Enhanced Polymer Grafting from Multiwalled Carbon Nanotubes through Living Anionic Surface-Initiated Polymerization

Anionic surface-initiated polymerization of ethylene oxide and styrene has been performed using multiwalled carbon nanotubes (MWNTs) functionalized with anionic initiators. The surface of MWNTs was modified via covalent attachment of precursor anions such as 4-hydroxyethyl benzocyclobutene (BCBEO) and 1-benzocyclobutene-1′-phenylethylene (BCB-PE) through Diels-Alder cycloaddition at 235 °C. Surface-functionalized MWNTs-g-(BCB-EO) n and MWNTs-g-(BCB-PE) n with 23 and 54 wt % precursor initiators, respectively, were used for the polymerizations. Alkoxide anion on the surface of MWNTs-g-(BCB-EO) n was generated through reaction with potassium triphenylmethane for the polymerization of ethylene oxide in tetrahydrofuran and phenyl substituted alkyllithium was generated from the surface of MWNTs-g-(BCB-PE) n using sec-butyllithium for the polymerization of styrene in benzene. In both cases, the initiation was found to be very slow because of the heterogeneous reaction medium. However, the MWNTs gradually dispersed in the reaction medium during the polymerization. A pale green color was noticed in the case of ethylene oxide polymerization and the color of initiator as well as the propagating anions was not discernible visually in styrene polymerization. Polymer grafted nanocomposites, MWNTs-g-(BCB-PEO) n and MWNTs-g-(BCB-PS) n containing a very high percentage of hairy polymer with a small fraction of MWNTs (<1 wt %) were obtained. The conversion of ethylene oxide and the weight percent of PEO on the surface of the MWNTs increased with increasing reaction time indicating a controlled polymerization. The polymer-grafted MWNTs were characterized using FTIR, 1H NMR, Raman spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and transmission electron microscopy (TEM). Size exclusion chromatography of the polymer grafted MWNTs revealed broad molecular weight distributions (1.3 < Mw/Mn < 1.8) indicating the presence of different sizes of polymer nanocomposites. The TEM images showed the presence of thick layers of polymer up to 30 nm around the MWNTs. The living nature of the growing polystyryllithium was used to produce diblock copolymer grafts using sequential polymerization of isoprene on the surface of MWNTs.

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Characterization of Primary Amine End-Functionalized Polystyrene and Poly(methyl methacrylate) Synthesized by Living Anionic Polymerization Techniques

The reaction of living anionic polymers with 2,2,5,5-tetramethyl-1-(3-bromopropyl)-1-aza-2,5- disilacyclopentane (1) was investigated using coupled thin layer chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Structures of byproducts as well as the major product were determined. The anionic initiator having a protected primary amine functional group, 2,2,5,5-tetramethyl- 1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane (2), was synthesized using all-glass high-vacuum techniques, which allows the long-term stability of this initiator to be maintained. The use of 2 in the preparation of well-defined aliphatic primary amine R-end-functionalized polystyrene and poly(methyl methacrylate) was investigated. Primary amino R-end-functionalized poly(methyl methacrylate) can be obtained near-quantitatively by reacting 2 with 1,1-diphenylethylene in tetrahydrofuran at room temperature prior to polymerizing methyl methacrylate at -78 °C. When 2 is used to initiate styrene at room temperature in benzene, an additive such as N,N,N',N'- tetramethylethylenediamine is necessary to activate the polymerization. However, although the resulting polymers have narrow molecular weight distributions and well-controlled molecular weights, our mass spectra data suggest that the yield of primary amine α-end-functionalized polystyrene from these syntheses is very low. The majority of the products are methyl α-end-functionalized polystyrene.

Well-Defined Poly(4-vinylbenzocyclobutene): Synthesis by Living Anionic Polymerization and Characterization

Living anionic polymerization of 4-vinylbenzocylobutene was performed in benzene at room temperature using sec-butyllithium as the initiator. Results of the kinetic studies indicated the termination- and transfer-free nature of the polymerization. Homopolymers with predictable molecular weights and narrow molecular weight distributions were produced, excluding the interference of the cyclobutene rings during initiation and propagation. Thermogravimetric analysis of poly(4-vinylbenzocyclobutene) in air showed a small weight gain at ~200 °C, a rapid decomposition at ~455 °C, and a gradual decomposition at ~566 °C. This behavior was attributed to the formation of radicals from the pendent benzocyclobutene functionality through o-quinodimethane intermediates and simultaneous decomposition/cross-linking reactions at high temperature. The living nature of the polymerization was also examined via sequential copolymerization with butadiene to form diblock copolymers.

