Anionic Synthesis of Heteroarm, Star-Branched Polymers. Scope and Limitations

Quirk, Roderic P.; Yoo, Taejun; Lee, Bumjae

doi:10.1080/10601329408545692

Cited by 31 publications

(46 citation statements)

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“…[1][2][3][4] The first few examples of the preparation of ABC miktoarm star terpolymers exclusively employed anionic polymerization, relying on the strict control of molar ratios between reactive species. [5][6][7][8][9][10][11][12][13] With the advent of controlled radical polymerizations, such as nitroxide-mediated radical polymerization (NMP), atom transfer radical polymerization (ATRP), and reversible addition-fragmentation chain transfer (RAFT) polymerization, the once challenging task of synthesizing ABC Correspondence to: S. Liu (E-mail: sliu@ustc.edu.cn) miktoarm star polymers has been rendered much easier. [14][15][16][17][18][19] Feng and Pan 14 successful prepared ABC miktoarm star terpolymers consisting of polystyrene (PS), poly(methyl acrylate) (PMA), and poly(ethylene glycol) (PEG) via successive RAFT polymerization of styrene, maleic anhydride (MAh), and methyl acrylate, followed by the esterification reaction with monohydroxyl-terminated PEG.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of amphiphilic and thermoresponsive ABC miktoarm star terpolymer via a combination of consecutive click reactions and atom transfer radical polymerization

Liu

et al. 2009

J. Polym. Sci. A Polym. Chem.

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Well-defined amphiphilic and thermoresponsive ABC miktoarm star terpolymer consisting of poly(ethylene glycol), poly(tert-butyl methacrylate), and poly(N-isopropylacrylamide) arms, PEG(-b-PtBMA)-b-PNIPAM, was synthesized via a combination of consecutive click reactions and atom transfer radical polymerization (ATRP). Click reaction of monoalkynyl-terminated PEG with a trifunctional core molecule bis(2-azidoethyl)amine, (N 3 ) 2 ANH, afforded difunctional PEG possessing an azido and a secondary amine moiety at the chain end, PEG-NHAN 3 . Next, the amidation of PEG-NHAN 3 with 2-chloropropionyl chloride led to PEG-based ATRP macroinitiator, PEG(AN 3 )ACl. The subsequent ATRP of N-isopropylacrylamide (NIPAM) using PEG(AN 3 )ACl as the macroinitiator led to PEG(AN 3 )-b-PNIPAM bearing an azido moiety at the diblock junction point. Finally, well-defined ABC miktoarm star terpolymer, PEG(-b-PtBMA)-b-PNIPAM, was prepared via the click reaction of PEG(AN 3 )-b-PNIPAM with monoalkynyl-terminated PtBMA. In aqueous solution, the obtained ABC miktoarm star terpolymer self-assembles into micelles consisting of PtBMA cores and hybrid PEG/PNIPAM coronas, which are characterized by dynamic and static laser light scattering, and transmission electron microscopy. On heating above the phase transition temperature of PNIPAM in the hybrid corona, micelles initially formed at lower temperatures undergo further structural rearrangement and fuse into much larger aggregates solely stabilized by PEG coronas.

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Section: Introductionmentioning

confidence: 99%

Synthesis of amphiphilic and thermoresponsive ABC miktoarm star terpolymer via a combination of consecutive click reactions and atom transfer radical polymerization

Liu

et al. 2009

J. Polym. Sci. A Polym. Chem.

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“…The active sites are subsequently used as initiators of another monomer to give the A 2 B 2 structure. (PS) 2 polyisoprene (PI) 2 (where PS is polystyrene) and (PS) 2 (PBd) 2 (where PBd is polybutadiene) were thus prepared by Quirk et al, 4 and later (PS) 2 (PEO) 2 [where PEO is poly(ethylene oxide)] was prepared by Mays et al 5 Bae and Faust 6 were the first to use cationic polymerization to synthesize (PIB) 2 poly (methyl vinyl ether) [PmeVE] 2 (where PIB is polyisobutylene).…”

Section: Introductionmentioning

confidence: 99%

“…First, two living PS chains were reacted with SiCl 4 , and second, the remaining SiÀ ÀCl bonds were used for the linking reaction of living PEO chains. (PS) 2 (PBd) 2 , 8 (PS) 2 (PI) 2 , 9 and (PI) 2 (PBd) 2 10 were also obtained with these linking reactions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of A₂B₂ star block copolymers from a heterotetrafunctional initiator

