Stable Carbanions by Quantitative Metalation of Cationically Obtained Diphenylvinyl and Diphenylmethoxy Compounds:  New Initiators for Living Anionic Polymerizations

Feldthusen, Jesper; Iván, Béla; Müller, Axel H. E.

doi:10.1021/ma9704166

Cited by 31 publications

(21 citation statements)

References 17 publications

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“…A mixture of BCl 3 –TiCl 4 coinitiators has been used for the one‐pot synthesis of block star copolymers consisting of PIB‐ b ‐PS arms 15, 16. PIB‐based block copolymers have also been prepared, with the site‐transformation techniques, by sequential synthesis combining cationic→anionic polymerization17–25 or cationic→ATRP26–28 with end‐functionalized PIBs used as macroinitiators.…”

Section: Introductionmentioning

confidence: 99%

Heat makes a difference in activity‐based anorexia: A translational approach to treatment development in anorexia nervosa

Cerrato

Carrera

Vázquez

et al. 2010

Intl J Eating Disorders

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Section: Introductionmentioning

confidence: 99%

Heat makes a difference in activity‐based anorexia: A translational approach to treatment development in anorexia nervosa

Cerrato

Carrera

Vázquez

et al. 2010

Intl J Eating Disorders

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“…A variety of methods have already been reported. For instance, Müller et al reported the synthesis of PIB-b-poly( t butyl methacrylate) (P t BMA) and poly(methyl methacrylate) (PMMA)-b-PIB-b-PMMA by metalation of DPE end-capped PIB with Na/K alloy or cesium followed by anionic polymerization (3,4). Another attempt demonstrated by Müller et al involved the preparation of thiophene end-functionalized PIB and subsequent metalation of the polymer chain end with an alkyllithium compound, followed by polymerization of t BMA with the generated macroanion (5).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Poly(methyl methacrylate‐co‐hydroxyethyl methacrylate)‐b‐polyisobutylene‐b‐poly(methyl methacrylate‐co‐hydroxyethyl Methacrylate) Triblock Copolymers

Feng

Chandekar

Whitten

et al. 2007

Journal of Macromolecular Science, Part A

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The synthesis of poly[(methyl methacrylate-co-hydroxyethyl methacrylate)-b-isobutylene-b-(methyl methacrylate-co-hydroxyethyl methacrylate)] P(MMA-co-HEMA)-b-PIB-b-P(MMA-co-HEMA) triblock copolymers with different HEMA/MMA ratios has been accomplished by the combination of living cationic and anionic polymerizations. P(MMA-co-HEMA)-b-PIB-b-P(MMA-co-HEMA) triblock copolymers with different compositions were prepared by a synthetic methodology involving the transformation from living cationic to anionic polymerization. First, 1,1-diphenylethylene end-functionalized PIB (DPE-PIB-DPE) was prepared by the reaction of living difunctional PIB and 1,4-bis(1-phenylethenyl)benzene (PDDPE), followed by the methylation of the resulting diphenyl carbenium ion with dimethylzinc (Zn(CH 3 ) 2 ). The DPE ends were quantitatively metalated with n-butyllithium in tetrahydrofuran, and the resulting macroanion initiated the polymerization of methacrylates yielding triblock copolymers with high blocking efficiency. Microphase separation of the thus prepared triblock copolymers was evidenced by the two glass transitions at 264 and þ1208C observed by differential scanning calorimetry. These new block copolymers exhibit typical stress-strain behavior of thermoplastic elastomers. Surface characterization of the samples was accomplished by angle-resolved X-ray photoelectron spectroscopy (XPS), which revealed that the surface is richer in PIB compared to the bulk. However, a substantial amount of P(MMA-co-HEMA) remains at the surface. The presence of hydroxyl functionality at the surface provides an opportunity for further modification.

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“…The key process in this method is the precocious control of a or w-end functionality, capable of initiating the second monomer. Recently a novel site-transformation reaction, the quantitative metalation of DPE-capped PIB carrying methoxy or olefin functional groups, has been reported [90]. This method has been successfully employed in the synthesis of poly(IB-b-tBMA) diblock and poly (MMA-b-IB-b-MMA) triblock copolymers [91].…”

Section: Synthesis Of Hetero-arm Star-block Copolymers Using Bis-dpe mentioning

confidence: 99%

Synthesis of Polyisobutylene-Based Block Copolymers with Precisely Controlled Architecture by Living Cationic Polymerization

Kwon

Faust

2004

New Synthetic Methods

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During the last two decades we have witnessed the discovery and development of living cationic polymerization. As a result of persistent growth in this field, today living cationic polymerization is an equal counterpart of anionic living polymerization although the latter has a considerably longer history. Living cationic polymerization is an indispensable tool for the preparation of a wide variety of homo-, block-, graft-and functional polymers. This chapter reviews recent efforts in cationic macromolecular engineering with emphasis on fundamental concepts and advanced technologies for polyisobutylene block copolymer synthesis. For block copolymer synthesis by the simple sequential monomer addition technique rationalization is given for the selection of polymerization conditions and monomer addition order. The application of non-(homo)polymerizable monomers such as 1,1-diarylethylenes and furan analogues, coupled with changes in the synthetic approaches for various block copolymer architectures, is described in terms of three categories; capping, coupling, and living coupling reactions. These appear to be versatile synthetic tools for numerous linear di-and triblock copolymers, and block copolymers with non-linear architectures. Finally, current developments in the combination of different polymerization mechanisms are illustrated.

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Stable Carbanions by Quantitative Metalation of Cationically Obtained Diphenylvinyl and Diphenylmethoxy Compounds: New Initiators for Living Anionic Polymerizations

Cited by 31 publications

References 17 publications

Heat makes a difference in activity‐based anorexia: A translational approach to treatment development in anorexia nervosa

Heat makes a difference in activity‐based anorexia: A translational approach to treatment development in anorexia nervosa

Synthesis and Characterization of Poly(methyl methacrylate‐co‐hydroxyethyl methacrylate)‐b‐polyisobutylene‐b‐poly(methyl methacrylate‐co‐hydroxyethyl Methacrylate) Triblock Copolymers

Synthesis of Polyisobutylene-Based Block Copolymers with Precisely Controlled Architecture by Living Cationic Polymerization

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