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One-pot synthesis of charged amphiphilic diblock and triblock copolymers via high-throughput Cu(0)-mediated polymerization

Lenny Voorhaar (UGent) and Richard Hoogenboom (UGent)
(2017) POLYMERS. 9(8).
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Abstract
Block copolymers containing functionalized monomers, for example those containing charged groups, can be used for many purposes, one of which is the design of polymeric supramolecular materials based on electrostatic interactions. In this paper the synthesis of diblock copolymers and ABA-triblock copolymers containing poly(n-butyl acrylate) as a first or middle block and poly(2-(dimethylamino) ethyl acrylate), poly(1-ethoxyethyl acrylate) and poly(1-ethoxyethyl-2-carboxyethyl acrylate) as second or outer blocks, resulting in block copolymers that can contain positive or negative charges, is reported. The polymerizations were performed and optimized via one-pot sequential monomer addition reactions via Cu(0)-mediated polymerization using an automated parallel synthesizer. Different initiators, monomer concentrations and polymerization times were tested. While a bromide-containing initiator led to the best results for most monomers, when polymerizing 2-(dimethylamino) ethyl acrylate the use of a chloride-containing initiator was necessary. Due to the slower polymerization using this initiator, a longer polymerization time was needed before addition of the second monomer. Using the optimized conditions, the diblock and triblock copolymers could be synthesized with good control over molecular weight and dispersities around 1.1 were obtained.
Keywords
TRANSFER RADICAL POLYMERIZATION, BLOCK-COPOLYMERS, SET-LRP, MULTIBLOCK, COPOLYMERS, ACRYLATE, ROUTE, ACID), controlled radical polymerization, high-throughput polymerization, poly(acrylate)s

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Chicago
Voorhaar, Lenny, and Richard Hoogenboom. 2017. “One-pot Synthesis of Charged Amphiphilic Diblock and Triblock Copolymers via High-throughput Cu(0)-mediated Polymerization.” Polymers 9 (8).
APA
Voorhaar, L., & Hoogenboom, R. (2017). One-pot synthesis of charged amphiphilic diblock and triblock copolymers via high-throughput Cu(0)-mediated polymerization. POLYMERS, 9(8).
Vancouver
1.
Voorhaar L, Hoogenboom R. One-pot synthesis of charged amphiphilic diblock and triblock copolymers via high-throughput Cu(0)-mediated polymerization. POLYMERS. 2017;9(8).
MLA
Voorhaar, Lenny, and Richard Hoogenboom. “One-pot Synthesis of Charged Amphiphilic Diblock and Triblock Copolymers via High-throughput Cu(0)-mediated Polymerization.” POLYMERS 9.8 (2017): n. pag. Print.
@article{8534830,
  abstract     = {Block copolymers containing functionalized monomers, for example those containing charged groups, can be used for many purposes, one of which is the design of polymeric supramolecular materials based on electrostatic interactions. In this paper the synthesis of diblock copolymers and ABA-triblock copolymers containing poly(n-butyl acrylate) as a first or middle block and poly(2-(dimethylamino) ethyl acrylate), poly(1-ethoxyethyl acrylate) and poly(1-ethoxyethyl-2-carboxyethyl acrylate) as second or outer blocks, resulting in block copolymers that can contain positive or negative charges, is reported. The polymerizations were performed and optimized via one-pot sequential monomer addition reactions via Cu(0)-mediated polymerization using an automated parallel synthesizer. Different initiators, monomer concentrations and polymerization times were tested. While a bromide-containing initiator led to the best results for most monomers, when polymerizing 2-(dimethylamino) ethyl acrylate the use of a chloride-containing initiator was necessary. Due to the slower polymerization using this initiator, a longer polymerization time was needed before addition of the second monomer. Using the optimized conditions, the diblock and triblock copolymers could be synthesized with good control over molecular weight and dispersities around 1.1 were obtained.},
  articleno    = {320},
  author       = {Voorhaar, Lenny and Hoogenboom, Richard},
  issn         = {2073-4360},
  journal      = {POLYMERS},
  keyword      = {TRANSFER RADICAL POLYMERIZATION,BLOCK-COPOLYMERS,SET-LRP,MULTIBLOCK,COPOLYMERS,ACRYLATE,ROUTE,ACID),controlled radical polymerization,high-throughput polymerization,poly(acrylate)s},
  language     = {eng},
  number       = {8},
  pages        = {13},
  title        = {One-pot synthesis of charged amphiphilic diblock and triblock copolymers via high-throughput Cu(0)-mediated polymerization},
  url          = {http://dx.doi.org/10.3390/polym9080320},
  volume       = {9},
  year         = {2017},
}

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