Supramolecular polymers from amines and phosphoric acid

Abstract

The present disclosure provides a supramolecular polymer comprising phosphate and a organic ammonium. The organic ammonium may be HNR3 + where each R is independently selected from hydrogen or an organic substituent and at least one R is the organic substituent. Each R may be independently selected from optionally substituted aliphatic or benzyl groups. The present disclosure also provides methods for making and using the same.

Description

[0001] SUPRAMOLECULAR POLYMERS FROM AMINES AND PHOSPHORIC ACID

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] The present application claims priority to U.S. Provisional Patent Application No. 63 / 734,042 that was filed December 14, 2024, the entire contents of which are hereby incorporated by reference.

[0004] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0005] This invention was made with government support under 2105848 awarded by National Science Foundation. The Government has certain rights in the invention.

[0006] BACKGROUND OF THE INVENTION

[0007] Cations are emerging as functional and active partners in the hierarchical assembly of anion-driven architectures. Examples include use of cations as templates in phosphate-driven cages, fluorescent cations in optical materials, and as structural partners in chemically-driven crystallization. At the heart of these assemblies is a receptor-anion complex. They serve as the primary structure upon which higher levels of structural order are layered. Charge-balancing organic and inorganic cations are a potential source of a higher level of structural order. Some early studies use quaternary (4°) ammonium as inert cations and tetra-n-butylammonium cation (TBA+). The N-substitution with four alkyl chains turns off specific interactions, e.g., H-bonds. When primary, secondary and tertiary ammoniums are used as cations, these specific interactions turn on and they lead to enhanced interaction strengths, e.g., H-bonds and electrostatics, while also promoting structural ordering.

[0008] Building upon these insights, researchers have begun to explore how such interactions can be extended into larger and more complex cation-anion assemblies, without the use of receptors. The principles of charge balance, structural organization and topology, and controlled interactions provide a foundation for designing dynamic systems composed of cations and anions that go beyond discrete cages or crystalline architectures. Despite great scientific advances in the field of supramolecular polymers, polymer materials that can be easily made from organic amines and phosphoric acid (H3PO4), and the corresponding cation-anion pairs formed after proton transfer, do 1

[0009] QB\144578.00471\99948109.1 not exist. Accordingly, there is a need in the art for materials produced from a 2-pot synthesis which are remoldable, self-adaptive and recyclable.

[0010] BRIEF SUMMARY OF THE INVENTION

[0011] The present technology provides supramolecular polymers that are easy to manufacture from commodity chemicals, specifically organic amines and phosphoric acid. These materials offer significant advantages including being remoldable, self-adaptive, and recyclable. The supramolecular polymers can be reversibly made and remolded by heating or treating with other chemicals, enabling reusability and environmental responsiveness. The materials can be produced efficiently and at relatively low cost, and the properties can be finely tuned through selection from a vast library of commercially available amines.

[0012] The technology relates to a supramolecular polymer comprising phosphate and a organic ammonium. The organic ammonium may be HNR3+where each R is independently selected from hydrogen or an organic substituent, with at least one R being the organic substituent. Each R may be independently selected from optionally substituted aliphatic or benzyl groups, which may be optionally substituted with a halo, a substituent containing oxygen, or a substituent containing silicon. The organic ammonium may comprise at least one primary ammonium , secondary ammonium, or tertiary ammonium. The phosphate and organic ammonium are made by mixing phosphoric acid with the corresponding organic amine that undergo spontaneous proton transfer to make the ionized forms as conjugate base and acid, respectively. In some embodiments, the organic amine and phosphoric acid differ in pKa by greater than 3 units. The supramolecular polymer may be configured as a linear polymer or a network polymer and may exhibit adhesive properties.

[0013] In the present disclosure, it is understood that the organic amine is converted into the organic ammonium by mixing with phosphoric acid. It is understood that identification of an organic amine or organic ammonium is sufficient to describe the composition of the resulting supramolecular polymer.

[0014] The present disclosure also provides a method for preparing the supramolecular polymer comprising mixing an unprotonated organic amine into a phosphoric acid solution and drying the mixture. The phosphoric acid solution may comprise an alcohol solvent such as methanol. The

[0015] 2

[0016] QB\144578.00471\99948109.1 molar ratio of amine to phosphoric acid may be between 0.1 : 1 and 1 : 1. The properties are expected to be tunable based on the ratio, which is not limited by 0.1 : 1 and 1 : 1 described herein.

