Recyclable DMAP-Functionalized polymeric nanoreactors for highly efficient acylation of alcohols in aqueous systems

Qiu, Jiaqi; Meng, Fuliang; Wang, Maolin; Huang, Jinjin; Wang, Chengzhan; Li, Xiao; Yang, Guang; Hua, Zan; Chen, Tao

doi:10.1016/j.polymer.2021.123660

Cited by 8 publications

(4 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The synthesis of OH-DMAP was followed by our previous report . 4-chloropyridine hydrochloride (3.0 g, 20.0 mmol), 2-(methylamino)ethanol (15.0 g, 200.0 mmol) and 2-methyl-2-butanol (50 mL) were charged in a round-bottom flask equipped with a stirring rod.…”

Section: Methodsmentioning

confidence: 99%

“…The synthesis of OH-DMAP was followed by our previous report. 4 4-chloropyridine hydrochloride (3.0 g, 20.0 mmol), 2-(methylamino)ethanol (15.0 g, 200.0 mmol) and 2-methyl-2butanol (50 mL) were charged in a round-bottom flask equipped with a stirring rod. After the mixture was stirred and dissolved, ZnCl 2 (136.0 mg, 1.0 mmol) was added and the solution was then refluxed for 24 h. After the reaction, the volatiles were removed at reduced pressure and the residue was added into HCl aqueous solution (6 M, 30 mL).…”

Section: Methodsmentioning

confidence: 99%

“…Polymeric micelles, processing the characteristics of easy to prepare, well dispersed, and structurally tunable, have been widely used in the fields of imaging, diagnosis, drug release, etc. The introduction of homogeneous catalysts into polymer-based micelles can perfectly combine the well-known advantages of homogeneous catalysis, such as high efficiency, with those of the heterogeneous catalysis, such as recyclability. In addition, the micellar nanoreactor with the substrate concentration effect and confinement effect can be effectively utilized for catalysis applications .…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Self-Assembled Catalytic Nanoreactors from Molecular Brushes by Utilizing Postpolymerization Modification for Catalyst Attachment

Wang

Min

Huang

et al. 2022

ACS Appl. Polym. Mater.

Self Cite

View full text Add to dashboard Cite

Polymer-based catalytic nanoreactors, with the characteristics of easy preparation, good dispersion, and facile modulation of molecular structures, have been widely applied for various organic transformations. Usually, polymeric nanoreactors are fabricated via the self-assembly of amphiphilic copolymers in water, while the disassembly and instability of the relevant nanoreactors often compromise their potential applicability. Molecular brushes (MBs), as a kind of polymer with high-density grafted side chains on the linear polymer main chain, can be rapidly self-assembled into highly ordered nanostructures even at low concentrations. This study reports the fabrication of catalytic nanoreactors from molecular brushes of poly[norbornene–poly(bromoethyl methacrylate-co-methyl methacrylate)]-co-poly[norbornene polyethylene glycol monomethyl ether] (P[NB-(BEMA-co-MMA)]-co-P[NB-PEG]). The amphiphilic molecular brush was synthesized by combining reversible addition–fragmentation chain transfer (RAFT) polymerization and ring-opening metathesis polymerization (ROMP) techniques. Homogeneous catalysts, such as triethylenediamine and 4-(dimethylamino)pyridine analogues, were introduced by nucleophilic substitution with alkyl bromide on the side chain of molecular brushes. Furthermore, micellar catalytic nanoreactors were fabricated via self-assembly in deionized water. The resulted nanoreactors display high catalytic activities toward the Knoevenagel condensation reaction and acylation reaction of alcohol in water, respectively. This contribution describes a general method for constructing highly efficient molecular brush-based catalytic nanoreactors utilizing postpolymerization modification (PPM) for aqueous catalysis.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Self-Assembled Catalytic Nanoreactors from Molecular Brushes by Utilizing Postpolymerization Modification for Catalyst Attachment

Wang

Min

Huang

et al. 2022

ACS Appl. Polym. Mater.

Self Cite

View full text Add to dashboard Cite

show abstract

“…The self-assembled micelles having the characteristics of easy preparation, good dispersion in the water phase, and facile modulation of molecular structures have been widely used in many fields, such as separation, sensing, , electronics, drug delivery, − and so on. In recent years, polymeric nanoreactors based on organocatalysts such as l -proline, chiral imidazolinone (Macmillan catalyst), DMAP, , and TEMPO, − and organometallic catalysts such as Pd complex, , Mn III , chiral salen Ti IV − etc., have been prepared and successfully applied to various organic transformations in water. The macromolecular characteristic of the nanoreactors makes the recycle of the catalyst possible. , Besides, the substrate concentration effect of the hydrophobic core greatly improves the reactive activity of the loading catalyst.…”

Section: Introductionmentioning

confidence: 99%

TEMPO-Functionalized Nanoreactors from Bottlebrush Copolymers for the Selective Oxidation of Alcohols in Water

Wang

Shi

et al. 2021

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

Polymeric nanoreactors in water fabricated by the self-assembly of amphiphilic copolymers have attracted much attention due to their good catalytic performance without using organic solvents. However, the disassembly and instability of relevant nanostructures often compromise their potential applicability. Herein, the preparation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-containing nanoreactors by the self-assembly of amphiphilic bottlebrush copolymers has been demonstrated. First, a macromonomer having a norbornenyl polymerizable group was prepared by RAFT polymerization of hydrophobic and hydrophilic monomers. The macromonomer was further subjected to ring-opening metathesis polymerization to produce an amphiphilic bottlebrush copolymer. Further, TEMPO, as a catalyst, was introduced into the hydrophobic block through the activated ester strategy. Finally, TEMPO-functionalized polymeric nanoreactors were successfully obtained by self-assembly in water. The nanoreactors exhibited excellent catalytic activities in selective oxidation of alcohols in water. More importantly, the reaction kinetics showed that the turnover frequency is greatly increased compared to that of the similar nanoreactor prepared from liner copolymers under the same conditions. The outstanding catalytic activities of the nanoreactors from bottlebrush copolymers could be attributed to the more stable micellar structure using the substrate concentration effect. This work presents a new strategy to fabricate stable nanoreactors, paving the way for highly efficient organic reactions in aqueous solutions.

show abstract

Design strategies, surface functionalization, and environmental remediation potentialities of polymer-functionalized nanocomposites

Betrehem

Ali

et al. 2022

Chemosphere

View full text Add to dashboard Cite

Recyclable DMAP-Functionalized polymeric nanoreactors for highly efficient acylation of alcohols in aqueous systems

Cited by 8 publications

References 43 publications

Self-Assembled Catalytic Nanoreactors from Molecular Brushes by Utilizing Postpolymerization Modification for Catalyst Attachment

Self-Assembled Catalytic Nanoreactors from Molecular Brushes by Utilizing Postpolymerization Modification for Catalyst Attachment

TEMPO-Functionalized Nanoreactors from Bottlebrush Copolymers for the Selective Oxidation of Alcohols in Water

Design strategies, surface functionalization, and environmental remediation potentialities of polymer-functionalized nanocomposites

Contact Info

Product

Resources

About