Solvent-free ionic liquid epoxy resin

Abstract

A solvent-free epoxy system is disclosed, which may include: a hardener compound H, which comprises: a molecular structure (R1-(Y 1 ) n ), wherein R1 is an ionic part, Y 1 is a nucleophilic group, n is between 2 and 10; and an ionic portion A acting as a counter ion of R1; and an epoxy compound E, which comprises: a molecular structure (R2-Z 1 ) n ), wherein R2 is an ionic moiety, Z 1 The epoxy group comprises an epoxy group, n is between 2 and 10, and an ionic moiety B that acts as a counterion of R2. In an embodiment, the epoxy compound E and / or the hardener H are contained in a solvent-free ionic liquid. The system may also include an accelerator, a crosslinker, a plasticizer, an inhibitor, an ionic hydrophobic and / or superhydrophobic compound, an ionic hydrophilic compound, an ionic transitional hydrophobic / hydrophilic compound, a biologically active compound and / or a plasticizer compound. Polymers made from the disclosed epoxy system and methods of using the same are described.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This disclosure claims the benefit of earlier filing date U.S. Provisional Application No. 62 / 807,134, filed on February 18, 2019, which is hereby incorporated by reference in its entirety. Technical Field

[0003] The present disclosure relates to novel ionic epoxy resins, systems containing such resins, and methods of making or using such resins. Background Art

[0004] Conventional epoxy systems typically include thermosetting polymers that are widely used in dental fillings, printed circuit boards, wind turbines, light vehicles, coatings, jacketing, flooring, adhesives, aerospace applications, and various other applications. This wide range of applications is facilitated by the availability of various curing reactions - and associated chemical compositions and structures - that provide the desired hardness, flexibility, adhesion, degree of crosslinking, nature of interchain bonds, high strength (tensile, compression, and flexural), chemical resistance, fatigue resistance, corrosion resistance, and electrical resistance. The properties of uncured epoxy resins, such as viscosity, facilitate processability through the proper selection of monomers, curing agents, and catalysts. According to sources, it is estimated that the global epoxy resin market may increase from USD 6.0 to 7.1 billion in 2015 to USD 9.2 to 10.5 billion by 2024, with an average production of 2.5 million metric tons per year.

[0005] Traditionally, many of the superior properties of epoxy systems have come at the expense of significant volatile organic compound (VOC) emissions and health risks to operators. As a result, conventional epoxies cannot be considered green technologies and require Environmental Protection Agency (EPA) regulation (e.g., EPA requires that at least 80% of VOCs be captured in industrial processes), with significant impacts on overall operating costs and health risks to operators involved in manufacturing. Summary of the invention

[0006] Disclosed are low or no solvent ionic epoxy systems comprising a hardener compound H and an epoxy compound E. In some embodiments, the hardener compound comprises a molecular structure (Y 1 -R1-Y 2 ), wherein R1 is an ionic part, Y 1 is a nucleophilic group, and Y 2 is a nucleophilic group; and an ionic portion A serving as a counter ion of R1. In some embodiments, the epoxy compound comprises a molecular structure (Z 1 -R2-Z 2 ), wherein R2 is an ionic part, Z 1 Contains epoxy groups, and Z 2comprising an epoxy group; and an ionic portion B serving as a counterion to R2. In some embodiments, the low or no solvent epoxy system comprises a hardener compound H comprising: a molecular structure (R1-(Y 1 ) n ), wherein R1 is an ionic part, Y 1 is a nucleophilic group, n is between 2 and 10; and an ionic portion A acting as a counter ion of R1; and an epoxy compound E comprising: a molecular structure (R2-Z 1 ) n ), wherein R2 is an ionic part, Z 1 comprises an epoxy group, n is between 2 and 10, and an ionic portion B that serves as a counter ion for R2. In some embodiments, Y 1 Contains a nucleophile independently selected from the following: an NH2 group, an SH group, an OH group, a SeH group and a PH2 group.

[0007] In some embodiments, the epoxy compound E and / or the hardener H are contained in a solvent-free ionic liquid, which significantly solves the VOC problem of conventional epoxy resins. In some embodiments, the hardener compound is 1,3,5-tris[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-iummethylene]benzene tribromide. In some embodiments, the epoxy compound is tetrakis[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-iummethyl]methane tetrabromide.

[0008] In some embodiments, a low or no solvent ion thermosetting epoxy system is disclosed, comprising: a hardener crosslinker compound H, wherein the hardener crosslinker compound H comprises: a molecular structure (R1-(Y 1,2,3 )3), wherein R1 is an ionic part, Y 1 is a nucleophilic group, Y 2 is a nucleophilic group and Y 3 is a nucleophilic group; and an ionic portion serving as a counter ion of R1; and an epoxy crosslinking agent compound E, the epoxy crosslinking agent compound E comprising: a molecular structure (R2-(Z 1,2,3 )3), wherein R2 is an ionic part, Z 1 Contains epoxy groups, Z 2 Contains epoxy groups and Z 3 comprises an epoxy group; and an ionic portion B serving as a counter ion of R2. In some embodiments, the epoxy crosslinker compound E is a solvent-free ionic thermosetting crosslinker resin. In some embodiments, Y 1 , Y 2 and Y 3Contains a nucleophile independently selected from the following: NH2 group, SH group, OH group, SeH group and PH2 group. In some embodiments, the hardener crosslinker compound H is a solvent-free ionic thermosetting crosslinker hardener. In some embodiments, the hardener crosslinker compound is 1,3,5-tris[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-iummethylene]benzene tribromide. In some embodiments, the epoxy crosslinker compound is tetrakis[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-iummethyl]methane tetrabromide.

[0009] In some embodiments, the disclosed systems further comprise accelerators, crosslinkers, plasticizers, inhibitors, ionic hydrophobic and / or super hydrophobic compounds, ionic hydrophilic compounds, ionic transitional hydrophobic / hydrophilic compounds and / or biologically active (BAIL, biologically active ionic liquid) compounds.

[0010] Also disclosed are polymers made from the disclosed epoxy systems and methods of using the same. In certain embodiments, the polymer produced after the polymerization of the hardener compound H and the epoxy compound E may include self-healing properties due to the presence of stable charges along the polymer chain, driving the repair process by electrostatic attraction. In embodiments, the polymer produced after the polymerization of the hardener compound H and the epoxy compound E forms a highly and regularly porous system, which can be used for, but is not limited to: filter membranes, solid electrolytes after replacement of a second ionic liquid, exchange membranes, etc. In certain embodiments, the polymer includes a solid electrolyte, which can be used as an electronic component, such as a component of a battery, a capacitor, a piezoelectric material, and / or an electric actuator.

[0011] The foregoing and other features of the present disclosure will become more apparent from the following detailed description made with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 is an example of a typical NMR spectrum of 1,3-bis(2'-aminoethylidene)-2-methylimidazolium bromide.

[0013] Figure 2 is an example of a typical NMR spectrum of γ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy)phenyl]-benzenebutyric acid methyl ester.

[0014] Figure 3 An example of a typical NMR spectrum of γ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy)phenyl]-phenylbutyric acid

[0015] Figure 4 Shown are chemical structures of examples of solvent-free ionic liquid epoxy resins and hardeners according to embodiments disclosed herein.

[0016] Figure 5 Shown is a chemical structure of an example of an ionic liquid epoxy system including a superhydrophobic anionic moiety that produces a superhydrophobic material after polymerization according to embodiments disclosed herein.

[0017] Figure 6 Shown is the chemical structure of an example ionic liquid epoxy system including a superhydrophobic cation that produces a superhydrophobic material after polymerization according to embodiments disclosed herein.

[0018] Figure 7 Shown is the chemical structure of an ionic liquid epoxy system that produces a transitional hydrophobic-hydrophilic material after polymerization according to embodiments disclosed herein.

[0019] Figure 8 Shown is the chemical structure of an ionic liquid epoxy system including pharmaceutically active anions and cations and producing a drug release material after polymerization according to embodiments disclosed herein.

[0020] Figures 9A-9F shows the chemical structure of an exemplary pharmacologically active ion for a solvent-free ionic liquid epoxy resin according to embodiments disclosed herein, Fig. 9A ) Antihistamines, Fig. 9B ) Emollients, Fig. 9C ) Anti-inflammatory, Fig.9D )Pain relievers, Fig.9E Anti-inflammatory and Fig.9F ) Anticholinergic.

[0021] Figures 10A-10I shows the chemical structures of exemplary ionic liquid examples according to embodiments disclosed herein, Fig. 10A )and Fig. 10B )Ionic liquid hardener, Fig. 10C ) self-catalytic ionic liquid hardener, Fig. 10D ) ionic liquid promoter, Fig.10E )Ionic liquid epoxy resin, Fig.10F ) ionic liquid promoter, Figure 10G )and Fig. 10H ) an ionic liquid crosslinker, and Fig.10I )Ionic liquid promoter.

[0022] Fig.11 Shown are chemical structures of examples of hydrophobic anions useful in the synthesis of ionic liquid epoxides and hardeners according to embodiments disclosed herein.

[0023] Fig.12 Shown are chemical structures of examples of hydrophobic cations that may be used in the synthesis of ionic liquid epoxides and hardeners according to embodiments disclosed herein.

[0024] Fig.13 Shown are chemical structures of examples of hydrophilic anions useful in the synthesis of ionic liquid epoxides and hardeners.

[0025] Fig.14 Shown are chemical structures of examples of hydrophilic cations that may be used in the synthesis of ionic liquid epoxides and hardeners according to embodiments disclosed herein.

