New Class of Alkoxyamines for Efficient Controlled Homopolymerization of Methacrylates

Ballard, Nicholas; Aguirre, Miren; Simula, Alexandre; Agirre, Amaia; Leiza, José R.; Asúa, José M.; Es, Steven van

doi:10.1021/acsmacrolett.6b00547

Cited by 59 publications

(73 citation statements)

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“…NMP of methacrylates using conventional BlocBuilder or NHS‐BB is improved by adding a small portion of controlling comonomer, and recently a new class of alkoxyamines was developed via a readily scalable process that was able to homopolymerize methacrylates by NMP . One alkoxyamine in particular, D7, showed good control over the polymerization of MMA with a fast rate of polymerization, and can be easily synthesized from readily available reagents .…”

Section: Resultsmentioning

confidence: 99%

“…2‐([ tert ‐Butyl[1‐(diethoxy‐phosphoryl)‐2,2‐dimethylpropyl]amino]oxy)‐2‐methylpropionic acid or BlocBuilder was purchased from Arkema and modified with an N ‐succinimidyl ester group following a method used in the literature to synthesize 2‐methyl‐2‐[ N ‐ tert ‐butyl‐ N ‐(1‐diethoxyphosphoryl‐2,2‐dimethylpropyl)‐aminoxy]‐ N ‐propionyloxysuccinimide or NHS‐BlocBuilder (NHS‐BB) . 3‐(((2‐Cyanopropan‐2‐yl)oxy)(cyclohexyl)amino)‐2,2‐dimethyl‐3‐phenylpropanenitrile, D7, was synthesized according to the method described by Ballard et al . Toluene (≥99%), methanol (MeOH, ≥99%), and tetrahydrofuran (THF, 99.9% HPLC grade) were obtained from Fisher Scientific and used as received.…”

Section: Methodsmentioning

confidence: 99%

“…An N ‐phenylalkoxyamine initiator ( N ‐(1‐methyl‐(1‐(4‐nitrophenoxy)carbonyl) ethoxy)‐ N ‐(1‐methyl‐(1‐(4‐nitrophenoxy)carbonyl)ethyl)benzenamine) was also able to homopolymerize MMA but only to low conversion ( X < 50%) . More recently, a new class of alkoxyamines was developed that is able to homopolymerize methacrylates without using controlling comonomer in solution and miniemulsion polymerization . This new alkoxyamine, 3‐(((2‐cyanopropan‐2‐yl)oxy)(cyclohexyl)amino)‐2,2‐dimethyl‐3‐phenylpropanenitrile, which the authors have named Dispolreg 007 (D7), has a higher k c , therefore exhibiting better control of the polymerization of methacrylates with minimal irreversible termination and successful chain extension with n ‐butyl acrylate.…”

Section: Introductionmentioning

confidence: 99%

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Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Luk

Marić

2019

Macro Reaction Engineering

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polymers with controlled architectures. [11,12] Styrene-butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS) triblock copolymers have long been commercialized too, such as the Kraton family of thermoplastic elastomers, which are made by anionic polymerization. [13,14] While many industrial applications use free radical polymerization, CRP precisely controls the molecular architecture of polymer chains, therefore making homopolymers, diblock and triblock copolymers with narrow molecular weight distributions (MWDs) and low dispersity. [15] Ionic polymerization is a truly "living" method, but it is intolerant to functional monomers and impurities. [16] CRP, more properly defined as reversible deactivation radical polymerization (RDRP), is a newer, more versatile technique to control the polymerization of free radicals. It utilizes activationdeactivation equilibrium or reversible chain transfer to suppress irreversible termination such that the propagating radical is primarily in its dormant state. [17] Amongst the several types of RDRP, atom transfer radical polymerization (ATRP) [18][19][20] and reversible additionfragmentation transfer (RAFT) [21][22][23] can polymerize a wide variety of functional monomers like vinyl esters and (meth) acrylates. This study will focus on nitroxide-mediated polymerization (NMP) as it is particularly adept for polymerization of styrene-diene systems. [24][25][26] NMP is able to polymerize functionalized styrene and acrylate monomers successfully, [27] however it is limited in its ability to maintain active chain ends in the polymerization of methacrylates. [28,29] It was discovered that the rate of dissociation (k d ) is very large because of steric stabilization of the propagating methacrylate radical, and the rate of combination (k c ) is very low due to steric hindrance provided by the bulky SG1-nitroxide (N-tert-butyl-N-[1-diethylphosphono-(2,2dimethylpropyl)] nitroxide). Consequently, the activationdeactivation equilibrium (K eq = k d /k c ) is high, resulting in termination by disproportionation. [30] To overcome this, small amounts of controlling comonomer like styrene or acrylonitrile can be added to effectively lower K eq . [28,31] Furthermore, the SG1-based nitroxide, BlocBuilder, can be modified with an N-succinimidyl ester group (N-succinimidyl modified commercial BlocBuilder [NHS-BB]) to better control the polymerization of methacrylates, [32] and successful polymerization of Nitroxide-Mediated Polymerization Farnesene (Far) is a bio-based terpene monomer that is similar in structure to commercially used dienes like butadiene and isoprene. Nitroxide-mediated polymerization (NMP) is adept for the polymerization of dienes, but not particularly effective at controlling the polymerization of methacrylates using commercial nitroxides. In this study, Far is statistically copolymerized with a functional methacrylate, glycidyl methacrylate (GMA), by NMP using N-succinimidyl modified commercial BlocBuilder (NHS-BB) initiator. Reactivity ratios are determined to be r Far = ...

