Self-healing laminate composition, related articles and related methods

Patent metadata

Field	Value
Publication number	US-11529648-B2
Application number	US-202017419781-A
Country	US
Kind code	B2
Filing date	Jan 29, 2020
Priority date	Jan 31, 2019
Publication date	Dec 20, 2022
Grant date	Dec 20, 2022

Abstract

The disclosure relates to a self-healing laminate composition. The composition includes a first, self-healing layer with a self-healing polymer and a second, mechanical layer adjacent to the first layer. The second layer includes any desired polymer, for example a crosslinked polymer, a thermoplastic polymer, or a functional thermoset polymer. Self-healing polymers with dynamic covalent bonds are suitable, for example those with dynamic urea bonds and/or dynamic urethane bonds. A self-healing polymer that is damaged can undergo autonomous repair when separated surfaces re-contact each other due to the soft nature of the self-healing polymer, whereupon reversible bonds can reform to rejoin and repair the damaged self-healing polymer. When the self-healing laminate according to the disclosure is damaged, the self-healing mechanism of the first layer can cause the repair of both layers. The self-healing laminate composition can be used as a coating on any of a variety of substrates to provide self-healing properties to a surface of the substrate.

First claim

What is claimed is:

1. A self-healing laminate composition comprising:
a first layer comprising a self-healing polymer; and
a second layer adjacent to the first layer and comprising a polymer comprising (A) at least one of the crosslinked polymer and the functional thermoset polymer, and (B) a crosslinked backbone comprising:
(i) first crosslinked backbone segments having a structure corresponding to at least one of a urethane reaction product and a urea reaction product from at least one second polyisocyanate;
(ii) second crosslinked backbone segments having a structure corresponding to a urethane reaction product from at least one second polyol;
(iii) optionally third crosslinked backbone segments having a structure corresponding to at least one of a urethane reaction product and a urea reaction product from at least one second reversible polyfunctional linker comprising at least one of a hindered secondary amino group and an aromatic hydroxy group;
(iv) first linking groups linking the first crosslinked backbone segments and the second crosslinked backbone segments, the first linking groups corresponding to a urethane reaction product of the second polyisocyanate and the second polyol; and
(v) optionally second linking groups reversibly linking the first crosslinked backbone segments and the third crosslinked backbone segments, the second linking groups comprising at least one of (A) a reversible urea reaction product between the second polyisocyanate and the hindered secondary amino group of the reversible polyfunctional linker and (B) a reversible urethane reaction product between the second polyisocyanate and the aromatic hydroxy group of the reversible polyfunctional linker;

wherein the self-healing polymer comprises backbone segments comprising reversible linking groups selected from the group consisting of non-covalent interactions, coatings with trapped unreacted reagents, dynamic covalent bonds, thermoreversible bonds, mechanically reversible bonds, UV-triggerable reversible bonds, and combinations thereof.

2. A self-healing laminate composition comprising:
a first layer comprising a self-healing polymer; and
a second layer adjacent to the first layer and comprising a polymer selected from the group consisting of a crosslinked polymer, a thermoplastic polymer, a functional thermoset polymer, and combinations thereof;
wherein the self-healing polymer comprises:
(i) first backbone segments having a structure corresponding to at least one of a urethane reaction product and a urea reaction product from at least one polyisocyanate;
(ii) second backbone segments having a structure corresponding to at least one of a urethane reaction product and a urea reaction product from at least one reversible polyfunctional linker comprising at least one of a hindered secondary amino group and an aromatic hydroxy group; and
(iii) first linking groups reversibly linking the first backbone segments and the second backbone segments, the first linking groups comprising at least one of (A) a reversible urea reaction product between the polyisocyanate and the hindered secondary amino group of the reversible polyfunctional linker and (B) a reversible urethane reaction product between the polyisocyanate and the aromatic hydroxy group of the reversible polyfunctional linker.

3. The self-healing laminate composition of claim 2 , wherein the reversible polyfunctional linker comprises at least two hindered secondary amino groups.

4. The self-healing laminate composition of claim 2 , wherein the reversible polyfunctional linker has one hindered secondary amino group.