[0017] The technology further encompasses a method of applying an adhesive comprising the supramolecular polymer to a first substrate and adhering a second substrate to the first substrate. The method may further comprise separating the first and second substrates and adhering a third substrate to either the first or second substrate with the adhesive, demonstrating the reusable nature of the material.

[0018] BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Non-limiting embodiments of the present disclosure will be described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale. In the figures, each identical or nearly identical component illustrated is typically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment shown where illustration is not necessary to allow those of ordinary skill in the art to understand the disclosure.

[0020] Figure 1 illustrates a 2-pot mix of a supramolecular polymer through mixing liquid phosphoric acid (H3PO4) and liquid amine (NR3).

[0021] Figure 2 shows the viscosity of (a) amine-acid ingredients both (b) after initial mixing and (c) after 3 minutes.

[0022] Figure 3 illustrates brittle powder (a) sample preparation followed by the addition of methanol for (b) adhesion test. Photos are shown in (c) of glued samples and the observations of the test (d).

[0023] Figure 4 shows liquid phosphoric acid in a vial where 1 mb of methanol is added followed by addition of 1 eq. of monoamine and 0.5 eq. of diamine which are then put under high vac to test viscosity.

[0024] Figure 5 shows exemplary aliphatic, glycol siloxane, and multi-topic primary amines.

[0025] Figure 6 shows exemplary aliphatic, glycol / fluorinated / siloxane, and multi-topic secondary amines.

[0026] Figure 7 shows exemplary aliphatic, glycol / fluorinated / siloxane, and multi-topic tertiary amines.

[0027] Figure 8 shows preparation and physical form of the material resulting from triethylammonium-phosphate.

[0028] 3

[0029] QB\144578.00471\99948109.1 Figure 9 shows preparation and physical form of the material resulting from diethylammonium phosphate.

[0030] Figure 10 shows preparation and physical form of the material resulting from tris(2- ethylhexyl)ammonium phosphate.

[0031] Figure 11 shows preparation and physical form of the material resulting from N,N,N',N'- tetraethyl-l,12-dodecayl ammonium phosphate.

[0032] Figure 12 shows labelled 'H NMR spectrum of the triethylammonium-phosphate ion pair dissolved in CD3OD (298 K, 500 MHz).

[0033] Figure 13 shows1H NMR spectrum of the diethylammonium phosphate ion pair dissolved in CD3OD (298 K, 500 MHz).

[0034] Figure 14 shows 'H NMR spectrum of the tris(2-ethylhexyl)ammonium phosphate ion pair dissolved in CD3OD (298 K, 500 MHz).

[0035] Figure 15 shows 'HNMR spectrum of theN,N,N',N'-tetraethyl-l,12-dodecayl ammonium phosphate ion pair dissolved in CD3OD (298 K, 500 MHz).

[0036] DETAILED DESCRIPTION OF THE INVENTION

[0037] The present disclosure is described herein using several definitions, as set forth below and throughout the application.

[0038] The present disclosure describes an easy-to-make supramolecular polymer from commodity chemicals derived from organic amines and phosphoric acid (H3PO4). The supramolecular polymer comprises phosphate and a organic ammonium. In some embodiments, the supramolecular polymer includes an anionic species derived from phosphoric acid and a cationic species derived from an amine. Upon proton transfer to an amine, the phosphoric acid is believed to generate an anionic conjugate base and an organic ammonium is HNR3+from an unprotonated organic amine. For the organic ammonium, each R is independently selected from hydrogen or an organic substituent provided that at least one R being the organic substituent. The unprotonated form of the organic ammonium is NR3. In some embodiments, the ammonium can be monotopic, ditopic, or polytopic, i.e., having one, two, three, more than three ammonium groups that may interact with phosphate to produce the supramolecular polymer. Where there is more than one ammonium group, the ammonium groups may be the same or different. In some instances, an organic substituent may be divalent and form a cyclic structure that includes one nitrogen of the

[0039] 4

[0040] QB\144578.00471\99948109.1 ammonium or bridges two or more different ammonium nitrogen atoms. In some instances, an organic substituent may be ramified. Ramified organic substituents include branched alkyl such as

[0041] ❖ those that comprise a central carbon and arms extending therefrom (e g CH(CH )3 or CfCFbj i where each methylene extending from a central carbon may be further bonded to other groups including an ammonium or amine as indicated by *), allowing for it to bridge three, four, or more than four nitrogens. The combination of the anionic species and the cationic (organic ammonium) species results in a supramolecular material stabilized by a network of non-covalent interactions. The assembly is driven by complementary electrostatics, hydrogen bonding, and cavity confinement, to yield the supramolecular complex.

