Functional materials with reversible crosslinking
View Patent ↗The present invention relates to an innovative method for the reversible crosslinking of, for example, adhesives or coating materials. The reversible crosslinking method allows very rapid crosslinking even at room temperature and undoing of the crosslinks at higher temperatures, thereby regaining the capacity for thermoplastic processing and allowing the originally bonded substrates to be separated from one another again with ease. A particular aspect in this context is that a plurality of cycles of crosslinking and undoing of the crosslinks are possible with the present system.
1. A formulation, comprising:
a component A comprising two dienophilic double bonds, and
a component B comprising two diene functionalities,
wherein A, B, or both comprises more than two functionalities,
A, B, or both is a polymer,
the formulation is reversibly crosslinkable at room temperature,
the formulation is crosslinkable via a Diels-Alder reaction or a hetero-Diels-Alder reaction, and
component A comprises a dienophile comprising a carbon-sulphur double bond.
2. The formulation of claim 1 , wherein the dienophile is a dithioester.
3. The formulation of claim 1 , wherein the dienophile is a compound having a structure:
wherein Z is an electron-withdrawing group,
R m is a polyvalent organic group or a polymer, and
n is a number between of from 2 to 20.
4. The formulation of claim 3 , wherein Z is a 2-pyridyl group and n is a whole number of from 2 to 4.
5. The formulation of claim 1 ,
wherein components A and B are each a polymer, and
components A and B are optionally identical or are optionally different polymers.
6. The formulation of claim 1 , wherein A, B, or both comprise three functionalities.
7. The formulation of claim 1 ,
wherein component B is a difunctional polymer prepared via ATRP and
a functionalization with the diene functionalities is through substitution of terminal halogen atoms.
8. The formulation of claim 3 ,
wherein component A is a low molecular mass organic compound comprising from 3 to 4 dithioester groups, and
Z is a 2-pyridyl group, a phosphoryl group, or a sulphonyl group.
9. A process for reversible crosslinking, comprising:
crosslinking the formulation of claim 1 via a Diels-Alder reaction or hetero-Diels-Alder reaction at room temperature, and
undoing at least 50% of crosslinks at a temperature higher than room temperature by means of a retro-Diels-Alder reaction or retro-hetero-Diels-Alder reaction.
10. The process of claim 9 , wherein, at a temperature above 80° C., at least 90% of the formulation is soluble in a solvent suitable for the formulation prior to crosslinking.
11. The process of claim 9 , wherein the crosslinking is within 2 minutes after mixing components A and B.
12. The process of claim 9 , wherein the crosslinking is within 2 minutes after mixing components A and B with a crosslinking catalyst.
13. The formulation of claim 1 , wherein each polymer for A, B, or both is at least one member selected from the group consisting of a polyacrylate; a polymethacrylate; a polystyrene; a copolymer of any combination of components selected from the group consisting of an acrylate, a methacrylate, and a styrene; a polyacrylonitrile; a polyether; a polyester; a polylactic acid; a polyamide; a polyesteramide; a polyurethane; a polycarbonate; an amorphous or partially crystalline poly-α-Olefin; EPDM; EPM; hydrogenated or unhydrogenated polybutadiene; ABS; SBR; a polysiloxane; any block, comb, or star copolymer thereof; or any combination of a block, comb, or star copolymer thereof.
14. The process of claim 10 , wherein, within 5 minutes, at least 90% of the formulation is soluble in a solvent suitable for the formulation prior to crosslinking.
15. The process of claim 9 , wherein component A, component B, or both comprise three functionalities.
16. The process of claim 10 , wherein component A, component B, or both comprise three functionalities.
17. An adhesive, sealant, molding compound, varnish, paint, coating, ink, or composite material, comprising the formulation of claim 1 .