DIVISION OF POLYMER CHEMISTRY

235th ACS National Meeting

New Orleans, LA

April 6-10, 2008

THURSDAY AFTERNOON

Polymers for Remediation and the Environment

Sponsored by POLY, Cosponsored by American Chemistry Council, ENVR, and ENGENV
A. B. Salamone, K. M. Levon, G. Coimbatore, and R. Krebs, Organizers
K. M. Levon and G. Coimbatore, Presiding

1:30 —704. Microbial decontamination of water using heterogeneous catalyst based Fenton's reaction. V. Shah, A. Angelov, M. Hill

2:00 —705. N-succinyl-chitosan and crosslinked n-succinyl-chitosan as novel absorbents toward metal ions. S. Sun, A. Wang, B. He, H. Xiao

2:30 —706. Surfactant modified membranes for the separation of oil-in-water emulsions. J. A. Howarter, J. P. Youngblood

3:00 —707. Plastics and energy usage – remediation and sustainability. R. Krebs

3:30 —708. Applications of recyclable polymeric materials in light frame construction to mitigate environmental damage in extreme events. V. Gopu

4:00 —709. New polymer systems from Baylis-Hillman chemistry and biorenewable feedstocks. P. Venkitasubramanian, E. C. Hagberg, P. D. Bloom

4:30 —710. Environmental solutions through chemical up cycling. K. F. Miller

5:00 —711. Polymer design using green chemistry principles: Importance of the radical cage effect in polymer photodegradation reactions. D. R. Tyler, B. C. Daglen

ABSTRACTS

POLY 704

Microbial decontamination of water using heterogeneous catalyst based Fenton's reaction

Vishal Shah1, Angel Angelov1, and Michael Hill2. (1) Department of Biology, Dowling College, Oakdale, NY 11769, ShahV@dowling.edu, (2) Long Island Pollution Strippers, Smithtown, NY 11787

Availability of pure water is becoming one of the most life threatening problems to many communities. Goal of the current research is to develop an efficient heterogenous catalyst system that would decontaminate water from microbial pollutants. The technology is based on modified Fenton's reaction wherein copper is bound on a polymeric ligand and this polymer is immersed into the contaminated water. Upon addition of hydrogen peroxide into the water, hydroxyl radicals are formed through the reaction of copper with peroxide. While in classical Fenton's reaction hydroxyl radicals diffuse into the water immediately upon formation and undergo decay within seconds, in the current system hydroxyl radicals remain bound to the catalyst to form a polymer-copper-radical complex. When bacteria come in contact with the radicals they are oxidized. In the earlier research carried out using Amberlite IRC748 as the ligand for copper, stability of the resin and copper leaching were the major concern. In the current research we present the data based on the use of Amberlyst 15 wet, as the ligand for copper and the ability of the system to microbially decontaminate water. Amberlyst 15 is a highly crosslinked styrenic resin and thus has higher affinity for copper and is stable over a prolonged period. In the research carried out using Amberlyst 15 wet, the bacterial load in contaminated water was reduced in six hours from 2.5 x 107 cells/mL to 0 cells/mL. Data will be presented on the intrinsic kinetics of reaction for E. coli and P. aeruginosa as a function of catalyst design and a reaction model will be proposed for the reaction mechanisms.

POLY 705

N-succinyl-chitosan and crosslinked n-succinyl-chitosan as novel absorbents toward metal ions

Shengling Sun1, Aiqin Wang2, Beihai He1, and Huining Xiao3. (1) State Key Lab of Pulp & Paper Eng, South China University of Technology, Wushan, Guangzhou 510640, China, slsun@scut.edu.cn, (2) Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China, (3) Department of Chemical Engineering, University of New Brunswick/South China University of Technology, Fredericton, NB E3B 5A3, Canada, hxiao@unb.ca

The adsorption behaviour of metal ions onto N-succinyl-chitosan (NSC) with various degrees of substitution controlled by reaction duration was investigated. Based on the optimum adsorption conditions, a novel absorbent, i.e., cross-linked NSC resins with M(II) as template ions (CNSC), was synthesized. The findings obtained from the single metal ions adsorption and the co-adsorption experiments of mixture solutions indicated that NSC and CNSC exhibited higher absorption capacities than native chitosan, implying that both NSC and CNSC are promising absorbents in the removal of heavy metal ions. Moreover, CNSC can selectively absorb the templated metal ions from the coexistence solution; and the sorption capacity of CNSC toward templated ions was always higher than that of the NSC. Furthermore, the improved reusability was observed for CNSC.. The analysis results revealed that the adsorption sites mainly occurred on the carboxyl groups of the succinyl groups in the adsorption process.

POLY 706

Surfactant modified membranes for the separation of oil-in-water emulsions

John A. Howarter and Jeffrey P. Youngblood, School of Materials Engineering, Purdue University, West Lafayette, IN 47907, jhowarte@purdue.edu

Stimuli-responsive polymer brushes sensitive to oil and water environments were used to modify silica filters of varying pore size. The polymer brushes on flat surfaces were both hydrophilic and oil-repellent. Filters showed the ability to selectively pass water and restrict the passage of oil, thus resulting in a reusable method of separating oil-water mixtures. Filters were characterized with respect to flow rate of individual droplets, and bulk fluid. In addition, the effectiveness of the filter was measured by the amount of oil in a fine dispersion which was able to pass through the filters.

