Chemistry & Materials

Lignin-Based Thermosets (RFT-542)

NDSU Researchers have developed a process to modify lignin, so as to produce acetoacetylated (AA-lignin) and methacrylated (MA-lignin) derivatives that are well suited for production of thermosets. This technology enables modification of full sized lignin molecules, and depolymerized lignin subunits, by attaching reactive groups to some or all of the hydroxy groups. The derivatized lignin has lower viscosity than (for example) kraft lignin. This makes it easy to handle and to control crosslinking reactions and can be readily crosslinked to form thermosets through several different mechanisms, including reaction with amines, polyisocyanates, or melamine-formaldehyde resins.

Block-Scaffolds for Bone Regeneration using Nanoclay-Polycaprolactone Scaffolds with Supplements (RFT-533)

Scientists at NDSU have developed a flexible, modular, bone scaffold for filling large bone gaps and accelerating bone growth with various additives, such as nutrients, cytokines, therapeutics and minerals incorporated into the scaffold.  The scaffold is made of a clay and a polymer.

Photoinitiators that Trigger Extremely Rapid and Efficient Polymer Synthesis using UV or Visible Light (RFT-530)

NDSU researchers have developed a range of Type I, Type II, and acidic photoinitiators, which provide polymerization of polyacrylate with good efficiency at low concentrations.  The synthesis of photoinitiators is efficient using routine chemistry, and their structures are easily manipulated to tune for low energy (including visible) light wavelengths.  These photoinitiators are each triggered by a very narrow and easily defined wavelength, making timing of polymerization easy to control (and avoiding inadvertent triggering of the reaction).  The photoinitiators may be produced from either bio-based or petroleum-based starting materials, including such readily available materials as vanillin.

Photodegradable Polymers Enable Recovery of High Value Components from Electronics and Composites (RFT-529)

Only about 10% of post-consumer plastic is recycled in the U.S., leading to waste of plastic and valuable materials embedded in plastic. NDSU researchers have developed a technology to make many plastics photodedgradable, enabling recovery of materials from plastics while broadly enhancing plastics recycling.  With respect to recovery of embedded materials, electronic devices and carbon fiber composites being two examples.  More than 30% of carbon fiber ends up discarded.  Electronics have an even worse recycling story.  Almost 90% of electronic waste is disposed without recycling, even though it is a gold mine … one ton of circuit boards contains 40 – 800 times more gold than a ton of ore.  There is also a tremendous amount of copper, silver, and palladium that is discarded rather than recovered.  The NDSU technology enables recovery of these valuable components, which is accomplished by including built-in photocleavable units into the plastic polymers. The resulting photodegradable polymers can be designed for degradation with specific wavelengths of UV and/or visible light by selecting the appropriate photocleavable unit(s).

Vanillin As A Biobased Phenolic Crosslinker for Melamine-Formaldehyde Coatings (RFT-520)

Scientists from North Dakota State University have utilized the vanillin that was derived from lignin as a bio-based cross-linker in melamine-formaldehyde coatings.  Vanillin is first reacted with any acetoacetylated polyol via a Knoevenagel Condensation, allowing production of a wide range of intermediates that are suitable for crosslinking with MF resins. The resulting products would have numerous potential applications, including laminate flooring, cabinetry, surface coatings, textile finishes, and paper processing.  The use of vanillin not only provides a bio-based alternative, but the resulting coatings were shown to provide increased impact resistance, hardness, and solvent resistance.

Novel Non-Isocyanate Siloxane-Polyurethane Coatings (RFT-517)

Glycidyl carbamate (GC) functional resins are used due to their high mechanical strength, toughness and abrasion and chemical resistance associated with polyurethanes as well as the convenience of epoxy-amine chemistry. Webster et al. have combined these resins with polydimethylsiloxane to develop self-stratified coatings that yield coatings having low surface energy as well as reduce the hazards of isocyanates.