5. The self-healing laminate composition of claim 2 , wherein the reversible polyfunctional linker is selected from the group consisting of N,N′-di(t-butyl) ethylenediamine, N,N′-di(iso-propyl) ethylenediamine, N,N′-di(iso-butyl) ethylenediamine and combinations thereof.

6. The self-healing laminate composition of claim 2 , wherein the reversible polyfunctional linker comprises at least two aromatic hydroxy groups.

7. The self-healing laminate composition of claim 2 , wherein the reversible polyfunctional linker has one aromatic hydroxy group.

8. The self-healing laminate composition of claim 2 , wherein the reversible polyfunctional linker is selected from the group consisting of gallic acid esters, benzene diols, halo-substituted benzene diols, alkyl-substituted benzene diols, bisphenols, ubiquiniol, genistein, gallic acid, pyrogailol, aloe emodin, poly(caffeic acid methyl ester), modified lignins, and combinations thereof.

9. The self-healing laminate composition of claim 2 , wherein the polyisocyanate comprises a diisocyanate.

10. The self-healing laminate composition of claim 2 , wherein the polyisocyanate comprises a polyurethane prepolymer diisocyanate.

11. The self-healing laminate composition of claim 2 , wherein the polyisocyanate comprises a triisocyanate.

12. The self-healing laminate composition of claim 2 , wherein:
the polyisocyanate comprises (i) a diisocyanate and (ii) a tri- or higher isocyanate; and
the tri- or higher isocyanate is present in an amount from 0.01 to 20 mol. % relative to total polyisocyanates in the self-healing polymer.

13. The self-healing laminate composition of claim 2 , wherein the polyisocyanate is selected from the group consisting of 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), hydrogenated MDI, xylene diisocyanate (XDI), tetramethylxylol diisocyanate (TMXDI), 4,4′-diphenyl-dimethylmethane diisocyanate, di- and tetraalkyl-diphenylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, one or more isomers of tolylene diisocyanate (TDI), 1-methyl-2,4-diiso-cyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethyl-hexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-iso-cyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane, chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, 4,4′-diisocyanatophenyl-perfluoroethane, tetramethoxybutane 1,4-diisocyanate, butane 1,4-diisocyanate, hexane 1,6-diisocyanate (HDI), HDI dimer (HDID), HDI trimer (HDIT), HDI biuret, 1,5-pentamethylene diisocyanate (PDI), PDID (dimer of PDI), PDIT (trimer of PDI), PDI biuret, dicyclohexylmethane diisocyanate, cyclohexane 1,4-diisocyanate, ethylene diisocyanate, phthalic acid bisisocyanatoethyl ester, 1-chloromethylphenyl 2,4-diisocyanate, 1-bromomethylphenyl 2,6-diisocyanate, 3,3-bischloromethyl ether 4,4′-diphenyldiisocyanate, trimethylhexamethylene diisocyanate, 1,4-diisocyanato-butane, 1,2-diisocyanatododecane, and combinations thereof.

14. The self-healing laminate composition of claim 1 , wherein the self-healing polymer has a glass transition temperature (T g ) of 45° C. or less.

15. The self-healing laminate composition of claim 1 , wherein the first layer further comprises one or more additives selected from the group consisting of nanoclay, graphene oxide, graphene, graphite, silicon dioxide (silica), aluminum oxide, cellulose nanocrystals, carbon nanotubes, zirconia, titanium dioxide (titania), diatomaceous earth, biocides, pigments, dyes, thermoplastics, low and high molecular weight poly(ethylene oxide), salts, non-ionic ingredients, polyhedral oligomeric silsesquioxane (POSS) and POSS derivatives, functional agents, reaction (polymerization) catalyst, and combinations thereof.

16. The self-healing laminate composition of claim 1 , wherein the second layer comprises the crosslinked polymer.

17. The self-healing laminate composition of claim 1 , wherein the second layer comprises the thermoplastic polymer.

Assignees

• Univ Michigan State

Inventors

• Rabnawaz Muhammad
• Khan Ajmir

Classifications

• B05D2420/01

  first layer from the substrate side · CPC title

• B05D7/546 Primary

  each layer being cured, at least partially, separately · CPC title

• C09D183/04

  Polysiloxanes · CPC title

• C09D175/12

  from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group · CPC title

• C09D167/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds (C09D167/06 takes precedence) · CPC title