Recyclable and reconfigurable high-performance polymer networks and uses thereof

Patent metadata

Field	Value
Publication number	US-12281100-B2
Application number	US-202016877336-A
Country	US
Kind code	B2
Filing date	May 18, 2020
Priority date	Nov 16, 2017
Publication date	Apr 22, 2025
Grant date	Apr 22, 2025

Abstract

The present invention relates to a composition of polymers comprising dynamic covalent diketoenamine bonds. This composition allows the formulation of polymeric materials with a wide range of architectures and properties, and further allows these materials to be recycled using thermal, chemical, or mechanical processes.

First claim

What is claimed is:

1. A composition comprising a polymer, or polymer network, having at least one unit of the formula (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX), and/or (XX), or a mixture thereof;

wherein said polymer, or polymer network, is obtained by connecting one compound Y comprising at least two functional groups selected from the group (A), (B), (C), (D), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (Q), (R), (S), (T), (U), (V), and/or (W), or a mixture thereof;

with at least one compound Z comprising at least two amine functional groups of the type —NH 2 , —NHR 4 , —NH 3 + and/or —NHR 4 R 5+ groups, or at least two functional groups that generates —NH 2 , —NHR 4 , —NH 3 + and/or —NHR 4 R 5+ in situ, or a mixture thereof;
wherein said amine is optionally (C 1-20 )alkyl, (C 2-20 )alkenyl; (C 2-20 )alkynyl; (C 6-12 )aryl, (C 3-8 )cycloalkyl; (C 6-12 )aryl(C 1-20 )alkyl; (C 3-8 )cycloalkyl(C 1-20 )alkyl; hetero (C 1-20 )alkyl; heterocyclyl; heterocyclyl(C 1-20 )alkyl; heteroaryl; or heteroaryl(C 1-20 )alkyl;
wherein said (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 3-8 )cycloalkyl(C 1-20 )alkyl; (C 6-12 )aryl(C 1-20 )alkyl, heterocyclyl(C 1-20 )alkyl; and heteroaryl(C 1-20 )alkyl, optionally comprises one or more heteroatoms in the alkyl, alkenyl, alkynyl, moiety, said heteroatoms being each independently a C, Si, chalcogenide, or a pnictide;
wherein at least one carbon atom or heteroatom of said (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 )cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, hetero (C 1-20 )alkyl; heterocyclyl; heteroaryl; (C 3-8 )cycloalkyl(C 1-20 )alkyl; heterocyclyl(C 1-20 )alkyl; and
heteroaryl(C 1-20 )alkyl, can optionally be oxidized to form at least one C═O, C═S, N═O, N═S, S═O or S(O) 2 ;
wherein said (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 )cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, hetero (C 1-20 )alkyl; heterocyclyl; heteroaryl; (C 3-8 )cycloalkyl(C 1-20 )alkyl; heterocyclyl(C 1-20 )alkyl; and heteroaryl(C 1-20 )alkyl, can be unsubstituted or substituted with one or more Z 1 ;
each Z 1 is independently selected from the group consisting of halogen; (C 1-20 )alkyl; (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 )cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, hetero (C 1-20 )alkyl; heterocyclyl; heteroaryl; (C 3-8 )cycloalkyl(C 1-20 )alkyl; heterocyclyl(C 1-20 )alkyl; heteroaryl(C 1-20 )alkyl; halo(C 1-20 )alkyl; halo(C 1-20 )alkyloxy; —OR 5 ; —SR 5 ; —S(O)R 4 ; —S(O) 2 R 4 ; —SO 2 NR 6 R 7 ; —NO 2 ; —NR 5 C(O)R 4 ; —NR 5 S(O) 2 R 4 ; —NR 5 C(O)NR 6 R 7 ; NR 6 R 7 ; cyano; —CO 2 R 5 ; —C(O)NR 6 R 7 ; and —C(O)R 4 , and
wherein the ratio R is less than, or equal to 1 (R≤1), where R=(sum (functionality of compound Y (F Y )×number of moles of compound Y (N Y ))/(sum (functionality of compound Z (F Z )×number of moles of all molecules of compound Z (N Z )):

