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Extramural Research

2003 Progress Report: Towards Elimination of Transition Metals and VOCs from the Environmentally Benign Materials Made by Atom Transfer Radical Polymerization (ATRP)

EPA Grant Number: R829580
Title: Towards Elimination of Transition Metals and VOCs from the Environmentally Benign Materials Made by Atom Transfer Radical Polymerization (ATRP)
Investigators: Matyjaszewski, Krzysztof , Iovu, Mihaela , Lee, Sang Boom , Li, Mei , Tsarevsky, Nick
Current Investigators: Matyjaszewski, Krzysztof , Braunecker, Wade , Iovu, Mihaela , Itami, Yujiro , Lee, Sang Boom , Li, Mei , Lutz, Jean Francois , McKenzie, Blayne , Min, Ke , Tsarevsky, Nick
Institution: Carnegie Mellon University
Current Institution: Carnegie Mellon University
EPA Project Officer: Richards, April
Project Period: January 1, 2002 through December 31, 2004
Project Period Covered by this Report: January 1, 2003 through December 31, 2004
Project Amount: $350,000
RFA: Technology for a Sustainable Environment (2001)
Research Category: Nanotechnology , Pollution Prevention/Sustainable Development



The objective of this research project is to eliminate transition metals and volatile organic compounds (VOCs) from the materials synthesized by atom transfer radical polymerization (ATRP). This requires improvement of the catalytic system as well as the selection of environmentally friendly media, including solventless bulk polymerization, for carrying out the polymerization (e.g., in water).

Progress Summary:

During Year 2 of the project, we focused on the synthesis of well-defined polymers, including block, random, and gradient copolymers and end functional copolymers using an immobilized/soluble hybrid ATRP catalyst, as well as aqueous miniemulsion. The first ever well-defined star block copolymers were prepared in waterborne media.

A level of residual catalyst in these systems was reduced by 1,000 times from approximately 10,000 ppm (1%) to 10 ppm without a loss of molecular control. Moreover, a specially designed ligand with alkoxysilyl group, which can either crosslink in the presence of water or be trapped by silicagel, reduced a level of residual copper below 1 ppm.

We successfully adopted ATRP to miniemulsion. Because of the correct selection of ligands and surfactants, the content of solids nearly doubled (from 13 to 20%) and the amount of surfactant decreased sixfold (from 13 to 2%) versus monomer. Moreover, simultaneous reverse and normal initiation processes allowed for a decrease in the amount of copper five to eight times in comparison with a regular reverse ATRP. The removal of copper from miniemulsion is facilitated by a large surface area of colloidal dispersion of nanoparticles.

Collaborations With Industry

At Carnegie Mellon University, we have an industrial consortium on Controlled Radical Polymerization. There are approximately 15 members who come to the semiannual meetings at Carnegie Mellon University. We signed four license agreements and commercialization is at different stages, but they cannot be disclosed specifically.

Examples of Commercial Application

At the American Chemical Society (ACS) Anaheim Meeting at the Symposium honoring the Principal Investigator for his ACS Award in Cooperative Research in Polymer Science and Engineering, representatives from PPG, Ciba, Degussa, and Kaneka will discuss their projects related to ATRP. Information indicates that the research has or soon will lead to applications with positive environmental outcomes.

Other Relevant Information

Nick Tsarevsky received an ACS 2003 Kenneth G. Hancock Memorial Award in Green Chemistry for graduate students. In addition, he got the award from the Pittsburgh ACS section for the best graduate research. Kris Matyjaszewski received an ACS 2004 Award in Cooperative Research in Polymer Science and Engineering.

Future Activities:

We will continue our work in environmentally friendly media and prepare well-defined polymers and block copolymers in water and in bulk to reduce VOCs. This will include homogeneous polymerization in water with more active catalysts adopted for emulsion/suspension systems. We also will start our work on degradable polymers.