Metal-Free Synthesis of N-Containing Compounds Using Stabalized Photoreactive Hydrazide Scaffolds (RFT-514)

NDSU Scientists have developed highly stable hydrazide-based scaffolds that use visible light and a metal-free process to produce molecules and polymers that contain nitrogen (positioned singly or as a pair of adjacent nitrogen atoms).  This scaffold begins with a N-N bond that can be used as a catalyst to make anything from drug and specialty molecules to complex polymers.  The N-N moiety allows creation of unique N-containing molecules, using visible light rather than higher energy UV.  The unique approach is possible because the NDSU team as developed handling procedures that stabilize the hydrazide scaffold until a light sensitizer (such as thioxanthone) is added.  The scaffold utilizes photoinduced excited state chemistry rather than ground state redox chemistry, providing substantially different Styrenated Soybean Oil Derivatives as a Replacement for Naphthenic and Aromatic Rubber Processing Oils

Styrenated Soybean Oil Derivatives as a Replacement for Naphthenic and Aromatic Rubber Processing Oils (RFT-512/513)

Scientists at NDSU have developed styrenated soybean oil derivatives that can be used as a direct replacement for naphthenic and aromatic oils in rubber processing. A particularly promising derivative is soybean oil (SBO) modified with polystyrene (SBO-PS). Tests using this bio-based rubber processing oil produced rubber with improved wet and ice traction with preserved low rolling resistance, while also providing better tensile properties, and similar durometer hardness and tear resistance, as compared with naphthenic and aromatic oils. These results demonstrate that non-toxic soybean oil derivatives can provide high performing alternatives to the more toxic naphthenic and aromatic oils that are currently used for rubber processing. See for example the figure below, comparing naphthenic oil (NO), SBO-PS, and a 50/50 mixture of the two.

Smart Coating for Corrosion Mitigation in Metallic Structures (RFT-509)

Though corrosion is well understood in terms of mechanisms and methods of control, it still accounts for a notable number of failures in pipelines buried or on the ground. This is due to a large number of potential complications such as varying soil properties along the pipeline and over time, local cracks on the soft coating surface, separation of coating from the pipeline surface, and corrosive environments. To address this, Azarmi et al developed smart coatings which can both prevent and monitor corrosion of steel through the use of a hard coating deposited by thermal spraying with embedded Fiber Bragg Grating (FBG) sensors.

Hard and Flexible, Degradable Thermosets from Renewable Bioresources with the Assistance of Water and Ethanol (RFT-502/521)

Thermosets are widely used in industry due to their superior dimensional stability, good processing ability, and high formulation flexibility for tailoring the desired properties such as high modulus, strength, durability, and thermal and chemical resistance. However, they may release VOCs, cannot be reprocessed by heat or solvent, and depend on non-renewable resources. To address these issues, Webster et al. developed degradable bio-based thermosets. These novel thermosets achieve high hardness while maintaining excellent flexibility as well as outstanding adhesion and solvent resistance, which is unprecedented in the field. Further, they degrade rapidly in aqueous base conditions in addition to being thermally degradable.

Polymers Derived from Bio-Diesel Waste for Road Dust Control (RFT-499)

Scientists at NDSU have developed a new material that can be applied to gravel roads for suppression of road dust. The material is made from the huge waste stream that is generated during the production of biodiesel which is primarily glycerol and biodegradable or bio-derived fatty acid esters. The new material is made up of mono- and di-gylcerides that are synthesized from a combination of waste glycerol and soybean oil triglycerides. Upon application to the road surface, the glycerides undergo crosslinking reactions to form a larger, more stable molecule.

Epoxidized Sucrose Esters of Fatty Acids (RFT-RFT-314, 422, 459, 488, 489, 502)

Scientists at North Dakota State University have developed a method to produce epoxidized sucrose esters of fatty acids (ESEFAs).  These are macromolecules with a rigid sucrose core from which 8 arms extend, the arms derived from fatty acids.  ESEFAs have extraordinary versatility with respect to potential uses and manufacturing processes. 

Novel Monomers from Biomass (RFT-478)

The majority of biomass polymers, when broken down into their constituents, consist of cellulose derived sugars of 5 or 6 carbon atoms and lignin-derived aromatic building blocks. These building blocks are relatively highly oxidized and thus, without further chemical conversion, are not well-suited for fuels and chemicals. Scientists at NDSU have recently invented novel methods for the conversion of renewable resources to feedstock chemicals. The lignin and cellulose degradation products are converted to higher quality monomers through certain chemical reactions for use in polymer synthesis.

