University of Delaware

US Government As Represented by the Secretary of the Army

Government of the United States, As Represented by the Defense Threat Reduction Agency

Thomas H Epps, Iii

Angela L Holmberg

Gregory William Peterson

Dionisios Vlachos

Shu Wang

Kaleigh Havery Reno

Basudeb Saha

Kaleigh H Nicastro

Li Shuai

Norman Joseph Wagner

Richard Patrick Wool

Joseph Francis Stanzione, Iii

Melody A Morris

Robert M O'Dea

Cameron Shelton

Wei-Fan Kuan

Elvis O Ebikade

Eric R Gottlieb

Christopher J Kloxin

Melissa B Gordon

Grant Alexander Knappe

Annie Lu

Jean S Epps

Disclosed herein are systems and methods of depolymerizing a lignin component of a lignin-containing material. The method comprising contacting the lignin-containing material with a solvent and optionally a catalyst at a temperature in the range of 180-300° C. and at a maximum operating pressure of less than 10 barG during the depolymerization of the lignin component of the material and collecting at least one volatile stream comprising one or more depolymerized lignin products. In an embodiment, the step of contacting is carried out in a reactive distillation reactor, and the step of collecting comprises concurrently collecting at least one volatile stream via distillation apparatus connected to the reactive distillation reactor, at least one of the one or more depolymerized lignin products comprises a substituted phenol having the following general formula: (I) wherein Ris H, methyl, ethyl, n-propyl, propenyl, or allyl, and Rand Rare independently selected from H or methoxy group.

Low-pressure depolymerization of lignocellulosic biomass

Disclosed herein is a bio-based copolymer comprising in polymerized form (i) at least one polymerizable bio-based monomer containing one phenolic hydroxyl group which has been derivatized to provide at least one polymerizable functional group which is an ethylenically unsaturated functional group (such as a [meth]acrylate group), where the precursors of the polymerizable bio-based monomers are derived from raw lignin-containing biomass, and (ii) at least one ion-conducting co-monomer other than the bio-based monomer. Also disclosed herein are binders comprising the bio-based copolymer, electrodes comprising the binder, polymer electrolytes comprising the bio-based copolymer and an electrochemical device comprising an electrode in electrical contact with a polymer electrolyte, wherein at least one of the electrode and the polymer electrolyte comprises the bio-based copolymer.

Ion-conducting bio-based polymers from raw lignocellulosic biomass

A composition having the structure of formula I:[R—Ar—(COOH)][Ar—(COOH)]M  (I)is provided where M is Mn, Cu, Co, Fe, Zn, Cd, Ni, or Pt; R is a bromine, nitro, a primary amine, C-Calkyl secondary amine, C-Calkyl oxy, Br—(C-Calkyl), NO—(C-Calkyl), a mercaptan, and reaction products of any of the aforementioned with acyl chlorides of the formulas: CH(CH)C(O)Cl, or CH(CH(C-Calkyl)CH)C(O)Cl, or CH(CH)-Ph-(CH)C(O)Cl, where Ph is a Cphenyl or Cphenyl with one or more hydrogens replaced with F, C-Cfluoroalkyl, or C-Cperfluoroalkyl; m is independently in each occurrence an integer of 0 to 12 inclusive; p is an integer of 0 to 36 inclusive, to form an amide, a thioamide, or an ester; Ar is a 1,3,5-modified phenyl, and 1.4>x>0. A process of synthesis thereof and the use to chemically modify a gaseous reactant are also provided.

Multivariate carboxylate derivatized phenyl-based metal-organic frameworks

Dimethoxyphenol-based monomers containing polymerizable functional groups such as [meth]acrylate groups are useful for the preparation of polymers, wherein one or more dimethoxyphenyl moieties are part of side chains pendant to the backbones of the polymers. The polymers thereby obtained may have different, improved properties, such as higher glass transition temperatures, thermal stability and solvent resistance, as compared to polymers based on other types of lignin-derived monomers.

Functionalized dimethoxyphenol monomers and methods for preparing such monomers

Disclosed herein is a method of making polymerizable bio-based monomers containing one phenolic hydroxyl group which has been derivatized to provide at least one polymerizable functional group which is an ethylenically unsaturated functional group (such as a [meth]acrylate group), where the precursors of the polymerizable bio-based monomers are derived from raw lignin-containing biomass. Also disclosed herein are bio-based copolymers prepared from such bio-based monomers and a co-monomer, and methods of making and using such bio-based copolymers. In particular, the bio-based copolymers can be used as pressure sensitive adhesives, binders, and polymer electrolytes.

