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Final 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 , Braunecker, Wade , Iovu, Mihaela , Itami, Yujiro , Lee, Sang Boom , Li, Mei , Lutz, Jean Francois , McKenzie, Blayne , Min, Ke , Tsarevsky, Nick
Institution: Carnegie Mellon University
EPA Project Officer: Richards, April
Project Period: January 1, 2002 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 was to eliminate the transition metal and volatile organic compounds (VOCs) from the materials synthesized by atom transfer radical polymerization (ATRP). This required improvement to the catalytic system as well as selection of environmentally friendly media, including solventless bulk polymerization, for carrying out the polymerization (e.g., in water).
Summary/Accomplishments (Outputs/Outcomes):The primary focus has been on the synthesis of well-defined polymers—including block, random, and gradient copolymers and end functional copolymers—by ATRP in aqueous media. Several monomers were polymerized in a controlled fashion in aqueous media for the first time, including monomers with ammonium or sulfonate groups. The factors affecting the performance of ATRP catalysts and rules for selection of complexes suitable for the ATRP of hydrophilic monomers in aqueous media were outlined. Several side reactions taking place in aqueous ATRP and ways to suppress them were described quantitatively. This will expand the utility of aqueous ATRP.
We successfully carried out ATRP of several monomers in aqueous miniemulsion. By correct selection of ligands and surfactants, the content of solids nearly doubled, from 13 to 20 percent, and the amount of surfactant was reduced six-fold, from 13 percent to 2 percent, versus monomer. Moreover, simultaneous reverse and normal initiation processes allowed a decrease in the amount of copper five to eight times compared to a regular reverse ATRP. Additionally, removal of copper from miniemulsion is facilitated by a large surface area of colloidal dispersion of nanoparticles.
For the first time, miniemulsion polymerization was applied to the synthesis of hybrid materials such as polymer-silica composites, where the reaction could be carried out until high monomer conversion was reached. Moreover, the range of synthesized polymeric materials synthesized by ATRP in miniemulsion was extended to star-shaped copolymers with segmented (blocky) structure of the arms.
The concentration of catalyst in ATRP systems was reduced substantially using a suitable reducing agent: from approximately 10,000 ppm (1%) to 10 ppm or less without a loss of molecular control.
Novel biodegradable materials (including linear polymers, star copolymers, and polymeric gels) were prepared by ATRP using initiators and/or monomers containing the disulfide functionality, which can be reversibly cleaved in reducing environments.
Conclusions:At Carnegie Mellon, we have established an industrial consortium on Controlled Radical Polymerization. There are approximately 15 members who come to semiannual meetings at Carnegie Mellon. We signed six license agreements. Commercialization is at different stages, but we cannot disclose them precisely. At the 2004 American Chemical Society (ACS) National 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 discussed their projects related to ATRP. To evaluate the performance of a catalyst for aqueous ATRP, the determination of stability constants of various metal complexes is crucial. For this purpose, we have started a collaboration with expert coordination chemists, including Professors Alberto Vacca (University of Florence) and Peter Gans (Leeds University).
During the period 2003-2005, Dr. Matyjaszewski received a 2004 ACS Award in Cooperative Research in Polymer Science and Engineering. Nick Tsarevsky was recognized with an ACS 2003 Kenneth G. Hancock Memorial Award in Green Chemistry for graduate students. In addition, he received the award from the Pittsburgh ACS section for the best graduate research. He also was awarded the 2004 ACS Excellence in Graduate Polymer Research award for his work on the rational design of ATRP catalysts for aqueous media.
We plan to continue our work in environmentally friendly reaction media and to prepare well-defined double hydrophilic block copolymers in aqueous media. The theoretical description of the factors governing catalyst performance will lead to the development of novel, more active ATRP catalysts that can be used at low (ppm) concentrations. To evaluate the performance of metal complexes as ATRP catalysts, the determination of stability constants will be necessary. Not only aqueous homogeneous but also aqueous dispersed systems will be studied, including the relatively insufficiently studied reverse miniemulsion polymerization. The work on (bio)degradable polymers with biomedical applications, including tissue engineering and drug delivery, will be continued.