[0026] Figures 15A-15F shows the chemical structure of an example of a biologically active ionic liquid (BAIL) for use as an active material in an ionic liquid epoxide system according to embodiments disclosed herein, Fig.15A )1-Alkyl-1-methylpiperidinium-4-(4-chloro-2-methylphenoxy)butyrate, herbicide; Fig. 15B ) cholinium pyrazinolate, cytotoxic; Fig. 15C ) Tri(2-hydroxyethyl)methylammonium salicylate, anticoagulant-anti-inflammatory; Fig.15D ) Ranitidinium docusate, a histamine emollient; Fig.15E ) lidocainium docusate, a pain reliever-emollient; and Fig.15F )Binoprofen acid didecyldimethylammonium, antibacterial-anti-inflammatory.

[0027] Figures 16A-16F The chemical structure of an example of an ionic liquid used as a plasticizer in a polymer and epoxide system is shown. According to the embodiments disclosed herein, Fig.16A ) 1-butyl-3-methylimidazolium tetrafluoroborate, Fig. 16B )1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, Fig. 16C ) tetrahexylphosphonium decanoate, Fig.16D )1-ethylpyridinium bis(2-ethylhexyl)sulfosuccinate, Fig.16E ) 1-butyl-3-methylimidazolium hexafluorophosphate, and Fig.16F )1-octyl-3-methylimidazolium chloride.

[0028] Figures 17A-17D shows the chemical structure of a BPA-free ionic liquid epoxy system according to an embodiment disclosed herein, Fig.17A ) Examples of aliphatic epoxy resins, Fig. 17B ) Examples of aliphatic hardeners, Fig. 17C ) a second example of an aliphatic epoxy resin, and Fig.17D )Aromatic non-phenolic examples of epoxy resins.

[0029] Fig.18A and 18B According to the embodiments disclosed herein, the solid electrolyte components ( Fig.18A) and electrochemical actuators whose volume changes in electrodes due to an applied potential ( Fig.18B ) is a schematic diagram of an example of an electrochemical cell.

[0030] Fig.19 A set of cross-sectional schematic diagrams showing the repair process of a polymer system containing fixed charges in the main chain of the polymer structure. According to the embodiments disclosed herein, after mechanical damage (such as cracking), the electrostatic attraction of the charges in the polymer structure "repairs" the material.

[0031] Fig. 20 A set of scanning electron microscope (SEM) images of Jeffamine-BPA films cured in the presence of 50% w / w tetrabutylphosphonium TFSI ionic liquid. According to the embodiments disclosed herein, the films were washed several times with methanol to remove the ionic liquid and dried in a vacuum oven (35°C full vacuum, 48 hours) before SEM analysis.

[0032] Figures 21A-21E For electrochemical impedance spectroscopy of polymers using imidazolium BF4 resin, imidazolium bromide hardener and tetraimidazolium bromide crosslinker (molar ratio 10:9:1), the polymer sample was placed between two Zn plates (99.99% purity, polished with 0.05 μm alumina), and 20% m / m additional ionic liquids were as follows: 21A) 20% w / w diethylmethylammonium trifluoromethanesulfonate, 21B) 20% w / w 0.2M ZnCl / P4448Br, 21C) 20% w / w 0.2M LiTFSI / P4448Br, 21D) 20% w / w 1M LiClO3 / P4448Br, and 21E) 20% w / w 1M LiPF6 / P4448Br.

[0033] Fig.22A and 22B Strength versus strain plots recorded for commercial epoxy polymers without (22A, ovals) and with 40% additional P4448Br ionic liquid (22A, triangles), and comparison of commercial epoxy resin samples (22B, rectangles) with polymers (imidazolium BF4 resin, imidazolium bromide hardener, and tetraimidazolium bromide or linear triamine crosslinker (molar ratio 10:9:1)) tetraimidazolium crosslinker (22B, triangles) and triamine linear crosslinker (22B, ovals), the polymers containing 20% ​​additional ionic liquid, tributyloctylphosphonium bromide.

[0034] Fig.23Plot of the water absorption mass change with respect to relative humidity for imidazolium BF4 resin (diamonds), imidazolium bromide hardener (red squares), triamine linear crosslinker (circles), DABCO onium bromide (DABCOnium) accelerator (triangles), BF4 polymer (stars), and PF6 polymer (diamonds) by a surface adsorption analyzer. The equilibrium time was set to a mass change as low as 0.05% and recorded in both the forward and reverse directions. DETAILED DESCRIPTION

[0035] Overview

[0036] Various embodiments are based on the inventors' recognition of improved epoxy chemistries that limit VOC emissions - for example, at low vapor pressures while maintaining the broad applicability of current systems - to significantly reduce processing costs and mitigate associated health hazards. The present disclosure is generally directed to techniques and mechanisms for providing reactive ionic liquid systems in various ways according to various embodiments that react when combined to form high-strength, multifunctional and / or functionalized epoxy-based thermosets. These epoxy systems address the aforementioned VOC outgassing issues.

[0037] Some embodiments include synthetic ionic liquids, for example, incorporating anions substituted with epoxides (glycidyl groups) on the anions. Another such ionic liquid may contain cations of diamines and triamines. Still another such ionic liquid may contain an alkylated DABCO cationic catalyst. Room temperature ionic liquids are organic salts that melt under substandard conditions and form solvent-free liquids with many unique physical properties, including zero vapor pressure. It is estimated that there are about 10 6 There are several possible ion pair combinations that form ionic liquids. Synthesis of organic salts incorporating reactive moieties can be achieved without solvents and without volatile chemicals. Below is a set of examples of reduction practices.

[0038] To illustrate certain features of various embodiments, the solvent-free ionic liquid epoxy system is described in different ways with respect to ionic moiety groups R1 and ionic moiety B having corresponding positive charges, and further with respect to ionic moiety groups R2 and ionic moiety A having negative charges. For example, Scheme 1 shows a positive R1 in a hardener ionic liquid (IL). + and negative R2 in resin IL - As an illustrative example, however, in other embodiments, the signs of the respective charges of the ionic moieties R1, R2 may be reversed (ie, wherein the signs of the respective charges of the ionic moieties A, B are also reversed).

[0039] In the following detailed description, reference is made to the accompanying drawings which form a part of this specification, in which embodiments that can be practiced are shown by way of illustration. It should be understood that other embodiments may be utilized and structural or logical changes may be made without departing from the scope. Therefore, the following detailed description should not be regarded as having a limiting meaning, and the scope of the embodiments is defined by the appended claims and their equivalents.

[0040] Various operations may be described as multiple discrete operations in turn, in a manner that may aid in understanding the embodiments; however, the order of description should not be construed as to imply that these operations are order dependent.

[0041] For the purposes of the description, phrases in the form "A / B" or in the form "A and / or B" mean (A), (B), or (A and B). For the purposes of the description, phrases in the form "at least one of A, B, and C" mean (A), (B), (C), (A and B), (A and C), (B and C), or (A, B, and C). For the purposes of the description, phrases in the form "(A)B" mean (B) or (AB), i.e., A is an optional element.

[0042] The description may use the term "embodiment", which may each refer to one or more of the same or different embodiments. In addition, the terms "comprising", "including", "having", etc. as used with respect to the embodiments are synonymous and are generally intended to be "open" terms (e.g., the term "including" should be interpreted as "including but not limited to", the term "having" should be interpreted as "at least having", the term "including (including)" should be interpreted as "including but not limited to", etc.).

[0043] With respect to the use of any plural and / or singular terms herein, those skilled in the art may convert from the plural to the singular and / or from the singular to the plural as appropriate to the context and / or application. For clarity, various singular / plural arrangements may be explicitly listed herein.

[0044] Unless the context clearly indicates otherwise, the singular terms "a / an", and "the" include plural referents. Similarly, the word "or" is intended to include "and" unless the context clearly indicates otherwise. It should be further understood that all molecular weight or molecular mass values ​​are approximate and are for illustrative purposes only. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described below. All disclosures, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. In the event of a conflict, the present specification (including explanations of terms) shall prevail. In addition, materials, methods and examples are for illustration only and are not intended to be limiting.

[0045] As used herein, unless otherwise indicated, the following terms are used. For purposes of the present invention, chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th edition. In addition, the general principles of organic chemistry are described in "Organic Chemistry" Thomas Sorrell, University Science Books, Sausalito: 1999, and "March's Advanced Organic Chemistry", 5th edition, editors: Smith, MB and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are hereby incorporated by reference.

[0046] As used herein, the term "aliphatic" or "aliphatic group" means a straight chain (i.e., unbranched chain) or branched substituted or unsubstituted hydrocarbon chain that is fully saturated or contains one or more unsaturated units, or a monocyclic hydrocarbon or bicyclic hydrocarbon that is fully saturated or contains one or more unsaturated units but is not aromatic (also referred to herein as "carbocycle", "cycloaliphatic" or "cycloalkyl"), which has a single point of attachment to the rest of the molecule. Unless otherwise specified, an aliphatic group contains 1-6 aliphatic carbon atoms. In some embodiments, an aliphatic group contains 1-5 aliphatic carbon atoms. In other embodiments, an aliphatic group contains 1-4 aliphatic carbon atoms. In yet other embodiments, an aliphatic group contains 1-3 aliphatic carbon atoms, and in yet other embodiments, an aliphatic group contains 1-2 aliphatic carbon atoms. In some embodiments, "cycloaliphatic" (or "carbocycle" or "cycloalkyl") refers to a monocyclic C3-C6 hydrocarbon that is fully saturated or contains one or more unsaturated units but is not aromatic, and the hydrocarbon has a single point of attachment to the rest of the molecule. Suitable aliphatic groups include, but are not limited to, substituted or unsubstituted straight or branched chain alkyl, alkenyl, alkynyl, and mixtures thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

[0047] The term "lower alkyl" refers to C 1-4 Straight or branched chain alkyl. Exemplary lower alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.

