Synthesis of phosphonated polymer resins for the extraction of rare-earth elements

Patent metadata

Field	Value
Publication number	US-2025188222-A1
Application number	US-202318841084-A
Country	US
Kind code	A1
Filing date	Feb 23, 2023
Priority date	Feb 23, 2022
Publication date	Jun 12, 2025
Grant date	—

Abstract

In one aspect, the disclosure relates to the use of poly(diethylenepolyamine) derivatives for the extraction of metals, in particular rare-earth metals. In another aspect the disclosure relates to articles and methods for extracting rare-earth metals.

First claim

1 . A network polymer comprising a unit of formula (I):

wherein m is an integer from 1 to 4;
R 1 and R 2 are independently H, D, C 1 -C 6 alkyl, or C 6 -C 12 aryl,;
or a salt thereof.

2 . The polymer of claim 1 wherein m is 1, 2, or 3.

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5 . The polymer of claim 1 wherein R 1 is H.

6 . The polymer of claim 1 wherein R 2 is H.

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8 . The polymer of claim 1 wherein R 1 is CH 3 .

9 . The polymer of claim 1 wherein R 2 is CH 3 .

10 . The polymer of claim 1 wherein R 1 is CH 2 CH 3 .

11 . The polymer of claim 1 wherein R 2 is CH 2 CH 3 .

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17 . A method of isolating an element selected from the group consisting of Lithium, Lead, Scandium, Titanium, Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper, Zinc, Yttrium, Zirconium, Niobium, Molybdenum, Technetium, Ruthenium, Rhodium, Palladium, Silver, Cadmium, Lutetium, Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, Mercury, Lanthanum, Cerium, Praseodymium, Neodymium, Promethium, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Ytterbium, Lutetium, Lawrencium, Rutherfordium, Dubnium, Seaborgium, Bohrium, Hassium, Meitnerium, Darmstadtium, Roentgenium, Copernicium, Actinium, Thorium, Protactinium, Uranium, Neptunium , Plutonium, Americium, Curium, Berkelium, Californium, Einsteinium, Fermium, Mendelevium, and Nobelium, the method comprising contacting a liquid composition comprising the element with the polymer of claim 1 to form an element-polymer adduct.

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44 . A polymer comprising the free bases and/or acid addition salts of a cross-linked copolymerization product of (a) a polyethylenepolyamine containing from about two to about 10 ethylene units and (b) a second member selected from the group consisting of epichlorohydrin, 1,3-dichloro-2-propanol, diepoxybutane, bis-(2,3-epoxy)propyl ether, ethylene glycol bis-(2,3-epoxy)propyl ether, 1,4-butanediol bis-(2,3-epoxy)propyl ether, 1,3-dibromopropane, 1,3-dichloropropane, 1,4-dibrombutane, and 1,4-dichlorobutane, wherein the product contains by weight from about 10 percent to about 50 percent of said second member; and wherein the polymer comprises a multiplicity of —C(R 1 R 2 P(O)(OH) 2 moieties, or salts thereof, wherein the carbon atoms of the —C(R 1 R 2 P(O)(OH) 2 moieties are covalently bonded to nitrogens, wherein R 1 and R 2 are independently H, C 1 -C 6 alkyl, or C 6 -C 12 aryl.

45 . The polymer of claim 44 wherein the polyethylenepolyamine is selected from the group consisting of diethylenetriamine, triethylenetetramine, and tetraethylenepentaamine.

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48 . The polymer of claim 44 wherein R 1 is H.

49 . The polymer of claim 44 wherein R 2 is H.

50 . (canceled)

51 . The polymer of claim 44 wherein R 1 is CH 3 .

52 . The polymer of claim 44 wherein R 2 is CH 3 .

53 . The polymer of claim 44 wherein R 1 is CH 2 CH 3 .

54 . The polymer of claim 44 wherein R 2 is CH 2 CH 3 .

55 . The polymer of claim 44 wherein the second member is selected from the group consisting of epichlorohydrin, 1,3-dichloro-2-propanol, and diepoxybutane.

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58 . The polymer of claim 44 wherein the amount of phosphorous in the polymer by weight is from about 5% to about 30%.

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Assignees

• Virginia Tech Intellectual Properties Inc

Inventors

• Archer William Ryan
• Schulz Michael D

Classifications

• C22B59/00

  Obtaining rare earth metals · CPC title

• C22B3/205

  using adducts or inclusion complexes · CPC title

• Y02P10/20

  Recycling · CPC title

• C08G73/0246 Primary

  Polyamines containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain · CPC title

• C08G73/022 Primary

  from polyamines and epihalohydrins · CPC title