IP Library › Granted Patent US 12,448,482
Granted Patent B2
US 12,448,482 · App. 18/746,395 · Granted Oct 21, 2025

Compositions and methods for biodegradable, biomass-based polyesters

Inventors: John Klier (Leverett, MA); Kelsi Marie Skeens Rehmann (Amherst, MA); Lei Zheng (Boston, MA)
Assignee: University of Massachusetts
C08G63/183
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,448,482
App. No.
18/746,395
Granted
Oct 21, 2025
Kind
B2
Abstract

The disclosure relates to biomass-based polyester materials; methods of making biomass-based polyester materials; polyester compositions comprising the disclosed biomass-based polyester materials; polymer compositions comprising the biomass-based polyester materials and one or more additional polymer, including a conventional or non-biomass-based polymer; and articles comprising the disclosed biomass-based polyester materials or disclosed polymer compositions comprising a disclosed biomass-based polyester materials.

Claims (15)

1. A biomass-based polyester material comprising:

repeating units derived from a first monomer component, wherein the first monomer component is 1,5-pentanediol (1,5-PDO), wherein 1,5-pentanediol (1,5-PDO) is a biomass-based monomer component, and

repeating units derived from a pair of second monomer components, wherein the pair of second monomer components are adipic acid and terephthalic acid (TPA);

wherein the repeating units derived from the first monomer component are present in an amount of from about 25 mol % to about 75 mol %;

wherein the repeating units derived from the pair of second monomer components are present in an amount of from about 25 mol % to about 75 mol %;

wherein the ratio of the first monomer component to the pair of second monomer components, on a molar basis, is from about 1.5:1 to about 1:1.5; and

wherein the mol % is based on the total of the repeating units derived from the first monomer component and the repeating units derived from the pair of second monomer components.

2. The biomass-based polyester material of claim 1 , wherein the repeating units derived from the first monomer component are present in an amount of from about 35 mol % to about 65 mol %.

3. The biomass-based polyester material of claim 1 , wherein the biomass-based polyester material has a molecular weight of from about 70 kDa to about 200 kDa.

4. The biomass-based polyester material of claim 1 , wherein the biomass-based polyester material has melting temperature (T m ) of from about 90° C. to about 115° C., wherein the biomass-based polyester material has a molecular weight (weight average) of from about 80 kDa to about 200 kDa, and wherein the glass transition temperature (Tg) is less than or equal to about −10° C.

5. The biomass-based polyester material of claim 1 , wherein the repeating units derived from the first monomer component are present in an amount of from about 45 mol % to about 55 mol %.

6. The biomass-based polyester material of claim 1 , wherein the ratio of the first monomer component to the pair of second monomer components, on a molar basis, is about 1:1.

7. The biomass-based polyester material of claim 1 , wherein the ratio of the first monomer component to the pair of second monomer components, on a molar basis, is about 1:1.1 to 1.1:1.

8. The biomass-based polyester material of claim 1 , wherein the ratio of the adipic acid to the terephthalic acid (TPA) is about 1:2 to 2:1.

