Method for directly creating a film of 2D polymers from monomer solutions

Patent metadata

Field	Value
Publication number	US-12319787-B2
Application number	US-202117195263-A
Country	US
Kind code	B2
Filing date	Mar 8, 2021
Priority date	Feb 18, 2016
Publication date	Jun 3, 2025
Grant date	Jun 3, 2025

Abstract

Two-dimensional (2D) polymers and methods for their formation are described herein. To create oriented 2D polymer films, monomers are combined with processing additives within a solvent, creating a solution that can be cast and dried to remove the solvent and form a solid film. The methods can enable transformation of the monomers into oriented films. Film quality can be controlled via multiple processing parameters, including monomer and additive concentrations, shear and elongational flow rates during casting, evaporation rates, and post-process rinsing, buffering, stretching, and thermal treatments. By combining stiff carbon-containing cyclic polymer nodal units with more compliant linear polymer bridge units in an ordered, 2D repeating molecular structure it is possible to tailor the mechanical properties of 2D polymers and their assemblies to provide high stiffness, strength, and toughness. The 2D polymer can also be combined with other 2D materials, linear polymers, or reinforcing materials to create 2D polymer composites.

First claim

We claim:

1. A method of producing a two-dimensional (2D) polymer film comprising:
(a) providing one or more first monomers comprising three or more reactive groups per molecule;
(b) providing one or more second monomers comprising two or more reactive groups per molecule;
(c) dissolving or dispersing the first and second monomers in a solvent;
(d) reacting the first and second monomers to form 2D bond network;
(e) removing the solvent,
wherein the first and second monomers are selected so as to form 2D polymer comprising:
a regular, repeating, 2D bond network of (i) a plurality of nodes comprised one or more nodal units which are joined by (ii) one or more linear polymer bridge units, wherein:
(vii) the bridge units are between 0.1-100 nm long;
(viii) each node is bonded to 3 or more bridge units;
(ix) the bridge units maintain the overall planarity of the 2D polymer, wherein the majority of bonds of the bridge units and their adjacent nodal units are located within a limiting distance measured perpendicularly from a single plane upon which the molecule substantially lies corresponding to three times the length of a carbon-carbon single bond; and
(x) the polymer comprises a single molecule having a length greater than 50 nm in both lateral in-plane dimensions.

2. A method of producing a two-dimensional (2D) polymer film comprising:
(a) providing one or more first monomers comprising three or more reactive groups per molecule;
(b) providing one or more second monomers comprising two or more reactive groups per molecule;
(c) dissolving or dispersing the first and second monomers in a solvent;
(d) reacting the first and second monomers to form 2D bond network;
(e) removing the solvent,
wherein the first and second monomers are selected so as to form 2D polymer comprising:
a regular, repeating, 2D bond network of (i) a plurality of nodes comprised one or more carbon-containing cyclic nodal units which are joined by (ii) one or more linear polymer bridge units, wherein:
(iii) the bridge units are between 0.1-100 nm long;
(iv) each node is bonded to 3 or more bridge units;
(v) the bridge units maintain the overall planarity of the 2D polymer, wherein the majority of bonds of the bridge units and their adjacent nodal units are located within a limiting distance measured perpendicularly from a single plane upon which the molecule substantially lies corresponding to three times the length of a carbon-carbon single bond; and
(vi) the polymer comprises a single molecule having a length greater than 50 nm in both lateral in-plane dimensions.

3. The method of claim 2 , wherein the bridge units of the 2D polymer comprise, wholly or in part, a ladder polymer.

4. The method of claim 2 , further comprising: adding one or more processing additives to the dissolved/dispersed solvent/monomer mixture.

5. The method of claim 4 , wherein the processing additives comprise a 2D polymer or 2D oligomer.

6. The method of claim 4 , wherein the processing additives comprise a linear, branched, star, comb, and/or hyper-branched polymer.

7. The method of claim 4 , wherein the processing additives comprise catalyst, reaction modulators, surfactants, and/or dispersants.

8. The method of claim 4 , wherein the processing additive comprises a cross-linkable polymer.

9. The method of claim 4 , wherein the processing additives comprise nanoparticles, nano-platelets, and/or nanofibers.

10. The method of claim 2 , comprising: confining the dissolved/dispersed solvent/monomer mixture in a gap between two surfaces during and/or after polymerization.

