Limonene-based, non-halogenated flame retardants for polymeric applications

Patent metadata

Field	Value
Publication number	US-11053264-B2
Application number	US-202016732994-A
Country	US
Kind code	B2
Filing date	Jan 2, 2020
Priority date	Dec 4, 2017
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

A limonene-based flame-retardant compound, a method of making a flame-retardant polymer, and an article of manufacture comprising a material that includes a limonene-based flame-retardant compound are provided. In an embodiment, the method includes forming a limonene-based derivative; forming a phosphorus-based flame-retardant molecule; reacting the limonene-based derivative with the phosphorus-based flame-retardant molecule to form a limonene-based flame-retardant compound; and forming a flame-retardant polymer from the limonene-based flame-retardant compound. In some embodiments, the limonene-based flame-retardant compound has variable functionality including vinyl, epoxide, methylene bridges, and thioethers.

First claim

What is claimed is:

1. A method of forming a limonene-based polymer, comprising:
reacting a limonene-based derivative with a phosphorous-containing molecule to form a limonene-based compound having the structure

each FR includes a phosphonate group, and
each R is independently alkyl, substituted alkyl, alkenyl, or substituted alkenyl; and

polymerizing the limonene-based compound to form the limonene-based polymer.

2. The method of claim 1 , wherein the limonene-based derivative is synthesized from limonene that has been obtained from a bio-based source.

3. The method of claim 1 , wherein the phosphorus-containing molecule is represented by formula

wherein:
X is chlorine or hydroxyl,
R′ is alkyl, substituted alkyl, aryl, or substituted aryl, and
R is an allyl group, an alkenyl group, an epoxy group, a carbonate group, or a thioether group.

4. The method of claim 1 , wherein the polymerizing comprises performing a base-initiated polymerization or a Ziegler-Natta type polymerization.

5. The method of claim 1 , wherein the substituted alkyl includes an epoxide functional group or a carbonate functional group.

6. The method of claim 1 , wherein the substituted alkyl includes one or more of

wherein:
y is an integer between 1 and 12, and
the dotted line bond indicates a connection to the phosphonate group.

7. The method of claim 1 , wherein each R is a hydroxyl-functionalized limonene.

8. The method of claim 1 , wherein the substituted alkyl is

wherein:
y is an integer between 1 and 12, and
the dotted line bond indicates a connection to the phosphonate group.

9. The method of claim 1 , wherein the substituted alkyl is

wherein:
y is an integer between 1 and 12, and
the dotted line bond indicates a connection to the phosphonate group.

10. A method of forming a polymer, comprising:
reacting a limonene-based derivative with a phosphorous-containing molecule to form a limonene-based compound having the structure

each FR includes a phosphonate group, and
each R is independently alkyl, substituted alkyl, alkenyl, or substituted alkenyl; and

chemically reacting the limonene-based compound with one or more polymers to form the polymer.

11. The method of claim 10 , wherein the one or more polymers comprises polyhydroxylurethanes, polycarbonates, polymers obtained by radical polymerization, polyurethanes, polyesters, polyacrylates, polyimides, polyureas, polyamides, or poly(vinyl-esters).

12. The method of claim 10 , wherein the substituted alkyl includes an epoxide functional group or a carbonate functional group.

13. The method of claim 10 , wherein the substituted alkyl includes one or more of

wherein:
y is an integer between 1 and 12, and
the dotted line bond indicates a connection to the phosphonate group.

14. The method of claim 10 , wherein each R is a hydroxyl-functionalized limonene.

15. The method of claim 10 , wherein the substituted alkyl is

wherein:
y is an integer between 1 and 12, and
the dotted line bond indicates a connection to the phosphonate group.

16. A method of forming a composition, comprising:
reacting a limonene-based derivative with a phosphorous-containing molecule to form a limonene-based compound having the structure

each FR includes a phosphonate group, and
each R is independently alkyl, substituted alkyl, alkenyl, or substituted alkenyl; and

blending the limonene-based compound with one or more polymers to form the composition.

17. The method of claim 16 , wherein the one or more polymers comprises polyhydroxylurethanes, polycarbonates, polymers obtained by radical polymerization, polyurethanes, polyesters, polyacrylates, polyimides, polyureas, polyamides, or poly(vinyl-esters).

18. The method of claim 16 , wherein the substituted alkyl includes one or more of

wherein:
y is an integer between 1 and 12, and
the dotted line bond indicates a connection to the phosphonate group.

19. The method of claim 16 , wherein each R is a hydroxyl-functionalized limonene.

20. The method of claim 16 , wherein the substituted alkyl is

wherein:
y is an integer between 1 and 12, and
the dotted line bond indicates a connection to the phosphonate group.

Assignees

• IBM

Inventors

• Kobilka Brandon M
• Wertz Jason T
• King Scott B
• Kuczynski Joseph

Classifications

• H10W72/354

  comprising polymers · CPC title

• H10W74/47

  comprising organic materials, e.g. plastics or resins · CPC title

• C07F9/65502 Primary

  the oxygen atom being part of a three-membered ring · CPC title

• C08G64/302

  and cyclic ethers · CPC title

• C07F9/3276

  Esters with cycloaliphatic alcohols · CPC title