[0048] The term "lower haloalkyl" refers to a C 1-4 Straight chain or branched chain alkyl.

[0049] The term "heteroatom" means one or more of oxygen, sulfur, nitrogen, phosphorus or silicon (including any oxidized form of nitrogen, sulfur, phosphorus or silicon; the quaternized form of any basic nitrogen; or a substitutable nitrogen of a heterocyclic ring, such as N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl) or NR + (such as in N-substituted pyrrolidinyl)).

[0050] As used herein, the term "unsaturated" means a moiety having one or more units of unsaturation.

[0051] As used herein, the term "divalent C 1-8 (or C 1-6 ) saturated or unsaturated, straight or branched hydrocarbon chain” refers to straight or branched divalent alkylene, alkenylene and alkynylene chains as defined herein.

[0052] The term "alkylene" refers to a divalent alkyl group. An "alkylene chain" is a polymethylene group, i.e., -(CH2) n-, wherein n is a positive integer, preferably 1 to 6, 1 to 4, 1 to 3, 1 to 2 or 2 to 3. The substituted alkylene chain is a polymethylene chain in which one or more methylene hydrogen atoms are replaced by a substituent. Suitable substituents include the substituents described below for substituted aliphatic groups.

[0053] The term "alkenylene" refers to a divalent alkenyl group. Substituted alkenylene chains are polymethylene groups containing at least one double bond in which one or more hydrogen atoms are replaced by a substituent. Suitable substituents include the substituents described below for substituted aliphatic groups.

[0054] “Alkoxy” refers to the group “alkyl-O—.” Examples of alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, n-hexoxy, and 1,2-dimethylbutoxy.

[0055] The term "halogen" means F, Cl, Br or I.

[0056] The term "ring" means a cycloalkyl or heterocycle as defined herein.

[0057] The term "aryl" as used alone or as part of a larger moiety in "aralkyl", "aralkyloxy" or "aryloxyalkyl" refers to a monocyclic or bicyclic ring system having a total of five to fourteen ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains 3 to 7 ring members. The term "aryl" is used interchangeably with the term "aryl ring".

[0058] The term "aryl" as used alone or as part of a larger moiety in "aralkyl", "aralkyloxy" or "aryloxyalkyl" refers to monocyclic and bicyclic ring systems having a total of five to ten ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to seven ring members. The term "aryl" may be used interchangeably with the term "aryl ring". In certain embodiments of the present invention, "aryl" refers to an aromatic ring system, which includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracenyl, etc., which may bear one or more substituents. As used herein, also included within the scope of the term "aryl" are groups in which an aromatic ring is fused to one or more non-aromatic rings, such as indanyl, phthalimidyl, naphthimidyl, phenanthridinyl or tetrahydronaphthyl, etc.

[0059] The term "aralkyl" refers to an aryl-alkylene group wherein aryl and alkylene are as defined herein.

[0060] The term "aralkoxy" refers to an aryl-alkoxy group wherein aryl and alkoxy are as defined herein.

[0061] The term "aryloxyalkyl" refers to an aryl-O-alkylene group wherein aryl and alkylene are as defined herein.

[0062] The terms "heteroaryl" and "heteroar-", used alone or as part of a larger moiety, such as "heteroaralkyl" or "heteroaralkoxy", refer to groups having 5 to 10 ring atoms, preferably 5, 6 or 9 ring atoms; sharing 6, 10 or 14 π electrons in the ring array; and having one to five heteroatoms in addition to carbon atoms. Heteroaryl includes, but is not limited to, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, and pteridinyl. As used herein, the terms "heteroaryl" and "heteroar-" also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic or heterocyclyl rings, wherein the radical or point of attachment is on the heteroaromatic ring. Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzothiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenathiazinyl, phenoxazinyl, tetrahydroquinolyl, tetrahydroisoquinolyl and pyrido[2,3-b]-1,4-oxazin-3(4H)-one. Heteroaryl can be monocyclic or bicyclic. The term "heteroaryl" can be used interchangeably with the term "heteroaryl ring", "heteroaryl group" or "heteroaromatic", any of which includes rings that are optionally substituted. The term "heteroaralkyl" refers to an alkyl group substituted by a heteroaryl group, wherein the alkyl and heteroaryl portions independently are optionally substituted.

[0063] As used herein, the terms "heterocycle", "heterocyclyl", "heterocyclic radical" and "heterocyclic ring" are used interchangeably and refer to a saturated or partially unsaturated stable 5- to 7-membered monocyclic or 7- to 10-membered bicyclic heterocyclic moiety and having, in addition to carbon atoms, one or more, preferably one to four heteroatoms as defined above. When used with respect to a ring atom of a heterocycle, the term "nitrogen" includes substituted nitrogen. For example, in a saturated or partially unsaturated ring having 0 to 3 heteroatoms selected from oxygen, sulfur or nitrogen, nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl) or + NR (as in pyrrolidinyl substituted on N).

[0064] Heterocycle can be connected to its side group at any heteroatom or carbon atom to produce a stable structure, and any ring atom can be optionally substituted. Examples of such saturated or partially unsaturated heterocyclic radicals include, but are not limited to, tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, piperidinyl, pyrrolinyl, tetrahydroquinolyl, tetrahydroisoquinolyl, decahydroquinolyl, oxazolidinyl, piperazinyl, dioxane-based, dioxolane-based, diazepine-based, oxazolyl, thiazolyl, morpholinyl and quinuclidine-based. The terms "heterocycle", "heterocyclyl", "heterocyclyl ring", "heterocyclic group", "heterocyclic moiety" and "heterocyclic radical" are used interchangeably herein and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl or cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl, phenanthridinyl or tetrahydroquinolinyl, wherein the radical or point of attachment is on the heterocyclyl ring. The heterocyclyl group may be monocyclic or bicyclic. The term "heterocyclylalkyl" refers to an alkyl group substituted with a heterocyclyl, wherein the alkyl and heterocyclyl portions are independently optionally substituted.

[0065] As used herein, the term "partially unsaturated" refers to a ring moiety that includes at least one double or triple bond. The term "partially unsaturated" is intended to encompass rings with multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties as defined herein.

[0066] As described herein, the compounds of the present invention may contain "optionally substituted" moieties. In general, the term "substituted", whether or not preceded by the term "optionally", means that one or more hydrogens of the specified moiety are replaced by suitable substituents. Unless otherwise indicated, the "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted by more than one substituent selected from a specified group, the substituent may be the same or different at each position. The combination of substituents contemplated by the present invention is preferably a combination of substituents that allows the formation of stable or chemically feasible compounds. As used herein, the term "stable" refers to a compound that is substantially unchanged when subjected to conditions that allow its production, detection, and in certain embodiments, its recovery, purification, and use for one or more purposes disclosed herein.

[0067] Suitable monovalent substituents on a substitutable carbon atom of an "optionally substituted" group are independently halogen; -(CH2) 0-4 R o ; -(CH2) 0-4 ORo ; -O(CH2) 0-4 R o 、-O-(CH2) 0-4 C(O)OR o ; -(CH2) 0-4 CH(OR o )2; -(CH2) 0- 4SR o ; -(CH2) 0-4 Ph, which can be o Substitution; -(CH2) 0-4 O(CH2) 0-4 Ph, which can be o Substituted; -CH═CHPh, which can be replaced by R o Substitution; (CH2) 0-4 O(CH2) 0-1 -pyridyl, which may be R o Substitution; -NO2; -CN; -N3; ​​-(CH2) 0-4 N(R o )2; -(CH2) 0-4 N(R o )C(O)R o ;-N(R o )C(S)R o ; -(CH2) 0-4 N(R o )C(O)NR o 2;-N(R o )C(S)NR o 2; -(CH2) 0-4 N(R o )C(O)OR o ;-N(R o )N(R o )C(O)R o ;-N(R o )N(R o )C(O)NR o 2;-N(R o )N(R o )C(O)OR o ; -(CH2) 0-4 C(O)R o ;-C(S)R o ; -(CH2) 0-4 C(O)OR o ; -(CH2) 0-4 C(O)SR o ; -(CH2) 0-4 C(O)OSiR o3; -(CH2) 0-4 OC(O)R o ;-OC(O)(CH2) 0-4 SR o -; -(CH2) 0-4 SC(O)R o ; -(CH2) 0-4 C(O)NR o 2; -C(S)NR o 2; -C(S)SR o ;-SC(S)SR o 、-(CH2) 0-4 OC(O)NR o 2; -C(O)N(OR)R o ; -C(O)C(O)R o ; -C(O)CH2C(O)R o ;-C(NOR)R o ; -(CH2) 0- 4SSR o ; -(CH2) 0-4 S(O)2R;-(CH2) 0-4 S(O)2OR o ; -(CH2) 0-4 OS(O)2R o ; -S(O)2NR o 2; -(CH2) 0-4 S(O)R o ;-N(R o )S(O)2NR o 2;-N(R o )S(O)2R o ;-N(OR o )R o ; -C(NH)NR o 2;-P(O)2R o ;-P(O)R o 2;-OP(O)R o 2;-OP(O)(OR o )2;SiR o 3;-(C 1-4 Straight chain or branched chain alkylene)ON(R o )2; or -(C 1-4 Straight or branched alkylene)C(O)ON(R o )2, where each R o may be substituted as defined below and are independently hydrogen, C 1-6 Aliphatic, -CH2Ph, -O(CH2) 0-1Ph, -CH2-(5-6 membered heteroaryl ring), or a 5-6 membered saturated, partially unsaturated, or aryl ring having 0-4 independently selected from nitrogen, oxygen or sulfur, or, notwithstanding the above definitions, two independently occurring R o Together with its central atom it forms a 3-12 membered saturated, partially unsaturated or aromatic monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, which may be substituted as defined below.