[0042] The cationic (organic ammonium) species derived from amines may include primary, secondary, or tertiary amino groups and any combination thereof. Where the organic ammonium comprises two or more ammonium groups, the ammonium groups may be primary, secondary, or tertiary and the ammonium groups may be the same or different. The organic ammonium may be characterized by HNR3+and the unprotonated form NR3. Each R may be independently selected from optionally substituted aliphatic or benzyl groups. In some embodiments, at least one R of the organic ammonium is optionally substituted with a halo, a substituent containing oxygen, or a substituent containing silicon. Suitably, the organic groups of the ammonium may be selected from alkyl, cycloalkyl, aryl, or the like. The organic group may be optionally substituted. For example, the organic group may be optionally substituted with a group containing oxygen (e.g., -OCH3, a glycol), fluorine, or a group containing silicon (e.g., -Si(OCH3)3). The ammonium may be a cyclic ammonium, such as a heterocycle or heteroaryl. In some embodiments, the organic ammonium and phosphoric acid differ in pKa by greater than 3 units to ensure proton transfer and formation of the cationic and anionic partners. The first pKa of phosphoric acid is 2.3. Therefore, any amine with a pKa value higher than 5.3 will undergo spontaneous proton transfer and be capable of forming supramolecular polymers. The examples described herein are intended to illustrate the practicality of amine / phosphoric acid supramolecular materials and are not meant to limit the scope of the disclosed subject matter. Rather, they demonstrate the wide range of structural possibilities and functional outcomes achievable through selection of amine building blocks. The facile preparation method allows for numerous cationic or unprotanated amines to be used to prepare the supramolecular polymers. For example, review of database entries identified approximately 7,000 primary (1°) amines, approximately 17,000 secondary (2°) amines, and approximately 3,000

[0043] 5

[0044] QB\144578.00471\99948109.1 tertiary (3°) amines available from commercial suppliers. This diversity enables the design of supramolecular systems with tunable properties based on amine selection. Various material forms including gels, viscous liquids, elastomers, adhesives, and fibers can be made by selection of the amines from commercial suppliers. Exemplary organic amines are provided below. However, the present disclosure is not limited to the exemplary organic amines. In some embodiments, the organic ammonium comprises at least one primary amine having an unprotonated structure selected from the group consisting of:

[0045] In some embodiments, the organic ammonium comprises at least one secondary amine having an unprotonated structure selected from the group consisting of:

[0046] 6

[0047] QB\144578.00471\99948109.1

[0048]

[0049] In some embodiments, the organic ammonium comprises at least one tertiary amine having an unprotonated structure selected from the group consisting of:

[0050] In some embodiments, the supram olecul ar polymer is a linear polymer. In some embodiments, the supramolecular polymer is a network polymer.

[0051] Amine variability will allow the material properties to be varied systematically to produce polymers with a variety of base mechanical properties, e.g., gels, elastomers, adhesives, fibers, although these are largely untested to date. In some embodiments, the polymer materials made will provide a customer with the property of being reversible aka reconfigurable, healable, and environmentally responsive. Thus, the material will be remoldable, self-adaptive and recyclable. The supramolecular material may be used as pressure sensitive adhesives, bio-interfaced adhesives, bio-interfaced polymers, recycling / recyclable polymers, and materials for 3D printed polymers. In some embodiments, the composition is used to make glues / adhesives that can be reversibly made, broken and remade again like post-it notes. In some embodiments, these materials will be easy to make by mixing the components together. In some embodiments, no heating is required. In some embodiments, the supramolecular polymers are expected to be reversibly made and remolded by heating or treating with other chemicals, like water. The materials produced can be manufactured efficiently and at relatively low cost. Moreover, incorporating mixtures of two or

[0052] QB\144578.00471\99948109.1 more different organic amines allows the properties of the resulting materials to be finely tuned for their intended applications.

