Active Ligand for Low PPM Miniemulsion Atom Transfer Radical Polymerization

Elsen, Andrea M.; Burdyńska, Joanna; Park, Sangwoo; Matyjaszewski, Krzysztof

doi:10.1021/ma301647w

Cited by 43 publications

(63 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Miniemulsion ARGET ATRP using a more active ligand, BPMODA modified with six electron donor groups, bis[2-(4-methoxy-3,5-dimethyl)pyridylmethyl] octadecylamine (BPMODA*), was previously reported. 106 Heterogeneous polymerization showed linear evolution of MW with conversion and narrow molecular-weight distribution (MWD) using only 250 ppm of Cu complex. Herein, both Cu/BPMODA and Cu/BPMODA* were tested as organic phase catalysts for miniemulsion e ATRP.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Atom Transfer Radical Polymerization in Miniemulsion with a Dual Catalytic System

et al. 2016

Self Cite

View full text Add to dashboard Cite

An electrochemical approach was used to control atom transfer radical polymerization (ATRP) of n-butyl acrylate (BA) in miniemulsion. Electropolymerization required a dual catalytic system, composed of an aqueous phase catalyst and an organic phase catalyst. This allowed shuttling the electrochemical stimulus from the working electrode (WE) to the continuous aqueous phase and to the dispersed monomer droplets. As aqueous phase catalysts, the hydrophilic Cu complexes with the ligands N,N-bis( 2-pyridylmethyl)-2-hydroxyethylamine (BPMEA), 2,2′-bipyridine (bpy), and tris(2-pyridylmethyl)amine (TPMA) were tested. As organic phase catalysts, the hydrophobic complexes with the ligands bis(2-pyridylmethyl)-octadecylamine (BPMODA) and bis[2-(4-methoxy-3,5-dimethyl)-pyridylmethyl]octadecylamine (BPMODA*) were evaluated. Highest rates and best control of BA electropolymerization were obtained with the water-soluble Cu/BPMEA used in combination with the oil-soluble Cu/BPMODA*. The polymerization rate could be further enhanced by changing the potential applied at the WE. Differently from traditional ATRP systems, reactivity of the dual catalytic system did not depend on the redox potential of the catalysts but instead depended on the hydrophobicity and partition coefficient of the aqueous phase catalyst.

show abstract

Section: Resultsmentioning

confidence: 99%

Electrochemical Atom Transfer Radical Polymerization in Miniemulsion with a Dual Catalytic System

et al. 2016

Self Cite

View full text Add to dashboard Cite

show abstract

“…49 BPMODA* was prepared as described in the Supporting Information. Under the same conditions used for Cu/TPMA, Cu/BPMODA* gave well-controlled polymers, but particles size was 80% larger, suggesting potential destabilization of the droplets’ surface.…”

Section: Resultsmentioning

confidence: 99%

Miniemulsion ARGET ATRP via Interfacial and Ion-Pair Catalysis: From ppm to ppb of Residual Copper

et al. 2017

Self Cite

View full text Add to dashboard Cite

It was recently reported that copper catalysts used in atom transfer radical polymerization (ATRP) can combine with anionic surfactants used in emulsion polymerization to form ion pairs. The ion pairs predominately reside at the surface of the monomer droplets, but they can also migrate inside the droplets and induce a controlled polymerization. This concept was applied to activator regenerated by electron transfer (ARGET) ATRP, with ascorbic acid as reducing agent. ATRP of n-butyl acrylate (BA) and n-butyl methacrylate (BMA) was carried out in miniemulsion using CuII/tris(2-pyridylmethyl)amine (TPMA) as catalyst, with several anionic surfactants forming the reactive ion-pair complexes. The amount and structure of surfactant controlled both the polymerization rate and the final particle size. Well-controlled polymers were prepared with catalyst loadings as low as 50 ppm, leaving only 300 ppb of Cu in the precipitated polymer. Efficient chain extension of a poly(BMA)-Br macroinitiator confirmed high retention of chain-end functionality. This procedure was exploited to prepare polymers with complex architectures such as block copolymers, star polymers, and molecular brushes.

show abstract

“…The experimental process was similar to the method described in literature and the synthetic process was as follows. MPEG 350 –NH 2 (5.5 g, 15.7 mmol), BPMA (8.7 g, 39.3 mmol, 2.5 equiv), Bu 3 N + Br − (51 mg, 1.6 mmol, 0.1 equiv) were dissolved in THF (100 mL), followed by 5 m NaOH aq (160 mL).…”

Section: Methodsmentioning

confidence: 99%

AGET ATRP of Methyl Methacrylate Based on Thermoregulated Phase Transfer Catalysis in Organic/Aqueous Biphasic System: Facile and Highly Efficient In Situ Catalyst/Ligand Separation and Recycling

Jiang

Liu

Ding

et al. 2015

Macromol. Chem. Phys.

View full text Add to dashboard Cite

A novel polymerization system with activators generated by electron transfer for atom transfer radical polymerization (ATRP) for sustainable catalyst/ligand separation and recycling in situ is developed based on thermoregulated phase transfer catalysis in organic/aqueous biphasic system. Herein, a typical iniferter agent 1-cyano-1-methylethyldiethyldithiocarbamte is used as the initiator, and CuBr 2 , monomethoxy poly(ethylene glycol)-350-supported substituted dipicolylamine (L 350 ), ascorbic acid, and methyl methacrylate are employed as the catalyst, thermoresponsive ligand, reducing agent, and the model monomer, respectively. The "living" nature of the system is confi rmed by polymerization kinetics with recycled catalyst complex aqueous solution and chain-extension experiments via iniferter and ATRP mechanism, respectively. In addition, the catalyst residue in polymers is less than 2 ppm and the recycling effi ciency of catalyst complex in water kept more than 95% even after 5 times of recovery experiments while keeping narrow molecular weight distribution ( M w / M n < 1.33).

show abstract

Active Ligand for Low PPM Miniemulsion Atom Transfer Radical Polymerization

Cited by 43 publications

References 47 publications

Electrochemical Atom Transfer Radical Polymerization in Miniemulsion with a Dual Catalytic System

Electrochemical Atom Transfer Radical Polymerization in Miniemulsion with a Dual Catalytic System

Miniemulsion ARGET ATRP via Interfacial and Ion-Pair Catalysis: From ppm to ppb of Residual Copper

AGET ATRP of Methyl Methacrylate Based on Thermoregulated Phase Transfer Catalysis in Organic/Aqueous Biphasic System: Facile and Highly Efficient In Situ Catalyst/Ligand Separation and Recycling

Contact Info

Product

Resources

About