Photodegradable Polymers Enable Recovery of High Value Components from Electronics and Composites (RFT-477)

Only about 10% of post-consumer plastic is recycled in the U.S., leading to waste of plastic and valuable materials embedded in plastic. NDSU researchers have developed a technology to make many plastics photodedgradable, enabling recovery of materials from plastics while broadly enhancing plastics recycling.  With respect to recovery of embedded materials, electronic devices and carbon fiber composites being two examples.  More than 30% of carbon fiber ends up discarded.  Electronics have an even worse recycling story.  Almost 90% of electronic waste is disposed without recycling, even though it is a gold mine … one ton of circuit boards contains 40 – 800 times more gold than a ton of ore.  There is also a tremendous amount of copper, silver, and palladium that is discarded rather than recovered.  The NDSU technology enables recovery of these valuable components, which is accomplished by including built-in photocleavable units into the plastic polymers. The resulting photodegradable polymers can be designed for degradation with specific wavelengths of UV and/or visible light by selecting the appropriate photocleavable unit(s).

Acrylic Monomers Derived from Plant Oils - Synthesis and Use in High Value Polymers (RFT-462)

Scientists at NDSU have developed an efficient and cost-effective one-step method to convert plant oils into acrylic monomers that substitute for petroleum-based monomers in the production of acrylic polymers.  This method can use essentially any plant oil, animal fat, or other fatty esters as the raw material.  The output is a combination of (meth) acrylic fatty monomers that can be used directly in the production of latexes, adhesives, surfactants, sizing agents, resins, binders, and other products that utilize acrylic polymers.  Additionally, the NDSU monomers contain two types of double bonds.  The one within the acrylic group is reactive in conventional addition free radical polymerization, which allows formation of linear polymers.  The double bonds within the fatty chain remain unaffected during free radical polymerization, so remain available for oxidative cross-linking and additional tuning of the polymer performance characteristics.  This is in contrast to existing plant oil based monomers, which produce non-linear branched and cross-linked polymers (because their fatty chain double bonds may react during the polymerization reaction).

Epoxidized Sucrose Esters of Fatty Acids (RFT-RFT-314, 422, 459, 488, 489, 502)

Scientists at North Dakota State University have developed a method to produce epoxidized sucrose esters of fatty acids (ESEFAs).  These are macromolecules with a rigid sucrose core from which 8 arms extend, the arms derived from fatty acids.  ESEFAs have extraordinary versatility with respect to potential uses and manufacturing processes.

High Performance, Bio-based Polyamides for Injection Moldable Products (RFT-452)

Scientists working at NDSU have discovered a method for making thermoplastics for injection molding that are based, in part, on renewable resources. Unlike other bio-based polyamides, these possess the high melting temperatures, fast crystallization rates, low moisture uptake, and good mechanical properties associated with engineering thermoplastics. These polymers can be used to replace the petroleum-based nylon 6,6 and nylon 6 for high end injection molding applications such as the electronic and automotive parts. 

Silicon Thin Films with Embedded Heteroatoms (RFT-449)

Scientists at NDSU have discovered methods for forming silicon thin films and structures with incorporated metals, non-metals, and combinations thereof. The precursor compositions useful in such methods are generally liquid at ambient temperature and are comprised of liquid silane(s) and metal and/or non-metal source(s). The compositions may be processed by printing, coating, or spraying onto a substrate and subjected to UV, thermal, IR, and/or laser treatment to form silicon films or structures with embedded heteroatom(s). These compositions allow for the control of dopant level prior to film processing allowing for very high doping levels with minimal out-diffusion. The available dopants are not highly toxic (as is the case for phosphine and diborane) and provide a means for film deposition without the use of expensive vacuum chambers.

Roll-to-Roll Synthesis of Silicon Thin Films from Liquid Silanes (RFT-447)

Silicon thin films are fundamental in solar and microelectronic industries, and are presently obtained using expensive low-pressure plasma enhanced chemical vapor deposition (PECVD) using gaseous silanes despite of its low precursor utilization efficiency. Instability and low vapor-pressure of liquid hydrosilanes have limited their use in the semiconductor industries for longtime. Researchers at NDSU have developed a process to synthesis silicon thin films from liquid hydrosilane (Si6H12) at ambient pressure in a roll-to-roll method using atmospheric pressure aerosol assisted chemical vapor deposition (AA-APCVD) that has higher deposition rates compared to the state-of-the-art PECVD. Solubility of solid dopants in the liquid hydrosilane facilitate the deposition of degenerately doped (n & p –type) Si thin films opposed to compressed toxic phosphine and borane gases used in other techniques. Low decomposition temperature (higher activation energy) of cyclohexasilane (Si6H12), a liquid hydrosilane, benefits for a new plasma-free process for the synthesis of silicon nitride films and Si nanowires (with suitable catalyst) at temperatures as low as 350 oC using the AA-APCVD, readily adoptable for large-scale roll-to-roll continuous manufacturing. Liquid hydrosilane compositions consisting of nanomaterials enable hybrid Si films with embedded nanomaterials that have applications in energy harvesting and light emitting devices.  