[0053] The present disclosure also provides a method of the preparation of the supramolecular material described herein. The method includes making the anionic species and the cationic species by mixing the neutral amine and the neutral phosphoric acid into solution. In some embodiments, the method includes mixing an amine into a phosphoric acid solution and drying the mixture. The phosphoric acid solution includes an alcohol solvent, such as methanol, ethanol, or isopropanol. In some embodiments, the phosphoric acid solution solvent is a blend of alcohol and water. In other embodiments, the phosphoric acid solution solvent is water. In some embodiments, the molar ratio of amine to phosphoric acid in the solution is between 0.1: 10, 10:0.1, 0.1 :1, 1 :0.1, 0.5: 1, 1 :0.5, and 1 : 1. In certain embodiments, the molar ratio of amine to phosphoric acid is 0.5: 1, 1 :1, or 1 :0.5. In some embodiments, the volume-to-volume ratio of phosphoric acid to solvent in the solution is between 0.1: 10, 10:0.1, 0.1 :1, 1 :0.1, 1 :4, 4: 1, and 1 : 1. In certain embodiments, the volume-to-volume ratio of phosphoric acid to methanol is 1 :4 or 1 :2. In some embodiments, the amine is added dropwise to the mixture. The mixture may be stirred for between 15 seconds and 4 hours, between 30 seconds and 1 hour, between 30 seconds and 5 minutes, between 30 seconds and 1 minute, or for about 1 minute. After the mixture is stirred, the solvent may be removed under high vacuum to afford the supramolecular material.

[0054] The disclosed subject matter may be further described using definitions and terminology as follows. The definitions and terminology used herein are for the purpose of describing particular embodiments only and are not intended to be limiting.

[0055] As used in this specification and the claims, the singular forms "a," "an," and "the" include plural forms unless the context clearly dictates otherwise. For example, the term "a substituent" should be interpreted to mean "one or more substituents," unless the context clearly dictates otherwise.

[0056] As used herein, "about", "approximately," "substantially," and "significantly" will be understood by persons of ordinary skill in the art and will vary to some extent on the context in which they are used. If there are uses of the term which are not clear to persons of ordinary skill in the art given the context in which it is used, "about" and "approximately" will mean up to plus or minus 10% of the particular term and "substantially" and "significantly" will mean more than plus or minus 10% of the particular term.

[0057] 8

[0058] QB\144578.00471\99948109.1 As used herein, the terms "include" and "including" have the same meaning as the terms "comprise" and "comprising." The terms "comprise" and "comprising" should be interpreted as being "open" transitional terms that permit the inclusion of additional components further to those components recited in the claims. The terms "consist" and "consisting of should be interpreted as being "closed" transitional terms that do not permit the inclusion of additional components other than the components recited in the claims. The term "consisting essentially of should be interpreted to be partially closed and allowing the inclusion only of additional components that do not fundamentally alter the nature of the claimed subject matter.

[0059] The phrase "such as" should be interpreted as "for example, including." Moreover, the use of any and all exemplary language, including but not limited to "such as", is intended merely to better illuminate the disclosed subject matter and does not pose a limitation on the scope of the disclosed subject matter unless otherwise claimed.

[0060] Furthermore, in those instances where a convention analogous to "at least one of A, B and C, etc." is used, in general such a construction is intended in the sense of one having ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B and C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together.). It will be further understood by those within the art that virtually any disjunctive word and / or phrase presenting two or more alternative terms, whether in the description or figures, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" will be understood to include the possibilities of "A" or B or "A and B."

[0061] All language such as "up to," "at least," "greater than," "less than," and the like, include the number recited and refer to ranges which can subsequently be broken down into ranges and subranges. A range includes each individual member. Thus, for example, a group having 1-3 members refers to groups having 1, 2, or 3 members. Similarly, a group having 6 members refers to groups having 1, 2, 3, 4, or 6 members, and so forth.

[0062] The modal verb "may" refers to the preferred use or selection of one or more options or choices among the several described embodiments or features contained within the same. Where no options or choices are disclosed regarding a particular embodiment or feature contained in the same, the modal verb "may" refers to an affirmative act regarding how to make or use and aspect of a described embodiment or feature contained in the same, or a definitive decision to use a

[0063] 9

[0064] QB\144578.00471\99948109.1 specific skill regarding a described embodiment or feature contained in the same. Tn this latter context, the modal verb "may" has the same meaning and connotation as the auxiliary verb "can."

[0065] Certain aspects of the disclosed subject matter are described herein. Variations of those aspects may become apparent to those of ordinary skill in the art upon reading the foregoing description. Those of ordinary skill in the art are expected to employ such variations as appropriate, and the disclosed subject matter is intended to be practiced otherwise than as specifically described herein. Accordingly, the disclosed subject matter includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosed subject matter unless otherwise indicated herein or otherwise clearly contradicted by context.

