Archer Daniels Midland Company

Dupont Industrial Biosciences Usa, LLC

Other

Kenneth Stensrud

Erik Christopher Hagberg

Padmesh Venkitasubramanian

Erin Rockafellow

Brennan Alexander Smith

Alexandra Sanborn

Stephen J Howard

Stuart Fergusson

Joshua Terrian

Kevin J Martin

Chi-Cheng Ma

Mitchell J Schultz

Chi Cheng Ma

Erin M Rockafellow

Kevin Martin

Erik Hagberg

Compositions and methods are provided for the production of bio-based polymers (e.g., polymers made from glucose), including polyesters, as well as end products resulting from such production, in which one or more color stabilizing additive compounds is utilized. The additive(s) may be used in the stabilization of a monomer or prepolymer that is reacted in such production methods, prior to obtaining the polymer. Particular bio-based polymers are those having furandicarboxylate moieties or residues in their backbone structure, with poly(alkylene furan dicarboxylate) polymers, such as polyethylene furan dicarboxylate) (PEF) and poly(trimethylene furan dicarboxylate) (PTF) being representative.

Color stabilization of monomers and other reactants for forming bio-based polymers

Sugar-based mono and diesters are prepared by esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol in the presence of low loadings of a homogeneous organotin (IV) catalyst.

Organotin catalysts in esterification processes of furan-2,5-dicarboxylic acid (FDCA)

A method for preparing sugar-based mono and diesters is described. The process entails the esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol in the presence of low loadings of a homogeneous organotin (IV) catalyst.

Disclosed herein are methods for synthesizing 1,2,5,6-hexanetetrol (HTO), 1,6 hexanediol (HDO) and other reduced polyols from C5 and C6 sugar alcohols or R glycosides. The methods include contacting the sugar alcohol or R-glycoside with a copper catalyst, most desirably a Raney copper catalyst with hydrogen for a time, temperature and pressure sufficient to form reduced polyols having 2 to 3 fewer hydoxy groups than the starting material. When the starting compound is a C6 sugar alcohol such as sorbitol or R-glycoside of a C6 sugar such as methyl glucoside, the predominant product is HTO. The same catalyst can be used to further reduce the HTO to HDO.

Synthesis of R-glucosides, sugar alcohols, reduced sugar alcohols, and furan derivatives of reduced sugar alcohols

A method of making a furan dicarboxylate by means of reacting 2,5-furan dicarboxylic acid (FDCA) with an alcohol or mixture of alcohols in a CO-predominant atmosphere without the presence of any other acid catalyst is described. The reaction is conducted under conditions that correspond to either supercritical, critical or near-critical temperatures and pressures for the alcohol species and/or COgas.

Esterification of 2,5-furan-dicarboxylic acid

A process for producing biofuels compounds directly from carboxylic acid esters recovered from a fermentation system is described. The process involves taking a fermentation broth that has been reduced to a dry powder containing free organic acids; reacting the carboxylic acid in the powder with an alcohol solvent under a CO-containing atmosphere in substantial absence of any other acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for at least one of the alcohol or COto synthesize an ester, then subjecting the ester to either hydrogenolysis or hydrogenation to form a biofuel.

Biofuels production from bio-derived carboxylic-acid esters

An improved process for acid-catalyzed acylation using water-tolerant Lewis acid catalysts is described. The method involves reacting a reduction products of 5-(hydroxylmethyl)-furfural (HMF), in particular either furan-2,5-dimethanol (FDM) or bis-2,5-(hydroxymethyl)-tetrahydrofuran (bHMTHFs), with an excess of an organic acid in the presence of a Lewis acid metal triflate at a temperature and time sufficient to produce esters. The conversions of the reduction products of HMF to corresponding diesters can be quantitative with certain favored Lewis acids catalysts.

Method for acid-catalyzed acylation of the reduction products of 5-hydroxymethyl furfural

A method for acid-catalyzed acylation of an isohexide is described. The method involves a reaction of an isohexide and an excess of carboxylic acid in the presence of a Lewis acid or a Brnsted acid catalyst. One or more Lewis acid or Brnsted acid can facilitate conversion of isohexides to their corresponding mono and diesters with a pronounced greater regio-selectivity of exo-OH over endo-OH of the isohexide in the product. Particular catalytic acid species include zirconium chloride (ZrCl) and phosphonic acid (HPO), which manifest a ratio of exo:endo regioselectivity of about 5.0&#x2260;3:1 and about 4.00.3:1, respectively.

Enhanced regio-selectivity in glycol acylation

A process for preparing materials derived from sugar alcohols such that the dehydration products exhibit better accountability and improved color to water-clear or near water-white appearance is described. In particular, the process involves employing a reducing Brnsted acid (e.g., phosphonic acid) for the catalysis of sugar alcohols to their corresponding dehydrated-cyclized products.

Phosphonic acid catalyst in dehydrative cyclization of 5 and 6 carbon polyols with improved color and product accountability

Sugar-derived tetrol, non-ionic amphiphilic amine-esters are prepared facilely and efficaciously in a few steps. The process is initiated by the esterification of a sugar-derived tetrol with a fatty acid chloride, then, undergoing triflate esterification followed by nucleophilic displacement of the aforementioned hydrophilic amine. Each synthetic pathway is efficient and affords modest to high yields of target amphiphiles, which are valorized as practicable surfactant surrogates to petroleum incumbents.

Non-ionic amphiphiles and methods of making the same

The production of organic acids in low-cost, high-efficiency fermentation system makes available a new route to chemical production from biomass. A process for producing a hydrogenation product involving carboxylic acid esters recovered directly from a fermentation process is described.

Hydrogenation products from biologically-derived carboxylic-acid esters

A method of preparing a glycol mono-ether or mono-acetate, or carbonate involving either one of two pathways from alkylene glycols, HMF or its reduction derivative products (i.e., FDM, bHMTHFs), is provided. In particular, according to one pathway, the alkylene glycol, HMF or FDM, bHMTHFs are reacted with a dialkyl carbonate in the presence of a deprotonating agent, in substantial absence of an extrinsic catalyst, to produce an ether, and subsequently reacting the ether with an acid base. According to the other pathway, alkylene glycols are reacted with an acetate donor in the presence of an acid, base, to generate an alkylene mono-acetate, and etherified with a carbonate in the presence of a deprotonating agent.

Direct synthesis of bio-based alkyl and furanic diol ethers, acetates, ether-acetates, and carbonates

A process for preparing cyclic dehydration products from sugar alcohols is described. The process involve using a mixed-acid catalyst reaction mixture containing a reducing acid, having a pKa of about 1.0-1.5, and at least a strong Br&#xf8;nsted acid or a Lewis acid, having a pKa&#x2266;0, or both acids in a solution to dehydrate and ring close said sugar alcohol. Synergistically, the mixed-acid catalysis can produce greater amounts of the desired product at similar levels of compositional accountability than either of the component acid catalysts acting alone.

A process for recovering and using an organic/carboxylic acid or furanic molecule by means of making an ester of a free carboxylic acid or furanic molecule with an alcohol in carbon dioxide (CO) without the presence of any other acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for the alcohol and/or COis described. The process can constitute part of a general process of refining carboxylic acids derived from a fermentation broth or use in the production of a variety of chemical compounds, such as Cplatform compounds or polymers.

Use of carboxylic acids and furanic molecules for esterification

A method for preparing esters from isohexide compounds, and a means by which color bodies that may be made in situ during esterification of isohexide compounds are either prevented from forming or their amounts are minimized in the resultant product mixture are described.

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Decatur, IL, United States of America

Kenneth Stensrud