IP Library Granted Patent US 12,258,446
Granted Patent B2
US 12,258,446 · App. 18/289,857 · Granted Mar 25, 2025

Polyketone powder for laser sintering

Inventors: Steven Kubiak (Edina, MN); Zachary Peterson (New Hope, MN); Nicholas John Dippel (Burnsville, MN); Mathew Artin Torosian (Highlands Ranch, CO); Thomas Fry (Victoria, MN)
Assignee: LUMAS Polymers LLC
C08G67/02B29B9/02B29B13/021B29C64/314B33Y40/10B33Y70/00C08J3/12C08J3/14C08J9/0004C08J9/36C08L73/00C09D5/031C09D173/00B29C64/153B29K2061/00B29K2071/00B29K2995/004C08G2140/00C08G2150/20C08J2201/054C08J2361/02C08J2373/00C08L2205/025
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 12,258,446
App. No.
18/289,857
Granted
Mar 25, 2025
Kind
B2
Abstract

In one instance a semicrystalline polyketone powder useful for additive manufacturing is comprised of a bimodal melt peak determined by an initial differential scanning calorimetry (DSC) scan at 20° C./min and a D 90 particle size of at most 300 micrometers and average particle size of 1 micrometer to 150 micrometers equivalent spherical diameter. In another instance, A composition is comprised of a semicrystalline polyketone powder having a melt peak and a recrystallization peak, wherein the melt peak and recrystallization peak fail to overlap.

Claims (20)

1. A composition comprising an aliphatic semicrystalline polyketone powder comprising a mixture of a first aliphatic semicrystalline polyketone powder having a bimodal melt peak determined by an initial differential scanning calorimetry (DSC) scan at 20° C./min and a second aliphatic semicrystalline polyketone powder having a monomodal melt peak determined the DSC scan at 20° C./min and the aliphatic semicrystalline polyketone powder having a D 90 particle size of at most 300 micrometers and D50 particle size of 10 micrometers to 125 micrometers equivalent spherical diameter, wherein the semicrystalline polyketone powder is a copolymer of ethylene, carbon monoxide and at least one other alkene monomer.

2. The composition of claim 1 , wherein the semicrystalline polyketone powder is a copolymer of ethylene, carbon monoxide and at least one other alkene monomer that is an olefin.

3. The composition of claim 2 , wherein the other alkene monomer is an olefin having 3 to 12 carbons.

4. The composition of claim 2 , wherein the ethylene is present in a ratio of ethylene/other alkene of about 2 to 100.

5. The composition of claim 1 , wherein the first aliphatic semicrystalline polyketone powder has a recrystallization peak that overlaps a portion of the bimodal melt peak during the initial heating and cooling DSC scan.

6. The composition of claim 5 , wherein upon a subsequent DSC scan, the first aliphatic semicrystalline polyketone powder has a monomodal melt peak.

7. The composition of claim 6 , wherein the subsequent DSC scan has a recrystallization peak that overlaps a portion of the monomodal melt peak.

8. The composition of claim 1 , wherein the polyketone powder has a detectable amount of a group 8-10 transition metal catalyst.

9. The composition of claim 1 , wherein the melt peak has a melt enthalpy of at least 5 joules/gram of polyketone powder.

10. A composition comprised of an aliphatic semicrystalline polyketone powder having a melt peak and a recrystallization peak as determined by differential scanning calorimetry (DSC) scanned at a 20° C./min heating and cooling rate and a D 90 particle size of at most 300 micrometers and D50 particle size of 10 micrometers to 125 micrometers equivalent spherical diameter, wherein the melt peak is monomodal and the melt peak and recrystallization peak fail to overlap, wherein the semicrystalline polyketone powder is a copolymer of ethylene, carbon monoxide and at least one other alkene monomer.

11. The composition of claim 10 , wherein the melt peak has a melt peak onset temperature and the recrystallization peak has an onset recrystallization temperature that are at least separated by 10° C.

12. The composition of claim 10 , wherein the semicrystalline polyketone powder is a copolymer of ethylene, carbon monoxide and at least one other alkene monomer that is an olefin.

13. The composition of claim 12 , wherein the other alkene monomer is an olefin having 3 to 12 carbons.

14. The composition of claim 12 , wherein the ethylene is present in a ratio of ethylene to the other alkene in a ratio of about 2 to 100 by weight.