[0066] In the foregoing description, it will be readily apparent to one skilled in the art that varying substitutions and modifications may be made to the disclosed subject matter without departing from the scope and spirit of the disclosure. The disclosed subject matter illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the disclosed subject matter. Thus, it should be understood that although the present disclosure has been illustrated by specific embodiments and optional features, modification and / or variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of the disclosed subject matter.

[0067] Citations to a number of patent and non-patent references may be made herein. The cited references are incorporated by reference herein in their entireties. In the event that there is an inconsistency between a definition of a term in the specification as compared to a definition of the term in a cited reference, the term should be interpreted based on the definition in the specification.

[0068] EXAMPLES

[0069] The following Examples are illustrative and should not be interpreted to limit the scope of the claimed subject matter.

[0070] 10

[0071] QB\144578.00471\99948109.1 Summary

[0072] An easy-to-make supramolecular polymer from commodity chemicals derived from mixing (Figure 1) organic amines and phosphoric acid (H3PO4) is described herein. Acid-base supramolecular polymers, e.g., linear and network polymers are described herein. These supramolecular polymers are expected to be reversibly made and remolded by heating or treating with other chemicals, like water. These materials may have the property of being easy to make by mixing the components together solely from commercially available amines (as both bulk and specialty chemicals) and phosphoric acid. Two species are mixed to form a supramolecular polymer with only simple processing required.

[0073] In some embodiments, phosphoric acid (H3PO4) is dissolved in an alcohol, such as methanol. To this solution an amine is added. The mixture is then dried to generate the resulting supramolecular polymer as a bulk material (See procedure in Figure 4).

[0074] Pre-dissolving the acid in the alcohol facilitates formation of the polymer. The acid is H3PO4. The amine can be a primary (1°) amine (RNH2); commercial examples shown in Figure 5, secondary (2°) amine (RxRyNH; commercial examples shown in Figure 6) or a tertiary (3°) amine (RxRyRzN, commercial examples shown in Figure 7). In these cases, Rx, Ry and Rz are organic groups selected from aliphatic, benzyl, etc. with many examples shown in Figures 5-7.

[0075] Figures 2 and 3 show viscous liquids and weak adhesives at this stage for a tertiary (Figure 2) and primary (Figure 3) amine.

[0076] These supramolecular polymers can be made into various material forms, e g., viscoelastic materials (Figures 2, 8, 10), viscous liquids (Figure 11), and adhesives (Figure 3) with the potential to form gels, elastomers, fibers, by selection of the amines from commercial suppliers. Based on a search of Scifinder, there are -7,000 primary (1°) amines, -17,000 secondary (2°) amines and -3,000 tertiary (3°) amines totaling 27,000 to choose from commercial suppliers. The supramolecular material will be remoldable, self-adaptive and recyclable. It is expected that other compositions involving mixtures of more than two different organic amines will enable the properties of the materials to be finely tuned.

[0077] Discussion

[0078] The formation of the supramolecular materials was tested using six amines (Figures 2, 3, 8-11). Each of them was formed the same way following the general preparation method (Figure 4). Five of the materials form a viscoelastic material that flows slowly after inversion in a sample

[0079] 11

[0080] QB\144578.00471\99948109.1 vial (Figures 2, 4, 8, 10). One of the materials forms a solid based on formation of a white material (Figure 9). One of the materials forms a viscous liquid as based on the inversion of a vial of the material (Figure 11). One of the materials can be used as an adhesion to glue two glass slides together (Figure 3). The adhesive property is weak based on use of hand pressure to separate the glass slides. The adhesion was found to be reversible upon contacting the two separated glass slides together. The behavior observed indicates that the materials are reusable and are composed of supramolecular linkages. The adhesion was observed to retain its properties in harsh conditions including but not limited to an underwater environment. One of the materials was found to produce a pink color upon formation (Figure 10).

[0081] Conclusions

[0082] The acid-base supramolecular polymers disclosed herein (Figure 1) make linear and network polymers simply by mixing organic amines with phosphoric acid (H3PO4). These supramolecular polymers are expected to be reversibly made and remolded by heating or treating with other chemicals. These materials may be made by mixing the components together solely from commercially available amines (as both bulk and specialty chemicals) and phosphoric acid.

