Dynamic urea bonds for reversible and self-healing polymers

Patent metadata

Field	Value
Publication number	US-10000608-B2
Application number	US-201414776104-A
Country	US
Kind code	B2
Filing date	Mar 14, 2014
Priority date	Mar 15, 2013
Publication date	Jun 19, 2018
Grant date	Jun 19, 2018

Abstract

The disclosure provides reversible polymers from polyurea by modifying the nitrogen atom with hindered substituents. The reversibility of hindered urea bond (HUB) can be controlled by changing the bulkiness of the substituents, and N-tert-butyl-N-ethylurea (TBEU), with its high binding constant and short lifetime, is applicable in the design of reversible polymer and self-healing materials at mild temperatures without external stimuli. HUB can be used in the design of smart materials with its adjustable reversibility, facile synthesis, and compatibility with many other polymer structures.

First claim

What is claimed is:

1. A copolymer comprising a polyurea polymer, a polyurethane polymer, polyethylene glycol segments, and triethanolamine crosslinking moieties, wherein the polyurea polymer is selected from,
(A) A polyurea polymer of Formula (IIIa) consisting of:

wherein
R 2 is (C 2 -C 20 )alkyl or H;
R 2 is (C 2 -C 20 )alkyl or H;
R 3 is t-Bu;
X is O or S;
Z is O, S or NH;
L is a linear, branched or network polymer or a small molecule linker, (C 2 -C 20 )alkyl, (C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl(C 1 -C 20 )alkyl, (C 2 -C 20 )alkyl-TEG-(C 2 -C 20 )alkyl, phenyl, or (C 1 -C 20 )alkylphenyl(C 1 -C 20 )alkyl; and

y is about 5 to about 500, and wherein the polymer displays reversible dynamic properties where the substituted urea bonds of Formula (IIIa) dissociate into stable isocyanate and amine moieties and the dissociation has a K eq of less than 10 7 M −1 and a k −1 of at least 0.03 h −1 at 23° C.;
(B) a polyurea polymer of Formula (la) consisting of:

wherein
L is (C 2 -C 20 )alkyl, (C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl(C 1 -C 20 )alkyl, or (C 2 -C 20 )alkyl-TEG-(C 2 -C 20 )alkyl;
n is 2-12; and
y is about 5 to about 500, and wherein the polymer displays reversible dynamic properties where the t-Bu urea bonds of Formula (la) dissociate into stable isocyanate and amine moieties and the dissociation has a K eq of less than 10 7 M −1 and a k −1 of at least 0.03 h −1 at 23° C.;

(C) a polyurea polymer of Formula (IVa) consisting of:

wherein
L is (C 2 -C 20 )alkyl, (C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl, C 1 -C 20 )alkyl(C 6 -C 10 )aryl(C 1 -C 20 )alkyl, (C 2 -C 20 )alkyl-TEG-(C 2 -C 20 )alkyl, phenyl, or C 1 -C 20 )alkylphenyl(C 1 -C 20 )alkyl;
M is (C 2 -C 20 )alkyl, (C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 2 -C 20 )alkyl-TEG-(C 2 -C 20 )alkyl, phenyl, or C 1 -C 20 )alkylphenyl(C 1 -C 20 )alkyl;
R 1 is (C 2 -C 20 )alkyl, H
R 2 is (C 2 -C 20 )alkyl, H
R 3 is t-Bu;
X is O or S; and
Y is about 5 to about 500, and wherein the polymer displays reversible dynamic properties where the substituted urea bonds of Formula (IVa) dissociate into stable isocyanate and amine moieties and the dissociation has a K eq of less than 10 7 M −1 and a k −1 of at least 0.03 h −1 at 23° C.; or

(D) a polyurea polymer of Formula (Va) consisting of:

wherein
L is (C 2 -C 20 )alkyl, (C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl, C 1 -C 20 )alkyl(C 6 -C 10 )aryl(C 1 -C 20 )alkyl, (C 2 -C 20 )alkyl-TEG-(C 2 -C 20 )alkyl, phenyl, or C 1 -C 20 )alkylphenyl(C 1 -C 20 )alkyl;
M is alkyl or phenyl;
R is t-Bu;
X is O or S; and
Y is about 5 to about 500, and wherein the polymer displays reversible dynamic properties where the substituted urea bonds of Formula (Va) dissociate into stable isocyanate and amine moieties and the dissociation has a K eq of less than 10 7 M −1 and a k −1 of at least 0.03 h −1 at 23° C.