[0068] In R o (or through two independent R o Suitable monovalent substituents on the ring formed by combining with its intermediate atom are independently halogen, -(CH2) 0-2 R · 、-(haloR · )、-(CH2) 0-2 OH, -(CH2) 0-2 OR · 、-(CH2) 0-2 CH(OR · )2. -O(haloR · )、-CN、-N3、-(CH2) 0-2 C(O)R · 、-(CH2) 0-2 C(O)OH, -(CH2) 0-2 C(O)OR · 、-(CH2) 0-2 SR · 、-(CH2) 0-2 SH, -(CH2) 0-2 NH2, -(CH2) 0-2 NHR · 、-(CH2) 0-2 NR · 2. -NO2, -SiR · 3. -OSiR · 3. -C(O)SR · 、-(C 1-4 Straight or branched chain alkylene)C(O)OR · , or -SSR · ; where each R · is unsubstituted, or, in the case of "halo", is substituted only by one or more halogens, and is independently selected from C 1-4 Aliphatic, -CH2Ph, -O(CH2) 0-1 Ph, or a 5-6 membered saturated, partially unsaturated or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur. oSuitable divalent substituents on a saturated carbon atom of include ═O and ═S.

[0069] Suitable divalent substituents on a saturated carbon atom of an "optionally substituted" group include the following: =O, =S, =NNR*2, =NNHC(O)R*, =NNHC(O)OR*, =NNHS(O))2R*, =NR*, =NOR*, -O(C(R*2)) 2-3 O-, or -S(C(R*2)) 2-3 S-, wherein each independently occurring R* is selected from hydrogen, C 1-6 aliphatic, which may be substituted as defined below, or an unsubstituted 5-6 membered saturated, partially unsaturated or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur. Suitable divalent substituents attached to an ortho-substitutable carbon of an "optionally substituted" group include: -O(CR * 2) 2-3 O-, where each independent R * is selected from hydrogen, C which may be substituted as defined below 1-6 aliphatic or an unsubstituted 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur.

[0070] Suitable substituents on the aliphatic group of R* include halogen, -R · 、-(haloR · ), -OH, -OR · 、-O(haloR · )、-CN、-C(O)OH、-C(O)OR · 、-NH2、-NHR · 、-NR · 2 or -NO2, where each R · is unsubstituted, or, in the case of "halo" preceding it, is substituted only by one or more halogens, and is independently C 1-4 Aliphatic, -CH2Ph, -O(CH2) 0-1 Ph or a 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur.

[0071] Suitable substituents on a substitutable nitrogen of an "optionally substituted" group include or Each of these are independently hydrogen, C 1-6aliphatic, which may be substituted or unsubstituted as defined below -OPh, or an unsubstituted 5-6 membered saturated, partially unsaturated or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, or, notwithstanding the above definition, two independently present Together with its central atom, it forms an unsubstituted 3-12 membered saturated, partially unsaturated or aromatic monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur.

[0072] exist Suitable substituents on the aliphatic group are independently halogen, -R · 、-(haloR · ), -OH, -OR · 、-O(haloR · )、-CN、-C(O)OH、-C(O)OR · 、-NH2、-NHR · 、-NR · 2 or -NO2, where each R · is unsubstituted, or, in the case of "halo", is substituted only by one or more halogens, and is independently C 1-4 Aliphatic, -CH2Ph, -O(CH2) 0-1 Ph, or a 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur.

[0073] Unless otherwise stated, structures depicted herein are also meant to include all isomeric (e.g., enantiomeric, diastereomeric, and geometric (or conformational)) forms of the structure; for example, R and S configurations about each asymmetric center, Z and E double bond isomers, and Z and E conformational isomers. Therefore, single stereochemical isomers as well as enantiomeric, diastereomeric, and geometric (or conformational) mixtures of the compounds of the invention are within the scope of the invention. Unless otherwise stated, all tautomeric forms of the compounds of the invention are within the scope of the invention.

[0074] The term "accelerator" is intended to refer to a substance that initiates or speeds up (eg, accelerates) a chemical reaction without being affected itself.

[0075] The term "crosslinker" is intended to refer to an additive that connects two polymer chains by covalent or ionic bonds. Crosslinkers are generally selected based on their reactivity, length and solubility. Crosslinkers can also react spontaneously when added to a sample or at a specific time, such as by activation of photoreactive groups. In traditional epoxy resin systems, crosslinkers are a group of compounds with more than two electrophilic groups that can open the epoxide ring. In addition to common linear hardeners, the introduction of tri- or tetrafunctional crosslinkers creates a multidimensional polymer network, which improves hardness, strength and chemical resistance over linear epoxy resins, and produces thermosetting polymers with higher melting temperatures. In some embodiments, ionic liquids are modified to be used as ionic thermosetting crosslinkers (IT-crosslinkers).

[0076] The term "plasticizer" is intended to refer to substances that change the mechanical properties of a material. Plasticizers change the physical properties of the material to which they are added. For example, plasticizers can reduce the attractions between polymer chains to make them more flexible. Plasticizers can impart flexibility, processability, durability, or stretchability. Plasticizers can change the rigidity, deformability, elongation; toughness, processing viscosity, use temperature, etc. of a material (such as a polymer). Plasticizers are generally liquids or solids with low volatility. Some ionic liquids used as plasticizers are Figures 16A-16F and they can all be used as the second ionic liquid in the ionic liquid epoxide system.

[0077] The term "inhibitor" is intended to refer to a substance that reduces the rate of a chemical reaction or prevents a chemical reaction.

[0078] The term "ionic liquid" is a salt in liquid form. Ionic liquids are mainly made of ions and short-lived ion pairs. By definition, ionic liquids have no vapor pressure. These substances are called liquid electrolytes, ionic melts, ionic fluids, molten salts, liquid salts or ionic glasses. Any salt that melts without decomposing or evaporating usually produces an ionic liquid. Room temperature ionic liquids are organic salts that melt and form solvent-free liquids at less than 100°C, with some unique physical properties, including zero vapor pressure. It is estimated that there are 106 to 1014 possible ion pair combinations that form ionic liquids. In general, ionic liquids that are incorporated into reactive moieties can be synthesized to achieve solvent-free and volatile chemical-free use for a wide range of purposes. Specifically, in some embodiments, a synthesized ionic liquid is disclosed herein that incorporates anions / cations substituted by epoxides (glycidyl groups), and corresponding anions / cations substituted by diamine moieties designed for epoxide polymerization reactions.

[0079] "Bioactive ionic liquids" (BAILs) are a type of ionic liquids that are biologically active. Figure 8 , 9A Exemplary BAILs are provided in 15A-15F and 15A-15F.

[0080] The term "ionic hydrophobic compound" refers to a compound made of a positive and negative ion pair that is immiscible with water but has a certain solubility for and in water.

[0081] The term "superhydrophobic compound" refers to a compound that is immiscible in water and has a solubility in water of no more than 10% by weight.

[0082] The term "ionic hydrophilic compound" refers to a compound made of a positive and negative ion pair, soluble in water, and showing the ability to accumulate dissolved water from the gas phase.

[0083] The term "ionic transitional hydrophobic / hydrophilic compound" refers to a compound composed of a pair of positive and negative ions whose hydrophobic or hydrophilic characteristics as described above can be switched from one to the other depending on chemical or environmental inputs such as (but not limited to) pH, CO2 partial pressure, relative humidity or temperature.

[0084] The term "reaction conditions" is intended to refer to the physical and / or environmental conditions for carrying out a chemical reaction. The term "under conditions sufficient to ... " or "under reaction conditions sufficient to ... " is intended to refer to the reaction conditions under which a desired chemical reaction can be carried out. Examples of reaction conditions include, but are not limited to, one or more of the following: reaction temperature, solvent, pH, pressure, reaction time, the molar ratio of reactants, the presence of a base or acid or catalyst, radiation, concentration, etc. The reaction conditions can be named according to the specific chemical reaction in which the conditions are adopted, such as coupling conditions, hydrogenation conditions, acylation conditions, reduction conditions, etc. The reaction conditions for most reactions are usually known to those skilled in the art or can be easily obtained from the literature. Exemplary reaction conditions sufficient to carry out the chemical transformations provided herein can be found in the full text, particularly in the following examples. It is also contemplated that the reaction conditions may include reagents other than those listed in the specific reaction.

[0085] Description of Several Embodiments

[0086] An epoxy system is disclosed herein, which includes a hardener compound (H) and an epoxy compound (E). Typically, the hardener compound and the epoxy compound are provided separately and then mixed to form a polymer when used. In an embodiment, the hardener compound has a molecular structure according to the following:

[0087] Y 1 -R1-Y 2 ,

[0088] Where R1 is an ionic moiety, and Y 1 and Y 2 Bonded to R1. In certain embodiments, Y 1 is or includes a nucleophilic group. In certain embodiments, Y 2 is or includes a nucleophilic group. In certain embodiments, Y1 and Y 2 In certain embodiments, Y 1 and Y 2 In the specific example, Y 1 and Y 2 comprising a nucleophile independently selected from the group consisting of an NH2 group, an SH group, an OH group, a SeH group, and a PH2 group. In certain embodiments, the hardener compound (H) is part of, such as a component of, a solvent-free ionic liquid, for example, as a molecular complex having an ionic portion A that serves as a counterion to R1. Y 1 -R1-Y 2 Examples are shown in Table 1 and Figure 4 , 5 , 6, 7, 8, 10A-10I and 17A-17D. Examples of ionic counterions are shown in Figure 4 , 5 , 6, 7, 8, 9, 10A-10I, 13A-17D.

