A controlled synthesis method of alkyl methacrylate block copolymers <i>via</i> living anionic polymerization at ambient temperature

Li, Zheng; Chen, Jianding; Zou, Guijin; Zhang, Tongyuan; Wei, Dafu; Xu, Xiang; Guan, Yong; Zheng, Anna

doi:10.1039/c9ra01577a

Cited by 5 publications

(3 citation statements)

References 23 publications

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“…Depending on the alcohol reactant, the conversion of MACR varied; however, a desirable ester product was dominantly produced with more than 80% selectivity in all the reactions (entries 1-4 in Table 3). This level of broad alcohol scope for MACR conversion is practically significant because the resulting alkyl methacrylate products can be used as monomers or additives for the synthesis of poly(alkyl methacrylate) with tailored polymeric properties [61]. In addition to MACR, larger aldehydes such as benzaldehyde can be oxidatively esterified with methanol using the 3AuCM catalyst, and high conversion of benzaldehyde (59.4%) was achieved with 100% selectivity to a desirable ester product within 1 h (entry 5 in Table 3).…”

Section: Reaction Studiesmentioning

confidence: 99%

A Multifunctional Au/CeO2-Mg(OH)2 Catalyst for One-Pot Aerobic Oxidative Esterification of Aldehydes with Alcohols to Alkyl Esters

et al. 2021

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Au nanoparticles bound to crystalline CeO2 nanograins that were dispersed on the nanoplate-like Mg(OH)2, denoted as Au/CeO2-Mg(OH)2, were developed as the highly active and selective multifunctional heterogeneous catalyst for direct oxidative esterification of aldehydes with alcohols to produce alkyl esters under base-free aerobic conditions using oxygen or air as the green oxidants. Au/CeO2-Mg(OH)2 converted 93.3% of methacrylaldehyde (MACR) to methyl methacrylate (MMA, monomer of poly(methyl methacrylate)) with 98.2% selectivity within 1 h, and was repeatedly used over eight recycle runs without regeneration. The catalyst was extensively applied to other aldehydes and alcohols to produce desirable alkyl esters. Comprehensive characterization analyses revealed that the strong metal–support interaction (SMSI) among the three catalytic components (Au, CeO2, and Mg(OH)2), and the proximity and strong contact between Au/CeO2 and the Mg(OH)2 surface were prominent factors that accelerated the reaction toward a desirable oxidative esterification pathway. During the reaction, MACR was adsorbed on the surface of CeO2-Mg(OH)2, upon which methanol was simultaneously activated for esterifying the adsorbed MACR. Hemiacetal-form intermediate species were subsequently produced and oxidized to MMA on the surface of the electron-rich Au nanoparticles bound to partially reduced CeO2−x with electron-donating properties. The present study provides new insights into the design of SMSI-induced supported-metal-nanoparticles for the development of novel, multifunctional, and heterogeneous catalysts.

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Section: Reaction Studiesmentioning

confidence: 99%

A Multifunctional Au/CeO2-Mg(OH)2 Catalyst for One-Pot Aerobic Oxidative Esterification of Aldehydes with Alcohols to Alkyl Esters

et al. 2021

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“…The initial PBMA spectrum 5a.0/5b.0 predominantly shows C=O, C−O−R, CH 3 stretching, and CH 2 stretching peaks at 1720 cm −1 , 1132 cm −1 , 2974 cm −1 , and 2934 cm −1 , respectively. 68,69 After the first TMA exposure (spectrum 5a.1/S4a.1), we see nearly complete consumption of the C=O and C−O−R peaks from PBMA (as seen from the peak intensity reversal). We also observe two red-shifted C=O peaks at 1606 and 1546 cm The reaction mechanism for the process is proposed as the polymer functional groups (C=O and C−O−R) interact/react with TMA in the first step of the binary reaction.…”

