Investigation of the features in living anionic polymerization with styrene derivatives containing annular substituents

Bai, Hongyuan; Zhang, Zhi; Ma, Hongwei; Han, Li; Mu, Xiaochun; Huang, Wei; Liu, Pibo; Wu, Yibo

doi:10.1039/c8py01825a

Cited by 6 publications

(8 citation statements)

References 56 publications

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“…AMROP was realized with the unique structure of vinyl monomers, and more than four carbon atoms can be introduced into the backbone. The molecular structure of CBVB is similar to that of CPVB, except that the substituent group of CBVB is cyclobutyl and the ring strain is still higher than that of other annular substituents . Similarly, the cyclobutyl group in CBVB can undergo a ring-opening reaction when sec -BuLi is added, and detailed discussions about its addition reaction are showed in the Supporting Information (corresponding results are shown in Figures S4 and S5).…”

Section: Resultsmentioning

confidence: 86%

“…The molecular structure of CBVB is similar to that of CPVB, except that the substituent group of CBVB is cyclobutyl and the ring strain is still higher than that of other annular substituents. 32 Similarly, the cyclobutyl group in CBVB can undergo a ring-opening reaction when sec-BuLi is added, and detailed discussions about its addition reaction are showed in the Supporting Information (corresponding results are shown in Figures S4 and S5). Moreover, the AMROP of CBVB cannot occur at 20 °C but can be achieved at a high temperature (i.e., 60 °C), which also provides abundant possibilities for switching chain propagation on/off in anionic polymerization.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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C5 and C6 Polymerizations by Anion Migrated Ring-Opening of 1-Cyclopropylvinylbenzene and 1-Cyclobutylvinylbenzene

Bai

Han

Li³

et al. 2021

Macromolecules

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As an emerging method, anion migrated ringopening polymerization (AMROP) can effectively regulate the carbon skeletons of polymer backbones with specific vinyl monomers. As reported here, polymers with C5 and C6 skeletons were synthesized by AMROP of 1-cyclopropylvinylbenzene (CPVB) and 1-cyclobutylvinylbenzene (CBVB). Moreover, C4 polymerization of 1-phenyl-1,3-butadiene (1-PB) was also conducted (in a general anionic polymerization process) for comparison with C5 and C6 polymerizations. Among the three base polymers prepared with the C4, C5, and C6 polymerizations, PCBVB exhibited the most flexible carbon skeleton structure and the lowest glass transition temperature (T g = −18.8 °C). Then, the resultant base polymers with different carbon skeletons were hydrogenated and cyclized. The hydrogenation of P(1-PB), PCPVB, and PCBVB resulted in the formation of products with unique alternating styrene/ethylene (alt-SE), periodic styrene/ethylene/methylene (pd-SEM), and periodic styrene/ethylene/ethylene (pd-SEE) structures. Moreover, pd-SEM and pd-SEE can be considered as sequence-defined template polymers, and these structures cannot be synthesized through general copolymerization of styrene and ethylene. Owing to the specific carbon skeletons exhibited in alt-SE, pd-SEM, and pd-SEE, their T g values showed significant differences (24.6, 10.9, and −6.0 °C, respectively). Additionally, the specific carbon skeletons of the base polymers resulted in the formation of cyclized polymers with different annular substituents. Moreover, diverse annular substitutes endowed the cyclized polymers with prominent thermal resistance and luminescence properties. Through the above investigations, it is clearly demonstrated that small changes in carbon skeleton structure can remarkably affect the polymer properties. Moreover, AMROP provides a new strategy to design novel polymers with C5 and C6 skeleton structures.

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Section: Resultsmentioning

confidence: 86%

Section: ■ Results and Discussionmentioning

confidence: 99%

C5 and C6 Polymerizations by Anion Migrated Ring-Opening of 1-Cyclopropylvinylbenzene and 1-Cyclobutylvinylbenzene

Bai

Han

Li³

et al. 2021

Macromolecules

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“…1-Cyclopropylvinylbenzene (CPVB) (for characterization, see Figure S1), which possesses dissociative cyclopropyl, was designed as a potential monomer for sequence control. 37 The ring tension of the cyclopropyl group was high enough for possible ring opening. For instance, vinyl cyclopropane (VCP) has been widely applied to produce novel polymers with utterly different structures, 38,39 and poly(vinylcyclopropane) derivatives have been further modified to prepare periodic functional polymers.…”

Section: Resultsmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

“…As deduced, the total ring opening of the cyclopropyl group that existed during the addition process to form new living species is beyond the existing knowledge in anionic polymerization. In previous knowledge, ,,, only a simple addition reaction occurs, and two alkyl carbons are introduced into the main chain during the anionic polymerization of the styrene α-substituent. In this work, cyclopropyl is opened during the addition process, and the corresponding mechanism is deduced as the anion migrated ring opening (AMRO) based on an in situ characterization of the adduct of CPVB and sec -BuLi.…”

Section: Results and Discussionmentioning

confidence: 99%

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Thermally Controlled On/Off Switch in a Living Anionic Polymerization of 1-Cyclopropylvinylbenzene with an Anion Migrated Ring-Opening Mechanism

et al. 2020

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A reversible on/off switch to control chain growth in a living anionic polymerization is a meaningful challenge for its profound potential in both polymerization mechanisms and the preparation of advanced materials. Herein, we report a thermally controlled on/off switch for chain propagation in an anionic polymerization that is realized with a 1-cyclopropylvinylbenzene (CPVB) monomer. Interestingly, the specific ring-opening manner and thermal sensitivity are shown in the addition reaction of CPVB with the initiator or living chains. The ring opening of the cyclopropyl group in CPVB is observed to be a possible anion migrated ring-opening mechanism in the addition reactions. Additionally, the polymerization of CPVB occurs only at high temperature, and the chain growth constant kCC is near 0 at 20 °C, 0.0039 (L/mol)1/2 min–1 at 50 °C, and 0.016 (L/mol)1/2 min–1 at 60 °C. Thus, based on its unique characteristics, an ingenious design of “heat (60 °C)–cool (20 °C)” cycles is employed to achieve a thermally controlled on/off switch for chain growth in an anionic polymerization. It is expected that this finding can provide new insights into both controlling the monomer or multiblock sequence and raise a novel technique to stage control the chain growth with temperatures in living anionic polymerization.

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Precise construction of polymer brush on a nanosilica surface via the combination of anionic polymerization and Ugi-4CR

Leng

Han

et al. 2020

Polymer

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Investigation of the features in living anionic polymerization with styrene derivatives containing annular substituents

Abstract: Five styrene derivatives with annular substituents (SAs), called CPBE, CHBE, THNE, THBE and META, were successfully synthesized and living anionic polymerization was conducted.

Cited by 6 publications

References 56 publications

C5 and C6 Polymerizations by Anion Migrated Ring-Opening of 1-Cyclopropylvinylbenzene and 1-Cyclobutylvinylbenzene

C5 and C6 Polymerizations by Anion Migrated Ring-Opening of 1-Cyclopropylvinylbenzene and 1-Cyclobutylvinylbenzene

Thermally Controlled On/Off Switch in a Living Anionic Polymerization of 1-Cyclopropylvinylbenzene with an Anion Migrated Ring-Opening Mechanism

Precise construction of polymer brush on a nanosilica surface via the combination of anionic polymerization and Ugi-4CR

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