[0089] In an embodiment, the hardener compound has a molecular structure according to:

[0090] R1-(Y 1 ) n ,

[0091] Where R1 is an ionic moiety and Y 1 Bonded to R1. In certain embodiments, Y 1 is or includes a nucleophilic group. In certain embodiments, each Y 1 In certain embodiments, each Y is an integer between 2 and 10, such as 2, 3, 4, 5, 6, 7, 8, 9 or 10, or any subset thereof. 1 In the specific example, each Y 1 The group comprises a nucleophile independently selected from the group consisting of an NH2 group, an SH group, an OH group, a SeH group, and a PH2 group. In certain embodiments, the hardener compound (H) is part of, such as a component of, a solvent-free ionic liquid, for example, as a molecular complex having an ionic portion A that serves as a counterion to R1. R1-(Y 1 ) n Examples are shown in Table 1 and Figure 4 , 5 , 6, 7, 8, 10A-10I and 17A-17D. Examples of ionic counterions are shown in Figure 4 , 5 , 6, 7, 8, 9, 10A-10I, 13A-17D.

[0092] The disclosed epoxy system also includes an epoxy compound E. In an embodiment, the epoxy compound has a molecular structure according to the following:

[0093] Z 1 -R2-Z 2 ,

[0094] Where R2 is the ion part, Z 1 is or includes an epoxy group, and Z 2 is or includes an epoxy group. In certain embodiments, Z 1 and Z 2 In certain embodiments, Z 1 and Z 2 In certain embodiments, the epoxy compound (E) is part of, such as a component of, a solvent-free ionic liquid, for example, as a molecular complex having an ionic portion B that serves as a counterion to R2. 1 -R1-Z 2 Examples are shown in Table 1 and Figure 4 , 5 , 6, 7, 8, 10A-10I and 17A-17D. Examples of ionic counterions are shown in Figure 4 , 5 , 6, 7, 8, 9, 10A-10I, 13A-17D.

[0095] In an embodiment, the epoxy compound has a molecular structure according to the following:

[0096] R2-(Z 1 ) n ,

[0097] Where R2 is the ion part, Z 1 is or includes an epoxy group. In certain embodiments, each Z 1 In certain embodiments, each Z 1 The groups are different. In an embodiment, n is an integer between 2 and 10, such as 2, 3, 4, 5, 6, 7, 8, 9 or 10 or any subset thereof. In certain embodiments, the epoxy compound (E) is part of a solvent-free ionic liquid, such as a component thereof, for example as a molecular complex having an ionic portion B that serves as a counterion of R2. R2-(Z 1 ) n Examples are shown in Table 1 and Figure 4 , 5 , 6, 7, 8, 10A-10I and 17A-17D. Examples of ionic counterions are shown in Figure 4 , 5 , 6, 7, 8, 9, 10A-10I, 13A-17D.

[0098] In certain embodiments, the epoxy system further comprises one or more of an accelerator, a crosslinker, a plasticizer, or an inhibitor. The accelerator, crosslinker, plasticizer, and / or inhibitor may be included with the hardener compound, the epoxy compound, or even as a separate component of the system. Examples of accelerators, crosslinkers, plasticizers, and inhibitors are described in Figures 10A-10I and 16A-16F.

[0099] In certain embodiments, the epoxy system further comprises an ionic hydrophobic and / or super hydrophobic compound. In embodiments, the ionic hydrophobic and / or super hydrophobic compound may be provided with either or both of the epoxy and hardener compounds, the hardener compound, for example, as counter ion A, the epoxy compound, for example, as counter ion B, or both, for example, as counter ion A and counter ion B. In embodiments, after polymerization of the hardener compound H and the epoxy compound E, the ionic hydrophobic and / or super hydrophobic compound is released as an ionic liquid to modify the properties of the resulting polymer. Such ionic hydrophobic and / or super hydrophobic compounds are known in the art, and representative examples may be found in Figure 5 and 6 Found in.

[0100] In a certain embodiment, the epoxy system further comprises an ionic hydrophilic compound. In an embodiment, the ionic hydrophilic compound may be provided with either or both of the following: a hardener compound, for example as a counterion A, an epoxy compound, for example as a counterion B, or both, for example as counterion A and counterion B. In an embodiment, after polymerization of the hardener compound H and the epoxy compound E, the ionic hydrophilic compound is released as an ionic liquid to change the properties of the resulting polymer. Such ionic hydrophilic compounds are known in the art.

[0101] In certain embodiments, the epoxy system further comprises an ionic transitional hydrophobic / hydrophilic compound. In embodiments, the ionic transitional hydrophobic / hydrophilic compound may be provided with either or both of the following: a hardener compound, for example as counterion A, an epoxy compound, for example as counterion B, or both, for example as counterion A and counterion B. In embodiments, after polymerization of the hardener compound H and the epoxy compound E, the ionic transitional hydrophobic / hydrophilic compound is released as an ionic liquid to modify the properties of the resulting polymer. Such ionic transitional hydrophobic / hydrophilic compounds are known in the art, and representative examples may be found in Figure 7 Found in.

[0102] In certain embodiments, the epoxy system further comprises a biologically active (BAIL, biologically active ionic liquid) compound. In embodiments, the biologically active (BAIL, biologically active ionic liquid) compound may be provided with either or both of the following: a hardener compound, e.g., as counterion A, an epoxy compound, e.g., as counterion B, or both, e.g., as counterion A and counterion B. In embodiments, after polymerization of the hardener compound H and the epoxy compound E, the biologically active (BAIL, biologically active ionic liquid) compound is released as an ionic liquid to modify the properties of the resulting polymer. Such biologically active (BAIL, biologically active ionic liquid) compounds are known in the art, and representative examples may be found at Figure 8 , 9A -9F and 15A-15F.

[0103] In certain embodiments, the epoxy system further comprises a plasticizer compound. In embodiments, the plasticizer compound may be provided with either or both of the following: a hardener compound, for example as counterion A, an epoxy compound, for example as counterion B, or both, for example as counterion A and counterion B. In embodiments, after polymerization of the hardener compound H and the epoxy compound E, the plasticizer compound is released as an ionic liquid to modify the properties of the resulting polymer. Such plasticizer compounds are known in the art, and representative examples may be found in Figures 16A-16F In certain embodiments, the plasticizer compound has a low (less than 10 -7 bar vapor pressure) to zero volatility.

[0104] Solution 1

[0105] Scheme 1 shows an example of a polymerization reaction between a first compound and a second compound each including a respective ionic moiety and a corresponding counter ion according to disclosed embodiments.

[0106]

[0107] Scheme 1. Simplified polymerization reaction of epoxide system.

[0108] More specifically, Scheme 1 illustrates an example of a disclosed epoxy system according to an embodiment. As shown, the epoxy system includes a hardener compound H and an epoxy compound E. As depicted, the hardener compound H includes a cationic molecular structure (Y 1 -R1-Y 2 ), which contains an ionic moiety R1, and a bonded Y 1 and Y 2 The hardener compound H also includes an anionic portion A as shown in the first reaction. -, such as a counterion, which is bonded to the cation molecule structure (Y 1 -R1-Y 2 ) combination. As shown in the figure, epoxy compound E has an anionic molecular structure (Z 1 -R2-Z 2 ), which includes an ionic moiety group R2 and two epoxide / electrophilic (herein represented by "Z") groups bonded to R2. In addition, the epoxy compound E includes an anionic molecular structure (Z 1 -R2-Z 2 ) Combined cationic part B + , for example, acting as a counterion for R2. As shown in the second reaction, the hardener compound H also includes an anionic portion A + , such as a counterion, which is bonded to the anionic molecular structure (Y 1 -R1-Y 2 ) combination. As shown in the figure, epoxy compound E has a cationic molecular structure (Z 1 -R2-Z 2 ), which includes an ionic moiety group R2 and two epoxide / electrophilic (herein represented by "Z") groups bonded to R2. In addition, the epoxy compound E includes an anionic moiety B - , and the anion molecular structure (Z 1 -R2-Z 2 ) is combined, for example, to act as a counterion of R2. As shown in the third reaction, the hardener compound H also includes an anionic portion A - , such as a counterion, which is bonded to the cation molecule structure (Y 1 -R1-Y 2 ) combination. As shown in the figure, epoxy compound E has a cationic molecular structure (Z 1 -R2-Z 2 ), which includes an ionic moiety group R2 and two epoxide / electrophilic (herein represented by "Z") groups bonded to R2. In addition, the epoxy compound E includes an anionic moiety B - , combined with the anionic molecular structure (Z-R2-Z), for example, acting as a counter ion of R2. As shown in the fourth reaction, the hardener compound H also includes a cationic portion A + , such as a counterion, which is bonded to the cation molecule structure (Y 1 -R1-Y 2 ) combination. As shown in the figure, epoxy compound E has a cationic molecular structure (Z 1 -R2-Z 2 ), which includes an ionic moiety group R2 and two epoxide / electrophilic (herein represented by "Z") groups bonded to R2. In addition, the epoxy compound E includes an anionic molecular structure (Z 1 -R2-Z2 ) Combined cationic part B + , for example, serving as a counterion for R2.