11. The method of claim 2 , wherein the dissolved/dispersed solvent/monomer mixture undergoes flow before, during, or after polymerization.

12. The method of claim 2 , comprising: subjecting the resulting 2D polymer film to one or more of the following post-treatments: rinsing, neutralizing, thermal annealing, solvent annealing, UV exposure, radiation exposure, e-beam exposure, uniaxial stretching, biaxial stretching, and through-thickness compression.

13. The method of claim 2 , wherein the one or more solvents comprise water, trifluoroacetic acid, sulfuric acid, anhydrous sulfuric acid, nitric acid, phosphoric acid, dimethylformamide, dimethylacetamide, n-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylpropyleneurea, hexamethylphosphoramide, hexafluoro-2-propanol, trifluoroethanol, nitromethane, and/or dimethyl sulfoxide.

14. The method of claim 2 , further comprising: chemically treating the resulting 2D polymer film to chemically convert a first bond into a second bond.

15. The method of claim 14 , wherein the chemical conversion of a first bond and to a second bond comprises: oxidation of imines to amides; reduction of imines to amines; cyclization of an imine to a thiazole, oxazole, quinolone, pyridine, carbamate or thiocarbamate; linker exchange with an orthohydroxy aldehyde to form a keto-enamine; linker exchange of an imine with hydrazide to form an acyl hydrazone; exchange with hydrazine hydrate to form an azine; and/or exchange with phenyl hydrazine to form a phenylhydrazone.

16. The method of claim 14 , wherein the chemical conversion results in subtraction, addition, or re-arrangement of atoms or bonding electrons in the 2D bond network.

17. The method of claim 2 , further comprising: casting the 2D polymer film in the presence of fibers, yarns, textiles, fabric, knits, braids, and/or felts to form a fiber-reinforced composite.

18. The method of claim 2 , wherein the first and/or second monomers are selected from the group consisting of:

where R comprises one or more chemical functional species capable of reacting to form one or more bonds as part of a chemical linkage.

19. The method of claim 18 , wherein the resulting chemical linkage is selected from the group consisting of: imine, phenazine, imide, azine, cyanovinylene, boronic ester, hydrazone, ester, benzoxazole, polyhydroquinone-diimidazopyridine and β-ketoenamine.

20. The method of claim 18 , wherein the resulting chemical linkage is formed by a Diels-Alder reaction in which a conjugated diene reacts with a substituted alkene to form a substituted cyclohexene derivative.

21. The method of claim 18 , wherein the first monomer comprises a first R and the second monomer comprises a second R which are selected so as to react to form a chemical linkage B, and wherein the first R, second R, and chemical linkage B are selected from the group consisting of: an aldehyde and an amine to form an imine; 1,2 diamine and tetraone to form a phenazine; amine and cyclic anhydride to form an imide; aldehyde and hydrazine to form an azine; aldehyde and phenylacetonitrile to form a cyanovinylene; phenolic and carboxylic acid or ester to form a ester; boronic acid and catechol to form a boronic ester; aldehyde and hydrazide to form a hydrazone; aldehyde and 2-aminophenol to form a benzoxazole; a tetraaminopyridine and dihydroxyterephthalic acid to form a polyhydroquinone-diimidazopyridine and/or diamine and phloroglucinol to form a b-ketoenamine.

22. A two-dimensional (2D) polymer film formed by the method of claim 2 .

23. The film of claim 22 , wherein the film has one or more of the following properties:
(a) a modulus of at least 10 GPa and a strength of at least 1 GPa;
(b) a dielectric constant less than 2.5;
(c) a glass transition temperature of a

Assignees

• U S Army Combat Capabilities Development Command Army Res Laboratory
• Us Army

Inventors

• Mcleod David C
• Lambeth Iii Robert H
• Waters Kevin R
• Sandoz-Rosado Emil J
• Wetzel Eric D

Classifications

• H05K1/0366

  reinforced, e.g. by fibres, fabrics (H05K1/036 takes precedence) · CPC title

• C08G63/133

  Hydroxy compounds containing aromatic rings · CPC title

• C08G73/028

  Polyamidoamines · CPC title

• C08G69/32

  from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound · CPC title

• C08G63/127

  Acids containing aromatic rings · CPC title