An Immobilized/Soluble Hybrid Catalyst System for Atom Transfer Radical Polymerization

Hong, Sung Chul; Paik, Hyun‐jong; Matyjaszewski, Krzysztof

doi:10.1021/ma0101052

Cited by 85 publications

(143 citation statements)

References 15 publications

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“…Special handling procedures are often required to remove all oxygen and oxidants from these systems. Previous research intending to streamline the process and products of ATRP has focused on maximizing the efficiency of catalyst removal or recycling through the use of ion-exchange resins (13), biphasic systems (14), immobilized͞solid-supported catalysts (12), and immobilized͞soluble hybrid catalyst systems (15). By contrast, the work presented hereafter demonstrates how several recently developed ATRP initiation systems can be implemented to both scavenge oxidants and decrease the amount of catalyst needed (to ppm levels) where its removal or recycling would be unwarranted for many industrial applications.…”

mentioning

confidence: 99%

Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents

Matyjaszewski

Jakubowski

Min

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

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832

819

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The concept of initiators for continuous activator regeneration (ICAR) in atom transfer radical polymerization (ATRP) is introduced, whereby a constant source of organic free radicals works to regenerate the Cu I activator, which is otherwise consumed in termination reactions when used at very low concentrations. With this technique, controlled synthesis of polystyrene and poly-(methyl methacrylate) (Mw͞Mn < 1.2) can be implemented with catalyst concentrations between 10 and 50 ppm, where its removal or recycling would be unwarranted for many applications. Additionally, various organic reducing agents (derivatives of hydrazine and phenol) are used to continuously regenerate the Cu I activator in activators regenerated by electron transfer (ARGET) ATRP. Controlled polymer synthesis of acrylates (Mw͞Mn < 1.2) is realized with catalyst concentrations as low as 50 ppm. The rational selection of suitable Cu complexing ligands {tris[2-(dimethylamino)-ethyl]amine (Me6TREN) and tris[(2-pyridyl)methyl]amine (TPMA)} is discussed in regards to specific side reactions in each technique (i.e., complex dissociation, acid evolution, and reducing agent complexation). Additionally, mechanistic studies and kinetic modeling are used to optimize each system. The performance of the selected catalysts͞reducing agents in homo and block (co)polymerizations is evaluated.controlled radical polymerization ͉ electron transfer ͉ catalysis ͉ green chemistry ͉ block copolymer T he widespread industrial application of chemical synthetic techniques is often contingent upon the efficiency with which these processes can be implemented. This dependency is particularly true in the field of controlled radical polymerization (CRP). The vast array of polymeric materials that have been produced in the last decade by atom transfer radical polymerization (ATRP) (1, 2), an especially powerful CRP technique, is striking. The extraordinary control over topologies, compositions, microstructures, and functionalities (3-6) that ATRP can provide in polymeric synthesis has led to an explosive development in nanocomposites, thermoplastic elastomers, bioconjugates, drug delivery systems, etc. (7-10).While such polymers are finding industrial applications, (11), the large-scale production of these materials has been rather limited. This fact can be attributed mostly to the high catalyst concentrations required by ATRP, often approaching 0.1 M in bulk monomer. Added expense is therefore associated with purifying any polymers generated in these homogenous reactions (12). An additional problem of industrial relevance involves the use of highly active (i.e., very reducing) ATRP catalysts. Special handling procedures are often required to remove all oxygen and oxidants from these systems. Previous research intending to streamline the process and products of ATRP has focused on maximizing the efficiency of catalyst removal or recycling through the use of ion-exchange resins (13), biphasic systems (14), immobilized͞solid-supported catalysts (12), and immobilized͞soluble h...

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mentioning

confidence: 99%

Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents

Matyjaszewski

Jakubowski

Min

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

832

819

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“…Again a decrease in activity, indicating loss of metal, was reported. A two-component catalyst system with a polymer-bound and a soluble Cu species was reported by Matyjaszewski and co-workers [138]. As might have been anticipated, the metal contents were in the range of 15-150 mg /kg.…”

Section: Cu-and Rh-based Systemsmentioning

confidence: 65%

Transition metal-based polymer chemistry: a critical micro-review

Buchmeiser¹

2002

Designed Monomers and Polymers

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Abstract-This micro-review summarizes mainly recent (i.e. mostly later than 1995) and important developments in transition metal-catalyzed polymerization and their impact on polymer synthesis. It is not intended to be entirely comprehensive, yet will focus on signi cant improvements or interesting aspects in certain areas of polymer chemistry. For this particular reason, not all transition metal-based polymerizations will be fully covered. Instead, besides providing a 'snapshot' of the state of the art, it was a major intention to outline the main advantages and disadvantages of certain important polymerizations in a critical, yet hopefully objective way.

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“…In the recent literature [20 -22] there are also some examples of successful immobilization of catalysts that maintain their activity on a solid support. Matyjaszewski et al [23] reported a new two-component catalyst system consisting of an immobilized catalyst and a soluble catalyst in ppm quantities and applied this system in ATRP successfully. A high monomer conversion (>90%) was achieved with a predetermined molecular weight and narrow molecular weight distribution (M w /M n 1.1-1.3) in the ATRP of MMA and MA.…”

Section: Introductionmentioning

confidence: 99%

Immobilized copper catalyst for atom transfer radical addition and polymerization

Wang¹,

Yan²,

Fu³

et al. 2010

Applied Organom Chemis

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A novel multidentate amine grafted on silica gel and magnetic microsphere was prepared. Its chemical structure was confirmed by C 13 NMR, XPS and FTIR, and the nitrogen content was determined by elemental analysis. It was also used as a ligand for CuCl and successfully catalyzed the atom transfer radical addition of both carbon tetrachloride (CCl 4 ) to methyl methacrylate and methyl trichloroacetate to styrene, repeatedly. The conversion and purity of the product were determined through gas chromatography and 1 H NMR, respectively. The immobilized copper catalyst complex was also used in atom transfer radical polymerization of styrene initiated by 1,1,1,3-tetrachloro-3-phenylpropane and methyl methacrylate initiated by methyl 2-methyl-2,4,4,4-tetrachlorobutyrate, respectively. Although the polymerization took place successfully, it did not proceed in a controlled fashion.

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An Immobilized/Soluble Hybrid Catalyst System for Atom Transfer Radical Polymerization

Cited by 85 publications

References 15 publications

Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents

Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents

Transition metal-based polymer chemistry: a critical micro-review

Immobilized copper catalyst for atom transfer radical addition and polymerization

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