[0109] Unless otherwise indicated, "anion" - as used in the specific context of "anionic molecular structure", "anionic moiety", "anionic moiety group", etc. - refers to the property of an atom or molecular structure (e.g., a molecule or portion thereof) that provides a negative charge to facilitate binding to the positive charge of a corresponding "cationic" structure / moiety / group. For example, anionic moiety A - can be bonded by ionic bonds (e.g., where A - is a single atom) or is bonded to the ionic moiety group R1 by, for example, an intermolecular bond. Alternatively or additionally, the cationic moiety B + can be bonded by ionic bonds (e.g. + is a single atom) or is bonded to the ionic moiety group R2 through an intermolecular bond. In some examples, the cationic moiety A + can be bonded by ionic bonds (e.g., where A + is a single atom) or is bonded to the ionic moiety group R1, for example, by intermolecular bonds. Alternatively or additionally, the anionic moiety B - can be bonded by ionic bonds (e.g. - is a single atom) or is bonded to the ionic part group R2 through an intermolecular bond.

[0110] In the example reaction pathway shown in Scheme 1, Y 1 And / or Y2 may be a nucleophilic group - for example, including but not limited to -NH2, -SH, -OH, -SeH, -PH2 or other nucleophilic substituents. 1 -R1-Y 2 ), at least one of these Y groups may be associated with the molecular structure (Z 1 -R2-Z 2 ) to react with the epoxy groups to form stable chemical bonds - for example to form dimers - in the completed polymerization reaction.

[0111] Table 1 shows examples of molecular structures that can be used in various ways for the corresponding ionic liquid epoxy systems. 1 , R 2 , R 3 , R 4 , etc.) are used herein to indicate component structures of a moiety, for example, alternatively identified using subscript numbers (eg, R1, R2).

[0112] Table 1: Examples of possible structures of R1 and R2 in Scheme 1

[0113]

[0114]

[0115]

[0116]

[0117] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Can be any suitable chain, Y 1 and / or Y 2 It may be a nucleophilic group - for example, including but not limited to -NH2, -SH, -OH, -SeH, -PH2. 1 and / or Y 2 and epoxy moiety (epoxy group may be any suitable 1 and / or Y 2 An example of a Z group that is an electrophilic group that reacts and forms a permanent chemical bond) can be exchanged between R1 and R2. The anionic portion can be any suitable anionic substituent.

[0118] As illustrated by the example shown in Scheme 1, Y bonded to the ionic moiety R1 1 and / or Y 2 The group may be an amine group (for example, 1 and / or Y 2 The hardener compound H can be used as a hardener to react with the epoxy compound E. The reaction of the compounds H and E can result in one of the epoxy groups reacting with Y. 1 and / or Y 2 One of the groups forms a chain - for example, where individual byproduct molecules are connected by anionic moieties A - and cationic part B + Certain embodiments facilitate the selection of R1, R2, Z in different ways. 1 and / or Z 2 , Y 1 and / or Y 2 , A - , A + and B - and B + Various combinations of materials can be used to achieve desired material properties while providing significantly reduced VOC byproducts.

[0119] In the example embodiment shown in Scheme 1, the first compound includes an ionic moiety R1 and a corresponding counterion A, and the second compound includes an ionic moiety R2 and a corresponding counterion B. The illustrative reaction pathway shown in Scheme 1 represents an example of dimer formation by polymerization.

[0120] Various combinations of the ionic moieties R1 and R2 groups are possible, and if the corresponding counterions (A and B) are carefully chosen, the two compounds can form a second ionic liquid (A - B + ), limiting or even avoiding the possibility of VOC emissions from ionic liquid epoxy systems. It is also contemplated to use ionic liquid resins and ionic liquid hardeners of the same charge, where no second ionic liquid is generated, but permanent charges remain in the polymer chains to compensate for the corresponding counterions, as shown in the last two examples in Scheme 1. In the last four examples shown in Table 1, B + Indicates that the R1 and R2 groups are ionic in nature.

[0121] Aspects of the present disclosure also relate to polymers produced by polymerization of the epoxide systems disclosed herein. In embodiments, the polymer produced after polymerization of the hardener compound H and the epoxide compound E may include self-healing properties due to the presence of stable charges along the polymer chain, driving the repair process by electrostatic attraction. In embodiments, the polymer produced after polymerization of the hardener compound H and the epoxide compound E forms a highly and regularly porous system, which can be used for, but is not limited to: filter membranes, solid electrolytes after replacement of a second ionic liquid, exchange membranes, and the like. In certain embodiments, the polymer comprises a solid electrolyte. Electronic components comprising polymers are disclosed herein. In embodiments, the electronic component is a component of a battery, a capacitor, a piezoelectric material, and / or an electric actuator.

[0122] Synthesis method

[0123] Solution 2

[0124] Scheme 2 shows an example reaction for synthesizing hardener compounds for epoxy systems according to embodiments disclosed herein. Such reactions can facilitate the manufacture of some or all of hardener compounds H, for example as shown in Scheme 1.

[0125] As shown in Scheme 2, the class of diamine imidazolium ionic liquids provides amine chemistries useful as hardeners in epoxy polymer systems, such as those disclosed herein. For example, the illustrative reaction of Scheme 2 provides 1,3-bis(2'-aminoethylidene)-2-methylimidazolium bromide.

[0126] The first step of the synthesis is to protect the amino group in bromoethylamine (1) using trityl chloride (2) and displace the resulting compound (3) in 2-methylimidazole (4) under alkaline conditions (reflux in dimethylformamide (DMF) for 12 hours) to obtain the disubstituted intermediate (5). Deprotection of the amine group is carried out in dioxane in an acidic medium to obtain the hydrochloride derivative (6), and neutralization is carefully completed by using NaOH to obtain the target compound (7).

[0127]

[0128]

[0129] Scheme 2. Synthesis of 1,3-bis(2'-aminoethylidene)-2-methylimidazolium bromide

[0130] The full proton NMR spectrum of the target compound (7) was obtained (see Figure 1 ), showing appropriate peaks associated with expected features. The material obtained was a highly viscous brown liquid. Additional studies indicated the stability of this hardener over a time window of at least 6 months (storage in a laboratory shelf, in a closed container without an inert atmosphere) with no signs of decomposition. Ionic liquid hardeners including compound (7) were tested against commercially available resins (mass ratio 1:1) in the absence of a polymerization accelerator or modifier. The tests showed that the hardener effectively produced a brown solid material at a curing temperature of 120°C for two hours.

[0131] Solution 3

[0132] Scheme 3 shows the synthesis of an anionic molecular structure (Z) as shown in Scheme 1 according to the embodiments disclosed herein. 1 -R2-Z 2 ) is an example of a reaction in a method of preparing an epoxy compound. As shown, a modified Arbuzov reaction can be used to produce the synthesis of a diepoxy acid phosphinate. In the example reaction shown in Scheme 3, the acidic compound (9) is neutralized with a tetraalkylphosphonium hydroxide to obtain the corresponding phosphonium ionic liquid, wherein R 5 It can be an alkyl group, such as an alkyl group having between 1 and 16 carbon atoms, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 carbon atoms.

[0133]

[0134] Scheme 3. Synthesis of diepoxy acid phosphinates, wherein R 5 It is an alkyl group.

[0135] Solution 4

[0136] Scheme 4 shows the synthesis of a molecule including an anionic molecular structure (Z) as shown in Scheme 1 according to the embodiments disclosed herein. 1 -R2-Z 2 ) is another example of a reaction in a method of preparing an epoxy compound of ). More specifically, Scheme 4 shows the synthesis of a bisphenol A diglycidyl ether (2,2-bis[4-(glycidyloxy)phenyl]propane) analog by adding an ionic moiety to the monomer structure (Scheme 4).

[0137]

[0138] Scheme 4. General bisphenol A diglycidyl ether ionic liquid structure.

[0139] Solution 5

[0140] Scheme 5 shows the synthesis of a molecule including an anionic molecular structure (Z) as shown in Scheme 1 according to embodiments disclosed herein. 1 -R2-Z 2 ) is another example of a reaction in the process of preparing an epoxy compound. In the illustrative diglycidylation reaction of Scheme 5, 4-hydroxy-γ-(4-hydroxyphenyl)-γ-methyl-benzenebutyric acid methyl ester (10) is reacted with epichlorohydrin (11) under basic conditions at 100°C for 15 minutes. This type of reaction can result in γ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy)phenyl]-benzenebutyric acid methyl ester (12) in a yield greater than 90%. Figure 2 Proton NMR analysis of material produced by one such reaction is shown in . Figure 2 Characteristic peaks indicating compound (12) as the main component are shown.

[0141]

[0142] Scheme 5. General procedure for the diglycidylation of 4-hydroxy-γ-(4-hydroxyphenyl)-γ-methyl-benzenebutyric acid methyl ester.

[0143] Solution 6

[0144] Scheme 6 shows the synthesis of an anionic molecular structure (Z) as shown in Scheme 1 according to the embodiments disclosed herein. 1 -R2-Z 2 ) is another example of a reaction in a method of preparing an epoxy compound. For example, the reaction shown in Scheme 6 can be continued from the reaction shown in Scheme 5.

[0145] As shown in Scheme 6, the -OMe (oxygen / methyl) moiety can be hydrolyzed - for example, without further purification - using a mixture of NaOH (3 eq) / acetone / water at 0°C and allowed to warm to room temperature for 1.5 hours, (Scheme 6). When TLC was performed after the reaction, the extended reaction time did not show deviation from the desired product. The free acid derivative (13), γ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy)phenyl]-benzenebutanoic acid was obtained in quantitative yield and was fully characterized by proton NMR in CDCl3.