Journal Articles on this Report : 27 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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Davis KA, Matyjaszewski K. Effect of (pseudo)halide initiators and copper complexes with non-halogen anions on the atom transfer radical polymerization. Journal of Macromolecular Science, Part A-Pure and Applied Chemistry 2004;41(5):449-465. |
R829580 (Final) |
not available |
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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) |
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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) |
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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) |
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Li Mei, Jahed NM, Min Ke, Matyjaszewski K. Preparation of linear and star-shaped block copolymers by ATRP using simultaneous reverse and normal initiation process in bulk and miniemulsion. Macromolecules 2004;37(7):2434-2441. |
R829580 (Final) |
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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) |
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Lutz JF, Jahed N, Matyjaszewski K. Preparation and characterization of graft terpolymers with controlled molecular structure. Journal of Polymer Science, Part A: Polymer Chemistry 2004;42(8):1939-1952. |
R829580 (Final) |
not available |
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Lutz JF, Matyjaszewski K. NMR monitoring of chain-end functionality in atom transfer radical polymerization of styrene. Journal of Polymer Science, Part A: Polymer Chemistry 2005;43(4):897-910. |
R829580 (Final) |
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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) |
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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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Lutz JF, Matyjaszewski K. Nuclear magnetic resonance monitoring of chain-end functionality in the atom transfer radical polymerization of styrene. Journal of Polymer Science Part A-Polymer Chemistry 2005;43(4):897-910 |
R829580 (Final) |
not available |
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Matyjaszewski K, Spanswick J. Controlled/living radical polymerization. Materials Today 2005;8(3):26-33. |
R829580 (Final) |
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Min Ke, Li Mei, Jahed NM, Matyjaszewski K. Synthesis of star block copolymers via SR&NI ATRP in minimemulsion. American Chemical Society Polymer Preprints 2004;45(2):682-683. |
R829580 (Final) |
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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) |
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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) |
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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) |
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Sun F, Sheiko SS, Moeller M, Beers K, et al. Conformational switching of molecular brushes in response to the surface energy of the substrate. Journal of Physical Chemistry A 2004;108(45):9682-9686. |
R829580 (Final) |
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Sarbu T, Lin KY, Spanswick J, Gil RR, Siegwart DJ, Matyjaszewski K. Synthesis of hydroxy-telechelic poly(methyl acrylate) and polystyrene by atom transfer radical coupling. Macromolecules 2004;37(26):9694-9700 |
R829580 (Final) |
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Tsarevsky NV, Pintauer T, Matyjaszewski K. Deactivation efficiency and degree of control over polymerization in ATRP in protic solvents. Macromolecules 2004;37(26):9768-9778 |
R829580 (Final) |
not available |
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Tsarevsky NV, Matyjaszewski K. Rational design of the catalyst for atom transfer radical polymerization in aqueous media. American Chemical Society Polymer Preprints 2004;45(2):89-90. |
R829580 (Final) |
not available |
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Tsarevsky NV, Matyjaszewski K. Synthesis of well-defined (co)polymers with ionic or ionizable groups by ATRP. American Chemical Society Polymer Preprints 2004;45(2):288-289. |
R829580 (Final) |
not available |
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Tsarevsky NV, Matyjaszewski K. Combining atom transfer radical polymerization and disulfide /thiol redox chemistry: a route to well-defined (Bio)degradable polymeric materials. Macromolecules 2005;38(8):3087-3092. |
R829580 (Final) |
not available |
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Tsarevsky NV, Matyjaszewski K. Synthesis of well-defined (Bio)degradable polymeric materials with disulfide bonds by atom transfer radical polymerization. American Chemical Society Polymer Preprints 2005;46(1):339-340. |
R829580 (Final) |
not available |
water, bulk, VOC, heavy metals, solvents, recycling,
modeling, environmental polymer chemistry, degradable polymers, atom transfer
radical polymerization,
,
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.epa.gov/ncer/events/news/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
2003 Progress Report
Original Abstract