Glaied

Delaite

Dumas

2007

J. Polym. Sci. A Polym. Chem.

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“…By developing this methodology, the synthesis of ABC and A 2 B 2 star polymers containing poly(alkyl methacrylate) segments have been real-ized. [47][48][49][50][51][52][53][54] In addition, some other methods that are similar in part to the above-mentioned methods have been reported. [55][56][57][58][59][60][61][62][63][64] Hadjichristidis and his coworkers have well reviewed the recent advances of these synthetic methodologies.…”

mentioning

confidence: 99%

“…[65][66][67] Some other excellent reviews on the same subject have also recently appeared. 51,[68][69][70][71][72][73][74] Several research groups have widely studied the methodology in which difunctional monomers such as divinylbenzene and ethyleneglycol dimethacrylate are reacted with anionic species present at the initiation or termination stages of living polymerization to synthesize star polymers. [75][76][77][78][79][80][81][82][83][84][85][86][87][88][89][90][91][92][93][94] Since well control of such reactions is difficult, the core parts of the resulting star polymers have always some distributions.…”

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confidence: 99%

Precise Synthesis of Regular and Asymmetric Star Polymers and Densely Branched Polymers with Starlike Structures by Means of Living Anionic Polymerization

Hirao

Hayashi

Tokuda

et al. 2002

Polym J

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ABSTRACT:The subject of this review is to present new synthetic methodologies recently developed by us, which are applicable to both regular and asymmetric star polymers with well-defined architectures. The first methodology involves the coupling reaction of a variety of living anionic polymers of styrene, α-methylstyrene, isoprene, tert-butyl methacrylate, and ethylene oxide with novel chain-end-and in-chain-functionalized polymers with a definite number of benzyl halide moieties intentionally designed as polymeric coupling agents. In the second methodology, we propose a new concept based on iterative approach, with which star polymers can be successively and, in principle, unlimitedly synthesized by repeating the iterative reaction sequence. Finally, a convenient synthesis of densely branched polymers with starlike structures is presented by the quantitative coupling reaction of living anionic polymers with reactive benzyl halide-functionalized backbone polymers based on a grafting-onto method.KEY WORDS Star Polymer / Asymmetric Star Polymer / Living Anionic Polymerization / Iterative Methodology / Polymeric Coupling Agent / 1,1-Diphenylethylene Derivative / Star polymers are branched polymers in which more than three linear polymer chains are linked together at one end of each chain by a central core or a single branch. They have physical properties in bulk, melt, and solution quite distinct from linear analogues. For this reason, star polymers have been widely studied from both synthetic and theoretical points of view. [1][2][3][4][5][6][7][8][9] It is of course essential to use star polymers with welldefined structures for evaluating fundamental understanding regarding the effect of chain branching on such physical properties.At the present time, the most successful methodologies for the synthesis well-defined regular star polymers have been developed mainly based on coupling reactions of living anionic polymers of styrene and 1,3-dinene monomers with multifunctional chlorosilane compounds as electrophilic coupling agents. A variety of star polymers with a definite number of three to eighteen arms have been synthesized. [10][11][12][13][14][15][16][17][18][19] Furthermore, the successful syntheses of the 32-, 64-, and even 128-arm star polymers by using specially designed carbosilane dendrimers have been reported so far. 20,21 Currently, great attention has been paid to more complex asymmetric star polymers whose arms differ in molecular weight and chemical composition, since star polymers of this type are expected to exhibit interesting and unique physical performance originated from their † To whom correspondence should be addressed.branched architectures as well as heterophase structures. [22][23][24][25][26][27][28][29][30][31][32][33] Synthesis of asymmetric star polymers is generally more difficult than that of regular star polymers. In the synthesis of regular star polymers, for example, their arms can be simultaneously introduced by one reaction. On the other hand, two or more highyielding reactions...

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Anionic Synthesis of Heteroarm, Star-Branched Polymers. Scope and Limitations

Cited by 31 publications

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Synthesis of amphiphilic and thermoresponsive ABC miktoarm star terpolymer via a combination of consecutive click reactions and atom transfer radical polymerization

Synthesis of amphiphilic and thermoresponsive ABC miktoarm star terpolymer via a combination of consecutive click reactions and atom transfer radical polymerization

Synthesis of A₂B₂ star block copolymers from a heterotetrafunctional initiator

Precise Synthesis of Regular and Asymmetric Star Polymers and Densely Branched Polymers with Starlike Structures by Means of Living Anionic Polymerization

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Anionic Synthesis of Heteroarm, Star-Branched Polymers. Scope and Limitations

Cited by 31 publications

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Synthesis of amphiphilic and thermoresponsive ABC miktoarm star terpolymer via a combination of consecutive click reactions and atom transfer radical polymerization

Synthesis of amphiphilic and thermoresponsive ABC miktoarm star terpolymer via a combination of consecutive click reactions and atom transfer radical polymerization

Synthesis of A2B2 star block copolymers from a heterotetrafunctional initiator

Precise Synthesis of Regular and Asymmetric Star Polymers and Densely Branched Polymers with Starlike Structures by Means of Living Anionic Polymerization

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Synthesis of A₂B₂ star block copolymers from a heterotetrafunctional initiator