9. The biomass-based polyester material of claim 1 , wherein adipic acid is present in an amount of about 5 mol % to about 40 mol % and terephthalic acid (TPA) is present in an amount of about 60 mol % to about 95 mol %.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 24, 2025
From: KLIER, JOHN; SKEENS REHMANN, KELSI MARIE; ZHENG, LEI
To: UNIVERSITY OF MASSACHUSETTS
Reel/Frame 072353/0755 →
Continuity (3)
Continuation 17935252 · Sep 26, 2022
Provisional Application 63248646 · Sep 27, 2021
Related Publication 20240336728A1 · Oct 10, 2024
References Cited (71)
US 5376735A · Sublett · 1994 [cited by applicant]
US 5580911A · Buchanan et al. · 1996 [cited by applicant]
US 5868438A · Svetlik · 1999 [cited by applicant]
US 6140422A · Khanarian et al. · 2000 [cited by applicant]
US 6201034B1 · Warzelhan et al. · 2001 [cited by applicant]
US 6740377B2 · Pecorini et al. · 2004 [cited by applicant]
US 8273846B2 · Nefzger et al. · 2012 [cited by applicant]
US 8772515B2 · Dumesic et al. · 2014 [cited by applicant]
US 9242952B2 · Dumesic et al. · 2016 [cited by applicant]
US 9255194B2 · Allen et al. · 2016 [cited by applicant]
US 9617234B1 · Dumesic et al. · 2017 [cited by applicant]
US 10077224B1 · Huber et al. · 2018 [cited by applicant]
US 20050261465A1 · Nagarajan · 2005 [cited by applicant]
US 20080103340A1 · Binder et al. · 2008 [cited by applicant]
US 20110112270A1 · Meltzer · 2011 [cited by applicant]
US 20150111450A1 · Nederberg et al. · 2015 [cited by applicant]
US 20170145153A1 · Jacquel et al. · 2017 [cited by applicant]
US 20170190832A1 · Jacquel · 2017 [cited by applicant]
EP 2431456A1 · 2012 [cited by applicant]
EP 2628758A1 · 2013 [cited by applicant]
WO 03066704A1 · 2003 [cited by applicant]
WO 2015045562A1 · 2015 [cited by applicant]
WO 2015156802A1 · 2015 [cited by applicant]
WO 2016102361A1 · 2016 [cited by applicant]
WO 2017156269A1 · 2017 [cited by applicant]
WO WO2025079717A1 · 2025 [cited by examiner]
WO 2025079717 Machine Translation (Year: 2025). [cited by examiner]
Alamillo et al., “The selective hydrogenation of biomass-derived 5-hydroxymethylfurfural using heterogeneous catalysts,” Green Chemistry, May 2012, vol. 14, No. 5, pp. 1413-1419. [cited by applicant]
Barnett et al., “Autocatalytic Hydration of Dihydropyran to 1,5-Pentanediol Precursors via in situ Formation of Liquid- and Solid-Phase Acids,” ACS Sustainable Chemistry & Engineering, Sep. 2017, vol. 5, pp. 10223-10230. [cited by applicant]
Brentzel et al., “Chemicals from Biomass: Combining Ring-Opening Tautomerization and Hydrogenation Reactions to Produce 1,5-Pentanediol from Furfural,” ChemSusChem, Apr. 2017, vol. 10, pp. 1351-1355. [cited by applicant]
Bruyn et al., “A new perspective in bio-refining: levoglucosenone and cleaner lignin from waste biorefinery hydrolysis lignin by selective conversion of residual saccharides,” Energy & Environmental Science, Aug. 2016, … [cited by applicant]
Burgess et al., “Carbon Dioxide Sorption and Transport in Amorphous Poly(ethylene furanoate),” Macromolecules, Apr. 2015, vol. 48, pp. 2184-2193. [cited by applicant]
Burgess et al., “Oxygen sorption and transport in amorphous poly(ethylene furanoate),” Polymer, Aug. 2014, vol. 55, pp. 4748-4756. [cited by applicant]
Burt et al., “Production of 1,6-hexanediol from tetrahydropyran-2-methanol by dehydration-hydration and hydrogenation,” Green Chemistry, Feb. 2017, vol. 19, pp. 1390-1398. [cited by applicant]
Cao et al., “Dehydration of cellulose to levoglucosenone using polar aprotic solvents,” Energy & Environmental Science, May 2015, vol. 8, pp. 1808-1815. [cited by applicant]
