IonE & IREE Projects Database

Sustainable Polymers: Tomorrow's Advanced Materials

Status: Closed Start Date: 05/25/2009
Project Number: RL-0009-09 End Date: 06/30/2012
Amount Awarded: $800,000 Leveraged Funds: $674,558

Principal Investigator
Marc Hillmyer Chemistry, CSE (UMNTC)

Co PIs
William Tolman Chemistry, CSE (UMNTC)
Frank Bates Chemical Engineering and Material Science, CSE (UMNTC)
Thomas Hoye Chemistry, CSE (UMNTC)
Chris Macosko Chemical Engineering and Material Science, CSE (UMNTC)
Steve Severtson Bioproducts and Biosystems Engineering, CFANS (UMNTC)
William Tolman Chemistry, CSE (UMNTC)

Project Overview

The two goals of this project are to design, prepare and implement advanced polymers derived from renewable resources for a wide range of applications and to establish a center for sustainable polymers at the University of Minnesota. Polymers are found in a variety of materials, like plastics, rubber, and glue. The researchers hope to decrease dependence on fossil fuels by replacing petroleum-based polymers with energy-efficient and environmentally friendly polymer technologies that capitalize on the biobased products market. Currently, researchers are seeking to develop commercially feasible and renewably resourced pressure-sensitive adhesives, toughened plastics and polyurethanes. This project is leveraging partners in industry to accomplish its goals, gaining funding and applied knowledge. Establishing a Center for Sustainable Polymers at the U of M facilitates the cultivation of the governmental, industrial and academic partnerships required to create a sustainable polymer industry. The proposed Center also provides infrastructure and support for the development of other sustainable large-scale industrial materials currently dependent on petroleum-based raw materials.

www.chem.umn.edu/CSP

Project Impacts

(1) We have developed several new renewable polyester and polyether polyols for both thermoplastic and
thermosetting polyurethanes. The precision synthesis of these new polyols using catalytic ring-opening
polymerization has allowed for the systematic tuning of polyurethane properties. These new polyurethane
structures are currently being explored as replacements for petroleum-based systems that have broad utility
in applications ranging from elastomers to adhesives.
(2) We have discovered a simple and efficient method for the conversion of carboxylic acid containing
molecules derived from biomass into olefins through a catalytic decarbonylation process. We successfully
demonstrated that the monomers styrene, several acrylates, and acrylonitrile could be prepared on
preparative scale from abundant starting materials. This work has recently been published. In our most recent
effort, we have identified inexpensive metal/ligand systems that render this process even more efficient using
a high-throughput approach.
(3) A fundamentally important advance in the understanding of how cyclic ester polymerization catalysts
operate has come from center research and was recently published. In this work, the deconvolution of the
monomer coordination and monomer insertion events in a series of metal alkoxide catalysts was
accomplished through a detailed kinetic study. This key finding will enable the development of next
generation cyclic ester polymerization catalysts that are more active and selective. This is the first
demonstration of a deeper understanding of these ubiquitous catalysts systems, and will have lasting impact
in the field.
(4) New renewable thermoplastic elastomers were discovered and developed, using a combination of
controlled polymer synthesis techniques. These materials combine a soft aliphatic polyester midblock derived
from the natural product menthol with hard end blocks derived from the natural product tulipalin A. The
important finding here is not only the renewable nature of the materials, but also the advanced properties
carried by these materials by virtue of the unusually high glass transition temperature of the hard end blocks.
Unlike both their petroleum and other renewable analogs, these materials have outstanding mechanical
performance at elevated temperature thus expanding the applicability of this class of hybrid macromolecules.
This work will be submitted for publication shortly.
(5) Multiblock polymers exhibit properties that are often significantly superior to their di- and triblock
counterparts. We have prepared and characterized a new class of multiblock polymers that contain
polylactide as a majority component. The aim is to develop new tougher, stronger, and more durable versions
of this leading biorenewable polymer. A pair of efficient synthetic protocols have been demonstrated and
initial results on the phase behavior of these new systems are promising.
(6) We prepared a set of polyester macromonomers and used them as a renewable component in
miniemulsion polymerization system for the preparation of new water-borne adhesives. These new adhesives
contain a significant fraction of renewable content and show performance that is comparable or superior to
analogous commercial products. This new system represents a significant advance in the development of
renewable adhesives and we will submit a manuscript for publication on these results in the near future.
By establishing the Center for Sustainable Polymers (CSP), not only have the scientific advances noted above
been achieved, but an infrastructure was created that has resulted in leveraging more than $170,000 in gifts
from industrial partners and another $1.5 million from the NSF (in conjunction with IREE award RM-0017-11).
The CSP is also now eligible to receive another $20 million from the NSF in 2014 (application and decision
pending) to further this research. The CSP has also provided the public with the opportunity to learn about
our research by partnering with the Minnesota Pollution Control Agency and hosting a booth in their Eco-
Experience Building at the Minnesota State Fair, hosting workshops for high school teachers, and working
with elementary and middle-school students on projects related to energy, energy consumption, and
concepts of sustainability. Moreover through partnerships with the Center for Science, Technology, and Public Policy and the Bio-Business Alliance of Minnesota we have co-hosted tours of bio-based chemical companies and round tables for MN State Commissioners and the Governor’s Office.