[0083] General Methods:

[0084] All reagents were obtained from commercial suppliers. Nuclear magnetic resonance (NMR) spectra were recorded on Varian Inova (600 MHz) spectrometers at room temperature (298 K). Chemical shifts were referenced to residual solvent peaks.

[0085] The supramolecular polymers were prepared using a methanol solution of from phosphoric acid (>97%, Sigma-Aldrich) to which is added one equivalent of commercially available amines (1.0 M solution in methanol, Sigma-Aldrich). The resulting viscous liquid were dried in vacuo for 2 h to remove solvents and was used without further purification.

[0086] Experimental method for NMR titration

[0087] As a prepared solution of the supramolecular polymer was added to an NMR tube sealed with a silicon septum and a spectrum recorded. All the spectral data were analyzed using MestReNova software.

[0088] General method for preparing a supramolecular polymer:

[0089] Methanol (2.0 mL) was placed in a 20 mb glass vial, and phosphoric acid (0.50 mL, commercial grade) was added with stirring at room temperature until a homogeneous solution was obtained. An amine (0.5-1.0 eq.) was added dropwise under constant stirring, resulting in the

[0090] 12

[0091] QB\144578.00471\99948109.1 immediate formation of a viscous gel. The mixture was stirred for an additional 5 minutes, after which the solvent was removed under high vacuum to afford the corresponding ammoniumphosphate supram olecular polymer often in the form of a gel. The resulting material was used directly in characterization.

[0092] T riethylammonium-phosphate

[0093] Phosphoric acid (0.50 mL) was added to stirred methanol (2.0 mL). The mixture was stirred for 1 min. Triethylamine (0.48 mL, 1 eq.) was added dropwise under constant stirring, resulting in the formation of a viscous gel. The mixture was stirred for an additional 5 minutes, after which the solvent was removed under high vacuum to afford a highly viscous triethylammonium phosphate gel. See Figure 12. *HNMR (500 MHz, CD3OD): 5 = 18.01 (s, OH), 9.5 (s, NH), 5.44 (s, 1H), 3.22 (q, 6H), 1.25 (t, 9H) ppm.

[0094] When TEA was added dropwise, a gel-like response was observed. This material dissolved with stirring. The gel remained after all of the amine was added.

[0095] Diethylammonium phosphate

[0096] Phosphoric acid (0.50 mL) was added to a 20 mL glass vial containing methanol (2.0 mL) and the mixture was stirred for 1 min. Diethylamine (1 eq., 0.38 mL) was then added dropwise under constant stirring, which resulted in the formation of a cloudy solution. The mixture was stirred for an additional 5 minutes, after which the solvent was subsequently removed under high vacuum to yield a diethylammonium phosphate gel. See Figure 13. 'H NMR (500 MHz, CD3OD): 8 = 17.59 (s, OH), 9.23 (s, NH), 7.54 (s, NH), 6.96 (s, NH), 3.03 (q, 4H), 1.34 (t, 6H) ppm.

[0097] A,A',A'',A''-Tetramethyl-l,6-hexanediammonium phosphate

[0098] A 20 mL glass vial was charged with methanol (1.0 mL), and the mixture was stirred for 1 min. Then phosphoric acid (0.50 mL) was added and the mixture was stirred at room temperature for 1 minute to give a homogeneous solution. A solution of N, N,N', N '-tetramethyl -1,6- hexanediamine (0.5 eq, 0.629 g) in methanol (1.0 mL) was added dropwise under continuous stirring, which produced a transparent reaction mixture. The mixture was stirred for an additional 5 minutes, and the solvent was subsequently removed under high vacuum to afford a viscous diammonium phosphate liquid.

[0099] Tris(2-ethylhexyl)ammonium phosphate

[0100] Phosphoric acid (0.50 mL, commercial grade) was added to a 20 mL glass vial pre-charged with methanol (2.0 mL) and stirred at room temperature for 1 min. Upon dropwise addition of the

[0101] 13

[0102] QB\144578.00471\99948109.1 tris(2-ethylhexyl)amine (1.0 eq., 1.58 mL), the mixture forms two layers. When the mixture is stirred, it forms a viscous transparent liquid. The mixture was stirred for an additional 5 minutes, after which the solvent was removed under high vacuum. As the overall concentration of the initially colorless acid-base solution increases, the mixture gradually develops a more intense pink coloration and form a highly viscous tris(2-ethylhexyl)ammonium phosphate pink colored gel. See Figure 14. 'H NMR (500 MHz, CD3OD): 5 = 16.95 (s, OH), 16.51 (s, OH), 9.81 (s, NH), 9.41 (s, NH), 8.06 (s, NH), 3.10 ( m, 6H), 1.82 (m, 3H) 1.83 (m, 6H), 1.55 (m, 6H), 1.35 (m, 18H), 0.97 (sext, 18H) ppm.