Bio-based polymers from raw lignocellulosic biomass

Disclosed herein are multi-layer structures comprising a first composite layer disposed over a second composite layer, wherein the first composite layer contains a first active material dispersed in a first polymer containing an elastomeric polymer and the second composite layer contains a second polymer which may have a second active material dispersed therein, wherein the first active material chemically or physically interacts with at least one toxic chemical and is selected from the group consisting of metal-organic frameworks (MOFs), metal oxides, metal hydroxides, zeolites, and combinations thereof, and wherein the active material and the second active material (if present) are the same as or different from each other, and the first polymer and second polymer are the same as or different from each other, subject to the proviso that the first composite layer and the second composite layer compositionally differ from each other in at least one respect.

Layered mixed-matrix membranes and mixed-matrix composites from polymers and active materials

A composition having the structure of formula I:[R&#x2014;Ar&#x2014;(COOH)][Ar&#x2014;(COOH)]M&#x2003;&#x2003;(I)is provided where M is Mn, Cu, Co, Fe, Zn, Cd, Ni, or Pt; R is a bromine, nitro, a primary amine, C-Calkyl secondary amine, C-Calkyl oxy, Br&#x2014;(C-Calkyl), NO&#x2014;(C-Calkyl), a mercaptan, and reaction products of any of the aforementioned with acyl chlorides of the formulas: CH(CH)C(O)Cl, or CH(CH(C-Calkyl)CH)C(O)Cl, or CH(CH)-Ph-(CH)C(O)Cl, where Ph is a Cphenyl or Cphenyl with one or more hydrogens replaced with F, C-Cfluoroalkyl, or C-Cperfluoroalkyl; m is independently in each occurrence an integer of 0 to 12 inclusive; p is an integer of 0 to 36 inclusive, to form an amide, a thioamide, or an ester; Ar is a 1,3,5-modified phenyl, and 1.4&#x3e;x&#x3e;0. A process of synthesis thereof and the use to chemically modify a gaseous reactant are also provided.

The present disclosure is directed to stress-responsive compositions comprising (1) at least one (co)polymer comprising at least one mechanophore comprising at least one thiocarbonylthio functional group or derivative thereof and (2) at least one compound comprising at least one functional group capable of reacting with a free radical, The present disclosure is also directed to articles, coatings, and 3D printing binders comprising such stress-responsive compositions, as well as to processes of imparting the abilities of forming and maintaining protective barriers and mechanical self-healing to such articles, coatings, and 3D printing binders by incorporating such stress-responsive compositions therein.

Stress-responsive compositions and uses thereof

A coating head includes a coating device and at least a first flexible blade that is capable of being shaped into contact with a solvent-containing film on a substrate upon pressing the first flexible blade against the film, thereby providing contact between the blade and the film over a contact distance when the coating head is drawn over the substrate. The coating device and the blade are separated by a spacing distance such that partial loss of solvent occurs from a starting film formed on the substrate by the coating device as the coating head is drawn over the substrate, the partial solvent loss forming the solvent-containing film. A method of producing a film having a hierarchical structure includes drawing a coating head across a substrate to form on the substrate via the coating device a starting film including a solvent and a material for forming the hierarchical structure.

Device and method for making shear-aligned, solvent-cast films

Polymers prepared from functionalized dimethoxyphenol monomers

Copolymers useful as components of polymer electrolytes are provided in which the copolymer comprises at least one block sequence represented by formula (I):A&#x2014;(T)&#x2014;B &#x2003;&#x2003;(I)wherein A is a vinyl aromatic block, T is a tapered copolymer region copolymerized from a vinyl aromatic monomer and an oligo(oxyalkylene) acrylate monomer and B is an oligo(oxyalkylene) acrylate block.

Tapered block copolymer electrolytes

The present invention pertains to bio-based block polymers synthesized from functionalized lignin-based molecules (A-monomer) and functionalized fatty acids or fatty alcohols (B-monomer) derived from plant or animal oils, waxes or fats. The block polymers can be synthesized via numerous polymerization techniques, such as reversible addition-fragmentation chain transfer (RAFT). Most importantly, this class of bio-based block polymers shows promise as providing sustainable yet scalable and tunable thermoplastic elastomers and pressure-sensitive adhesives, among other applications.

Growing community of inventors

Bear, DE, United States of America

Thomas H Epps, Iii