Improving the Structural Control of Graft Copolymers by Combining ATRP with the Macromonomer Method

Shinoda, Hosei; Miller, Peter J.; Matyjaszewski, Krzysztof

doi:10.1021/ma001943j

Cited by 158 publications

(168 citation statements)

References 22 publications

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“…Various polymerization processes have already been used to design well-defined comb shaped or graft copolymers: anionic [1,2] , free radical [3][4][5][6] or controlled free radical [7] and ring opening metathesis polymerization processes [8,9] whereby no control of the backbone tacticity is possible.…”

Section: Introductionmentioning

confidence: 99%

Homo‐ and Copolymerization of ω‐Functional Polystyrene Macromonomers via Coordination Polymerization

Lahitte

Peruch

Meneghetti

et al. 2002

Macro Chemistry & Physics

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Macromonomers have been extensively used, as well defined building blocks for various macromolecular architectures via anionic, ROMP and free radical homo‐ or copolymerization processes. The purpose of the present work was to examine the homopolymerization and copolymerization of ω‐allyl, ω‐undecenyl and ω‐vinylbenzyl polystyrene (PS) macromonomers, in the presence of early or late transition metal catalysts. The influence of several parameters (type of catalytic system, nature of polymerizable end‐group and molar mass of the macromonomer) on the homopolymerization was first investigated. Whereas ω‐allyl or ω‐undecenyl PS macromonomers were not very reactive in homopolymerization whatever the catalyst, ω‐vinylbenzyl PS macromonomers gave interesting results with CpTiCl3/MAO and Cp*TiCl3/MAO. The copolymerization of these macromonomers with ethylene was also studied in the presence of the following palladium catalyst: [(ArNC(Me)C(Me)NAr)Pd(CH2)3(COOMe)]+BAr4′−(VERSIPOL™) (Ar = 2,6‐iPr2–C6H3 and Ar′ = 3,5‐(CF3)2C6H3). ω‐vinylbenzyl PS macromonomers could not be incorporated into poly(ethylene) chains. On the contrary, the incorporation of ω‐allyl PS macromonomers was achieved. Moreover, for macromonomers containing an alkyl spacer between the allylic unit and the PS chain, the incorporation rate, the copolymerization yield and the molar masses of the copolymers were increased, giving access to a new type of graft copolymer structure. Synthesis of polystyrene macromonomers.magnified imageSynthesis of polystyrene macromonomers.

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Section: Introductionmentioning

confidence: 99%

Homo‐ and Copolymerization of ω‐Functional Polystyrene Macromonomers via Coordination Polymerization

Lahitte

Peruch

Meneghetti

et al. 2002

Macro Chemistry & Physics

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“…ATRP is an excellent and well-established method for obtaining block copolymers using simple experimental protocols and a large variety of the available monomers, especially for preparation of amphiphilic block copolymers with well-defined architecture and narrow molecular weight distribution [43][44][45][46][47][48][49][50]. This example demonstrates, in the best way, the features that must be considered for a successful employment of ATRP in block copolymer synthesis.…”

Section: Synthesis and Characterizationmentioning

confidence: 94%

Preparation and self-assembly behavior of polystyrene-block-poly (dimethylaminoethyl methacrylate) amphiphilic block copolymer using atom transfer radical polymerization

Zhu¹,

Tan²,

Du³

2008

Express Polym. Lett.

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Asymmetric and semi-symmetric amphiphilic diblock copolymers polystyrene-block-poly (dimethylaminoethyl methacrylate) (PS-b-PDMAEMA) with the same PS block length of 62 repeat units and quite short (3 repeat units) or equivalent (47 repeat units) length of PDMAEMA have been prepared simply by varying the ratio of the bromine-terminated macroinitiator polystyrene (PS-Br) to DMAEMA using atom transfer radical polymerization (ATRP). The chemical structures and compositions of the PS-b-PDMAEMA block copolymers are studied by nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), and elementary analysis (EA). The self-assembly behaviors of copolymers in N,N-dimethyl formamide (DMF) with different pH and dioxane/water binary solvent mixture by direct dissolution method (DD), are studied by transmission electron microscopy (TEM), electron diffracting analysis (EDA), and energy-dispersive analysis of X-rays (EDAX) techniques. Transmission electron microscopy results suggest that asymmetric block copolymer PS62-b-PDMAEMA3 (the numbers in the form of footnotes represent repeated units of each monomer in the copolymer) can form spherical core-shell micelles, large compound reverse micelles (LCRMs), hexagonal/rhombic phases, reverse hexagonal/rhombic phases, vesicles, reverse vesicles and necklace-like reverse micelles, controlled by common or selective solvent and pH, while most of the aggregates of semi-symmetric PS62-b-PDMAEMA47 are simply spherical, such as spherical core-shell micelles and reverse spherical core-shell micelles, besides hexagonal/rhombic phases. All above structures are controlled by three components of the free energy of aggregation: core-chain stretching, interfacial energy and intercoronal chain interaction

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“…relative reactivity of comonomers [20][21][22]. To estimate the relative reactivity of PCMMA and St in the atom transfer radical polymerization and conventional free radical polymerization, the KelenTüdõs [23] and Fineman-Ross [24] equations were used, which are η = (r 1 + r 2 /α)ξ -r 2 /α and G = r 1 H -r 2 , respectively (Notations in the equations have been described in Table 4 or 5).…”

Section: Calculation Of Monomer Reactivity Ratios Of Pcmma and Stmentioning

confidence: 99%

Conventional and atom transfer radical copolymerization of phenoxycarbonylmethyl methacrylate-styrene and thermal behavior of their copolymers

Barim¹,

Demirelli²,

Çoşkun³

2007

Express Polym. Lett.

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Abstract. The atom transfer radical polymerization (ATRP) of phenoxycarbonylmethyl methacrylate (PCMMA) with styrene (St) were performed in bulk at 110°C in the presence of ethyl 2-bromoacetate, cuprous(I)bromide (CuBr), and N,N,N',N",N"-pentamethyldiethyltriamine. Also, a series conventional free-radical polymerization (CFRP) of PCMMA and styrene were carried out in the presence of 2,2'-azobisisobutyronitrile in 1,4-dioxane solvent at 60°C. The structure of homo and copolymers was characterized by IR, 1 H and 13 C-NMR techniques. The composition of the copolymers was calculated by 1 H-NMR spectra. The average-molecular weight of the copolymers were investigated by Gel Permeation Chromatography (GPC). For copolymerization system, their monomer reactivity ratios were obtained by using both Kelen-Tüdõs and Fineman-Ross equations. Thermal analysis measurements of homo-and copolymers prepared CFRP and ATRP methods were measured by TGA-50 and DSC-50. Blends of poly(PCMMA) and poly(St) obtained via ATRP method have been prepared by casting films from dichlorormethane solution. The blends were characterized by differential scanning calorimetry. The initial decomposition temperatures of the resulting copolymers increased with increasing mole fraction of St.

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Improving the Structural Control of Graft Copolymers by Combining ATRP with the Macromonomer Method

Cited by 158 publications

References 22 publications

Homo‐ and Copolymerization of ω‐Functional Polystyrene Macromonomers via Coordination Polymerization

Homo‐ and Copolymerization of ω‐Functional Polystyrene Macromonomers via Coordination Polymerization

Preparation and self-assembly behavior of polystyrene-block-poly (dimethylaminoethyl methacrylate) amphiphilic block copolymer using atom transfer radical polymerization

Conventional and atom transfer radical copolymerization of phenoxycarbonylmethyl methacrylate-styrene and thermal behavior of their copolymers

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