Incorporating primary amine pendant groups into copolymers via nitroxide mediated polymerization

Marić, Milan; Lessard, Benoît H.; Consolante, Valerie; Ling, Edwin Jee Yang

doi:10.1016/j.reactfunctpolym.2011.09.006

Cited by 7 publications

(6 citation statements)

References 61 publications

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“…A commercially available SG1-based alkoxyamine, N -(2-methylpropyl)- N -(1-(diethylphosphono-2,2-dimethylpropyl)- O -(2-carboxylprop-2-yl)hydroxylamine) BlocBuilder-MA (termed herein as BB, from Arkema) has enabled homopolymerization of acrylates and acrylamides and, under certain conditions, methacrylates (Figure a shows the chemical structure of BB. ). ,, The polymerization of methacrylates using BB is problematic because of the high activation/deactivation equilibrium constant ( K ) of methacrylates and the cross-disproportionation effect. − To overcome this, the copolymerization method first described by Charleux and co-workers was applied, where methacrylates are copolymerized with a small amount of comonomer with very low K such as styrene, , acrylonitrile (AN), , 9-(4-vinylbenzyl)-9 H -carbazole, , or other styrenic derivatives. − As a result, the average K , ⟨ K ⟩, of the polymerization decreases and control is enhanced accordingly . Synthesizing an alkoxyamine applicable for a wide range of monomers with low dispersity, low reaction temperature, and active chain ends has always been challenging. ,, Recently, Ballard et al , reported a new group of alkoxyamines such as 3-(((2-cyanopropan-2-yl)oxy)-(cyclohexyl)amino)-2,2-dimethyl-3-phenylpropanenitrile (Dispolreg 007), which enabled homopolymerization of methacrylates without any comonomer at temperatures of <100 °C and allowed clean crossover from a methacrylic block to a styrenic block.…”

Section: Introductionmentioning

confidence: 99%

“…Further improvement occurred by the introduction of N-tert-butyl-N- BlocBuilder-MA (termed herein as BB, from Arkema) has enabled homopolymerization of acrylates and acrylamides and, under certain conditions, methacrylates (Figure 1a shows the chemical structure of BB.). 6,31,32 The polymerization of methacrylates using BB is problematic because of the high activation/deactivation equilibrium constant (K) of methacrylates and the cross-disproportionation effect. 33−35 To overcome this, the copolymerization method first described by Charleux and co-workers 36 was applied, where methacrylates are copolymerized with a small amount of comonomer with very low K such as styrene, 34,37 acrylonitrile (AN), 38,39 9-(4vinylbenzyl)-9H-carbazole, 31,40 or other styrenic derivatives.…”

Section: ■ Introductionmentioning

confidence: 99%

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Nitroxide-Mediated Miniemulsion Polymerization of Bio-Based Methacrylates

Tajbakhsh

Hajiali

Marić

2020

Ind. Eng. Chem. Res.

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Nitroxide-mediated homopolymerization and statistical copolymerization of commercially available methacrylates derived from sustainable feedstocks (isobornyl methacrylate (IBOMA) and a mixture of methacrylic esters with an average alkyl side chain length of 13 units (termed C13MA)) was conducted in organic solvent (toluene) and in dispersed aqueous media using an oil-soluble unimolecular initiator (Dispolreg 007) without any controlling comonomers in a controlled manner. IBOMA homopolymerization in emulsion at 83−100 °C revealed the optimal polymerization temperature of 90 °C giving relatively narrow molecular weight distributions (1.46 < dispersities (Đ) < 1.58) and conversion up to 83% in a relatively short time (2 h). IBOMA/C13MA statistical copolymerizations yielded copolymers with tunable glass transition temperature (T g ) prepared in emulsion (−52 °C < T g < 123 °C) and in organic solvent (−40 °C < T g < 169 °C). Resins made in emulsion at 90 °C proceeded up to 92.7% conversion with monomodal molecular weight distributions (M̅ n up to 68,000 g mol −1 and Đ = 1.62−1.72) and were colloidally stable (24% solids and final average particle sizes of 270−481 nm). Furthermore, chain end fidelity was verified by chain extensions with IBOMA and C13MA monomers in both emulsion and organic solvent. These results constitute a readily scalable route to make polymers via nitroxide-mediated polymerization with controlled architecture using biobased feedstocks without the hazards of bulk or homogeneous organic solvent polymerization.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Nitroxide-Mediated Miniemulsion Polymerization of Bio-Based Methacrylates

Tajbakhsh

Hajiali

Marić

2020

Ind. Eng. Chem. Res.