POLY 707

Plastics and energy usage – remediation and sustainability

Robert Krebs, Plastics Division, American Chemistry Council, 1300 Wilson Blvd., Arlington, VA 22209, rob_Krebs@americanchemistry.com

As a single digit user (2%-4%) of ALL our annual US energy (in both feedstock and energy to produce) the 100 billion pounds of plastics are about the only part of any DOE energy-usage pie-chart that doesn't disappear in flame. Plastics as carbon energy molecules make things that last decades. They preserve fossil fuel use in almost all other energy sectors remediating environmental impact. Insulation for offices/homes and lightweighted cars, trucks, trains and planes conserve fuel and pollution. Plastics do the same with packaging. In fact, all the energy saved by using plastic materials – by their presence alone – remediate quantifiable environmental impacts. Proof will be offered from the use of polymers and the audience will be invited to share their knowledge in real-time with infrared response keypads viewing their live input projected on the screen.

POLY 708

Applications of recyclable polymeric materials in light frame construction to mitigate environmental damage in extreme events

Vijaya Gopu, School of Civil and Environmental Engineering, Tulane University, 205 Walter E. Blessey Hall, New Orleans, LA 70118, Fax: 504-862-8941, vgopu@tulane.edu

Traditional light frame structures – residential and light commercial buildings -- are built with dimension lumber and wood based products. The low cost of these wood based materials coupled with the ease of wood construction has to date precluded the light frame construction industry from considering the application of alternate and more durable materials in these type of structures. The recent extreme events such as Hurricane Katrina have led to extensive damage and destruction of numerous thousands of light frame structures. The inability to recycle the construction materials in these destroyed structures has led to massive amounts of these materials being placed in landfills. New and innovative recyclable polymeric construction materials offer an opportunity to reduce the environmental damage by limiting the volume of material going to the landfill. This paper discusses the various polymeric construction materials that are being manufactured in the country and their application in a variety of structures. These materials are often made of recycled polymeric material and are recyclable. The increased application of these materials in a variety of structures leads to increased use of plastics in the industrial and municipal waste stream that can be recycled at the end of the useful life of the structure. An overview of the efforts undertaken to develop testing standards and design specifications for polymeric construction materials is also presented.

POLY 709

New polymer systems from Baylis-Hillman chemistry and biorenewable feedstocks

Padmesh Venkitasubramanian, Erik C. Hagberg, and Paul D. Bloom, Archer Daniels Midland, 1001 N. Brush College Rd, Decatur, IL 62521, Fax: 217-451-2457, erik_hagberg@admworld.com

A new polyester with an alkylacrylate functionality in the backbone resulting from the Baylis-Hillman self condensation of 5-hydroxymethylfurfural acrylate was successfully synthesized. The monomer was synthesized from the renewable, bioderived chemical feedstock 5-hydroxymethylfurfural. Polymerization under standard Baylis-Hillman conditions afforded high molecular weight material. This new class of polymers has the potential for use in a wide array of applications.

POLY 710

Environmental solutions through chemical up cycling

Kenneth F Miller, Crystalline Performance Products R&D, SABIC Innovative Plastics, 1 Lexan Lane, Mt Vernon, IN 47620, ken1.miller@sabic-ip.com

Several global mega-trends are clearly pointing to the undeniable fact that our current usage of non-renewable petrochemicals is not sustainable. For the last 200 years chemists and engineers have been responsible for facilitating the use of fossil fuels to drive the energy and material science behind our current quality of life. However, the non-sustainability of this approach is driving the scientific and business community to now develop new “green” technologies. Chemical up cycling is a technology strategy where post-industrial or post-consumer resource recovered materials can be chemically transformed into more useful monomers or polymers. The transformation of post-consumer poly(ethylene terephthalate) (PET) into virgin like poly(butylene terephthalate) (PBT) is an example of chemical up cycling,. This transformation converts largely disposable PET items into durable engineering thermoplastic resins and products. The energy and raw material saving will be reviewed as well as target products and applications.

POLY 711

Polymer design using green chemistry principles: Importance of the radical cage effect in polymer photodegradation reactions

David R. Tyler, Department of Chemistry, 1253 University of Oregon, Eugene, OR 97403, Fax: 541-346-0487, dtyler@uoregon.edu, and Bevin C. Daglen, Department of Chemistry, University of Oregon, Eugene, OR 97403

There are compelling “green” reasons for using degradable plastics in certain applications, and for that reason considerable research is now devoted to devising new photodegradable polymers with improved performance. To be practical, photodegradable plastics must have defined lifetimes, and this talk will present results showing the role that radical cage effects have in determining the lifetimes of photodegradable polymers. In the first study discussed, the accelerating effects of residual (internal) and external tensile stress on polymer degradation will be shown to result from radical cage effects. In a second investigation, the role of the cage effect in describing the accelerating effects of temperature was explored and the results will be discussed. The results of a third study explored the role of cage effects in describing the effects of polymer curing on polymer lifetime. All three studies made use of specially designed polymers that contain organometallic chromophores along their backbones.