Methods of chemical deconstruction and upcycling of waste polymers into versatile vitrimer adhesives

A vinylogous urethane compound having the following formula:

• wherein:
• L1 is independently selected, in each instance, from hydrocarbon linkers containing at least three carbon atoms and optionally one or more heteroatoms selected from N, O, S, and Si;
• R1 is independently, in each instance, selected from H atom and hydrocarbon groups containing 1-3 carbon atoms;
• R2 is independently, in each instance, selected from hydrocarbon groups containing at least one carbon atom and optionally containing one or more heteroatoms selected from N, O, S, and Si wherein, optionally, two R2 groups from different molecules of Formula (5) may interconnect, optionally repetitively, through a hydrocarbon linker L3 containing at least one carbon atom and optionally one or more heteroatoms selected from N, O, S, and Si;
• subscript a is independently selected, in each instance, from 0 or an integer of at least 1;
• and
• subscript b is independently selected, in each instance, from an integer of at least 1.

A vitrimer adhesive polymer comprising A and B units, defined as follows:

• wherein:
• the asterisks (*) in A units represent covalent bond connection points with asterisks in B units;
• L1 is independently selected, in each instance, from hydrocarbon linkers containing at least three carbon atoms and optionally containing one or more heteroatoms selected from N, O, S, and Si;
• L2 represents a hydrocarbon linker containing 1-50 carbon atoms and optionally containing one or more heteroatoms selected from N, O, S, and Si;
• R1 is independently, in each instance, selected from H atom and hydrocarbon groups containing 1-3 carbon atoms;
• subscript a is independently, in each instance, an integer of at least 1;
• subscript b is independently, in each instance, an integer of at least 1;
• and
• subscript p is an integer of 1-5.

A method of deconstructing and upcycling used polymeric material containing carbonyl groups in the backbone of the polymer, the method comprising:

• (i) reacting said polymeric material with a polyamine molecule under conditions that result in covalent attachment of the polyamine molecule with the polymer in the polymeric material to produce an aminated monomer, wherein said aminated monomer contains a multiplicity of free unreacted amino groups from the polyamine molecule, and said polyamine molecule contains at least three amino groups;
• and
• (ii) reacting said aminated monomer with a poly(acylacetate) compound of the formula:
• wherein:
• L2 represents a hydrocarbon linker containing 1-50 carbon atoms and optionally containing one or more heteroatoms selected from N, O, S, and Si, wherein L2 contains at least one ester-containing group of the formula —CH2C(O)O—;
• R1 is independently, in each instance, selected from H atom and hydrocarbon groups containing 1-3 carbon atoms;
• and
• p is an integer of 1-5;
• under conditions that result in reaction between a portion of said free unreacted amino groups in said aminated monomer and carbonyl groups in the bis(acylacetate) compound of Formula (3) to result in a crosslinked polymer containing vinylogous urethane covalent linkages and free unreacted amino groups.

A method of bonding first and second surfaces together, the method comprising placing an adhesive composition between the first and second surfaces and hot pressing the surfaces at a temperature of 80° C. to 200° C., wherein the adhesive composition comprises a vitrimer adhesive polymer comprising A and B units, defined as follows:

• wherein:
• the asterisks (*) in A units represent covalent bond connection points with asterisks in B units;
• L1 independently selected, in each instance, from hydrocarbon linkers containing at least three carbon atoms and optionally containing one or more heteroatoms selected from N, O, S, and Si;
• L2 represents a hydrocarbon linker containing 1-50 carbon atoms and optionally containing one or more heteroatoms selected from N, O, S, and Si;
• R1 is independently, in each instance, selected from H atom and hydrocarbon groups containing 1-3 carbon atoms;
• subscript a is independently, in each instance, an integer of at least 1;
• subscript b is independently, in each instance, an integer of at least 1;
• and
• subscript p is an integer of 1-5.