R
=

∑

F
Y

⁢

N
Y

∑

F
Z

⁢

N
Z

≤
1

;

wherein R 1 is selected from the group consisting of (C 1-20 )alkyl, (C 2-20 )alkenyl; (C 2-20 )alkynyl; (C 6-12 )aryl, (C 3-8 )cycloalkyl; (C 6-12 )aryl(C 1-20 )alkyl; (C 3-8 )cycloalkyl(C 1-20 )alkyl; hetero(C 1-20 )alkyl; heterocyclyl; heterocyclyl(C 1-20 )alkyl; heteroaryl; and heteroaryl(C 1-20 )alkyl;
wherein said (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 3-8 )cycloalkyl(C 1-20 )alkyl; (C 6-12 )aryl(C 1-20 )alkyl, heterocyclyl(C 1-20 )alkyl; and heteroaryl(C 1-20 )alkyl, optionally comprises one or more heteroatoms in the alkyl, alkenyl, alkynyl moiety, each heteroatom is independently a C, Si, chalcogenide, or a pnictid);
wherein at least one carbon atom or heteroatom of said (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-2 )cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, hetero(C 1-20 )alkyl; heterocyclyl; heteroaryl; (C 3-8 )cycloalkyl(C 1-20 )alkyl; heterocyclyl(C 1-20 )alkyl; and/or heteroaryl(C 1-20 )alkyl; can be oxidized to form at least one C═O, C═S, N═O, N═S, S═O or S(O) 2 ;
wherein said (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 )cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, hetero(C 1-20 )alkyl; heterocyclyl; heteroaryl; (C 3-8 )cycloalkyl(C 1-20 )alkyl; heterocyclyl(C 1-20 )alkyl; and/or heteroaryl(C 1-20 )alkyl; is unsubstituted or substituted with one or more Z 1 ;
each Z 1 is independently selected from the group consisting of halogen; (C 1-20 )alkyl; (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 )cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, hetero(C 1-20 )alkyl; heterocyclyl; heteroaryl; (C 3-8 )cycloalkyl(C 1-20 )alkyl; heterocyclyl(C 1-20 )alkyl; heteroaryl(C 1-20 )alkyl; halo(C 1-20 )alkyl; halo(C 1-20 )alkyloxy; OR 5 ; —SR 5 ; —S(O)R 4 ; —S(O) 2 R 4 ; —SO 2 NR 6 R 7 ; nitro; —NR 5 C(O)R 4 ; —NR 5 S(O) 2 R 4 , —NR 5 C(O)NR 6 R 7 ; NR 6 R 7 ; cyano; —CO 2 R 5 ; —C(O)NR 6 R 7 ; and —C(O)R 4 ; and
wherein R 2 is selected from the group consisting of (C 1-20 )alkyl, (C 2-20 )alkenyl; (C 2-20 )alkynyl; (C 6-12 )aryl, (C 3-8 )cycloalkyl; (C 6-12 )aryl(C 1-20 )alkyl; (C 3-8 )cycloalkyl(C 1-20 )alkyl; hetero(C 1-20 )alkyl; heterocyclyl; heterocyclyl(C 1-20 )alkyl; heteroaryl; and heteroaryl(C 1-20 )alkyl;
wherein said (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 3-8 )cycloalkyl(C 1-20 )alkyl; (C 6-12 )aryl(C 1-20 )alkyl, heterocyclyl(C 1-20 )alkyl; and heteroaryl(C 1-20 )alkyl, optionally comprises one or more heteroatoms in the alkyl, alkenyl, alkynyl moiety, each heteroatom is independently a C, Si, chalcogenid), or a pnictid);
wherein at least one carbon atom or heteroatom of said (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 )cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, hetero(C 1-20 )alkyl; heterocyclyl; heteroaryl; (C 3-8 )cycloalkyl(C 1-20 )alkyl; heterocyclyl(C 1-20 )alkyl; and/or heteroaryl(C 1-20 )alkyl; can be oxidized to form at least one C═O, C═S, N═O, N═S, S═O or S(O) 2 ;
wherein said (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-2 )cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, hetero(C 1-20 )alkyl; heterocyclyl;

Assignees

• Univ California

Inventors

• Helms Brett A
• Christensen Peter R

Classifications

• H01B3/30

  plastics; resins; waxes · CPC title

• H01B1/124

  Intrinsically conductive polymers · CPC title

• G10K11/18

  Methods or devices for transmitting, conducting or directing sound (G10K11/02, G10K11/36 take precedence) · CPC title

• G10K11/162

  Selection of materials · CPC title

• C09J179/02

  Polyamines · CPC title