Synthesis of Styrene Monomers Hydroxyl Functionalized

GonzÁlez-Pluma, Marisol; Elizalde, Luis E.; Saldívar‐Guerra, Enrique; Telles-Padilla, Guadalupe; Ledezma, Raquel; Flores-Guerrero, Mildred

doi:10.1080/10601325.2013.829357

Cited by 2 publications

(2 citation statements)

References 7 publications

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“…Among the prevalent techniques for the synthesis of functionalized styrene monomers, a one-step Grignard reaction is one of the established strategies. − (4-Vinylphenyl)magnesium bromide and (4-vinylphenyl)magnesium chloride have been employed for the synthesis of functionalized styrene monomers suitable for living anionic polymerization. ,, Because aryl Grignard reagents lack sufficient nucleophilicity to initiate anionic polymerization of styrene monomers, they are suitable for derivatization. In the present work, this strategy was used to synthesize the functional monomer, 4-allyldimethylsilylstyrene (4ADSS).…”

Section: Introductionmentioning

confidence: 99%

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: Introductionmentioning

confidence: 99%

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

et al. 2023

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“…To the best of our knowledge (4-vinylphenyl)magnesium bromide has rarely been utilized for the preparation of functional monomers for the carbanionic living polymerization . However, some works demonstrated the use of this approach for subsequent radical polymerization. − As aryl Grignard reagents do not possess sufficient nucleophilicity to initiate the anionic polymerization of styrene monomers, they are attractive for the rapid attachment of electrophilic compounds. Because of the high reactivity and selectivity, functional monomers can thus be easily synthesized (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

A Nonconventional Approach toward Multihydroxy Functional Polystyrenes Relying on a Simple Grignard Reagent

et al. 2020

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Capitalizing on the inertness of styrene toward Grignard reagents, 4-vinylphenylmagnesium bromide was utilized for the rapid and convenient preparation of the protected monomer 2,2-dimethyl-4-(4-vinylbenzyl)-1,3-dioxolane (DMVBDO), avoiding the use of catalysts and painstaking purification protocols. Well-defined homopolymers, statistical copolymers, and block copolymers with styrene (S) as a comonomer were prepared in THF at −78 °C via carbanionic living polymerization. The overall molecular weights ranged from 4.5 to 68.9 kg mol–1 with low dispersities (Đ 1.04–1.15). Copolymers were synthesized with styrene feed ratios (X feed) from 15 to 95 mol % with glass transition temperatures (T g) between 46 and 91 °C. Whereas polystyryllithium served as an excellent macroinitiator for the preparation of the block copolymer PS0.5-b-P(DMVBDO)0.5, the inverse block order, i.e., synthesis of P(DMVBDO)0.5-b-PS0.5, yielded a bimodal molecular weight distribution (MWD) with increased dispersity, which is ascribed to slow crossover. Rapid deprotection of both homo- and copolymers to release two hydroxyl groups per DMVBDO unit was achieved via acidic hydrolysis. The deprotected block copolymer PS0.5-b-P(VPPDO)0.5 showed phase separation, indicated by two T g values (68 and 86 °C). Homogeneous brush copolymers of the type P(S85-co-VPPDO5)-g-PLLA and P(S85-co-VPPDO6)-g-PEO were demonstrated by using quantitative “grafting from” with l-lactide and ethylene oxide, respectively. The brush-like copolymers were obtained in quantitative yields while maintaining monodisperse MWD.

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Synthesis of Styrene Monomers Hydroxyl Functionalized

Cited by 2 publications

References 7 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

A Nonconventional Approach toward Multihydroxy Functional Polystyrenes Relying on a Simple Grignard Reagent

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