Patents

  • US Application (2010) Hillmyer, M. A.; Theryo, G. C.; Jing, F. "Polylactide Copolymers"

Publications

  • Gramlich, W. M.; Robertson, M. L.; Hillmyer, M. A. – Reactive Compatibilization of Poly(L-lactide) and Conjugated Soybean Oil – Macromolecules 2010, 43, 2313–2321.
  • Robertson, M. L; Hillmyer, M. A.; Mortamet, A. -C.; Ryan, A. J. "Biorenewable Multiphase Polymers". MRS Bulletin, in press.
  • Pietrangelo, A.; Knight, S. C.; Gupta, A. K.; Yao, L. J.; Hillmyer, M. A.; Tolman, W. B. – Mechanistic Study of the Stereoselective Polymerization of D,L-Lactide using Indium(III) Halides – J. Am. Chem. Soc. Submitted 5 May 2010.
  • Theryo, G.; Jing, F.; Pitet, L. M.; Hillmyer, M. A. – Tough polylactide graft copolymers – Macromolecules submitted 24 May 2010.
  • Robertson, M. L.; Chang, K.; Gramlich, W. M.; Hillmyer, M .A. – Toughening of Polylactide with Polymerized Soybean Oil – Macromolecules 2010, 43, 1807–1814.
  • Shin, J.; Martello, M. T.; Tolman, W. B. – Pressure-Sensitive Adhesives from Renewable Triblock Copolymers – Macromolecules 2011, 44, 87–94
  • S. Tan, T. Abraham, D. Ference and C.W. Macosko, “Rigid Polyurethane Foam from a Soybean oil-based Polyol” Polymer 52, 2011, 2840-2846.
  • "Renewable Resource Block Polymers"ANTEC 2010 (Keynote) – Orlando, Florida – May 2010
  • "Renewable Resource Block Polymers" Virginia Tech Technical Conference and Review (Plenary) – Blacksburg, Virginia – October 2010
  • "Renewable thermoplastic elastomers and tough plastics" 241st ACS National Meeting – Anaheim, California – March 2011
  • Ding, K; Miranda, MO; Moscato-Goodpaster, B; Agellal, N.; Breyfogle, LE; Hermes, ED; Schaller, CP; Roe, SE; Cramer, CJ; Hillmyer MA; Tolman, WB, "The Roles of Monomer Binding and Alkoxide Nucleophilicity in Aluminum-Catalyzed Polymerization of e-Caprolactone",Macromolecules, p. 5387-5396, vol. 45, (2012).
  • Gramlich, WM; Theryo, G; Hillmyer, MA, "Copolymerization of isoprene and hydroxyl containing monomers by controlled radical and emulsion methods", POLYMER CHEMISTRY, p. 1510-1516, vol. 3, (2012)
  • Du, A; Koo, D; Theryo, G; Hillmyer, MA; Cairncross, RA, "Water transport and clustering behavior in homopolymer and graft copolymer polylactide", JOURNAL OF MEMBRANE SCIENCE, p. 50, vol. 396, (2012).
  • Martello, MT; Burns, A; Hillmyer, M, "Bulk Ring-Opening Transesterification Polymerization of the Renewable delta-Decalactone Using an Organocatalyst", ACS MACRO LETTERS, p. 131, vol. 1, (2012).
  • Miranda, MO; Pietrangelo, A; Hillmyer, MA; Tolman, WB, "Catalytic decarbonylation of biomass-derived carboxylic acids as efficient route to commodity monomers", GREEN CHEMISTRY, p. 490, vol. 14, (2012).
  • Senthil A. Gurusamy-Thangavelu, Susanna Emond, Aman Kulshrestha, Marc A. Hillmyer, Christopher W. Macosko, William B. Tolman and Thomas R. Hoye, "Polyurethanes based on renewable polyols from bioderived lactones", Polymer Chemistry,
  • Bill Tolman delivered the following lecture: Berkeley Green Chemistry Conference, UC Berkeley (4/3/12, 'Green Chemistry Education at the University of Minnesota').
  • Bill Tolman delivered the following lecture: 2011 Wisconsin Chemistry Faculties Meeting, UW-Stout (10/21/11, 'Teaching Green Chemistry at the University of Minnesota').
  • Bill Tolman delivered the following public lecture: University of New Hampshire, Harold A. Iddles Lecture (10/24/11, 'Plastics from Plants: Making Useful, Sustainable Polymers')
  • Bill Tolman delivered the following public lecture: George H. Cady Lecture University of Washington (5/29/12, 'Plastics from Plants: Using Metal Catalysts to Make Sustainable Polymers')
  • Marc Hillmyer delivered the following lectures, ""Polylactide triblock copolymers as pressure sensitive adhesives and thermoplastic elastomers" and "Organocatalytic polymerization of delta-decalactone" at the IUPAC World Polymer Congress in Blacksburg, VA (June 2012).
  • Marc Hillmyer delivered the following lecture, "Elastomers, adhesives, and tough plastics from sustainable block polymers," at the Ameican Chemical Society conference in San Diego, CA (March 2012)
  • Marc Hillmyer delivered the following lecture, "Green Chemistry research and the Center for Sustainable Polymers," at the E3 conference in Minneapolis, MN in Nov 2011.
  • Marc Hillmyer delivered the following lecture, "Sustainable polymers: Tomorrow's advanced materials" at the Twin Cities Society of Cosmetic Chemists meeting in Rosevill,e MN Oct 2011.
  • Marc Hillmyer delivered the following lecture, "Renewable thermoplastic elastomers and tough plastics” at the American Chemical Society meeting in Anaheim, CA in March 2011.

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