Self-assembly assisted additive manufacturing of thermosets

1. A method comprising:

providing a formulation comprising:

(i) an epoxy monomer comprising one or more epoxy groups;

(ii) a self-assembly monomer comprising a structure of formula (I) or (Ia):

or a salt thereof, wherein:

each of R U1 and R U2 is, independently, H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, or optionally substituted alkaryl,

each of R a1 is, independently, H or optionally substituted alkyl,

each of R S1 , R S2 , and R S3 is, independently, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkyleneoxy, optionally substituted heteroalkyleneoxy, optionally substituted arylene, optionally substituted aryleneoxy, an ether subunit, an arylether subunit, a polyethylene glycol subunit, or a combination thereof, and

each of R A1 is, independently, a reactive moiety configured to react with the one or more epoxy groups of the epoxy monomer;

(iii) a curative monomer comprising one or more reactive moieties configured to react with the one or more epoxy groups of the epoxy monomer; and

(iv) an optional filler;

printing a structure with the formulation at a first temperature of from about 20° C. to about 40° C., thereby providing a printed structure; and

curing the printed structure at a second temperature that is greater than the first temperature, thereby providing a cured structure.

2. The method of claim 1 , wherein each of R A1 in the self-assembly monomer is, independently, an amino.

3. The method of claim 1 , wherein a ratio of a number of the one or more epoxy groups and a number of reactive moieties of the self-assembly monomer and the curative monomer are of from about 4:1 to 1:4.

4. A method comprising:

providing a formulation comprising:

(i) an epoxy monomer comprising one or more epoxy groups;

(ii) a self-assembly monomer comprising a structure of formula (IV-1), (IV-2), (IV-3), (V-1), (V-2), (V-3), (VI-1), (VI-2), (VI-3)

or a salt thereof, and

wherein:

each of R U1 , R U2 , R U3 , R U4 , R U5 , and R U6 is, independently, H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, or optionally substituted alkaryl;

R S1 is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkyleneoxy, optionally substituted heteroalkyleneoxy, optionally substituted arylene, optionally substituted aryleneoxy, an ether subunit, an arylether subunit, a polyethylene glycol subunit, or a combination thereof, or a combination thereof;

each of R a , R b , and R c is, independently, —CR d — or —N—, wherein R d is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, or optionally substituted alkaryl; and

each of R A1 is, independently, a reactive moiety configured to react with one or more epoxy groups of the epoxy monomer; and

wherein the self-assembly monomer comprises at least one hydrogen-bond donating primary or secondary amine and at least one hydrogen-bond accepting carbonyl group or pyridine-based moiety to facilitate intermolecular reversible hydrogen bonding; and

(iii) a curative monomer comprising one or more reactive moieties configured to react with one or more epoxy groups of the epoxy monomer;

printing a structure with the formulation at a first temperature of from about 20° C. to about 40° C., thereby providing a printed structure; and

curing the printed structure at a second temperature that is greater than the first temperature, thereby providing a cured structure.

5. The method of claims 4 or 1 , wherein the curative monomer comprises a structure of formula (II), (IIa), or (IIb):

or a salt thereof, and wherein:

each of R C1 , R C2 , R C3 , and R C4 is, independently, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkyleneoxy, optionally substituted heteroalkyleneoxy, optionally substituted arylene, optionally substituted aryleneoxy, an ether subunit, an arylether subunit, a polyethylene glycol subunit, or a combination thereof;

R C is, independently, H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, or optionally substituted alkaryl;

each of c1, c2, c3, and c4 is, independently, a number of from about 1 to about 500; and

each of R A2 , R A3 , and R A4 is, independently, H, optionally substituted alkyl, or a reactive moiety, in which at least one of R A2 and R A3 and R A4 is a reactive moiety.

6. The method of claims 4 or 1 , wherein the epoxy monomer comprises a structure of formula (III), (IIIa), (IIIb), or (IIIc):

or a salt thereof, and wherein:

each of R E1 and R E2 is, independently, a moiety including one or more epoxy groups, optionally substituted alkyl, optionally substituted alkoxyalkyl, optionally substituted aryloxyalkyl, haloalkyl, optionally substituted aryl, or optionally substituted aryloxy;

each of R e1 , R e2 , R e3 , R e4 , R e5 , and R e6 is, independently, H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, or optionally substituted alkaryl, or in which each of R e1 and R e2 or R e2 and R e3 , taken together, form an optionally substituted cycloalkyl or an optionally substituted heterocyclyl;

e1 is, independently, a number of from about 1 to about 500;

R EL is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkyleneoxy, optionally substituted heteroalkyleneoxy, optionally substituted arylene, optionally substituted aryleneoxy, an ether subunit, an arylether subunit, a polyethylene glycol subunit, or a combination thereof, or a combination thereof; and

each R L is, independently, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted heteroalkylene, thio, oxy, optionally substituted alkyleneoxy, or optionally substituted thioalkylene.

