1999 Progress Report: Elimination of VOC's in the Synthesis and Application of Polymeric Materials Using Atom Transfer Radical Polymerization

EPA Grant Number: R826735
Title: Elimination of VOC's in the Synthesis and Application of Polymeric Materials Using Atom Transfer Radical Polymerization
Investigators: Matyjaszewski, Krzysztof
Institution: Carnegie Mellon University
EPA Project Officer: Hahn, Intaek
Project Period: October 1, 1998 through September 30, 2001
Project Period Covered by this Report: October 1, 1998 through September 30, 1999
Project Amount: $330,000
RFA: Technology for a Sustainable Environment (1998) RFA Text |  Recipients Lists
Research Category: Nanotechnology , Sustainability , Pollution Prevention/Sustainable Development


Atom transfer radical polymerization (ATRP) is an innovative technology for the preparation of well-defined (co)polymers with controlled molecular weight, polydispersity, composition, and functionalities. Such polymers can be recycled as thermoplastic elastomers and used without plastifiers. The polymers also have a strongly reduced content of organic solvents. ATRP can help reduce or eliminate volatile organic compunds (VOCs) from chemical processes, thereby protecting the environment and lowering hazardous waste costs. ATRP uses a transition metal catalyst and has successfully polymerized styrenes, (meth)acrylics, acrylonitrile, and other monomers to prepare well-defined block copolymers, hyperbranched (co)polymers, graft copolymers, gradient copolymers, telechelic (co)polymers, and others.

There is considerable industrial interest in ATRP because of the wide range of materials that can be prepared. The proposed research is focused on further improving ATRP by performing fundamental studies to develop next-generation catalysts (lowered amounts of catalyst required, and the development of solid-supported catalysts); determine the use of water-borne polymerization systems (suspensions, emulsions, and homogeneous polymerizations); and develop environmentally friendly polymerization processes and products.

Progress Summary:

Research has focused on three areas during the last year:

  1. Development of More Efficient Catalysts. We have used Cu-catalysts complexed with polydentate and tripodal ligands. These more efficient catalysts allow for a reduction in their concentrations from 1 percent to 0.01 percent versus monomer. Ligands such as tris[2-(dimethylamino)ethyl]amine (TREN) are excellent for the polymerization of various acrylates. In addition, various immobilized catalysts have been used because their recovery is easier.
  2. Water and CO2 as Reaction Medium for ATRP. ATRP has been performed successfully in CO2 by applying fluorinated ligands to complex Cu-catalysts. Polymerization in water was carried out under homogeneous conditions (2-hydroxyethyl acrylate) and in heterogeneous systems (suspensions, emulsions, and miniemulsions). The water-borne ATRP leads to stable latexes for various acrylates, methacrylates, and styrenes. The block copolymerization also was successful for water-borne systems. A key for the control in water is a proper choice of ligands (strongly hydrophobic) and surfactants (nonionic).
  3. Environmentally Friendly Products. Several products have been prepared, including polar thermoplastic elastomers (based on [meth]acrylates), telechelic products for solventless coatings, and self-plasticizing polyvinyl chloride (PVC).

Future Activities:

Continued research is planned in three areas: further development of more efficient catalysts together with their recovery and potential recycling; ATRP in water-borne systems; and more environmentally friendly polymeric materials.

Journal Articles on this Report : 6 Displayed | Download in RIS Format

Other project views: All 49 publications 16 publications in selected types All 15 journal articles
Type Citation Project Document Sources
Journal Article Kickelbick G, Paik H-J, Matyjaszewski K. Immobilization of the copper catalyst in atom transfer radical polymerization. Macromolecules 1999;32(9):2941-2947. R826735 (1999)
R826735 (Final)
  • Abstract: Macromolecules - Abstract
  • Journal Article Matyjaszewski K. Transition metal catalysis in controlled radical polymerization:atom transfer radical polymerization. Chemistry-A European Journal 1999;5(11):3095-3102. R826735 (1999)
    R826735 (Final)
  • Abstract: Wiley Online - Abstract
  • Journal Article Matyjaszewski K, Qiu J, Shipp DA, Gaynor SG. Controlled/"living" radical polymerization applied in water-borne systems. Macromolecular Symposia 2000;155(1):15-29. R826735 (1999)
    R826735 (2000)
    R826735 (Final)
  • Abstract: Wiley - Abstract
  • Journal Article Matyjaszewski K. Environmental aspects of controlled radical polymerization. Macromolecular Symposia 2000;152(1):29-42. R826735 (1999)
    R826735 (Final)
    R824995 (Final)
  • Abstract: Wiley Online-Abstract
  • Other: ReadCube-Preview
  • Journal Article Patten TE, Matyjaszewski K. Copper(I)-catalyzed atom transfer radical polymerization. Accounts of Chemical Research 1999;32(10):895-903. R826735 (1999)
    R826735 (Final)
  • Abstract: ACS-Abstract
  • Journal Article Xia JH, Johnson T, Gaynor SG, Matyjaszewski K, DeSimone J. Atom transfer radical polymerization in supercritical carbon dioxide. Macromolecules 1999;32(15):4802-4805. R826735 (1999)
    R826735 (Final)
  • Abstract: ACS-Abstract
  • Supplemental Keywords:

    water, air, chemicals, solvents, heavy metals, volatile organic compound, waste minimization, green chemistry, waste reduction, innovative technology., RFA, Scientific Discipline, Sustainable Industry/Business, Environmental Chemistry, Sustainable Environment, Technology for Sustainable Environment, atom transfer radical polymerization, cleaner production, environmentally benign solvents, alternative materials, catalysts, chemical reaction systems, solvent substitute, pollution prevention, Volatile Organic Compounds (VOCs), polymer design, alternative chemical synthesis, environmentally-friendly chemical synthesis, green chemistry

    Relevant Websites:

    http://polymer.chem.cmu.edu/ Exit EPA icon

    Progress and Final Reports:

    Original Abstract
  • 2000 Progress Report
  • Final Report