Anionic Copolymerization of 4-Trimethylsilylstyrene: From Kinetics to Gradient and Block Copolymers

Wadgaonkar, Shivani P.; Schüttner, Sandra; Berger‐Nicoletti, Elena; Müller, Axel H. E.; Frey, Holger

doi:10.1021/acs.macromol.2c00570

Cited by 9 publications

(28 citation statements)

References 61 publications

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“…The impact of the TMS group on the reactivity of the related 4TMSS monomer was unveiled via a kinetic study of its statistical copolymerization with styrene in previous work. The determined reactivity ratios, which define the relative rates of homopolymerization versus copolymerization (i.e., crossover), r 4TMSS = 2.76; r S = 0.087, 47 clearly indicated an enhanced reactivity of 4TMSS in comparison to styrene in a nonpolar solvent at room temperature. In consequence, the statistical copolymerization of 4TMSS with styrene resulted in copolymers with a moderate gradient microstructure.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…However, (ii) and (iii) permit a comparison with the T g value of P4TMSS. The T g of P4TMSS extrapolated to infinite M n was observed at 134 °C, 47 which is significantly higher than that of PS (T g = 106 °C). 69 This was tentatively attributed to two important factors; (i) restricted rotation in the polymer chains due to the bulky TMS group and (ii) d π −p π interactions between the silicon atom and the aromatic ring.…”

Section: ■ Thermal Propertiesmentioning

confidence: 99%

“…In the particular examples of 4MS and 4BuS, reactivity ratio values (r 4MS = 0.37; r S = 2.62, 44 r 4BuS = 0.96; r S = 3.07 46 ) indicated a lowered reactivity of these substituted styrene monomers in comparison to styrene, explained by the electron donating effect of 4-methyl and 4but-3-enyl substituent on the styrene scaffold. Conversely, in the case of 4TMSS (r 4TMSS = 2.76; r S = 0.087 47 ), an enhanced reactivity of the substituted styrene monomer in comparison to styrene was attributed to the electron-withdrawing characteristics of the attached trimethylsilyl group (TMS), which is explained by the presence of empty d-orbitals. These results demonstrated how a subtle change in the electronic nature of the substituent in functionalized styrene monomers can dramatically affect their reactivity and consequently the nature of the gradient in the synthesized statistical copolymers.…”

Section: ■ Introductionmentioning

confidence: 99%

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Anionic Polymerization of 4-Allyldimethylsilylstyrene: Versatile Polymer Scaffolds for Post-Polymerization Modification

et al. 2023

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A facile synthesis using a Grignard reaction was employed to prepare the silicon containing functional monomer 4-allyldimethylsilylstyrene (4ADSS). Detailed studies regarding the living nature of anionic polymerization of 4ADSS and its polymerization via the styrene vinyl bond in cyclohexane at room temperature were conducted, and P4ADSS samples with M n up to 80 kg mol–1 were accessible. This evidences that the 4ADSS structure disables undesired proton transfer side reactions, as known for the carbon-based analogue functional monomer 4-but-3-enyl-styrene. Real-time 1H NMR kinetics of the statistical copolymerization of 4ADSS with styrene (r 4ADSS = 3.55; r S = 0.047) revealed a remarkable gradient microstructure in the resulting copolymers. Based on this observation, a library of well-defined gradient copolymers P(4ADSS-co-S) with M n in the range of 5–50 kg mol–1 was synthesized, varying 4ADSS content. A comprehensive discussion regarding the glass transition temperatures (T g) of the synthesized homo- and copolymers is presented. Furthermore, thiol–ene click reactions at the pendant allyl moiety of P(4ADSS-co-S) were explored to introduce functional groups. Likewise, P(4ADSS-co-S) copolymers were subjected to hydrosilylation reactions, and the impact of the introduced siloxane moieties on the glass transition of the resulting copolymers is presented. Both thiol–ene reactions as well as hydrosilylation of the P(4ADSS-co-S) copolymers proceeded quantitatively. Consequently, copolymerization of 4ADSS provides access to a wide range of polystyrene-based functional materials with specific applications using versatile post-polymerization chemistry.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Thermal Propertiesmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Anionic Polymerization of 4-Allyldimethylsilylstyrene: Versatile Polymer Scaffolds for Post-Polymerization Modification