[0146]

[0147] Scheme 6. General procedure for the radical hydrolysis of γ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy)phenyl]-benzenebutyric acid methyl ester.

[0148] An example of a typical spectrum of compound (13) obtained is Figure 3 Shown in. Figure 3 All characteristic features of compound (13) were shown. NMR of the reaction product also showed the presence of the solvent (ethyl acetate) used during the cleanup process.

[0149] Solution 7

[0150] Scheme 7 shows the synthesis of an anionic molecular structure (Z) as shown in Scheme 1 according to the embodiments disclosed herein. 1 -R2-Z 2 ) is another example of a reaction in a method for producing an epoxy compound of (13). For example, the reaction shown in Scheme 7 can be continued from the reaction shown in Scheme 6. To mitigate the possibility of damage to the epoxy groups in compound (13), the ionic liquid formation can be carried out in methanol, using an equimolar amount of tetrabutylphosphonium hydroxide (14) to neutralize the phenylbutyric acid protons (Scheme 7), and the methanol MeOH (15 minutes mixing time) and the generated water are quickly removed under vacuum (30 mmHg) at 45°C for 4 hours, and dried at room temperature and full vacuum for 24 hours. In a pilot run of this type of process, a dark yellow viscous liquid was obtained.

[0151]

[0152] Scheme 7. General procedure for the synthesis of tetrabutylphosphonium γ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy)phenyl]-benzenebutyrate.

[0153] In an embodiment, equimolar amounts of compound (15) ionic liquid resin and compound (7) ionic liquid hardener can be combined - for example, manually mixed at room temperature and poured into a 1.5 ml silicon mold and placed in a vacuum oven at 120°C overnight for 12 hours. The reaction of the combined compounds (7) and (15) produces a solid material with greasy characteristics and rubbery toughness. In theory, such properties may be related to the relatively small amount of crosslinker in the epoxy system. To explore this hypothesis, a new ionic liquid hardener was prepared. The second ionic liquid generated during the polymerization process was tetrabutylphosphonium bromide

[0154] Solution 8

[0155] Scheme 8 shows an example of a reaction in a process for the synthesis of an epoxide of aliphatic nature: the tetrabutylphosphonium salt of 2,2-bis(glycidyloxymethyl)propionic acid (21). The synthetic route comprises three steps: Commercially available 2,2-bis(hydroxymethyl)propionic acid (16) is alkylated with allyl bromide (17) in toluene with NaOH. The reaction requires overnight reflux to complete and produces the diallyl intermediate (18) in 90% yield. The product is very pure and no further purification is required for the next step. The olefin intermediate (18) is oxidized to the epoxide (20) by standard methods with m-chloroperbenzoic acid (19) at room temperature overnight. This method requires tedious column purification, but the yield of the epoxidation product (20) is 90%. The formation of the target ionic liquid epoxy resin (21) is carried out in methanol with an equimolar amount of tetrabutylphosphonium hydroxide (14) by a similar method described for compound (15) in Scheme 7.

[0156]

[0157] Scheme 8. Synthesis of tetrabutylphosphonium 2,2-bis(glycidyloxymethyl)propionate

[0158] Solution 9

[0159] Scheme 9 shows an example of a reaction during the synthesis of an epoxy compound having a positively charged heterocyclic core. Such epoxy ionic resins can react with a negatively charged hardener (the second row in Scheme 1) or a similar positive hardener (the third row in Scheme 1). In the case of two positively charged components (the third row), no additional AB-type ionic liquid is formed, which may be suitable for some properties.

[0160]

[0161] Scheme 9. Example: Synthesis of 1,3-bis(2-oxiranylethyl)imidazolium bis(trifluoromethane)sulfonimide.

[0162] The synthetic route consists of two steps: alkylation and quaternization of commercially available imidazole (22) with 4-bromo-1-butene (23) under usual alkylation conditions (NaHCO3-acetonitrile, reflux overnight). The quaternized intermediate (24) was obtained in 99%. The crude product was pure enough and could be used in the next step without additional purification. Epoxidation of the olefin quaternized intermediate (24) was carried out with m-chloroperbenzoic acid (19) under standard procedures at room temperature overnight. As in the analogous case with aliphatic epoxy ion resins (Scheme 8, compound 20), the product required tedious column purification. The final yield was about 50%.

[0163] Solution 10

[0164] Scheme 10 shows an example of the reaction in the method of synthesizing the hardener compound of the epoxy system according to the embodiment. In this example embodiment, the new hardener is intended to have a multi-branched chain structure in order to promote crosslinking between polymer chains. N1,N1-bis(2-aminoethyl)-1,2-ethylenediamine (compound 26, Scheme 10) is protected with a BOC (e.g., tert-butyloxycarbonyl) protecting group at room temperature and stirred overnight. The protected compound (28) is then alkylated with methyl iodide at 120°C under reflux of acetonitrile with stirring overnight, the alkylation reaction is followed by TLC tracking until (28) is completely consumed, and the solvent and MeI (iodomethane) excess are removed by rotary evaporation at 45°C-50°C and 30 mmHg during 4 hours, followed by drying at room temperature and full vacuum. It is worth mentioning that MeI alkylating agent is selected because the reagent is easily available, but there are multiple options to choose from, and the final selection can be used to change the characteristics of the entire epoxy resin system. The BOC protection is removed using HCl-dioxane solution, and the remaining acid is neutralized using NaOH. After this step, the final ionic liquid was obtained by metathesis of the ionic liquid in aqueous LiTFSI solution, and the inorganic salts were removed by washing with nanopure water several times and rotary evaporation at 50 °C and 15 mmHg for 4 h. Compound (30) 2-amino-N,N-bis(2-aminoethyl)-N-methyl-ethylamine bis(trifluoromethane)sulfonamide was obtained as a viscous white liquid and dried at room temperature under full vacuum for 24 h.

[0165]

[0166] Scheme 10. Example: Synthesis of 2-amino-N,N-bis(2-aminoethyl)-N-methyl-ethylamine bis(trifluoromethane)sulfonimide.

[0167] Described herein are example results of test reactions with compounds (15) and (30). More specifically, one gram of 2-amino-N,N-bis(2-aminoethyl)-N-methyl-ethylamine bis(trifluoromethane)sulfonamide (30) was mixed with one gram of tetrabutylphosphonium γ-methyl-4-(2-oxiranylmethoxy)-γ-[4-(2-oxiranylmethoxy)phenyl]-phenylbutyrate (15) (molar ratio 1.5:1) and cured in a silica gel mold at 120°C for 12 hours to obtain a hard solid material with a light yellow color, wherein the second ionic liquid produced was tetrabutylphosphonium bis(trifluoromethane)sulfonamide.

[0168] Schemes 11 and 12

[0169] Below, Schemes 11 and 12 show two additional specific examples of multi-branched hardener compounds intended to promote crosslinking between polymer chains.

[0170] Scheme 11 shows an example of the synthesis of tetrakis[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-iummethyl]methane tetrabromide (34). The synthetic route starts with the quaternization of tetrakis(2-methylimidazol-1-ylmethyl)methane (also known as pentaerythritol tetraimidazole) (31) with the previously obtained trityl-protected bromoethylamine (3) by heating in DMF overnight. The quaternized tetrabromide intermediate (32) was isolated from the byproduct mixture in a MeOH-dichloromethane system (5% to 20% MeOH) in 62% yield.

[0171] Removal of the trityl protection was carried out according to standard procedures in aqueous methanol in a strongly acidic medium. After 16 hours at ambient temperature, the deprotection was complete and the triphenylmethane byproduct was removed by ether extraction. After evaporation from the aqueous phase and vacuum drying, the highly hygroscopic tetrabromide tetrahydrochloride (33) was obtained. Careful basification of this tetrahydrochloride (33) with NaOH in an aqueous medium, followed by evaporation of the solvent and extraction from NaCl ethanol provided the target-free tetraamino crosslinker (34) in quantitative yield.

[0172]

[0173]

[0174] Scheme 11. Synthesis of tetrakis\[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-ylmethyl]methane tetrabromide

[0175] Scheme 12 shows an example of the synthesis of 1,3,5-tris[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-methylene]benzene tribromide (39), which is also used as a new hardener for epoxy systems. In this example, the new hardener has a three-branched chain structure with a quaternized imidazolium moiety and an aromatic benzene core.

[0176] The first step of this hardener is the synthesis of monoalkylated 2-methylimidazole (35), which is considered a new cornerstone for the synthesis of this class of molecules. In fact, this synthesis is the first step in the preparation of the quaternized trityl-protected diamino intermediate (5) mentioned above. To obtain the monoalkylated intermediate, the reaction between reactants (3) and (4) is carried out at room temperature in an equimolar ratio. The inorganic byproduct NaBr is easily removed by water-dichloromethane work-up, after which the target compound (35) is isolated as a crystalline product from the dichloromethane phase in a yield of 78%. The product (35) obtained by this method is pure enough for further transformations, but can be recrystallized from hexane for analytical purposes.

[0177] The next step in this preparation route is the quaternization of the intermediate (35) with the previously synthesized 1,2,3-tri(bromomethyl)benzene (36) under heating in DMF at 80°C for 19 hours. After removal of the DMF, the quaternized tribromide intermediate (37) is separated from the impurities as a low-solubility precipitate by subsequent treatment with diethyl ether and acetone. Obtained in 98% yield, the product (37) is fairly pure (e.g., greater than 90% purity) and can be used further without additional purification. For analytical purposes, a sample of the product can be recrystallized from water.