Opening Remarks for Master Conservationist Presentations

It is a distinct honor for me to help recognize the 2003 Master Conservationists tonight. Tonight's event marks the 20th anniversary of the program sponsored by the Omaha World-Herald and the Institute of Agriculture and Natural Resources at the University of Nebraska-Lincoln.

Opening Comments Before Master Conservationist Presentations

It is a real pleasure to participate in this recognition program honoring the 2004 Master-Conservationists. We are grateful for the partnership with the Omaha World Herald in this unique program. In an effort to keep the program in tune with current developments in soil and waster conservation, a special committee is considering the idea of including conservation easements in the 2005 program. Some members of the committee are in the audience tonight. We appreciate the efforts of members of the Omaha World Herald, Natural Resources Districts, the USDA Natural-Resources Conservation Service and the Institute of Agriculture and Natural Resources in carrying out this program.

Deterministic Solutions for a Step-growth Polymerization

Chain topology, including branch node, chain link and cross-link dynamics that contribute to the number of elastically active strands and junctions, are calculated using purely deterministic derivations. Solutions are not coupled to population density distributions. An eigenzeit transformation assists in the conversion of expressions derived by chemical reaction principles from time to conversion space, yielding transport phenomena type expressions where the rate of change in the molar concentrations of branch nodes with respect to conversion is expressed as functions of the fraction of reactive sites on precursors and reactants. Analogies are hypothesized to exist in cross-linking space that effectively distribute branch nodes with i reacted moieties between cross-links having j bonds extending to the gel. To obtain solutions, reacted sites on nodes or links with finite chain extensions are examined in terms of stoichiometry associated with covalent bonding. Solutions replicate published results based on Miller and Macosko’s recursive procedure and results obtained from truncated weighted sums of population density distributions as suggested by Flory.

OPENING REMARKS - THIRD VERTEBRATE PEST CONFERENCE

To open this Third Vertebrate Pest Conference is a real privilege. It is a pleasure to welcome all of you in attendance, and I know there are others who would like to be meeting with us, but, for one reason or another cannot be. However, we can serve them by taking back the results of discussion and by making available the printed transactions of what is said here. It has been the interest and demand for the proceedings of the two previous conferen- ces which, along with personal contacts many of you have with the sponsoring committee, have gauged the need for continuing these meetings. The National Pest Control Association officers who printed the 1962 proceedings still are supplying copies of that conference. Two reprintings of the 1964 conference have been necessary and repeat orders from several universities indicate that those proceedings have become textbooks for special classes. When Dr. Howard mentioned in opening the first Conference in 1962 that publication of those papers would make a valuable handbook of animal control, he was prophetic, indeed. We are pleased that this has happened, but not surprised, since to many of us in this specialized field, the conferences have provided a unique opportunity to meet colleagues with similar interests, to exchange information on control techniques and to be informed by research workers of problem solving investigations as well as to hear of promising basic research. The development of research is a two-way street and we think these conferences also identify areas of inadequate knowledge, thereby stimulating needed research. We have represented here a number of types of specialists—animal ecologists, public health and transmissible disease experts, control methods specialists, public agency administration and enforcement staffs, agricultural extension people, manufacturing and sale industry representatives, commercial pest control operators, and others—and in addition to improving communications among these professional groups an equally important purpose of these conferences is to improve understanding between them and the general public. Within the term general public are many individuals and also organizations dedicated to appreciation and protection of certain animal forms or animal life in general. Proper concepts of vertebrate pest control do not conflict with such views. It is worth repeating for the record the definition of "vertebrate pest" which has been stated at our previous conferences. "A vertebrate pest is any native or introduced, wild or feral, non-human spe- cies of vertebrate animal that is currently troublesome locally or over a wide area to one or more persons either by being a general nuisance, a health hazard or by destroying food or natural resources. In other words, vertebrate pest status is not an inherent quality or fixed classification but is a circumstantial relationship to man's interests." I believe progress has been made in reducing the misunderstanding and emotion with which vertebrate pest control was formerly treated whenever a necessity for control was stated. If this is true, I likewise believe it is deserved, because control methods and programs have progressed. Control no longer refers only to population reductions by lethal means. We have learned something of alternate control approaches and the necessity for studying the total environment; where reduction of pest animal numbers is the required solution to a problem situation we have a wider choice of more selective, safe and efficient materials. Although increased attention has been given to control methods, research when we take a close look at the severity of animal damage to so many facets of our economy, particularly to agricultural production and public health, we realize it still is pitifully small and slow. The tremendous acceleration of the world's food and health requirements seems to demand expediting vertebrate pest control to effectively neutralize the enormous impact of animal damage to vital resources. The efforts we are making here at problem delineation, idea communication and exchange of methodology could well serve as both nucleus and rough model for a broader application elsewhere. I know we all hope this Third Conference will advance these general objectives, and I think there is no doubt of its value in increasing our own scope of information.