Section: Polycaprolactone (Pcl)mentioning

confidence: 87%

“…(Note: the thickness data fitting mean squared error in the ellipsometer was higher than the other three polymers in multiple trials.) The initial PBMA spectrum 5a.0/5b.0 predominantly shows C=O, C−O−R, CH 3 stretching, and CH 2 stretching peaks at 1720 cm −1 , 1132 cm −1 , 2974 cm −1 , and 2934 cm −1 , respectively 68,69. After the first TMA exposure (spectrum 5a.1/S4a.1), we see nearly complete consumption of the C=O and C−O−R peaks from PBMA (as seen from the peak intensity reversal).…”

mentioning

confidence: 99%

Sequential Infiltration Synthesis of Silicon Dioxide in Polymers with Ester Groups─Insight from In Situ Infrared Spectroscopy

Biswas,

Rozyyev,

Mane

et al. 2024

J. Phys. Chem. C

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New strategies to synthesize nanometer-scale silicon dioxide (SiO 2 ) patterns have drawn much attention in applications such as microelectronic and optoelectronic devices, membranes, and sensors, as we are approaching device dimensions shrinking below 10 nm. In this regard, sequential infiltration synthesis (SIS), a two-step gas-phase molecular assembly process that enables localized inorganic material growth in the targeted reactive domains of polymers, is an attractive process. In this work, we performed in situ Fourier transform infrared spectroscopy (FTIR) measurements during SiO 2 SIS to investigate the reaction mechanism of trimethylaluminum (TMA) and tri(tert-pentoxy) silanol (TPS) precursors with polymers having ester functional groups (poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), polycaprolactone (PCL), and poly(t-butyl methacrylate) (PBMA)), for the purpose of growing patterned nanomaterials. The FTIR results show that for PMMA and PEMA, a lower percentage of functional groups participated in the reactions and formed weak and unstable complexes. In contrast, almost all functional groups in PCL and PBMA participated in the reactions and showed stable and irreversible interactions with TMA. We discovered that the amount of SiO 2 formed is not directly correlated with the number of interacting functional groups. These insights into the SiO 2 SIS mechanism will enable nanopatterning of SiO 2 for low-dimensional applications.

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Initiating Mechanism of the Anionic Polymerization of Methacrylates with t‐BuOK and the Synthesis of ABA Type Triblock Copolymers

Zhang

Zheng

Zou

et al. 2019

Macro Chemistry & Physics

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Using potassium tert‐butoxide (t‐BuOK) as initiator, anionic polymerization and copolymerization of the methacrylate monomers are carried out in tetrahydrofuran at 0 °C or above. The polymers are characterized by gel permeation chromatography (GPC), proton nuclear magnetic resonance (1H‐NMR), Fourier transform infrared (FTIR), and dynamic mechanical analyzer (DMA). There is a critical concentration of the active species in t‐BuOK, above which no matter how much more t‐BuOK is added, it has no initiation activity. Among the active species of t‐BuOK, the main part possesses large average vibration distance between anion–cation pairs, which can initiate all methacrylate monomers in this study. While another part of the active species possesses the small average vibration distance, which can only initiate the polymerization of methyl methacrylate at slow rate. It provides an supporting evidence for the “channel idea” proposed previously. Finally, poly(methyl methacrylate)‐b‐poly(lauryl methacrylate)‐b‐poly(methyl methacrylate) (PMMA‐b‐PLMA‐b‐PMMA) three‐block copolymer is synthesized. This study paves the way for the synthesis of thermoplastic elastomers with full polar monomers and full saturated chains by anionic polymerization.

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A controlled synthesis method of alkyl methacrylate block copolymers via living anionic polymerization at ambient temperature

Abstract: A series of well-defined diblock copolymers containing PMMA, PEMA and PBMA blocks were synthesized with narrow MWDs and high yields via anionic polymerization, while t-BuOK was selected as initiator in THF at 0 °C. .

Cited by 5 publications

References 23 publications

A Multifunctional Au/CeO2-Mg(OH)2 Catalyst for One-Pot Aerobic Oxidative Esterification of Aldehydes with Alcohols to Alkyl Esters

A Multifunctional Au/CeO2-Mg(OH)2 Catalyst for One-Pot Aerobic Oxidative Esterification of Aldehydes with Alcohols to Alkyl Esters

Sequential Infiltration Synthesis of Silicon Dioxide in Polymers with Ester Groups─Insight from In Situ Infrared Spectroscopy

Initiating Mechanism of the Anionic Polymerization of Methacrylates with t‐BuOK and the Synthesis of ABA Type Triblock Copolymers

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