Plant Oil-Based Reactive Diluents for Coating and Composite Applications (RFT-438)

NDSU scientists have developed plant oil-based reactive diluents for coating and composite applications that possess both low viscosity and high reactive functionality. With these improved characteristics, these plant oil-based materials eliminate or reduce the need to be blended with petrochemicals thereby increasing the bio-based content of the product, which is environmentally more desirable. The fundamental aspect of the invention involves transesterification of a plant oil triglyceride with an alcohol that also contains at least one double bond. By completely replacing the glycerol component of the plant oil triglyceride with three equivalents of the unsaturated alcohol, fatty acids esters are produced containing at least one double bond that is not derived from the parent plant oil. Depending on the application requirements, a low-cost, bio-based unsaturated alcohol can be used to produce the reactive diluents of the invention.

Novel Polymers and Polymeric Materials Based on the Renewable Compounds, Eugenol and Iso-Eugenol (RFT-423)

Due to the finite supply of fossil resources and the growing environmental concern, there is a major need for chemicals and materials derived from renewable resources. Aromatic building blocks, such as phenols, are particularly important and can be derived from renewable sources. Chisholm et al are the first to convert eugenol and iso-eugenol into vinyl ether monomers via reaction of the hydroxyl group. The result is soluble, processable linear polymers that retain the allyl group for crosslinking reactions and incorporation of other functional groups.

Removal and Recovery of Phosphate from Water Bodies and Reuse as a Fertilizer (RFT-419)

Scientists at NDSU have developed biodegradable iron-containing alginate beads that remove phosphorus from water, and can then be beneficially reused to provide Phosphate fertilization. As a result, this dual-use technology can be used to clean water bodies that are eutrophic due to excess phosphorous, then use the phosphorous for fertilization in agricultural, nursery, and greenhouse settings where phosphorus is a limiting nutrient.

Vegetable Oil-Based Polymers for Nanoparticle Surface Modification (RFT-413)

The extremely high surface area of nanoparticles provides many advantages over conventional particles with dimensions in the micron scale. For a variety of applications, it is necessary to suspend the nanoparticles in a liquid medium. Researchers at NDSU have developed a new plant-oil-based polymer technology focused on the application of nanoparticle suspension in water.

Novel PEGylated Compounds and Process for Making Antifouling/Biocompatible Materials (RFT-380)

Surfaces having non-fouling characteristics are of great interest for the development of advanced materials in many different applications. In medical device applications, protein attachment can cause any number of unwanted immune reactions when exogenous materials are implanted into biological systems. Materials developed with polyethylene glycols, often referred to as PEGylated materials, are of great interest due to their protein resistance and nontoxic properties.
One of the most widely used biomaterials is Polyurethane, due to its biocompatibility and its mechanical properties. Researchers at NDSU have developed a new class of PEGylated polyurethane materials using a novel process which is much more effective than traditional procedures. The resulting compounds are novel siloxane-PEG copolymers having terminal amine functionality and a backbone of siloxane having a varied number of pendant hydrophilic PEG chains. The low surface energy siloxane can aid in bringing PEG chains to the surface, and the terminal amine functionality can be bound into the polyurethane by reaction with isocyanate. Therefore, the surface of the material will be amphiphilic while the underlying polyurethane bulk will give toughness to the system. This approach allows for precise control over the number of hydrophobic PEG chains, siloxane and PEG chain lengths, and terminal amine functionality.

Efficient Processes to Produce Polyalkylated Oligo-ethyl-polyamines (RFT-324)

Certain Polyalkylated Oligo-ethyl-polyamines such as TMEDA, TEEDA and PEDETA are useful intermediates in organic synthesis and analytical chemistry and used extensively in inorganic chemistry as ligands for a variety of metal complexes. In spite of high demands, PEDETA (penta-ethyl-di-ethylene-triamne) has not been available in industrial scales due to the difficulty in the realization of complete alkylation of the starting material using conventional methods. This novel method describes a process of obtaining PEDETA that is pure and without any side or incomplete alkylated product. The process involves no work-up and is thus environmentally friendly. In addition, the reaction time and work-up process is drastically reduced from the conventional synthesis method. 

