Catalytic processes for the controlled polymerization of free radically (Co)polymerizable monomers and functional polymeric systems prepared thereby
申请人:Carnegie Mellon University (a non-profit Pennsylvania organization)
公开号:US20040171779A1
公开(公告)日:2004-09-02
Further improvements have been made in processes for controlled polymerization of free radically (co)polymerizable monomers mediated by a transition metal complex participating in a redox reaction which involves transfer of a radically transferable atom or group to and from an initiator or dormant polymer and the growing active polymer chain ends. Two improvements involve the choice of counterion in the transition metal complex. In one improvement the transition metal is held in close conjunction with a solid support through interaction with a counterion directly attached to the support. This cognition also allows for improvements in catalyst utilization including catalyst recovery and recycle. In another improvement, particularly suitable for controlled polymerization of certain monomers with an expanded range of transition metals, the function of counterion and ligand in the development of the transition metal based catalyst is superseded by use of salt containing a soluble organic counterion. These and other process improvements have been employed to prepare an extended range of novel polymeric materials and novel processes for the preparation of functional polymers including a novel catalytic Atom Transfer Coupling Reaction.
A polymerization process is provided for the preparation of graft (co)polymers. An embodiment of the polymerization process of the present invention comprises copolymerizing macromonomers with (co)monomers utilizing a macroinitiator to form a graft (co)polymer. A further embodiment of a polymerization process of the present invention comprises (co)polymerizing macromonomers and monomers with a graft copolymer macroinitiator to form a block-graft (co)polymer. Another embodiment of the process of the present invention comprises (co)polymerizing macromonomers and monomers with a compatible macroinitiator. The chemical and structural properties of the product graft (co)polymer may be controlled by use of a compatible macroinitiator and the functional group on the macromonomer which effect the relative rates of incorporation of the macromonomer and the monomer. Graft (co)polymers may be prepared with homogeneous or heterogeneous distribution of grafts. In a further embodiment of the present invention, a copolymer with well-defined branches or grafts with predetermined molecular weights and low polydispersities can be obtained by preparing macromonomers by a living or a living/controlled polymerization process.
Patterning of a Surface Immobilized ATRP Initiator with an Inkjet Printer
作者:Sebastian G. J. Emmerling、Laura B. N. Langer、Sascha A. Pihan、Philipp Lellig、Jochen S. Gutmann
DOI:10.1021/ma902836n
日期:2010.6.8
A new technique for patterning polymer brushes on the micrometer scale has been developed in which an inkjet printer was used to deposit droplets of acid on a surface-immobilized initiator for atom transfer radical polymerization (ATRP). The acid cleaved an ester bond in the ATRP initiator in a saponification reaction. As a result. the ATRP initiator was rendered inactive. To control the degree of defunctionalization, a new initiator containing a weak ester bond was derived from a tertiary alcohol. Comparison to an established ATRP initiator, derived from a primary alcohol, showed that the novel initiator was defunctionalized with a higher efficiency. Control of the reaction time allowed to partially defunctionalize the initiator molecules, leading to control of grafting densities within the written patterns.
CATALYTIC PROCESSES FOR THE CONTROLLED POLYMERIZATION OF FREE RADICALLY (CO)POLYMERIZABLE MONOMERS AND FUNCTIONAL POLYMERIC SYSTEMS PREPARED THEREBY
申请人:CARNEGIE MELLON UNIVERSITY
公开号:EP1171496A1
公开(公告)日:2002-01-16
Catalytic processes for the controlled polymerization of free radically (co) polymerizable monomers and functional polymeric systems prepared thereby