to about a fivefold phase separation‐triggered fluorescent enhancements, likely due to enhanced fluorescence resonance energy transfer from BzMA to VBK being in close proximity during aggregation. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4702–4715

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Section: Resultsmentioning

confidence: 99%

Fluorescent, thermoresponsive copolymers via nitroxide-mediated polymerization: Synthesis and effect of fluorescent groups on phase transitions in an ionic liquid

Zhang

Marić

2013

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

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“…The cloud point temperature T cp determined here is below the 33°C reported by Idziak et al [37] for the homopolymer PDEAAm. This can be ascribed to the presence of the hydrophobic PPA segment, which tends to suppress the LCST of the copolymer [38][39][40]. Also, the block copolymer exhibited a slight hysteresis in cloud point temperature between the heating and the cooling cycles (T cp = 30°C for heating and T cp = 26°C for cooling), which has also been observed for thermo-responsive polymers bearing tertiary amines [40][41][42].…”

Section: Thermo-responsive Behavior Illustratedmentioning

confidence: 61%

Thermo-responsive, UV-active poly(phenyl acrylate)-b-poly(diethyl acrylamide) block copolymers

Wang¹,

Lessard²,

Marić

2013

Express Polym. Lett.

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Abstract. The homopolymerization of phenyl acrylate (PA) was investigated for the first time by nitroxide mediated polymerization (NMP) with the succinimidyl form of the SG1-based unimolecular initiator 2-[N-tert-butyl-2,2-(dimethylpropyl)-aminooxy]propionic acid (BlocBuilder MA). The control of PPA homopolymerization was improved by the use of 15 mol% additional free nitroxide SG1 ([tert-butyl[1-(diethoxyphosphoryl)-2,2-dimethylpropyl]amino]oxidanyl) and dispersities, M w /M n , of around 1.2 were achieved. A PPA homopolymer was then successfully chain-extended with diethyl acrylamide (DEAAm) to form a block copolymer of PPA-b-PDEAAm where the PDEAAm segment is thermo-responsive, while the PPA block is potentially UV-active. The thermo-responsive behavior of the block copolymer in 0.5 wt% aqueous solution was studied by UV-Vis spectrometry and dynamic light scattering (DLS), indicating cloud point temperatures of 26-30°C, close to that reported for PDEAAm homopolymers.

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“…Traditionally, NMP was restricted to the polymerization of styrenic monomers using 2,2,6,6‐tetramethyl‐piperidine 1‐oxyl initiator (TEMPO) . NMP's recent development has been accelerated by the development of initiators based on alkoxyamines such as N ‐tert‐butyl‐ N ‐[1‐diethylphosphono‐(2,2‐dimethylpropyl)]nitroxide (SG1) and 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐nitroxide (TIPNO), which have allowed the controlled polymerization of a wider range of monomers including acrylates, acrylamides, and methacrylates (with a small addition of “controlling” comonomers) . NMP controls the radical concentration for a significant period of the polymerization, thereby minimizing irreversible termination reactions.…”

Section: Introductionmentioning

confidence: 99%

“…Some other thermoresponsive poly(acrylamides) that have been studied are N , N ‐diethylacrylamide, N ‐ethylacrylamide, ( N ‐(3‐methoxypropyl) acrylamide, N‐n ‐propylacrylamide, N,N ‐ethylmethylacrylamide, to name a few. An important sub‐class of poly(acrylamides) are those based on a ring motif such as pyrrolidone, piperidine, and morpholine . 4‐acryloylmorpholine (4AM) has been polymerized in a controlled manner by our group and by Schubert and coworkers, using NMP.…”

Section: Introductionmentioning

confidence: 99%

Stimuli-responsive 4-acryloylmorpholine/4-acryloylpiperidine copolymers via nitroxide mediated polymerization

Savelyeva

Métafiot

et al. 2017

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

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4‐acryloylmorpholine/4‐acryloylpiperidine statistical copolymers were synthesized by nitroxide mediated polymerization (NMP) with BlocBuilder unimolecular initiator in dimethylformamide solution at 120 °C. The copolymers had narrow molecular weight distributions (dispersity Đ = 1.25–1.35, number average molecular weights Mn = 8.5–13.7 kg mol−1). The copolymer microstructure was essentially statistical (reactivity ratios r4AP = 0.81 ± 0.73, r4AM = 0.73 ± 0.68 based on non‐linear fitting of the Mayo‐Lewis equation). Cloud point temperatures (CPT) in aqueous media were tuned from 11 °C to 92 °C, merely by adjusting the initial monomer composition. Using NMP permitted sharper control of the CPT transitions, compared to the similar copolymer made using conventional radical polymerization. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2160–2170

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Smart morpholine-functional statistical copolymers synthesized by nitroxide mediated polymerization

Cited by 31 publications

References 59 publications

Fluorescent, thermoresponsive copolymers via nitroxide-mediated polymerization: Synthesis and effect of fluorescent groups on phase transitions in an ionic liquid

Fluorescent, thermoresponsive copolymers via nitroxide-mediated polymerization: Synthesis and effect of fluorescent groups on phase transitions in an ionic liquid

Thermo-responsive, UV-active poly(phenyl acrylate)-b-poly(diethyl acrylamide) block copolymers

Stimuli-responsive 4-acryloylmorpholine/4-acryloylpiperidine copolymers via nitroxide mediated polymerization

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