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“…Unlike alkyl halide or thiocarbonylthio groups, the alkoxyamine ω‐chain‐end groups produced in NMP are stable with respect to nucleophilic substitution, and successful NMP of monomers containing primary or secondary amines have been reported, but commercially available NMP agents such as N ‐(tert‐butyl)‐ N ‐(1‐diethylphosphono‐2,2‐dimethyl‐propyl)nitroxide (SG1) and 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐oxyl (TIPNO) generally require high reaction temperatures (>110 °C) in order to efficiently mediate the RDRP of styrenic monomers—conditions that are unsuitable for thermally sensitive moieties such as aziridines. Cameron et al recently demonstrated that well‐controlled NMP of styrene could be achieved in solution ( ca .…”

Section: Resultsmentioning

confidence: 99%

Reversible Deactivation Radical Polymerization of Monomers Containing Activated Aziridine Groups

McLeod

Tsarevsky

2016

Macromol. Rapid Commun.

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Polymers bearing activated aziridine groups are attractive precursors to α-substituted-β-amino-functionalized materials due to the enhanced reactivity of the pendant aziridine functionalities toward ring-opening by nucleophiles. Two aziridine-containing styrenic monomers, 2-(4-vinylphenyl)aziridine (VPA) and N-mesyl-2-(4-vinylphenyl)aziridine (NMVPA), were polymerized under a variety of reversible deactivation radical polymerization conditions. Low-catalyst-concentration atom transfer radical polymerization (LCC-ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization were ineffective at producing well-defined polymers from VPA due to side reactions between the aziridine functionalities and the agents controlling the polymerizations (catalysts or chain transfer agents). PolyVPA produced under nitroxide-mediated polymerization (NMP) conditions had narrow molecular weight distribution at low to moderate conversions of monomer, but branched and eventually cross-linked polymers were formed at higher conversions due to ring-opening reactions of the aziridine groups. Most of these undesirable side reactions were eliminated by attaching a methanesulfonyl (mesyl) group to the aziridine nitrogen atom, and well-defined linear homopolymers with targeted molecular weights were realized from NMVPA under RAFT and NMP conditions; however, side reactions between the aziridine groups and the catalyst in LCC-ATRP still occured and the polymerization was uncontrolled using this technique.

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“…Amine pendant functional poly(styrene) and poly(methyl methacrylate) block copolymers have been synthesized using 4-aminostyrene as a comonomer using NMP. [79] A cheaper alternative that may prove to be more feasible for large scale synthesis is 3-isopropenyl-α,α-dimethylbenzylamine which has been copolymerized with styrene and with methyl methacrylate (MMA) using conventional radical polymerization. [80] This could be a suitable monomer to impart pendant amine functionality into a SAN copolymer, and may lead to higher levels of compatibility within the MA-PE/SAN blends.…”

Section: Considerations For Future Workmentioning

confidence: 99%

Compatibilization of Poly(styrene‐acrylonitrile) (SAN)/Poly(ethylene) Blends via Amine Functionalization of SAN Chain Ends

Oxby

Marić

2013

Macro Reaction Engineering

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Styrene/acrylonitrile (SAN) copolymers with excellent chain-end fidelity and low polydispersity M w /M n (1.10 -1.30) were synthesized by nitroxide mediated polymerization (NMP) in dimethylformamide (DMF) solution with a succinimidyl ester (NHS) terminal group from the so-called SG1 nitroxide residue. These copolymers were thermally stabilized by removing the N-tertbutyl-N-[1-diethylphosphono-(2,2-dimethylpropyl) nitroxide] (SG1), and then modified to form primary amine end-functional SAN (SAN-NH 2 ). Homogeneous coupling reactions and Fourier-transform infrared spectroscopy (FTIR) indicated that the amine group was effectively placed at the chain end. SAN-NH 2 was reactively blended with maleic anhydride grafted poly(ethylene) (PE) at 20 wt.% loading at 180 °C and the resulting morphology was compared against the nonreactive blend. Scanning electron microscopy (SEM) indicated finer SAN domains ~ 1 μm which were thermally stable upon annealing in the reactive case.The dispersed SAN domains were reoriented using a channel die to impart elongated domains with aspect ratios ~ 14, which would be desirable for barrier materials.ii iii

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Incorporating primary amine pendant groups into copolymers via nitroxide mediated polymerization

Cited by 7 publications

References 61 publications

Nitroxide-Mediated Miniemulsion Polymerization of Bio-Based Methacrylates

Nitroxide-Mediated Miniemulsion Polymerization of Bio-Based Methacrylates

Reversible Deactivation Radical Polymerization of Monomers Containing Activated Aziridine Groups

Compatibilization of Poly(styrene‐acrylonitrile) (SAN)/Poly(ethylene) Blends via Amine Functionalization of SAN Chain Ends

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