How to Make Polymer Chains of Various Shapes, Compositions, and Functionalities by Atom Transfer Radical Polymerization

Gaynor, Scott G.; Matyjaszewski, Krzysztof

doi:10.1021/bk-1998-0685.ch024

Cited by 57 publications

(54 citation statements)

References 37 publications

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“…In recent years, several procedures for the controlled or ''living'' radical polymerization have been developed and used to prepare various well-defined polymers as well as materials with complex polymer architectures. [5][6][7] Among these methods, atom transfer radical polymerization (ATRP) [8,9] is of considerable efficiency. Indeed, well-defined star polymers have been synthesized Summary: Well-defined multi-arm star block copolymers, polyglycerol-block-poly(tert-butyl acrylate) (PG-b-PtBA), with average arm-numbers of 17,27,36,66 and 90 arms, respectively, have been prepared by atom transfer radical polymerization (ATRP) of tBA in acetone, using a core-first strategy.…”

Section: Introductionmentioning

confidence: 99%

Multi‐Arm Star Polyglycerol‐block‐poly(tert‐butyl acrylate) and the Respective Multi‐Arm Poly(acrylic acid) Stars

Shen

Chen

Barriau

et al. 2005

Macro Chemistry & Physics

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Summary: Well‐defined multi‐arm star block copolymers, polyglycerol‐block‐poly(tert‐butyl acrylate) (PG‐b‐PtBA), with average arm‐numbers of 17, 27, 36, 66 and 90 arms, respectively, have been prepared by atom transfer radical polymerization (ATRP) of tBA in acetone, using a core‐first strategy. After hydrolysis with excess concentrated HCl in refluxing dioxane, full hydrolysis of the tert‐butyl ester groups was achieved, resulting in multi‐arm star polyelectrolytes, polyglycerol‐block‐poly(acrylic acid) (PG‐b‐PAA). The hyperbranched macroinitiators employed were prepared on the basis of hyperbranched polyglycerols via esterification with 2‐bromoisobutyryl bromide. Both CuBr/PMDETA and CuBr/Me6TREN catalyst systems have been employed for ATRP of tBA. CuBr/PMDETA was found to permit good control. Polydispersity indices for the new multi‐arm stars were mainly in the range of 1.22 to 1.4, and the absolute $\overline M _{\rm n}$ data were in agreement with the calculated values. Moreover, kinetic curves show a linear dependence of ln([M]0/[M]t) on time, confirming that the polymerizations are controlled.

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Section: Introductionmentioning

confidence: 99%

Multi‐Arm Star Polyglycerol‐block‐poly(tert‐butyl acrylate) and the Respective Multi‐Arm Poly(acrylic acid) Stars

Shen

Chen

Barriau

et al. 2005

Macro Chemistry & Physics

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“…3035) is of interest as a polyisobutene macroinitiator. [3,12,31] Grafting-from by ATRP of methyl methacrylate (MMA) and styrene using PIB macroinitiator affords graft copolymers with a rubbery backbone and rigid glassy side chains. The graft copolymerization is shown in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Polyisobutene-graft-Poly(methyl methacrylate) and Polyisobutene-graft-Polystyrene with Different Compositions and Side Chain Architectures through Atom Transfer Radical Polymerization (ATRP)

Hong

Pakuła

Matyjaszewski³

2001

Macromol. Chem. Phys.

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Polyisobutene‐graft‐poly(methyl methacrylate) and polyisobutene‐graft‐polystyrene with controlled compositions and side chain architectures were prepared through atom transfer radical polymerization (ATRP). Poly[isobutene‐co‐(p‐methylstyrene)‐co‐(p‐bromomethylstyrene)] (PIB) was used as a macroinitiator in the presence of CuCl or CuBr as a catalyst and dNbpy as a ligand. The compositions were controlled by the conversion of the monomer with polymerization time. The molecular weight distributions of the side chains were controlled through ATRP in the presence/absence of a halogen exchange reaction. DSC and DMA measurements showed that graft copolymers have two glass transition temperatures suggesting microphase separated behavior, which was also confirmed by SAXS measurements. The phase and dynamic mechanical behaviors were strongly affected by the compositions and/or the side chain architectures. The properties of the graft copolymers were controlled in a wide range leading to toughened glassy polymers or elastomers.

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“…Atom transfer radical polymerization (ATRP) is one of the most robust controlled/ 'living' radical polymerization methods since it can be applied to a wide variety of monomers and provides well-defined polymers [1][2][3][4][5][6][7]. The basis of ATRP is the reversible transfer of a radically transferable atom, typically a halogen, from a monomeric or polymeric alkyl halide (macro)initiator to a transition metal complex in a lower oxidation state, forming an organic radical and a transition metal complex in a higher oxidation state.…”

Section: Introductionmentioning

confidence: 99%

“…Up to now, the removal of residual metal complex in ATRP has been achieved with variable success by using methods such as adsorption on alumina columns, selective precipitation of polymer in a non-solvent, treatment with an ion-exchange resin or liquid-liquid phase separation [5][6][7][8][10][11][12]16]. Because all these purification methods have been reported separately, i.e., for different monomers, catalytic complexes, solvents and polymerization conditions, there is no data available allowing to compare them to each other in terms of catalyst removal efficiency.…”

Section: Introductionmentioning

confidence: 99%

Removal of copper-based catalyst in atom transfer radical polymerization using different extraction techniques

et al. 2004

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Several methods allowing the removal of copper-based ATRP active complexes from crude amino-functionalized polymethacrylate chains are compared. Among them, precipitation in basic medium is one of the most efficient techniques since it allows high recovery yields (above 90%) with a residual metal content as low as 5 ppm. Extraction methods such as liquid-liquid phase separation and dialysis but also selective adsorption on acidic macroporous ion exchange resin constitute other attractive alternatives. As far as water-insoluble polymers are concerned, catalyst adsorption on alumina remains the most universal method and provides acceptable recovery efficiency. However, we want to stress the key-importance of the experimental adsorption conditions and above all the relative content of alumina used for catalyst extraction.

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How to Make Polymer Chains of Various Shapes, Compositions, and Functionalities by Atom Transfer Radical Polymerization

Cited by 57 publications

References 37 publications

Multi‐Arm Star Polyglycerol‐block‐poly(tert‐butyl acrylate) and the Respective Multi‐Arm Poly(acrylic acid) Stars

Multi‐Arm Star Polyglycerol‐block‐poly(tert‐butyl acrylate) and the Respective Multi‐Arm Poly(acrylic acid) Stars

Preparation of Polyisobutene-graft-Poly(methyl methacrylate) and Polyisobutene-graft-Polystyrene with Different Compositions and Side Chain Architectures through Atom Transfer Radical Polymerization (ATRP)

Removal of copper-based catalyst in atom transfer radical polymerization using different extraction techniques

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