Garcia et al., “The future of plastics recycling,” Science, Nov. 2017, vol. 358, Issue No. 6365, pp. 870-873. [cited by applicant]
Han et al., “Composition, Thermal Properties, and Biodegradability of a New Biodegradable Aliphatic/Aromatic Copolyester,” Journal of Applied Polymer Science, Apr. 2009, vol. 113, pp. 1298-1306. [cited by applicant]
He et al., “New catalytic strategies for α,ω-diols production from lignocellulosic biomass,” Farady Discuss, Mar. 2017, vol. 202, pp. 247-267. [cited by applicant]
He et al., “Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent-water mixture,” Green Chemistry, Jun. 2017, vol. 19, pp. 1-26. [cited by applicant]
Herrera et al., “Characterization and Degradation Behavior of Poly(butylene adipate-co-terephthalate)s,” Journal of Polymer Science: Part A: Polymer Chemistry, Dec. 2002, vol. 40, pp. 4141-4157. [cited by applicant]
Horn et al., “Mechanisms of Organocatalytic Amidation and Trans-Esterification of Aromatic Esters as a Model for the Depolymerization of Poly(ethylene) Terephthalate,” The Journal of Physical Chemistry, Nov. 2012, vol. … [cited by applicant]
Hu et al., “Upgrading biomass-derived furans via acid-catalysis/hydrogenation: the remarkable difference between water and methanol as the solvent,” Green Chemistry, Jan. 2015, vol. 17, pp. 219-224. [cited by applicant]
Huang et al., “Conversion of Furfural to 1,5-Pentanediol: Process Synthesis and Analysis,” ACS Sustainable Chemistry & Engineering, Apr. 2017, vol. 5, pp. 4699-4706. [cited by applicant]
Huang et al., “Improving economics of lignocellulosic biofuels: An integrated strategy for coproducing 1,5-pentanediol and ethanol,” Applied Energy, Mar. 2018, vol. 213, pp. 585-594. [cited by applicant]
Jambeck et al., “Plastic waste inputs from land into the ocean,” Science, Feb. 13, 2015, vol. 347, Issue No. 6223, pp. 768-771. [cited by applicant]
Jung et al., “Validation of ATR FT-IR to identify polymers of plastic marine debris, including those ingested by marine organisms,” Marine Pollution Bulletin, Feb. 2018, vol. 127, pp. 704-716. [cited by applicant]
Karayannidis et al., “Chemical Recycling of PET by Glycolysis: Polymerization and Characterization of the Dimethacrylated Glycolysate,” Macromolecular Materials and Engineering, Nov. 9, 2006, vol. 291, pp. 1338-1347. [cited by applicant]
Karayannidis et al., “Chemical Recycling of Poly(ethylene terephthalate),” Macromolecular Materials and Engineering, Feb. 2, 2007, vol. 292, pp. 128-146. [cited by applicant]
Kosmidis et al., “Poly(ethylene terephthalate) Recycling and Recovery of Pure Terephthalic Acid. Kinetics of a Phase Transfer Catalyzed Alkaline Hydrolysis,” Macromolecular Materials and Engineering, Oct. 2001, vol. 286… [cited by applicant]
Krishna et al., “Catalytic Production of Hexane-1,2,5,6-tetrol from Bio-renewable Levoglucosanol in Water: Effect of Metal and Acid Sites on (Stereo-Selectivity),” Green Chemistry, Sep. 2018, Issue 19, 18 pages. [cited by applicant]
Krishna et al., “Hydrogenation of Levoglucosenone to Renewable Chemicals,” Green Chemistry, Mar. 2017, Issue 5,16 pages. [cited by applicant]
Krishna et al., “Mechanistic Insights into the Hydrogenolysis of Levoglucosanol over Bifunctional Platinum Silic-Alumina Catalysts,” ACS Catalysis, Mar. 23, 2018, vol. 8, pp. 3743-3753. [cited by applicant]
Krishna et al., “Oxygenated Commodity Chemicals from Chemo-Catalytic Conversion of Biomass Derived Heterocycles,” American Institute of Chemical Engineers, Jun. 2018, vol. 64, No. 6, pp. 1910-1922. [cited by applicant]
