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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: R829580Title: 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: Pollution Prevention/Sustainable Development
Description:
Objective: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 : 15 Displayed | Download in RIS Format
| Other project views: | All 48 publications | 31 publications in selected types | All 29 journal articles |
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Davis KA, Matyjaszewski K. Statistical, Gradient and Segmented Copolymers by Controlled/Living Radical Polymerizations. Advances In Polymer Science. 2002;159:1-13. |
R829580 (2002) R829580 (2003) R829580 (Final) |
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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) |
not available |
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Hong SC, Matyjaszewski K. An immobilized/soluble hybrid catalyst systems for atom transfer radical polymerization. Abstracts of Papers of the American Chemical Society 2002;224(POLY Pt 2):460 |
R829580 (2003) R829580 (Final) |
not available |
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Hong SC, Neugebauer D, Inoue Y, Lutz JF, 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) |
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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 chain end functionality. Macromolecules 2003;36(4):1075-1082. |
R829580 (2002) R829580 (2003) R829580 (Final) |
not available |
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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) |
not available |
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Li M M, Matyjaszewski K. Reverse atom transfer radical polymerization in miniemulsion. Macromolecules 2003;36(16):6028-6035. |
R829580 (2003) R829580 (Final) |
not available |
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Lutz JF, Matyjaszewski K. 600 MHz 1h NMR study of chain-end functionality in atom transfer radical polymerization. Abstracts of Papers of the American Chemical Society 2002;224(POLY Pt 2):479 |
R829580 (2003) R829580 (Final) |
not available |
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Lutz JF, Matyjaszewski K. Synthesis of graft terpolymers poly(alkyl methacrylate)-g-poly(D-lactic acid)/poly(dimethyl siloxane) using the grafting through method in atom transfer radical polymerization. Abstracts of Papers of the American Chemical Society 2002;224(POLY Pt 2):480 |
R829580 (2003) R829580 (Final) |
not available |
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Lutz JF, 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) |
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Matyjaszewski K. From atom transfer radical addition to atom transfer radical polymerization. Current Organic Chemistry 2002;6(2):67-82. |
R829580 (2003) |
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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) |
not available |
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Sarbu T, Pintauer T, McKenzie B, Matyjaszewski K. ATRP 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) |
not available |
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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):3153-3163. |
R829580 (2003) R829580 (Final) |
not available |
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Sarbu T, Matyjaszewski K. Iron and copper mediated ATRP of methyl methacrylate in the presence of ionic liquids. ACS Polymer Preprints 2002;43(2):211. |
R829580 (2002) R829580 (2003) R829580 (Final) |
not available |
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,
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Sustainable Industry/Business, Scientific Discipline, RFA, Technology for Sustainable Environment, Sustainable Environment, Civil/Environmental Engineering, Chemistry, Environmental Engineering, cleaner production/pollution prevention, Chemistry and Materials Science, New/Innovative technologies, Engineering, heavy metals, Volatile Organic Compounds (VOCs), catalysts, solvents, homogeneous catalysis, recycling, polymer design, environmentally benign catalysts, environmental problems and polymers, polymers, polymerization chemistry, modeling, transition metal catalysts, atom transfer radical polymerization (ATRP), pollution prevention
Relevant Websites:
http://www.chem.cmu.edu/groups/maty
http://epa.gov/ncer/events/news/2002/08_20_02b.html
http://membership.acs.org/P/PMSE/awards/coop.html
http://www.chem.cmu.edu/about/news/about-news-200305-tsarev.html
Progress and Final Reports:
2002 Progress Report
Original Abstract
Final Report