15. A method for forming an aliphatic polyketone powder useful for making an additive manufactured article comprising:

(i) reacting carbon monoxide, alkene monomer in the presence of a group 8 through 10 transition metal catalyst to form a raw polyketone powder,

(ii) recovering the raw polyketone powder, and

(iii) separating the raw polyketone powder to form the polyketone powder having a D 90 particle size of at most 300 micrometers and D 50 particle size of 10 micrometer to 125 micrometers equivalent spherical diameter and an oversized polyketone powder, wherein the aliphatic polyketone powder is a copolymer of ethylene, carbon monoxide and at least one other alkene monomer and has a bimodal melt peak determined by an initial differential scanning calorimetry (DSC) scan at 20° C./min, wherein the polyketone powder, raw polyketone powder or oversized polyketone powder is subjected to conditions further crystallizing said polyketone powder.

16. The method of claim 15 , wherein the further crystallizing is comprised of heat treating any one of the said polyketone powders to a temperature with 50° C. below its peak melt temperature as determined by DSC for a time to increase the crystallinity forming an increased crystallinity polyketone.

17. The method of claim 16 , wherein the increased crystallinity polyketone has a melt peak onset temperature and a recrystallization onset temperature that are at least separated by 10° C.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 18, 2024
From: JABIL INC.
To: LUMAS POLYMERS LLC
Reel/Frame 069208/0334 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 8, 2023
From: KUBIAK, STEVEN; PETERSON, ZACHARY; DIPPEL, NICHOLAS JOHN; TOROSIAN, MATHEW ARTIN; FRY, THOMAS
To: JABIL INC.
Reel/Frame 065492/0254 →
Continuity (3)
Provisional Application 63217451 · Jul 1, 2021
Provisional Application 63189609 · May 17, 2021
Related Publication 20240247103A1 · Jul 25, 2024
References Cited (73)
US 3065205A · Bonner, Jr. · 1962 [cited by applicant]
US 3179631A · Endry · 1965 [cited by applicant]
US 3214407A · Butterworth · 1965 [cited by applicant]
US 3249588A · Gall · 1966 [cited by applicant]
US 3441538A · Marks · 1969 [cited by applicant]
US 3442857A · Thornton · 1969 [cited by applicant]
US 3516966A · Berr · 1970 [cited by applicant]
US 4704448A · Brugel · 1987 [cited by applicant]
US 4755555A · Manwiller et al. · 1988 [cited by applicant]
US 4816556A · Gay et al. · 1989 [cited by applicant]
US 4824720A · Malone · 1989 [cited by applicant]
US 4835250A · Drent · 1989 [cited by examiner]
US 4853462A · Hostetler et al. · 1989 [cited by applicant]
US 4894435A · Drent · 1990 [cited by applicant]
US 4895689A · Gerlowski · 1990 [cited by examiner]
US 4985278A · George · 1991 [cited by examiner]
US 5138032A · Mastenbroek · 1992 [cited by examiner]
US 5391640A · Akkapeddi et al. · 1995 [cited by applicant]
US 5395055A · Shutov et al. · 1995 [cited by applicant]
US 5527877A · Dickens, Jr. et al. · 1996 [cited by applicant]
US 5597589A · Deckard · 1997 [cited by applicant]
US 5670102A · Perman et al. · 1997 [cited by applicant]
US 5952066A · Schmidt et al. · 1999 [cited by applicant]
US 5977231A · Ash · 1999 [cited by applicant]
US 6136948A · Dickens, Jr. et al. · 2000 [cited by applicant]
US 6177518B1 · Lahijani · 2001 [cited by applicant]
US 6213540B1 · Tusim et al. · 2001 [cited by applicant]
US 6284810B1 · Burnham et al. · 2001 [cited by applicant]
US 7267534B2 · Xu · 2007 [cited by applicant]
US 10364349B1 · Bertelo et al. · 2019 [cited by applicant]
US 10479733B2 · Diekmann et al. · 2019 [cited by applicant]
US 11851526B2 · Louis et al. · 2023 [cited by applicant]
US 20030181538A1 · Martel et al. · 2003 [cited by applicant]
US 20050276967A1 · Prasad · 2005 [cited by applicant]
US 20080058494A1 · Shim et al. · 2008 [cited by applicant]
US 20120077010A1 · Manesis et al. · 2012 [cited by applicant]
US 20120114848A1 · M ller et al. · 2012 [cited by applicant]
US 20130323416A1 · Bertelo et al. · 2013 [cited by applicant]