2. A copolymer according to claim 1 wherein the polyurea polymer is a polyurea polymer of Formula (IIIa) consisting of:

wherein
R 1 is (C 2 -C 20 )alkyl or H;
R 2 is (C 2 -C 20 )alkyl or H;
R 3 is t-Bu;
X is O or S;
Z is O, S or NH;
L is a linear, branched or network polymer or a small molecule linker, (C 2 -C 20 )alkyl, (C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl(C 1 - C 20 )alkyl, (C 2 -C 20 )alkyl-TEG-(C 2 -C 20 )alkyl, phenyl, or (C 1 -C 20 )alkylphenylC 1 -C 20 )alkyl; and
y is about 5 to about 500, and wherein the polymer displays reversible dynamic properties where the substituted urea bonds of Formula (IIIa) dissociate into stable isocyanate and amine moieties and the dissociation has a K eq of less than 10 7 M -1 and a k −1 of at least 0.03 h −1 at 23 ° C.

3. A copolymer according to claim 1 wherein the polyurea polymer is a polyurea polymer of Formula (la) consisting of:

wherein
L is (C 2 -C 20 )alkyl, (C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl, C 1 -C 20 )alkyl(C 6 -C 10 )aryl(C 1 -C 20 )alkyl, or (C 2 -C 20 )alkyl-TEG-(C 2 -C 20 )alkyl;
n is 2-12; and
y is about 5 to about 500, and wherein the polymer displays reversible dynamic properties where the t-Bu urea bonds of Formula (la) dissociate into stable isocyanate and amine moieties and the dissociation has a K eq of less than 10 7 M −1 and a k −1 of at least 0.03 h −1 at 23° C.

4. A copolymer according to claim 3 wherein L is (C 2 -C 20 )alkyl.

5. A copolymer according to claim 3 wherein n is 4-8.

6. A copolymer according to claim 3 , wherein y is 10 to about 100.

7. A copolymer according to claim 1 wherein the polyurea polymer is a polyurea polymer of Formula (IVa) consisting of:

wherein
L is (C 2 -C 20 )alkyl, (C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl, C 1 -C 20 )alkyl(C 6 -C 10 )aryl(C 1 -C 20 )alkyl, (C 2 -C 20 )alkyl-TEG-(C 2 -C 20 )alkyl, phenyl, or C 1 -C 20 )alkylphenyl(C 1 -C 20 )alkyl;
M is (C 2 -C 20 )alkyl, (C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 2 -C 20 )alkyl-TEG-(C 2 -C 20 )alkyl, phenyl, or C 1 -C 20 )alkylphenyl(C 1 -C 20 )alkyl;
R 1 is (C 2 -C 20 )alkyl, H
R 2 is (C 2 -C 20 )alkyl, H
R 3 is t-Bu;
X is O or S; and
y is about 5 to about 500, and wherein the polymer displays reversible dynamic properties where the substituted urea bonds of Formula (IVa) dissociate into stable isocyanate and amine moieties and the dissociation has a K eq of less than 10 7 M −1 and a k −1 of at least 0.03 h −1 at 23° C.

8. A copolymer according to claim 1 wherein the polyurea polymer is a polyurea polymer of Formula (Va) consisting of:

wherein
L is (C 2 -C 20 )alkyl, (C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )a

Assignees

• Univ Illinois

Inventors

• Cheng Jianjun
• Ying Hanze

Classifications

• C09J175/04

  Polyurethanes · CPC title

• C08G71/02 Primary

  Polyureas · CPC title

• C08G18/758

  containing two or more cycloaliphatic rings · CPC title

• C08G18/73 Primary

  acyclic · CPC title

• C08G18/3246

  heterocyclic, the heteroatom being oxygen or nitrogen in the form of an amino group · CPC title