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Extramural Research

Final 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: Karn, Barbara
Project Period: October 1, 1998 through September 30, 2001
Project Amount: $330,000
RFA: Technology for a Sustainable Environment (1998)
Research Category: Nanotechnology , Pollution Prevention/Sustainable Development

Description:

Objective:

Atom transfer radical polymerization (ATRP) uses a transition metal catalyst to prepare well-defined (co)polymers with controlled molecular weight, polydispersity, composition, and functionalities. This innovative technique enables facile synthesis of novel environmentally friendly materials such as polar thermoplastic elastomers, coatings with the reduced amount of VOCs, or even solventless coatings. Other specialty materials such as efficient non-ionic surfactants, dispersants, lubricants, and adhesives, also are readily achievable. Thus, ATRP has a potential strong impact on various environmental aspects, and can help to reduce or eliminate VOCs from chemical processes and to lower hazardous waste costs.

The proposed research was focused on further improvement of ATRP by performing fundamental studies to develop: next generation catalysts (lower the amount of catalyst required and develop solid-supported catalysts); use of water-borne polymerization systems (suspensions, emulsion, homogeneous polymerizations); and environmentally friendly polymerization processes and products.

Summary/Accomplishments (Outputs/Outcomes):

We have focused on three areas:
  1. Environmentally friendly products. A number of well-defined water-soluble homopolymers, amphiphilic block copolymers, and gradient copolymers have been synthesized. These products potentially can be applied as non-ionic surfactants and blend compatibilizers. In addition, we prepared polar thermoplastic elastomers (based on [meth]acrylates), telechelic products for solventless coatings, and self-plasticizing PVC.

  2. Water and CO2 as reaction medium for ATRP. We have successfully performed ATRP in CO2 by application of 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 led to stable latexes for various acrylates, methacrylates, and styrenes. Moreover, the first block copolymerization also was successful for water-borne systems. A better mechanistic understanding of the novel system was achieved in terms of kinetics, molecular weight control, and colloidal stability. A key for the control in water is a proper choice of ligands (strongly hydrophobic) and surfactants (non-ionic). Stable latexes with particle size below micrometer were obtained using conventional radical initiators or miniemulsion processes. These latexes potentially can be used as water-based coatings.

  3. Improvement on the catalytic system. Fundamental studies were carried out to gain a deeper understanding of the catalyst structures and correspondingly the activity in ATRP. The metal complex remaining in the polymer product can be effectively removed using ion- exchanging resins. More efficient catalysts were developed. We have used Cu-catalysts complexed with polydentate and tripodal ligands. These more efficient catalysts allowed the reduction of their concentrations from 1 percent to 0.01 percent versus monomer. Ligands such as TREN are excellent for polymerization of various acrylates. In addition, we have used various immobilized and hybrid catalysts for their easier recovery.

We have accomplished the planned activity that was summarized in more than 30 publications and one patent; and we also presented at several national and international meetings. The research funded by EPA has been relevant not only to academia, but also to industry, because ATRP and other controlled/living radical polymerizations should be commercialized this year.


Journal Articles on this Report : 14 Displayed | Download in RIS Format

Other project views: All 48 publications 15 publications in selected types All 14 journal articles

Type Citation Project Document Sources
Journal Article Davis KA, Charleux B, Matyjaszewski K. Preparation of block copolymers of polystyrene and poly (t-butyl acrylate) of various molecular weights and architectures by atom transfer radical polymerization. Journal of Polymer Science Part A-Polymer Chemistry 2000;38(12):2274-2283. R826735 (2000)
R826735 (Final)
  • Abstract: Wiley Online-Abstract
    Exit
  • Journal Article Gaynor SG, Qiu J, Matyjaszewski K. Controlled/"living" radical polymerization applied to water-borne systems. Macromolecules 1998;31(17):5951-5954. R826735 (Final)
  • Abstract: ACS - Citation
    Exit
  • 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
    Exit
  • 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
    Exit
  • Journal Article Matyjaszewski K, Shipp DA, Qiu J, Gaynor SG. Water-borne block and statistical copolymers synthesized using atom transfer radical polymerization. Macromolecules 2000;33(7):2296-2298. R826735 (2000)
    R826735 (Final)
  • Abstract: ACS-Abstract
    Exit
  • 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
    Exit
  • Journal Article Matyjaszewski K, Qiu J, Tsarevsky NV, Charleux B. Atom transfer radical polymerization of n-butyl methacrylate in aqueous dispersed systems: a miniemulsion approach. Journal of Polymer Science Part A-Polymer Chemistry 2000;38(Suppl 1):4724-4734. R826735 (2000)
    R826735 (Final)
  • Abstract: Wiley Online-Abstract
    Exit
  • Journal Article Matyjaszewski K, Ziegler MJ, Arehart SV, Greszta D, Pakula T. Gradient copolymers by atom transfer radical copolymerization. Journal of Physical Organic Chemistry 2000;13(12):775-786. R826735 (2000)
    R826735 (Final)
  • Abstract: Wiley Online-Abstract
    Exit
  • Journal Article Matyjaszewski K, Pintauer T, Gaynor S. Removal of copper-based catalyst in atom transfer radical polymerization using ion exchange resins. Macromolecules 2000;33(4):1476-1478. R826735 (2000)
    R826735 (Final)
  • Abstract: ACS-Abstract
    Exit
  • 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-Abstract
    Exit
  • 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
    Exit
  • Journal Article Pintauer T, Jasieczek CB, Matyjaszewski K. Electrospray ionization mass spectrometric study of CuI and CuII bipyridine complexes employed in atom transfer radical polymerization. Journal of Mass Spectrometry 2000;35(11):1295-1299. R826735 (2000)
    R826735 (Final)
  • Abstract from PubMed
  • Abstract: Wiley Online-Abstract
    Exit
  • Journal Article Qiu J, Pintauer T, Gaynor SG, Matyjaszewski K, Charleux B, Vairon J-P. Mechanistic aspect of reverse atom transfer radical polymerization of n-butyl methacrylate in aqueous dispersed system. Macromolecules 2000;33(20):7310-7320. R826735 (2000)
    R826735 (Final)
  • Abstract: ACS-Abstract
    Exit
  • 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
    Exit
  • Supplemental Keywords:

    water, air, chemicals, solvents, heavy metals, VOC, 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
    1999 Progress Report
    2000 Progress 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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