Synthesis of Sequence-Specific Vinyl Copolymers by Regioselective ROMP of Multiply Substituted Cyclooctenes

Zhang, Jihua; Matta, Megan E.; Hillmyer, Marc A.

doi:10.1021/mz300535r

Cited by 156 publications

(142 citation statements)

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“…Results comparable to those reported for our original poly(3RCOE) [55,59] samples were observed for every poly(3FGCOE), namely high content of head-totail (HT) structure and E double bond configuration (Table 1). This result confirms our hypothesis that sufficiently bulky substituent at the 3-position gives rise to regioand stereo-selective polymerization [55][56][57][58][59]. Thermal characterization using differential scanning calorimetry (DSC) suggested nearly all poly(3FGCOE) are amorphous with glass transition temperatures (T g ) in the range of -69 to 58°C ( Table 1).…”

Section: Polymer Synthesis and Characterizationsupporting

confidence: 83%

“…We recently published a series of reports [55][56][57][58][59] demonstrating that single substitution at the 3-position (i.e., the allylic position) of cis-cyclooctene (COE) was an effective way to synthesize regio-and stereo-regular polyalkenamers by ROMP using the well-defined Grubbs second (G2) or third (G3) generation catalysts. Such substituents we have explored included hydrocarbon groups (3RCOE, R = methyl, ethyl, hexyl or phenyl) [55,56] and the acetoxy group [57][58][59].…”

Section: Introductionmentioning

confidence: 99%

“…Such substituents we have explored included hydrocarbon groups (3RCOE, R = methyl, ethyl, hexyl or phenyl) [55,56] and the acetoxy group [57][58][59]. All the reported polyalkenamers possess high levels ([95 %) of head-to-tail (HT) repeating unit connectivity and E double bond configuration.…”

Section: Introductionmentioning

confidence: 99%

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Functionalized regio-regular linear polyethylenes from the ROMP of 3-substituted cyclooctenes

et al. 2014

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We demonstrated that the ring-opening metathesis polymerization (ROMP) of 3-substituted cyclooctenes bearing polar substituents allows the synthesis of highly regio-and stereo-regular polymers. A series of polyalkenamers with 90-99 % head-to-tail/trans configuration were synthetized in good yields (33-87 % yield). Upon saturation of the backbone using diimide, these polymers represent a class of linear polyethylene derivatives where the polar side chain is located on every eighth carbon. The thermal properties of both the saturated and unsaturated polymers depend strongly on the size and polarity of the functional side groups. The results presented here demonstrate that the 3-substituted cyclooctenes can be used not only for the synthesis of precisely functionalized polyethylene derivatives, but also to participate in the ringopening metathesis copolymerization with unfunctionalized cyclic olefins to generate copolymers with tunable properties.

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Section: Polymer Synthesis and Characterizationsupporting

confidence: 83%

Section: Introductionmentioning

confidence: 99%

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Functionalized regio-regular linear polyethylenes from the ROMP of 3-substituted cyclooctenes

et al. 2014

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“…Hillmyer et al reported a novel approach to prepare regioselective terpolymers and quarterpolymers by ring opening metathesis polymerization (ROMP) of multi-substituted cyclooctenes. 5 In this case the sequence is built into the monomer which unfolds to create a perfectly ordered copolymer structure with high regio-and stereo-control. However, the synthesis of the multi-functional cyclooctene monomer is non-trivial.…”

mentioning

confidence: 99%

Monomer Sequence Control via Living Anionic Copolymerization: Synthesis of Alternating, Statistical, and Telechelic Copolymers and Sequence Analysis by MALDI ToF Mass Spectrometry

et al. 2015

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(2015) 'Monomer sequence control via living anionic copolymerization : synthesis of alternating, statistical, and telechelic copolymers and sequence analysis by MALDI ToF mass spectrometry. ', Macromolecules., 48 (3). pp. 610-628.Further information on publisher's website:Publisher's copyright statement:This document is the Accepted Manuscript version of a Published Work that appeared in nal form in Macromolecules, copyright c 2015 American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see http://dx.doi.org/10.1021/ma5016038. Additional information:Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. 3LE. United Kingdom ABSTRACT: Diphenylethylene (DPE) is a monomer which has attracted significant interest from both academia and industry. DPE can undergo (co)polymerization by living anionic polymerization but is incapable of forming a homopolymer due to steric hindrance. Herein the copolymerization of DPE and 1,1-bis(4-tert-butyldimethylsiloxyphenyl)ethylene (DPE-OSi)with styrene or butadiene is described in order to produce (functional) copolymers with controlled co-monomer sequences -either alternating or telechelic. The copolymer sequences are inherently controlled by relative reactivity ratios, which in turn can be tuned by both monomer structure and by the polarity of the polymerization solvent. The composition of the copolymers prepared in this study were analyzed by 1 H NMR spectroscopy and MALDI ToF 2 mass spectrometry, the latter offering a unique opportunity to demonstrate perfect alternating sequences and insight into other sequences such as telechelic polymers.

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“…Although these powerful methods have enabled transformative advances in biotechnology and have recently been revisited for the synthesis of sequencedefined synthetic polymers (14)(15)(16), alternative strategies are needed that provide a general solution for access to sequencedefined synthetic polymers in a scalable and sustainable manner. In contrast, step-or chain-growth polymerization methods that use differences in monomer reactivity, living polymerizations, monomer design, and/or templating strategies to impart sequence regulation have been recently reported (17)(18)(19)(20)(21)(22)(23). These scalable methods, however, still rely on stochastic monomer addition and thus do not generate unimolecular macromolecules.…”

mentioning

confidence: 99%

Scalable synthesis of sequence-defined, unimolecular macromolecules by Flow-IEG

Leibfarth

Johnson

Jamison

2015

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

161

118

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We report a semiautomated synthesis of sequence and architecturally defined, unimolecular macromolecules through a marriage of multistep flow synthesis and iterative exponential growth (Flow-IEG). The Flow-IEG system performs three reactions and an in-line purification in a total residence time of under 10 min, effectively doubling the molecular weight of an oligomeric species in an uninterrupted reaction sequence. Further iterations using the Flow-IEG system enable an exponential increase in molecular weight. Incorporating a variety of monomer structures and branching units provides control over polymer sequence and architecture. The synthesis of a uniform macromolecule with a molecular weight of 4,023 g/mol is demonstrated. The user-friendly nature, scalability, and modularity of Flow-IEG provide a general strategy for the automated synthesis of sequence-defined, unimolecular macromolecules. Flow-IEG is thus an enabling tool for theory validation, structure-property studies, and advanced applications in biotechnology and materials science.polymers | automation | continuous flow chemistry | unimolecular macromolecules | sequence-controlled polymers

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Synthesis of Sequence-Specific Vinyl Copolymers by Regioselective ROMP of Multiply Substituted Cyclooctenes

Cited by 156 publications

References 54 publications

Functionalized regio-regular linear polyethylenes from the ROMP of 3-substituted cyclooctenes

Functionalized regio-regular linear polyethylenes from the ROMP of 3-substituted cyclooctenes

Monomer Sequence Control via Living Anionic Copolymerization: Synthesis of Alternating, Statistical, and Telechelic Copolymers and Sequence Analysis by MALDI ToF Mass Spectrometry

Scalable synthesis of sequence-defined, unimolecular macromolecules by Flow-IEG

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