7. The method of claim 1 , wherein the second temperature is of from about 30° C. to about 130° C.

8. The method of claim 7 , further comprising:

treating the cured structure at a third temperature that is greater than the second temperature, thereby providing a fully cured structure.

9. The method of claim 8 , wherein the third temperature is of from about 80° C. to about 150° C.

10. The method of claims 4 or 1 , further comprising a filler.

11. The method of claim 10 , wherein the filler comprises clay, nanoclay, montmorillonite clay, silica, glass, carbon fiber, titanium oxide, aluminum oxide, barium sulfate, calcium carbonate, barium titanate, silicon oxide, talc, hydrotalcite, and/or mica.

12. The method of claims 4 or 1 , wherein the self-assembly monomer is present at an amount of from about 1 mol. % to about 30 mol. % of the combined epoxy monomer, self-assembly monomer, and curative monomer.

13. A method comprising:

providing a formulation comprising:

(i) an epoxy monomer comprising a structure of formula (III):

or a salt thereof, wherein:

R E1 is a moiety including one or more epoxy groups, optionally substituted alkyl, optionally substituted alkoxyalkyl, optionally substituted aryloxyalkyl, haloalkyl, optionally substituted aryl, or optionally substituted aryloxy; and

each of R e1 , R e2 , and R e3 is, independently, H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, or optionally substituted alkaryl, or in which each of R e1 and R e2 or R e2 and R e3 , taken together, form an optionally substituted cycloalkyl or an optionally substituted heterocyclyl;

(ii) a self-assembly monomer comprising a structure of formula (I) or (Ia):

or a salt thereof, wherein:

each of R U1 and R U2 is, independently, H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, or optionally substituted alkaryl,

each of R a1 is, independently, H or optionally substituted alkyl,

each of R S1 , R S2 , and R S3 is, independently, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkyleneoxy, optionally substituted heteroalkyleneoxy, optionally substituted arylene, optionally substituted aryleneoxy, an ether subunit, an arylether subunit, a polyethylene glycol subunit, or a combination thereof, and

each of R A1 is, independently, a reactive moiety configured to react with the one or more epoxy groups of the epoxy monomer;

(iii) a curative monomer comprising a structure of formula (II):

or a salt thereof, wherein:

R C1 is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkyleneoxy, optionally substituted heteroalkyleneoxy, optionally substituted arylene, optionally substituted aryleneoxy, an ether subunit, an arylether subunit, a polyethylene glycol subunit, or a combination thereof, or a combination thereof;

c1 is a number of from about 1 to about 500; and

each of R A2 and R A3 is, independently, H, optionally substituted alkyl, or a reactive moiety, in which at least one of R A2 and R A3 is a reactive moiety configured to react with the one or more epoxy groups of the epoxy monomer; and

(iv) an optional filler; and

wherein the formulation comprises

from about 10 wt. % to about 90 wt. % of the epoxy monomer;

from about 5 wt. % to about 40 wt. % of the self-assembly monomer;

from about 2 wt. % to about 15 wt. % of the curative monomer; and

from about 5 wt. % to about 60 wt. % of the filler; and

printing a structure with the formulation at a first temperature of from about 20° C. to about 40° C. thereby providing a printed structure; and

curing the printed structure at a second temperature that is greater than the first temperature, thereby providing a cured structure.

14. The method of claim 13 , wherein each of R A1 in the self-assembly monomer is, independently, an amino.

15. The method of claim 14 , wherein each of R A2 and R A3 in the curative monomer is, independently, an amino.

16. The method of claim 13 , wherein a ratio of a number of the one or more epoxy groups and a number of reactive moieties of the self-assembly monomer and the curative monomer are of from about 4:1 to 1:4.

17. A method comprising:

providing a formulation comprising:

(i) an epoxy monomer comprising one or more epoxy groups;

(ii) a self-assembly monomer comprising a structure of formula (I) or (Ia):

or a salt thereof, wherein:

each of R U1 and R U2 is, independently, H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, or optionally substituted alkaryl,

each of R a1 is, independently, H or optionally substituted alkyl,

each of R S1 , R S2 , and R S3 is, independently, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkyleneoxy, optionally substituted heteroalkyleneoxy, optionally substituted arylene, optionally substituted aryleneoxy, an ether subunit, an arylether subunit, a polyethylene glycol subunit, or a combination thereof, and

each of R A1 is, independently, a reactive moiety configured to react with the one or more epoxy groups of the epoxy monomer;

(iii) a curative monomer comprising one or more reactive moieties configured to react with the one or more epoxy groups of the epoxy monomer; and

(iv) an optional filler;

treating the formulation under a first stimulus, thereby providing a treated formulation;

printing a structure with the treated formulation, thereby providing a printed structure; and

curing the printed structure with a second stimulus, thereby providing a cured structure.

18. The method of claim 17 , wherein the first stimulus comprises exposure to a first temperature of from about 30° C. to about 130° C.; the second stimulus comprises exposure to an ultraviolet light or to a second temperature of from about 30° C. to about 130° C., in which the second temperature is greater than the first temperature.