Synthesis of α-Norbornenylpoly(ethylene oxide) Macromonomers and Their Ring-Opening Metathesis Polymerization

Héroguez, Valérie; Breunig, Stefan; Gnanou, Yves; Fontanille, Michel

doi:10.1021/ma951797v

Cited by 142 publications

(113 citation statements)

References 8 publications

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“…Recently, Heroguez and coworkers have reported that ROMP was the method of choice to prepare polymacromonomers within high yields and with precise control of the size, which is the major problem in the synthesis of this type of multibranched structures. 8 Based on the living/controlled ROMP, different combinations of polystyrene and poly(ethylene oxide) macromonomers, thus random and block copolymacromonomers, have been prepared by copolymerization of the parent norbornenyl-macromonomers. In this work, we have investigated the homopolymerization of the ␣-norbornenyl PCL macromonomers in order to prepare multibranched polyesters (Scheme 3).…”

Section: Ring-opening Polymerization Of the Pcl Macromonomersmentioning

confidence: 99%

Ring-opening metathesis polymerization of new ?-norbornenyl poly(?-caprolactone) macromonomers

Mecerreyes

Dahan

Lecomte

et al. 1999

J. Polym. Sci. A Polym. Chem.

156

171

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Section: Ring-opening Polymerization Of the Pcl Macromonomersmentioning

confidence: 99%

Ring-opening metathesis polymerization of new ?-norbornenyl poly(?-caprolactone) macromonomers

Mecerreyes

Dahan

Lecomte

et al. 1999

J. Polym. Sci. A Polym. Chem.

156

171

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“…There are many approaches to these macromolecules, each with their own obstacles (24,25). In the "grafting through" or macromonomer (MM) method, the side chain containing a terminal monomer is synthesized first and subsequently polymerized to yield the resulting brush polymer (24,26). This approach ensures complete grafting of a welldefined side chain on every backbone monomer unit; however, it requires an extremely robust polymerization mechanism to achieve high MW while maintaining control of the PDI (25).…”

mentioning

confidence: 99%

Rapid self-assembly of brush block copolymers to photonic crystals

Sveinbjörnsson

Weitekamp

Miyake

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

353

379

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The reduced chain entanglement of brush polymers over their linear analogs drastically lowers the energetic barriers to reorganization. In this report, we demonstrate the rapid self-assembly of brush block copolymers to nanostructures with photonic bandgaps spanning the entire visible spectrum, from ultraviolet (UV) to near infrared (NIR). Linear relationships were observed between the peak wavelengths of reflection and polymer molecular weights. This work enables "bottom-up" fabrication of photonic crystals with application-tailored bandgaps, through synthetic control of the polymer molecular weight and the method of self-assembly. These polymers could be developed into NIR-reflective paints, to combat the "urban heat island effect" due to NIR photon thermalization.

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“…[123][124][125][126][127][128][129][130][131] It has been believed for a long time that such densely branched polymers cannot be synthesized by means of "grafting-onto" method because of serious steric hindrance of branches. However, Deffieux and Schappacher have recently reported the first successful synthesis of such densely branched polymers by the coupling reaction of poly(2-chloroethyl vinyl ether) with polystyryllithium based on a graftingonto method.…”

Section: Synthesis Of Densely Branched Polymers With Starlike Structuresmentioning

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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Synthesis of α-Norbornenylpoly(ethylene oxide) Macromonomers and Their Ring-Opening Metathesis Polymerization

Cited by 142 publications

References 8 publications

Ring-opening metathesis polymerization of new ?-norbornenyl poly(?-caprolactone) macromonomers

Ring-opening metathesis polymerization of new ?-norbornenyl poly(?-caprolactone) macromonomers

Rapid self-assembly of brush block copolymers to photonic crystals

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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