Polymers Derived From Plant Oil Exhibit Increased Crosslink Density, Superior Properties (RFT-318)

This proprietary technology platform involves the conversion of plant oil triglycerides to polymerizable monomers that are subsequently used to produce a wide variety of bio-based polymers, tailored for specific applications in multiple industries. There are four major attributes of the proprietary polymerization process that set this technology apart from all other previously developed plant oil-based technologies developed to date. These key features also allow major material performance advantages that enable this renewable polymer technology to successfully compete with petroleum-based polymer materials.

Unique Electrospinning Process and Compositions for High-Volume Silicon Nanowire Productions (RFT-311)

North Dakota State University (NDSU) has developed unique synthetic routes to a novel liquid silicon precursor, cyclohexasilane (Si6H12), which is converted to silicon nanowires by electrospinning. Readily purified by distillation, the liquid nature of Si6H12 allows the development of a high-volume electrospinning route for silicon nanowire production. Because the spun wires convert to amorphous silicon at relatively low temperatures, formation of excessive surface oxide and carbide phases can be avoided which would otherwise negatively affect capacity and rate capabilities. The technology can be used in the development of anodes for use in next-generation lithium ion batteries, in which the traditional carbon-based anode is replaced with a silicon-based anode for a dramatic increase in capacity (theoretically over 1100% increase in capacity).

The Use of Fibers From Agricultural Waste Streams as a Reinforcing Agent in Commodity Thermoplastics (RFT-278)

This invention describes a process wherein lignocellulosic fibers recovered from various agricultural waste streams (such as crop waste otherwise discarded by ethanol plants) are combined with commodity thermoplastics as a means of reinforcing and strengthening the plastics. This method works with commodity thermoplastics and recycled plastics where other fiber reinforcing processes have not succeeded.

Composition and Method of Forming Functionalized Cyclohexasilanes (RFT-265)

This invention pertains to a composition of matter derived from cyclohexasilane. The compound has unique physical properties and can exist in a liquid state at standard temperature and pressure - a characteristic that renders them appropriate for applications in novel deposition routes including high-speed printing and direct-write. The invention has applications in the manufacture of silicon-bassed solar cell in the photovoltaic industry.

Modified Glycidyl Carbamate Resins Exhibiting Superior Mechanical Properties (RFT-226)

This invention pertains to novel glycidyl carbamate resins that have been modified with alkyl or ether alkyl groups. These resins have improved properties such as lower viscosity, which makes them good candidates for commercialization in the paint industry. In particular, it has potential for application as a coating on aircrafts.

Unique Sol-Gel Hybrid Coatings with Superior Properties for a Wide Rangeof Industrial Applications (RFT-225/240)

This invention pertains to the preparation of two-component polyurethane coating formulation comprising: an epoxy functional binder, and a blended curing component (having one sol-gel and one amine cross-linker.  

Novel Polyurethane/Epoxy Hybrid Coatings (RFT-219)

This invention involves the preparation of a novel coating composition comprising a glycidyl carbamate functional resin, an aromatic epoxy resin, and a polyamine cross-linker. This coating formulation with the aromatic epoxy resin has improved corrosion resistance over coatings that do not contain the aromatic epoxy resin. 

Novel Chemotherapeutic Agents for Anti-Tumor and Anti-Cancer Drugs (RFT-72)

This invention relates to novel, substituted (functionalized) polysiloxane compositions (and methods for synthesis of same) that may be useful as antineoplastics (chemotherapeutics) or other therapeutic agents. Since compositions of this type can transverse cellular membranes, they may also serve as delivery vehicles for other agents with biological activities in both animals and plants (e.g., drugs, herbicides, fungicides, anti-microbials, etc.).

Multi-use Aminofunctional Alkoxy Polysiloxanes (RFT-71)

Linear and cyclic polysiloxanes functionalized with amine moieties have been synthesized utilizing aminoalcohols. The reaction is cost effective and a one-pot process with minimal purification of end product required.
A diverse and versatile array of amino-silicone products are possible due to the variety of aminoalcohols commercially available. Potential market applications include coatings, adhesives, sealants, rubbers, elastomers, catalyst supports, sol-gel/ceramic precursers, and ionically conductive materials.