Closed-loop recycling of scalable plastics

Patent metadata

Field	Value
Publication number	US-12534581-B2
Application number	US-202318452270-A
Country	US
Kind code	B2
Filing date	Aug 18, 2023
Priority date	Aug 19, 2022
Publication date	Jan 27, 2026
Grant date	Jan 27, 2026

Abstract

The present disclosure relates to a nontoxic poly(ethyl cyanoacrylate) (PECA) plastic. The PECA-based plastic is sourced from non-petroleum feedstocks and can be thermally and/or mechanically converted back to the ethyl cyanoacrylate monomer in a closed-loop recycling system with high monomer recovery. The disclosure also provides for methods of making the PECA plastics and methods of recycling the PECA plastics.

First claim

What is claimed is:

1 . A method for preparing a poly(ethyl cyanoacrylate) plastic comprising:
polymerizing an ethyl cyanoacrylate monomer by combining the ethyl cyanoacrylate monomer with an initiator comprising a tertiary amine, a phosphine, an amine, an amine oxide, a betaine, a sulfoxide, or combinations thereof to form a poly(ethyl cyanoacrylate), and curing the poly(ethyl cyanoacrylate) to form a poly(ethyl cyanoacrylate) plastic, wherein the curing occurs in a mold to prepare a product or article comprising the poly(ethyl cyanoacrylate) plastic or the method further comprises thermoforming the poly(ethyl cyanoacrylate) plastic into an article or product.

2 . The method of claim 1 , wherein the initiator comprises dimethylformamide, trimethyl amine N-oxide, trimethylglycine, or dimethyl sulfoxide, or a combination thereof.

3 . The method of claim 1 , wherein the polymerizing occurs at ambient temperature or below, and wherein the curing occurs at ambient temperature or above.

4 . The method of claim 1 , wherein the polymerization and/or curing occurs in a vessel comprising poly(ethylene) or poly(propylene).

5 . The method of claim 1 , wherein the ethyl cyanoacrylate is combined with sub-stoichiometric quantities of the initiator.

6 . The method of claim 1 , wherein the method further comprises annealing the poly(ethyl cyanoacrylate) at a temperature of from about 120° C. to about 150° C. for about 1 minute to about 60 minutes.

7 . The method of claim 6 , wherein the poly(ethyl cyanoacrylate) plastic comprises a tensile strength of from about 15 MPa to about 30 MPa, an elongation at break percentage of from about 20% to about 50%, a Hardness Shore D value of from about 60 to about 80, a density of from about 1 g/mL to about 2 g/mL, an average molecular weight of from about 50 kDa to about 5,000 kDa, and an average polydispersity index of about 1.0 to about 1.4.

8 . The method of claim 1 , wherein the polymerization further comprises an additional component comprising a dye, a pigment, a fragrance, a solvent, a carrier, a thickener, a solidifying agent, a clarifying agent, a decoration, or mixtures thereof.

9 . An article or product comprising the poly(ethyl cyanoacrylate) plastic prepared by the method of claim 1 .

10 . A method for recycling the poly(ethyl cyanoacrylate) plastic of claim 1 comprising:
mechanical depolymerizing the poly(ethyl cyanoacrylate) plastic via mechanical forces;
repolymerizing poly(ethyl cyanoacrylate) plastic by heat pressing; and
optionally repeating the depolymerizing and repolymerizing at least two times, at least three times, or at least four times.

11 . The method of claim 10 , wherein the mechanical forces comprise grinding or milling the poly(ethyl cyanoacrylate) plastic into a powder, and wherein the heat-pressing comprises heating the powder to a temperature of from about 110° C. to about 175° C. and then pressing the powder into a PECA polymer.

12 . A method of recycling a poly(ethyl cyanoacrylate) plastic comprising:
depolymerizing the poly(ethyl cyanoacrylate) plastic into an ethyl cyanoacrylate monomer by combining the poly(ethyl cyanoacrylate) plastic with a reagent comprising hydroquinone, molecular sieves, sodium sulfate, magnesium sulfate, calcium carbonate, or phosphorus pentoxide, or a combination thereof, heating the poly(ethyl cyanoacrylate) plastic and reagent to a temperature of from about 180° C. to about 220° C., and extracting the ethyl cyanoacrylate monomer; and repolymerizing the ethyl cyanoacrylate monomer into poly(ethyl cyanoacrylate) plastic by combining the ethyl cyanoacrylate monomer with an initiator comprising a tertiary amine, a phosphine, an amine, an amine oxide, a betaine, a sulfoxide, or combinations thereof to form a poly(ethyl cyanoacrylate), and curing the poly(ethyl cyanoacrylate) to form a repolymerized poly(ethyl cyanoacrylate) plastic.

13 . The method of claim 12 , wherein the extracting occurs by distillation, and wherein the depolymerization yields at least about 75% monomer.

14 . The method of claim 12 , wherein the initiator comprises dimethylformamide, trimethyl amine N-oxide, trimethylglycine, or dimethyl sulfoxide, or a combination thereof and wherein the ethyl cyanoacrylate is combined with sub-stoichiometric quantities of the initiator.

15 . The method of claim 12 , wherein the repolymerizing occurs at ambient temperature or below, and wherein the curing occurs at ambient temperatures or above, and/or wherein the repolymerizing and/or curing occurs in a vessel comprising poly(ethylene) or poly(propylene).

16 . The method of claim 12 , wherein the repolymerization further comprises annealing the poly(ethyl cyanoacrylate) at a temperature of from about 120° C. to about 150° C. for about 1 minute to about 60 minutes.

17 . The method of claim 12 , wherein the repolymerized poly(ethyl cyanoacrylate) plastic comprises a tensile strength of from about 15 MPa to about 30 MPa, an average molecular weight of from about 50 kDa to about 5,000 kDa, an average polydispersity index of about 1.0 to about 1.4.

18 . The method of claim 12 , wherein the poly(ethyl cyanoacrylate) plastic is a part of a waste stream comprising other plastics, contaminants, or combinations thereof and yields at least about 50% monomer, and optionally wherein the poly(ethyl cyanoacrylate) and other plastics are separated from the contaminants prior to depolymerization and the depolymerization yields at least about 75% monomer.

19 . An article or product comprising the repolymerized poly(ethyl cyanoacrylate) plastic prepared by the method of claim 12 .

Assignees

• Univ Boise State

Inventors

• Phillips Scott
• Christy Allison

Classifications

• C08J2333/14

  of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen · CPC title

• B29K2049/00

  Use of polyacetylene or cyanic ester resins, i.e. polymers having one or more carbon-to-carbon triple bonds or derivatives thereof, as moulding material · CPC title

• C08J11/10

  by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation (depolymerisation to the original monomer C07) · CPC title

• B29B17/0404 Primary

  to powder · CPC title

• C08J3/247 Primary

  Heating methods · CPC title