Identifying the Nature of the Active Species in the Polymerization of Methacrylates:  Inhibition of Methyl Methacrylate Homopolymerizations and Reactivity Ratios for Copolymerization of Methyl Methacrylate/<i>n</i>-Butyl Methacrylate in Classical Anionic, Alkyllithium/Trialkylaluminum-Initiated, Group Transfer Polymerization, Atom Transfer Radical Polymerization, Catalytic Chain Transfer, and Classical Free Radical Polymerization

Haddleton, David M.; Crossman, Martin C.; Hunt, Kirsty H.; Topping, Clare; Waterson, Carl; Suddaby, Kevin G.

doi:10.1021/ma970303m

Cited by 129 publications

(115 citation statements)

References 31 publications

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“…Similar observations have been made with other comonomer pairs. [20][21][22][23][24] Using NiBr 2 (PPh 3 ) 2 as catalyst, Moineau et al 31 recently reported similar reactivity ratios (r MMA ) 1.7; r nBuA ) 0.34).…”

Section: Resultsmentioning

confidence: 99%

Copolymerization of n-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers: Comparison of Reactivity Ratios in Conventional and Atom Transfer Radical Copolymerization

1999

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The reactivity ratios of n-butyl acrylate (nBuA) with methyl methacrylate (MMA) and ω-methacryloyl-PMMA macromonomers (MM) in conventional and atom transfer radical copolymerization (ATRP) have been determined. For the copolymerization of nBuA with MMA, good agreement of the ratios is observed between conventional and controlled radical copolymerization, indicating that chemoselectivities in both processes are similar. The relative reactivity of the MM (1/r nBuA) in conventional copolymerization is significantly lower than that of MMA. It depends on the concentration of the comonomers but is not significantly influenced by the length of the MM. At high concentrations the relative reactivity decreases due to diffusion control of the MM addition. In ATRP the relative reactivity of the MM is much nearer to the value of MMA. This is explained by the different time scales of monomer addition in both processes: whereas the frequency for monomer addition is in the range of milliseconds for conventional polymerizations, it is in the range of seconds in ATRP; thus, diffusion control is less important here. This gives the opportunity to copolymerize at much higher concentrations than in conventional radical copolymerization. In addition, the graft copolymers obtained by ATRP have lower polydispersities.

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Section: Resultsmentioning

confidence: 99%

Copolymerization of n-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers: Comparison of Reactivity Ratios in Conventional and Atom Transfer Radical Copolymerization

1999

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“…Recently, there have been reports on the synthesis of gradient copolymers by ATRP. [9][10][11][12][13][14][15][16] Reactivity ratios and monomer infeed ratio play an important role in determining the structure of the copolymers. 17 In conventional radical polymerization, difference in the reactivity ratios of the monomers lead to variation of composition among the polymer chains.…”

Section: 2mentioning

confidence: 99%

Analysis of Compositional Drift in Methyl Methacrylate and n-Butyl Acrylate Copolymers Synthesized by Atom Transfer Radical Polymerization Using 13C{1H} NMR Spectroscopy

Brar

Kaur

2005

Polym J

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ABSTRACT:Compositional variations occurring along the chains in the copolymers of methyl methacrylate (M) and n-butyl acrylate (B) were investigated using 13 C{ 1 H} NMR spectroscopy. Copolymerization of methyl methacrylate and n-butyl acrylate with varying infeed ratio was done using Atom Transfer Radical Polymerization. Copolymer compositions were determined from 1 H NMR spectra. Percentage conversion was studied gravimetrically. Analysis of the variations of methylene dyads fractions and M-and B-centered triad fractions with conversion was done using Distortionless Enhancement by Polarization Transfer (DEPT) experiments to have a better insight to trend followed by the compositional drift with conversion. The experimental results were found to be in good agreement with the simulated data indicating towards the uniformity along the copolymer chains resulting in the formation of gradient copolymers.