Journal Articles on this Report : 9 Displayed | Download in RIS Format

Other project views: All 42 publications 23 publications in selected types All 18 journal articles

Type Citation Project Document Sources
Journal Article Gromada J, Spanswick J, Matyjaszewski K. Synthesis and ATRP activity of new TREN-based ligands. Macromolecular Chemistry and Physics 2004;205(5):551-566. R829580 (2003)
R829580 (Final)
  • Abstract: Wiley Online-Abstract
  • Journal Article Hong SC, Lutz J-F, Inoue Y, Strissel C, Nuyken O, Matyjaszewski K. Use of an immobilized/soluble hybrid ATRP catalyst system for the preparation of block copolymers, random copolymers, and polymers with high degree of chain end functionality. Macromolecules 2003;36(4):1075-1082. R829580 (2002)
    R829580 (2003)
    R829580 (Final)
  • Abstract: ACS -Abstract
  • Journal Article Hong SC, Neugebauer D, Inoue Y, Lutz J-F, Matyjaszewski K. Preparation of segmented copolymers in the presence of an immobilized/soluble hybrid ATRP catalyst system. Macromolecules 2003;36(1):27-35. R829580 (2002)
    R829580 (2003)
    R829580 (Final)
  • Abstract: American Chemical Society - Abstract
  • Journal Article Lee SB, Russell AJ, Matyjaszewski K. ATRP synthesis of amphiphilic random, gradient, and block copolymers of 2-(dimethylamino)ethyl methacrylate and n-butyl methacrylate in aqueous media. Biomacromolecules 2003;4(5):1386-1393. R829580 (2003)
    R829580 (Final)
  • Abstract from PubMed
  • Abstract: ACS - Abstract
  • Journal Article Li M, Matyjaszewski K. Reverse atom transfer radical polymerization in miniemulsion. Macromolecules 2003;36(16):6028-6035. R829580 (2003)
    R829580 (Final)
  • Abstract: ACS - Abstract
  • Journal Article Lutz J-F, Matyjaszewski K. Kinetic modeling of the chain-end functionality in atom transfer radical polymerization. Macromolecular Chemistry and Physics 2002;203(10-11):1385-1395. R829580 (2003)
    R829580 (Final)
  • Abstract: Wiley - Abstract
  • Journal Article Matyjaszewski K. From atom transfer radical addition to atom transfer radical polymerization. Current Organic Chemistry 2002;6(2):67-82. R829580 (2003)
  • Abstract: Bentham Science - Abstract
  • Journal Article Li M, Min K, Matyjaszewski K. ATRP in waterborne miniemulsion via a simultaneous reverse and normal initiation process. Macromolecules 2004;37(6):2106-2112. R829580 (2003)
    R829580 (Final)
  • Abstract: American Chemical Society - Abstract
  • Journal Article Sarbu T, Pintauer T, McKenzie B, Matyjaszewski K. Atom transfer radical polymerization of styrene in toluene/water mixtures. Journal of Polymer Science, Part A: Polymer Chemistry 2002;40(18):3153-3160. R829580 (2002)
    R829580 (2003)
    R829580 (Final)
  • Abstract: Wiley - Abstract
  • Supplemental Keywords:

    water, bulk, volatile organic compounds, VOCs, heavy metals, solvents, recycling, modeling, environmental polymer chemistry, atom transfer radical polymerization, ATRP, block copolymers, random copolymers, gradient copolymers, ATRP catalyst, miniemulsion, nanoparticles,, RFA, Scientific Discipline, Sustainable Industry/Business, cleaner production/pollution prevention, Sustainable Environment, Chemistry, Technology for Sustainable Environment, Civil/Environmental Engineering, New/Innovative technologies, Chemistry and Materials Science, Engineering, Environmental Engineering, transition metal catalysts, environmental problems and polymers, catalysts, modeling, polymerization chemistry, atom transfer radical polymerization (ATRP), recycling, polymers, homogeneous catalysis, environmentally benign catalysts, environmentally benign alternative, pollution prevention, Volatile Organic Compounds (VOCs), polymer design, heavy metals

    Relevant Websites:

    http://www.chem.cmu.edu/groups/maty Exit


    http://membership.acs.org/P/PMSE/awards/coop.html Exit

    http://www.chem.cmu.edu/about/news/about-news-200305-tsarev.html Exit

    Progress and Final Reports:
    Original Abstract
    2002 Progress Report
    Final Report

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    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.

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