The Dow Chemical Company

Colorado State University Research Foundation

Dow Global Technolgoies LLC

Dow Global Technology Inc.

Eugene Y Chen

William Jack Kruper, Jr

David R Wilson

Gordon R Roof

Jasson T Patton

David J Schwartz

Joey W Storer

David D Devore

Richard E Campbell, Jr

Jorge Soto

D Patrick Green

Xiaoyan Tang

Dajiang Liu

Jian-Bo Zhu

James C Stevens

Jerzy Klosin

Edmund M Carnahan

Peter N Nickias

Grant B Jacobsen

David D Graf

Robert E LaPointe

Shaoguang S Feng

Miao Hong

Yangjian Hu

Changxia Shi

Yuetao Zhang

A monomer design strategy based on a bridged bicyclic thiolactone that produces stereo-disordered to perfectly stereo-ordered polythioesters is disclosed. The described polythioesters exhibit high crystallinity and full chemical recyclability. Such polymers possess intrinsic tacticity-independent crystallinity and chemical recyclability, tunable tacticities from stereo-disorder to perfect stereoregularity, as well as combined high-performance properties such as high thermal stability and crystallinity, and high mechanical strength, ductility and toughness.

Pan-tactic crystalline and recyclable polythioesters

Biodegradable polymers with advantageous physical and chemical properties are described, as well as methods for making such polymers. In one embodiment, a new chemical synthesis route to technologically important biodegradable poly(3-hydroxybutyrate) (P3HB) with high isotacticity and molecular weight required for a practical use is described. The new route can utilize racemic eight-membered cyclic diolide (rac-DL), meso-DL, or a rac-DL and meso-DL mixture, derived from bio-sourced dimethyl succinate, and enantiomeric (R,R)-DL and (S,S)-DL, optically resolved by metal-based catalysts. With a stereoselective racemic molecular catalyst, the ROP of rac-DL under ambient conditions produces rapidly P3HB with essentially perfect isotacticity ([mm]&#x3e;99%), high crystallinity and melting temperature (T=171&#xb0; C.), as well as high molecular weight and low dispersity (M=1.54&#xd7;10g/mol, &#xd0;=1.01).

Synthesis of polymers from cyclic diolides

Synthesis of crystalline polymers from cyclic diolides

The invention discloses a class of new polymers, trans-ring-fused poly(4-hydroxybutyrate)s (RF-P4HB) that exhibit a unique set of properties, including robust thermal stability and mechanical strength, quantitative recyclability to the building block monomers via thermolysis and/or chemical catalysis, and convenient production from the chemical ring-opening polymerization under ambient temperature and pressure. Another unique property is the formation of crystalline stereocomplexed polymers with high melting temperature upon mixing the two enantiomeric RF-P4HB chains via stereocomplexing co-crystallization. This invention also provides the corresponding ring-fused lactone monomer structures that enable the synthesis of the RF-P4HB polymers, through trans-fusing of rings to the parent &#x3b3;-butyrolactone ring. Furthermore, a polymerization or copolymerization process for the synthesis of RF-P4HB polymers and copolymers is disclosed.

Recyclable polymers based on ring-fused gamma-butyrolactones

The invention provides polymers of Formulas I-III, such as polyesters and unsaturated polyesters, and crosslinked and copolymerized polymers thereof. The invention also provides methods to catalytically ring-open five-membered rings such lactones, lactams, and thiolactones, as via ring-opening polymerization. The polymerization products are recyclable and can be depolymerized back to their monomer form via thermolysis and acid or base catalysis.

Ring-opening polymerization methods and recyclable biorenewable polyesters

B/N Lewis pairs have been discovered to catalyze rapid epimerization of meso-lactide (LA) or LA diastereomers quantitatively into rac-LA. The obtained rac-LA can be kinetically polymerized into poly(-lactide) and optically resolved-LA, with a high stereoselectivity factor k/kof 53 and an ee value of 91% at 50.6% monomer conversion, by a bifunctional chiral catalyst. The epimerization and enantioselective polymerization can be coupled into a one-pot process for transforming meso-LA directly into poly(-lactide) and-LA.

Transformation of meso-lactide

The invention provides new methods for the direct umpolung self-condensation of 5-hydroxymethylfurfural (HMF) by organocatalysis, thereby upgrading the readily available substrate into 5,5'-di(hydroxymethyl) furoin (DHMF). While many efficient catalyst systems have been developed for conversion of plant biomass resources into HMF, the invention now provides methods to convert such nonfood biomass directly into DHMF by a simple process as described herein. The invention also provides highly effective new methods for upgrading other biomass furaldehydes and related compound to liquid fuels. The methods include the organocatalytic self-condensation (umpolung) of biomass furaldehydes into (C-C)furoin intermediates, followed by hydrogenation, etherification or esterification into oxygenated biodiesel, or hydrodeoxygenation by metal-acid tandem catalysis into premium hydrocarbon fuels.

Biorefining compounds and organocatalytic upgrading methods

The invention provides new methods for the direct umpolung self-condensation of 5-hydroxymethylfurfural (HMF) by organocatalysis, thereby upgrading the readily available substrate into 5,5'-di(hydroxymethyl)furoin (DHMF). While many efficient catalyst systems have been developed for conversion of plant biomass resources into HMF, the invention now provides methods to convert such nonfood biomass directly into DHMF by a simple process as described herein. The invention also provides highly effective new methods for upgrading other biomass furaldehydes and related compound to liquid fuels. The methods include the organocatalytic self-condensation (umpolung) of biomass furaldehydes into (C-C)furoin intermediates, followed by hydrogenation, etherification or esterification into oxygenated biodiesel, or hydrodeoxygenation by metal-acid tandem catalysis into premium hydrocarbon fuels.

The invention provides novel polymer compositions and methods for preparing such compositions. The invention also provides methods for polymerizing various unsaturated monomers, including naturally occurring or plant biomass-derived renewable acrylic monomers. The monomers can be rapidly polymerized using various organic catalysts or organometallic catalysts, as described herein. In one embodiment, nearly perfectly isotactic polymers (mmmm&#x3e;99%) can be prepared using a C-symmetric zirconocenium catalyst.

Polymerization catalysts, methods and products

Supported modified alumoxane catalyst activator

Dicationic or partially dicationic Group 4 metal compounds having utility has addition polymerization catalysts among other uses and a method of preparation.

Growing community of inventors

Fort Collins, CO, United States of America

Eugene Y Chen