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“…Two methacrylate monomers during ATRP usually have comparable values of relative reactivity ratios, such as MMA and n-butyl methacrylate (r 1 ¼0.98 and r 2 ¼1.26, respectively) 28 or the methacrylate macromonomers of poly(ethylene oxide) and poly(3-hydroxybutyrate) (r 1 ¼0.89 and r 2 ¼1.12, respectively). 29 A similar effect was shown for the FRP of the comonomer pair MMA and AMA (r 1 ¼1.34 and r 2 ¼0.92, respectively); 17 when r 1 Br 2 , the random composition of the copolymer was postulated.…”

Section: Polymethacrylates With Anthryl and Carbazolyl Groups D Neugementioning

confidence: 99%

Polymethacrylates with anthryl and carbazolyl groups prepared by atom transfer radical polymerization

Neugebauer

Charasim

Swinarew

et al. 2011

Polym J

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Monomers containing chromophore groups, that is, 9-anthrylmethyl methacrylate (AMA) and 2-(9-carbazolyl)ethyl methacrylate (CMA), were copolymerized with methyl methacrylate (MMA) using atom transfer radical polymerization (ATRP) conditions, resulting in two series of (co)polymers with various amounts of included chromophore units, namely P(MMA-co-AMA) (3-30 mol%) and PAMA and P(MMA-co-CMA) (3-20 mol%). The relative reactivity ratios of both comonomer pairs were determined using the Fineman-Ross method (r MMA ¼1.19, r AMA ¼0.48 and r MMA ¼1.10, r CMA ¼0.77). Glass transition temperatures (T g s) of the polymers increased with the content of chromophore groups. A comparison of luminescence demonstrated more intense light emission by polymethacrylates with carbazolyl groups than by copolymers with anthryl groups. The wavelength of emitted light also differed in the range of blue-violet and blue-green fluorescence for carbazolyl and anthryl copolymers, respectively. Polymer Journal (2011) 43, 448-454; doi:10.1038/pj.2011.10; published online 2 March 2011Keywords: anthracene; ATRP; carbazole; luminescence; polymethacrylates INTRODUCTION Luminescent polymers that have the ability to emit light in response to a stimulus are known as smart polymers. These polymers can be used for fabricating light-emitting diodes, electrophotographic and photorefractive materials, as well as photoluminescent and electroluminescent devices. 1 A proper design of the molecular structure of polymers with luminescence is required to tune the emission color in various regions of the visible spectrum. The parameters responsible for this effect are related to the types of chromophore groups, and their content and density of incorporation in the polymer chain. Particularly, carbazole-and anthracene-based polymers, belonging to a large family of luminescent macromolecules, have found increasing interest because of their numerous industrial applications, such as coatings, inks, adhesives and photolithography, as well as their use in the construction of electrical switching devices. 2 Previously, copolymers containing carbazolyl groups were synthesized using various polymerization methods, such as the cationic photopolymerization of epoxy, 3 oxetane 4 and vinyl ether monomers (2-(9-carbazolyl)ethyl vinyl ether); 5-7 anionic polymerization of oxiranes ([(9-carbazolyl)methyl] or [(9-carbazolyl)ethoxymethyl]oxirane) 8 or methacrylates (2-(N-carbazolyl)ethyl methacrylate) 9 and free radical polymerization (FRP) of vinyl monomers (N-vinylcarbazole), 10,11 including (meth)acrylates. 12,13 The other luminescent copolymers with anthryl substituents were prepared by conventional FRP.

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Cited by 129 publications

References 31 publications

Copolymerization of n-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers: Comparison of Reactivity Ratios in Conventional and Atom Transfer Radical Copolymerization

Copolymerization of n-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers: Comparison of Reactivity Ratios in Conventional and Atom Transfer Radical Copolymerization

Analysis of Compositional Drift in Methyl Methacrylate and n-Butyl Acrylate Copolymers Synthesized by Atom Transfer Radical Polymerization Using 13C{1H} NMR Spectroscopy

Polymethacrylates with anthryl and carbazolyl groups prepared by atom transfer radical polymerization

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