Linear-dendritic Block Copolymers Research Articles

Controlling surfaces and interfaces with functional polymers: Preparation and functionalization of dendritic–linear block copolymers via metal catalyzed “living” free radical polymerization

The preparation and chemical modification of dendritic–linear block copolymers with surface functionalized dendritic components are presented. Isophthalate ester-functionalized dendrons featuring benzylic halide groups at their focal points have been used for the metal catalyzed “living” radical polymerization of styrene. The molecular weight of the dendritic–linear block copolymers determined by MALDI-TOF and Size Exclusion Chromatography was found to be accurately controlled up to molecular weights of ca. 30,000 a.m.u., with polydispersities less than 1.2. Subsequent functional group modifications of the peripheral ethyl ester groups of the dendritic block have been successfully carried out leading to carboxylic acids, butyl amides, benzyl alcohols, benzyl halides, and also accelerated generation growth via transesterification with a first generation dendritic alcohol. Several of these new dendritic–linear block copolymers exhibit interesting aggregation characteristics as evidenced by 1H-NMR spectroscopic studies. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1–10, 1998

Controlling surfaces and interfaces with functional polymers: Preparation and functionalization of dendritic-linear block copolymers via metal catalyzed ?living? free radical polymerization

The preparation and chemical modification of dendritic–linear block copolymers with surface functionalized dendritic components are presented. Isophthalate ester-functionalized dendrons featuring benzylic halide groups at their focal points have been used for the metal catalyzed “living” radical polymerization of styrene. The molecular weight of the dendritic–linear block copolymers determined by MALDI-TOF and Size Exclusion Chromatography was found to be accurately controlled up to molecular weights of ca. 30,000 a.m.u., with polydispersities less than 1.2. Subsequent functional group modifications of the peripheral ethyl ester groups of the dendritic block have been successfully carried out leading to carboxylic acids, butyl amides, benzyl alcohols, benzyl halides, and also accelerated generation growth via transesterification with a first generation dendritic alcohol. Several of these new dendritic–linear block copolymers exhibit interesting aggregation characteristics as evidenced by 1H-NMR spectroscopic studies. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1–10, 1998

Dendritic Initiators for “Living” Radical Polymerizations: A Versatile Approach to the Synthesis of Dendritic-Linear Block Copolymers

The first use of polyether dendrons as macromolecular initiators for the controlled free radical polymerization of vinyl monomers has been demonstrated. Dendrons containing either a single benzylic TEMPO or halide functionality at their focal point have been used for the nitroxide mediated and atom transfer radical polymerizations, respectively. In both cases, hybrid dendritic-linear block copolymers with well-controlled molecular weights and low polydispersities can be obtained. The structure of the hybrid block copolymers is supported by SEC and spectral data. All the copolymers exhibit a single Tg, indicating that both blocks are miscible. Hybrid block copolymers difficult or impossible to prepare by previous techniques have been synthesized to demonstrate the versatility of this approach.

Hydraamphiphiles: Novel Linear Dendritic Block Copolymer Surfactants

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHydraamphiphiles: Novel Linear Dendritic Block Copolymer SurfactantsToby M. Chapman, Gregory L. Hillyer, Eric J. Mahan, and Katherine A. ShafferCite this: J. Am. Chem. Soc. 1994, 116, 24, 11195–11196Publication Date (Print):November 1, 1994Publication History Published online1 May 2002Published inissue 1 November 1994https://doi.org/10.1021/ja00103a060RIGHTS & PERMISSIONSArticle Views740Altmetric-Citations171LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (280 KB) Get e-AlertsSupporting Info (2)»Supporting Information Supporting Information Get e-Alerts

Solution and solid-state properties of hybrid linear-dendritic block copolymers

The solution and solid-state properties of hybrid linear-dendritic polyether copolymers are investigated by SEC with coupled viscometric detection, polarized light microscopy, and X-ray analysis. The results obtained show that the block copolymers are able to form mono- and multimolecular micelles depending on the dendrimer generation and the concentration in methanol/water (good solvent for the linear blocks). Only monomolecular micelles are observed in THF (good solvent for the dendritic blocks). The linear blocks are able to crystallize in spherulites, axialites, or unique dendritic structures depending on the overall composition of the copolymers and the solvent used

Synthesis and properties of novel linear-dendritic block copolymers. Reactivity of dendritic macromolecules toward linear polymers

The reactivity of benzylic dendritic polyethers toward linear polymers was investigated using coupling reactions of preformed dendritic and linear blocks in solution and in the melt. It was found that the rate constants for the Williamson reaction of poly(ethylene oxide)s (PEO) or poly(ethylene glycol)s (PEG) with dendritic bromides of various sizes increased with the length of the linear block and the generation of the dendrimer. Tits anomalous behavior is attributed to the increased reactivity of the PEO and PEG alcoholate anions due to the solvation of the counterion by the linear block and to the conformation changes occurring after attachment of the first dendritic block to PEG