Li et al., “Gas-phase dehydration of tetrahydrofurfuryl alcohol to dihydropyran over y-Al2O3,” Applied Catalysis B: Environmental, May 2019, vol. 245, pp. 62-70. [cited by applicant]
Lu et al., “High Molecular Weight Polyesters Derived from Biobased 1,5-Pentanediol and a Variety of Aliphatic Diacids: Synthesis, Characterization, and Thermo-Mechanical Properties,” ACS Sustainable Chemistry & Engineer… [cited by applicant]
Luterbacher et al., “Nonenzymatic Sugar Production from Biomass Using Biomass-Derived y-Valerolactone,” Science, Jan. 17, 2014, vol. 343, pp. 277-280. [cited by applicant]
Motagamwala et al., “Toward biomass-derived renewable plastics: Production of 2,5-furandicarboxylic acid from fructose,” Science Advances, Jan. 19, 2018, vol. 4, pp. 1-8. [cited by applicant]
Muller et al., “Biodegradation of polyesters containing aromatic constituents,” Journal of Biotechnology, Mar. 2001, vol. 86, pp. 87-95. [cited by applicant]
Nakagawa et al., “Catalytic Reduction of Biomass-Derived Furanic Compounds with Hydrogen,” ACS Catalysis, Oct. 6, 2013, vol. 3, pp. 2655-2668. [cited by applicant]
Peng et al., “Hydrolytic degradation of biobased poly(butylene succinate-co-furandicarboxylate) and poly(butylene adipate-co-furandicarboxylate) copolyesters under mild conditions,” Journal of Applied Polymer Science, A… [cited by applicant]
Sherwood et al., “Dihydrolevoglucosenone (Cyrene) as a bio-based alternative for dipolar aprotic solvents,” Chemical Communications, Jul. 2014, vol. 50, pp. 9650-9652. [cited by applicant]
Siracusa et al., “Biodegradable polymers for food packaging: a review,” Trends in Food Science & Technology, Dec. 2008, vol. 19, pp. 634-643. [cited by applicant]
Tosin et al., “Laboratory test methods to determine the degradation of plastics in marine environmental conditions,” Frontiers in Microbiology, Jun. 21, 2012, vol. 3, Article No. 225, pp. 1-9. [cited by applicant]
Tullo, A., “Breaking in the New,” C&EN Northeast News Bureau, Sep. 19, 2011, 5 pages. [cited by applicant]
Wang et al., “Biobased Amorphous Polyesters with High Tg: Trade-Off between Rigid and Flexible Cyclic Diols,” ACS Sustainable Chemistry & Engineering, Feb. 27, 2019, vol. 7, pp. 6401-6411. [cited by applicant]
Wang et al., “Catalytic dehydration of C6 carbohydrates for the production of hydroxymethylfurfural (HMF) as a versatile platform chemical,” Green Chemistry, Feb. 2014, vol. 16, pp. 548-572. [cited by applicant]
Weingarten et al., “Selective Conversion of Cellulose to Hydroxymethylfurfural in Polar Aprotic Solvents,” ChemCatChem, Aug. 2014, vol. 6, pp. 2229-2234. [cited by applicant]
Witt et al., “Biodegradation Behavior and Material Properties of Aliphatic/Aromatic Polyesters of Commercial Importance,” Journal of Environmental Polymer Degradation, Apr. 1997, vol. 5, No. 2, pp. 81-89. [cited by applicant]
Witt et al., “Biodegradation of aliphatic-aromatic copolyesters: evaluation of the final biodegradability and ecotoxicological impact of degradation intermediates,” Chemosphere, Jul. 2001, vol. 44, pp. 289-299. [cited by applicant]
Xu et al., “Ethylene versus ethane: A DFT-based selectivity descriptor for efficient catalyst screening,” Journal of Catalysis, Jun. 2018, vol. 362, pp. 18-24. [cited by applicant]
Zhu et al., “Synthesis and Biodegradation of Aliphatic Polyesters from Dicarboxylic Acids and Diols,” Journal of Applied Polymer Science, Oct. 2003, vol. 90, pp. 982-990. [cited by applicant]