Single-component adhesive compositions

Patent metadata

Field	Value
Publication number	US-12351745-B2
Application number	US-202017431392-A
Country	US
Kind code	B2
Filing date	Feb 14, 2020
Priority date	Feb 15, 2019
Publication date	Jul 8, 2025
Grant date	Jul 8, 2025

Abstract

Disclosed are single component, stimuli-responsive adhesives that cure in response to an applied stimulus, including single component moisture-curable adhesives (e.g., moisture-curable (meth)acrylate/polyurethane hybrid adhesives). These adhesive compositions can combine the non-toxic, high strength properties of (meth)acrylate adhesives with the bonding characteristics of polyurethanes. The compositions described herein employ imitator systems which trigger polymerization/curing of the adhesive composition in response to a stimulus, such as ambient moisture, mild heat, and/or by physical stress. These strategies eliminate the need for mixing or an external energy stimulus to initiate curing. In this way, the benefits of polyurethane adhesive chemistry can be brought to the consumer market, in a system that is readily usable by the average individual.

First claim

What is claimed is:

1. A single-component adhesive composition comprising:
a curable mixture comprising an ethylenically unsaturated monomer;
a microencapsulated hydrophobic amine having a molecular weight of at least 175 Da dispersed within the curable mixture; and
an oxidant that can generate a free radical upon reaction with the hydrophobic amine, such as a peroxide;
wherein the composition is packaged in a sealed container such that the composition protected from atmospheric moisture,
wherein when packaged in the sealed container, the adhesive composition remains uncured for a period of at least 90 days.

2. The composition of claim 1 , wherein the hydrophobic amine comprises a tertiary amine.

3. The composition of claim 1 , wherein the hydrophobic amine comprises an aromatic tertiary amine.

4. The composition of claim 1 , wherein the hydrophobic amine has a molecular weight of from 250 Da to 1,500 Da.

5. The composition of claim 1 , wherein the hydrophobic amine is defined by Formula II

wherein
R 11 is, independently for each occurrence, hydrogen, hydroxy, halogen, —CN, —NO 2 , silyl, amino, alkylamino, dialkylamino, alkyl, heteroalkyl, haloalkyl, alkylthio, haloalkylthio, alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, heterodialkylaminocarbonyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, aryl, alkylaryl, alkylaryl, heteroaryl, and alkylheteroaryl, each optionally substituted with one or more substituents individually selected from R 8 ;
R 12 is, independently for each occurrence, selected from alkyl, heteroalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, aryl, alkylaryl, heteroaryl, alkylheteroaryl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl, each optionally substituted with one or more substituents individually selected from R 8 ; and
R 8 is, independently for each occurrence, selected from hydroxy, halogen, —CN, —NO 2 , —SF 5 , amino, alkylamino, dialkylamino, alkyl, haloalkyl; alkylthio, haloalkylthio, alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl.

6. The composition of claim 1 , wherein the hydrophobic amine is defined by Formula IIA

wherein
R 12 is, independently for each occurrence, selected from alkyl, heteroalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, aryl, alkylaryl, heteroaryl, alkylheteroaryl, each optionally substituted with one or more substituents individually selected from R 8 ;
R 8 is, independently for each occurrence, selected from hydroxy, halogen, —CN, —NO 2 , —SF 5 , amino, alkylamino, dialkylamino, alkyl, haloalkyl; alkylthio, haloalkylthio, alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl; and
R 13 is alkyl, heteroalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, aryl, alkylaryl, alkylaryl, heteroaryl, and alkylheteroaryl, each optionally substituted with one or more substituents individually selected from R 8 .

7. The composition of claim 1 , wherein the hydrophobic amine includes an ethylenically unsaturated moiety.

8. The composition of claim 1 , wherein the hydrophobic amine is one of the following:

9. The composition of claim 1 , wherein the microencapsulated hydrophobic amine comprises microcapsules encapsulating the hydrophobic amine, wherein the microcapsules are rupturable upon the application of a stimulus.

10. The composition of claim 9 , wherein the stimulus comprises applied pressure, heat, or a combination thereof.

11. The composition of claim 9 , wherein the microcapsules have a diameter of from 5 to 1000 microns.

12. The composition of claim 9 , wherein the microcapsules have a shell thickness of from 1 nm to 100 nm.

13. The composition of claim 9 , wherein the microcapsules are formed from poly(urea-formaldehyde).

14. The composition of claim 1 ,
wherein when packaged in the sealed container, the adhesive composition remains uncured for a period of at least 365 days.

15. The composition of claim 1 , wherein the ethylenically unsaturated monomer comprises a urethane di(meth)acrylate.

16. The composition of claim 15 , wherein the urethane di(meth)acrylate comprises from 30% to 70% by weight of the adhesive composition, based on the total weight of the adhesive composition.

17. The composition of claim 1 , wherein the curable mixture further comprises an alkyleneoxy di(meth)acrylate.

18. The composition of claim 17 , wherein the alkyleneoxy di(meth)acrylate comprises from 10% to 40% by weight of the adhesive composition, based on the total weight of the adhesive composition.

19. The composition of any of claim 1 , wherein the hydrophobic amine comprises from 0.5% to 5% by weight of the adhesive composition, based on the total weight of the adhesive composition.

20. A single-component adhesive composition comprising:
a curable mixture comprising an ethylenically unsaturated monomer;
a microencapsulated hydrophobic amine having a molecular weight of at least 175 Da dispersed within the curable mixture; and
an oxidant that can generate a free radical upon reaction with the hydrophobic amine, such as a peroxide;
wherein the hydrophobic amine is defined by Formula IIA

wherein
R 12 is, independently for each occurrence, selected from alkyl, heteroalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, aryl, alkylaryl, heteroaryl, alkylheteroaryl, each optionally substituted with one or more substituents individually selected from R 8 ;
R 8 is, independently for each occurrence, selected from hydroxy, halogen, —CN, —NO 2 , —SF 5 , amino, alkylamino, dialkylamino, alkyl, haloalkyl; alkylthio, haloalkylthio, alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl; and

Assignees

• Ohio State Innovation Foundation

Inventors

• Parquette Jon
• Schricker Scott
• Bewick Nicholas

Classifications

• C08L61/24

  with urea or thiourea · CPC title

• C08K9/10

  Encapsulated ingredients · CPC title

• C08K5/18

  with aromatically bound amino groups · CPC title

• C08K5/14

  Peroxides · CPC title

• C08F220/14

  Methyl esters {, e.g. methyl (meth)acrylate} · CPC title