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Luk

Marić

2019

Macro Reaction Engineering

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“…Note that for a sufficiently high initial styrene amount thus similar degrees of microstructural control, at least based on Ð , are obtained as for the third generation nitroxides ( ca. Ð of 1.3) . The incorporation of styrene (blue units) can also be clearly seen in the chains in Figure .…”

Section: Resultsmentioning

confidence: 80%

“…However, DPAIO displays limitations toward NMP of styrenic and acrylate monomers. More recently, novel alkoxyamines bearing cyanopropyl groups have been developed by Ballard et al These alkoxyamines can be employed to acceptably control methacrylates ( Ð of ca . 1.3), which was mainly attributed to a lowering of k td ,X .…”

Section: Introductionmentioning

confidence: 99%

An evaluation of the impact of SG1 disproportionation and the addition of styrene in NMP of methyl methacrylate

et al. 2018

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A kinetic modeling study is presented for batch nitroxide mediated polymerization (NMP) of methyl methacrylate (MMA; nitroxide: N‐tert‐butyl‐N‐[1‐diethylphosphono‐(2,2‐dimethylpropyl)] (SG1)). Arrhenius parameters for SG1 disproportionation (A = 1.4 107 L mol−1 s−1; Ea = 23 kJ mol−1) are reported, based on homopolymerization data accounting for unavoidable temperature variations with increasing time, that is, nonisothermicity. For low targeted chain lengths (TCLs ≤ 300), this nonisothermicity is also relevant for NMP of MMA with a small amount of styrene. Parameter tuning to copolymerization data confirms a penultimate monomer unit effect for activation (sa2 = ka12/ka22=6.7; 363 K; 1: MMA; 2: styrene). To obtain, for a broad TCL range (up to 800), a dispersity well below 1.3 an initial styrene mass fraction of ca. 10% is required. An interpretation of the comonomer incorporation is performed by calculating the fractions of activation‐growth‐deactivation cycles with a given amount of monomer units and the copolymer composition distribution. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2545–2559, 2018

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Copolymers

Ballard

2023

Kirk-Othmer Encyclopedia of Chemical Technology

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This article provides an overview of the preparation, properties, use, and characterization of synthetic copolymers. The range of different copolymer structures that can be synthesized using current methods is detailed and the current IUPAC‐recommended nomenclature for naming these structures is explained. Techniques for the production of copolymers are discussed, with an emphasis on the types of copolymers and copolymer structures attainable through each polymerization technique. Industrially important random, alternating, block, graft, star, and hyperbranched copolymers are described in terms of the processes used to produce them and the properties achieved. Their main uses and major producers are also detailed.

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New Class of Alkoxyamines for Efficient Controlled Homopolymerization of Methacrylates

Cited by 59 publications

References 33 publications

Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

An evaluation of the impact of SG1 disproportionation and the addition of styrene in NMP of methyl methacrylate

Copolymers

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