et al. 2023

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“…The tapered system has been recently extended to several monomer pairs including Ip/4-methylstyrene, 14,16 Ip/p-alkylstyrene, 24 St/4-vinylbenzo cyclobutene, 25 St/β-farnesene, 26 St/β-myrcene, 27,60 and St(Ip)/4-trimethylsilylstyrene. 61 However, at present, the tapered star copolymers are rarely studied except for only two examples of the four-arm star. 28,29 As shown in Scheme 1, herein we focus on the preparation of eight-arm tapered star copolymers 8[P(I-co-S) x ]-POSS (x = 1, 2, and 3) with different tapered blocks by a combination of living anionic copolymerization and coupling reaction.…”

Section: Resultsmentioning

confidence: 99%

Investigation of eight-arm tapered star copolymers prepared by anionic copolymerization and coupling reaction

Wang

Wu²,

Zhu

et al. 2022

Polym. Chem.

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“…Our group has developed and established the use of 1 H NMR spectroscopy to track in real-time living oxy- and carbanionic homo- and copolymerizations. − ,− In a living polymerization, the comonomer conversions in real-time should represent its exact mean incorporation of comonomers along the growing polymer chain. This extremely sensitive and challenging method has been employed to track individual comonomer consumption, which can in turn be translated to the reactivity ratios and resulting gradient microstructure in the copolymer.…”

Section: Introductionmentioning

confidence: 99%

Anionic Polymerization of the Terpene-Based Diene β-Ocimene: Complex Mechanism Due to Stereoisomer Reactivities

et al. 2023

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Motivated by the need for sustainable, bio-based materials, the living anionic polymerization of the under-explored terpene monomer β-ocimene (Oc) was investigated for the first time. Homopolymers with M n up to 50 kg mol −1 of the Oc isomeric mixture (E:Z = trans:cis = 70:30) were synthesized in cyclohexane and analyzed with respect to molecular weight control, dispersity, microstructure, and glass transition temperature, T g . Employing styrene as a comonomer, diblock copolymers, and a series of statistical copolymers with M n up to 20 kg mol −1 with varying comonomer compositions offered the opportunity to tailor the glass transition of the copolymers. Real-time 1 H nuclear magnetic resonance (NMR) kinetics indicated a remarkably divergent reactivity of the trans and cis isomers. This unveiled the unique observation that the homopolymerization of Oc is in fact a copolymerization of the cis and trans isomers, which one might name as "stereo-copolymerization" (r trans = 3.16; r cis = 0.32). Kinetic studies of the statistical copolymerization of the Oc isomeric mixture with styrene revealed an astonishingly contradictory reactivity of the two isomers (r trans < r cis ). The reactivity differences of the cis and trans isomers in the polymerization were utilized to isolate the individual isomers for the first time. Subsequently, they were independently homo-and copolymerized with styrene. The complex mechanism of these polymerizations and the rather high polymer dispersities (Đ ≈ 1.6−2) are discussed using various kinetic models supported by density functional theory modeling. The surprisingly different behavior of the two isomers with styrene was validated experimentally via a 1 H NMR-monitored chemical titration.

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Anionic Copolymerization of 4-Trimethylsilylstyrene: From Kinetics to Gradient and Block Copolymers

Cited by 9 publications

References 61 publications

Anionic Polymerization of 4-Allyldimethylsilylstyrene: Versatile Polymer Scaffolds for Post-Polymerization Modification

Anionic Polymerization of 4-Allyldimethylsilylstyrene: Versatile Polymer Scaffolds for Post-Polymerization Modification

Investigation of eight-arm tapered star copolymers prepared by anionic copolymerization and coupling reaction

Anionic Polymerization of the Terpene-Based Diene β-Ocimene: Complex Mechanism Due to Stereoisomer Reactivities

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