US 20150011815A1 · Ma et al. · 2015 [cited by applicant]
US 20170282430A1 · Baldwin et al. · 2017 [cited by applicant]
US 20170326790A1 · Lee et al. · 2017 [cited by applicant]
US 20180200922A1 · DeFelice et al. · 2018 [cited by applicant]
US 20200247012A1 · DeFelice et al. · 2020 [cited by applicant]
US 20210277180A1 · Gardner et al. · 2021 [cited by applicant]
US 20210277192A1 · Gardner et al. · 2021 [cited by applicant]
US 20220363825A1 · Kubiak · 2022 [cited by examiner]
US 20220363826A1 · Fry · 2022 [cited by examiner]
CN 110655666A · 2020 [cited by applicant]
EP 121965 · 1984 [cited by examiner]
EP 0431924A2 · 1991 [cited by applicant]
KR 1020160108820A · 2016 [cited by applicant]
NL 8801276 · 1989 [cited by examiner]
WO 9606881A2 · 1996 [cited by applicant]
WO 0138061A1 · 2001 [cited by applicant]
WO 2017033146A1 · 2017 [cited by applicant]
WO 2021137086A1 · 2021 [cited by applicant]
ISM; Mesh and Micron Sizes (2020) pp. 1-7 (Year: 2020). [cited by examiner]
Bhamidipati, M., MS et al., “The Future of Carbon Dioxide for Polymer Processing in Tissue Engineering.” Tissue Engineering: Part B, vol. 19, No. 3, 2013. DOI: 10.1089/ten.teb.2012.0361. (12 pages). [cited by applicant]
Chen, Youming et al., “Effects of Cell Size and Cell Wall Thickness Variations on the Strength of Closed-Cell Foams Using Laguerre Tessellation.” 21st International Conference on Composite Materials, Aug. 2017 (15 pages… [cited by applicant]
Gendron, R. et al., “Supercritical Fluids in Thermoplastics Foaming: Facts or Fallacies?” Rapra Technology, 2006, Cellular Polymers. vol. 25, No. 4, 2006 (24 pages). [cited by applicant]
International Search Report and Written Opinion in co-pending application PCT/US2022/029424 mailed Sep. 1, 2022 (14 pages). [cited by applicant]
Jimenez, J. et al., “Foaming of PLA Composites by Supercritical Fluid-Assisted Processes: A Review.” Molecules 2020, 25, 3408; doi: 10.3390/molecule25153408 (39 pages). [cited by applicant]
Jin, Fan-Long et al., “Recent Trends of Foaming in Polymer Processing: A Review.” Polymers 2019, 11, 953; DOI: 10.3390/polym11060953 (23 pages). [cited by applicant]
Maloo et al.,“A Sneak Peek Toward Polyaryletherketone (PAEK) Polymer: A review”, Cureus, vol. 14, No. 11, Nov. 3, 2022. (9 pages). [cited by applicant]
Migliore, Nicola et al., “Effect of the Polyketone Aromatic Pendent Groups on the Electrical Conductivity of the Derived MWCNTs-Based Nanocomposities . . . ” Polymers 2018, 10, 618; doi: 10.3390/polym10060618 (16 pages). [cited by applicant]
Naitove, Matthew, “A Rare ‘Resurrection’ in Engineering Plastics.” Plastics Technology, Published Oct. 27, 2014. [cited by applicant]
Nalawade, S. et al., “Supercritical carbon dioxide as a green solvent for processing polymer melts: Processing aspects and applications.” Prog. Polym. Sci. 31 (2006) 19-43 (25 pages). [cited by applicant]
Olson, Eric, “Particle Shape Factors and Their Use in Image Analysis Part II: Practical Applications.” Journal of GXP Compliance, Autumn 2011 vol. 15 No. 4 (13 pages). [cited by applicant]
Sauceau, M. et al., “New challenges in polymer foaming: A review of extrusion processes assisted by supercritical carbon dioxide.” Progress in Polymer Science, (2011) 36: 749-766 (30 pages). [cited by applicant]
Schmid et al.,“Materials perspective of polymers for additive manufacturing with selective laser sintering”, Journal of Materials Research, vol. 29, No. 17, Sep. 14, 2014. (1824-1832 pages). [cited by applicant]
Sichina, W.J., “Measurement of Tg by DSC.” Perkin Elmer™ instruments. 2000 PerkinElmer, Inc., PETech-09 Thermal Analysis (5 pages). [cited by applicant]
Toncelli, Claudio, “Functional Polymers from Alternating Aliphatic Polyketones: Synthesis and Applications.” Publication date 2013, University of Groningen (136 pages). [cited by applicant]
International Preliminary Report on Patentability issued in co-pending Application No. PCT/US2022/029422 mailed Dec. 5, 2022 (18 pages). [cited by applicant]