[0103] A,A,A^',A^'-Tetraethyl-l,12-dodecayl ammonium phosphate

[0104] Phosphoric acid (0.50 mL) was added to a 20 mL glass vial containing methanol (2.0 mL) and stirred at room temperature for 1 min. 1,12-Diethylamine (1.0 eq, 1.15 mL) was added dropwise under continuous stirring to obtain a homogeneous solution mixture. The mixture was stirred for an additional 5 minutes, after which the solvent was removed under high vacuum to yield a viscous 1,12-di ethylammonium phosphate liquid. See Figure 15. 'H NMR (500 MHz, CD3OD): 5 = 11.28 (s, NH), 9.23 (s, NH), 8.32 (NH),3.33 (q, 4H), 3.19 (q, 6H), 3.07 (m, 4H), 1.37 (m, 8H), 1.37 (s, 10H), 1.32 (t, 12H) ppm.

[0105] 14

[0106] QB\144578.00471\99948109.1

Claims

CLAIMS1. A supramolecular polymer comprising phosphate and organic ammonium.

2. The supramolecular polymer of claim 1, wherein the organic ammonium is HNR3+where each R are independently selected from hydrogen or an organic substituent and at least one R is the organic substituent.

3. The supramolecular polymer of claim 2, wherein each R are independently selected from optionally substituted aliphatic or benzyl groups.

4. The supramolecular polymer of claim 3, wherein at least one R of the organic ammonium is optionally substituted with a halo, an substituent containing oxygen, or a substituent containing silicon.

5. The supramolecular polymer of any one of claims 1-4, wherein the organic ammonium comprises at least one primary ammonium.

6. The supramolecular polymer of claim 5, wherein the organic ammonium has an unprotonated structure selected from the group consisting of:

7. The supramolecular polymer of any one of claims 1-4, wherein the organic ammonium comprises at least one secondary ammonium.15QB\144578.00471\99948109.

18. The supramol ecul ar polymer of claim 7, wherein the secondary organic ammonium has an unprotonated structure selected from the group consisting of:

9. The supramol ecular polymer of any one of claims 1-4, wherein the organic ammonium comprises at least one tertiary ammonium.

10. The supramol ecul ar polymer of claim 9, wherein the organic ammonium has an unprotonated structure selected from the group consisting of:QB\144578.00471\99948109.

111. The supramolecular polymer of any one of claims 1-4, wherein the organic ammonium comprises a primary ammonium and a secondary ammonium, a primary ammonium and a tertiary ammonium, or a secondary ammonium and a tertiary ammonium.

12. The supramolecular polymer of any one of claims 1-10, wherein the organic ammonium is derived from an organic amine that differs from phosphoric acid in pKa by greater than 3 units.

13. The supramolecular polymer of any one of claims 1-12, wherein the supramolecular polymer is a linear polymer.

14. The supramolecular polymer of any one of claims 1-12, wherein the supramolecular polymer is a network polymer.

15. The supramolecular polymer of any one of claims 1-14, wherein the supramolecular polymer is adhesive.

16. A method for preparing the supramolecular polymer of any one of claims 1-15, the method comprising mixing an unprotanated organic amine or organic ammonium into a phosphoric acid solution and drying the mixture.

17. The method of claim 16, wherein the phosphoric acid solution comprises an alcohol solvent.

18. The method of claim 17, wherein the alcohol solvent is methanol.

19. The method of any one of claims 16-18, wherein the molar ratio of amine to phosphoric acid is between 0.1 :1 and 1 : 1.17QB\144578.00471\99948109.

120. A method comprising applying an adhesive to a first substrate and adhering a second substrate to the first substrate with the adhesive, the adhesive comprising a supramolecular polymer according to any one of claims 1-15.

21. The method of claim 20 further comprising separating the first substrate and the second substrate and adhering a third substrate to either the first substrate or the second substrate with the adhesive.18QB\144578.00471\99948109.1

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