[0178] The removal of the trityl protection was carried out according to standard procedures in aqueous methanol in a strongly acidic medium. After 18 hours at ambient temperature, the deprotection was complete and the triphenylmethane byproduct was removed by ether extraction. After evaporation from the aqueous phase and vacuum drying, the highly hygroscopic tribromide trihydrochloride (38) was obtained. Careful basification of this trihydrochloride (38) with NaOH in an aqueous medium followed by evaporation of the solvent and extraction from NaCl ethanol provided the target-free triamine crosslinker (39) in 94% yield. One of the advantages of the imidazolium multi-branched crosslinker ionic liquid additive is the improved miscibility with the imidazolium resin and hardener.

[0179]

[0180] Scheme 12. Synthesis of 1,3,5-tris[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-iummethylene]benzene tribromide

[0181] Solution 13

[0182] Scheme 13 shows an example of a reaction for the synthesis of a modifier (eg, promoter or catalyst) for promoting epoxy systems according to an embodiment. Such promoters / catalysts can accelerate reactions such as the reaction shown in Scheme 1.

[0183] Modifiers for polymerization reactions can be synthesized as ionic liquids or ionic compounds, which will reduce or even eliminate the possibility of VOC emissions. One of the most commonly used reaction modifiers is DABCO, whose catalytic effect in polymerization reactions helps to accelerate the curing process. Although the synthesis of ionic DABCO compounds is known, their ionic forms have been tested as antimicrobial agents, but have not been tested as polymerization modifiers. In an illustrative embodiment, dabco onium compounds can be synthesized, for example, by direct alkylation of 1,4-diazabicyclo[2.2.2]octane with 1-bromooctane in dichloromethane under reflux conditions and overnight stirring. Octyl Dabco onium bromide can be obtained in quantitative yields.

[0184]

[0185] Scheme 13. General synthetic procedure for N-octyl dabcolinium bromide.

[0186] One advantage of this epoxy technology approach is that the properties of the ionic liquid produced during the polymerization reaction can be tuned to impart different characteristics to the final product depending on the specific use of each material. This in-situ modifier can be designed to be hydrophobic or hydrophilic to act as a plasticizer and / or solidify the polymer network to act as a filler. Alternatively or in addition, such in-situ modifiers may be suitable for use in providing medical antibacterial ionic liquids.

[0187] Examples and Epoxy Systems

[0188] Figure 4 An example of an epoxy system according to an embodiment is shown, which includes some or all of the features shown in Scheme 1. More specifically, Figure 4 An example of a system comprising a solvent-free epoxy resin (tetrabutylphosphonium diepoxyphosphinate) and a hardener (dimethylaminoimidazole bromide) is shown. When the polymerization reaction of such a system is completed, the resulting ionic liquid obtained as a by-product may include tetrabutylphosphonium bromide, which in turn can be used as, for example, a plasticizer for the polymeric phosphinate / dimethylaminoimidazole network.

[0189] Figure 5 An example of an epoxy system according to an embodiment is shown, which includes some or all of the features shown in Scheme 1. More specifically, Figure 5An example of a possible solvent-free ionic liquid epoxy system is shown in FIG. 1 . For example, if a user requires a polymer with a superhydrophobic surface, the hardener and resin can be designed to produce a superhydrophobic ionic liquid after the polymerization reaction occurs, such as an imidazolium bis[bis(pentafluoroethyl)phosphinyl]imide ionic liquid, where the anionic portion is the hydrophobic portion of the ionic liquid. One such ionic liquid epoxy system is shown in FIG. Figure 5 Shown in.

[0190] Figure 6 An example of an epoxy system according to an embodiment is shown, which includes some or all of the features shown in Scheme 1. More specifically, Figure 6 Alternative uses of superhydrophobic cations such as tri(n-hexyl)[2-ethoxy-2-oxoethyl]ammonium are demonstrated.

[0191] Figure 7 An example of an epoxy system according to an embodiment is shown, which includes some or all of the features shown in Scheme 1. Figure 7 In the case of the example embodiments shown, the hydrophobic-hydrophilic properties of the final product can be tuned and can be changed after the polymerization process using an ionic liquid with a transitional hydrophobicity. In this case, the hydrophobicity is changed by the presence of carbon dioxide. In a CO2-free environment, the ionic liquid has hydrophobic properties. When the material is exposed to CO2, the ionic liquid changes to a hydrophilic state. This phenomenon is reversible and can provide a tunable material even after the epoxy resin is cured. The same properties have been observed in the anionic moieties derived from pyrazoles, imidazoles and triazoles.

[0192] Figure 8 An example of an epoxy system according to an embodiment is shown, which includes some or all of the features shown in Scheme 1. After the curing process, the production of a second ionic liquid can be suitable for various medical, pharmaceutical and / or other important application areas of ionic liquid epoxy resins. Some embodiments provide long-term release systems for drugs in different ways - for example, using pharmaceutically active ionic liquids, such as those derived from ibuprofen esters and lidocainium. According to various embodiments, several combinations can be obtained from these ionic liquids to open up the possibility of - for example - analgesic release sleeves ( Figure 8 ). The second ionic liquid thus produced will be lidocainium ibuprofen ester.

[0193] Figures 9A-9F Various examples of anionic and cationic parts of each of the epoxy systems according to the embodiments are shown - for example, each is used as the anionic part A of Scheme 1 in a different manner. - or cationic part B + Some embodiments combine epoxy polymer technology with the emerging field of pharmaceutically active ionic liquids in various ways. Figures 9A-9FSome examples of useful therapeutic materials that may be suitable for use in accordance with various embodiments are shown.

[0194] Figures 10A-10I Various examples of a hardener compound, an epoxy compound, and a modifier for each of the epoxy systems according to respective embodiments are shown. Figures 10A-10I Some or all of the compounds shown in may each be a component of a corresponding system having, for example, some of all of the features of the system shown in Scheme 1.

[0195] It is important to note that the presence of a large number of possible counterions allows the design of the final polymer to meet any of a variety of specifications desired by the end user of the solvent-free ionic liquid epoxy system. The combination of appropriate ions can tune polymer properties such as flexibility, hardness, hydrophobicity, cure time, cure temperature, establishment of secondary reactions, ionic conductivity, etc. In addition, ionic liquid crosslinkers, promoters and catalysts (in Figures 10A-10I The design of the example shown in ) will ensure that the entire epoxy system consists of zero vapor pressure components.

[0196] Due at least in part to some or all of these features, for example, thermosetting solid electrolytes can be produced, which is important in developing batteries for storing electrical energy. Solvent-free ionic liquid epoxy systems according to some embodiments allow the electrolyte to be injected into the battery structure, establishing a polymerization reaction to provide a fully polymerized, ionic liquid-filled solid electrolyte.

[0197] Fig.11 The anionic part of each of the corresponding epoxy systems according to the examples is shown - for example, the anionic part A shown in Scheme 1 - - various instances. Fig.12 The cationic moiety of each of the corresponding epoxy systems according to the examples is shown - for example, the cationic moiety B shown in Scheme 1 + - various instances.

[0198] As mentioned above, the hydrophobic material can be selected from the hardener and the corresponding counter ions of the epoxy ionic liquid produced by the ionic liquid epoxy resin. According to various embodiments, a variety of hydrophobic anions ( Fig.11 ) and hydrophobic cations ( Fig.12 ) can be used to facilitate the selection of a combination that is precisely tailored to the specific desired hydrophobicity level of the final material.

[0199] Fig.13 The anionic part of each of the corresponding epoxy systems according to the examples is shown - for example, the anionic part A shown in Scheme 1 - - Various examples. Fig.11 As shown in the examples shown, epoxide ionic liquids can be synthesized in which the second ionic liquid has significant hydrophilic properties. Many inorganic anions are highly hydrophilic ( Fig.13 ), a large amount of anions are required to produce ionic liquids.

[0200] Fig.14 The cationic moiety of each of the corresponding epoxy systems according to the examples is shown - for example, the cationic moiety B shown in Scheme 1 + - various instances. Fig.14 Inorganic cations and organic cations having hydrogen bond donor moieties that are also highly hydrophilic are illustrated.

[0201] Figures 15A-15F Various examples of ionic liquid epoxide compounds, such as shown in Scheme 1, are shown for each of the corresponding epoxide systems according to the examples. The range of biologically active ionic liquids (BAILs) is wide, ranging from ionic liquids with herbicidal properties to ionic liquids with antitumor activity. Some examples are Figures 15A-15F New BAILs are introduced regularly, and many of these BAILs can be used as the second ionic liquid in an ionic liquid epoxy system, providing a drug eluting material after an appropriate curing process. Other examples are ionic liquids derived from flufenamic acid (nonsteroidal anti-inflammatory drug) and ampicillin (anti-tumor activity).

[0202] Figures 16A-16F Various exemplary byproduct compounds formed by the reaction of the corresponding epoxy system according to the embodiments are shown. For example, Figures 16A-16F The compounds shown in can all be reacted by anion A shown in Scheme 1 - With cation B + reaction formed.

[0203] Plasticizers are used to modify the mechanical properties of different polymers - for example, to change rigidity, deformability, elongation; toughness, processing viscosity, use temperature, etc. Traditionally, there are two types of plasticizers: internal plasticizers and external plasticizers. Internal plasticizers are structural modifications to the polymer that affect its mechanical properties, i.e., the addition of copolymerized moieties, substituents, etc. External plasticizers are additives incorporated during polymer processing that have an effect on the crystallinity of the polymer. Organic solvents are commonly used as plasticizers, but their efficiency is generally related to the persistence of the solvent in the polymer structure. Many common plasticizers dissipate over time - for example, the dissipation rate depends on parameters such as volatility, boiling point, osmotic pressure, and solvent power. Due to such problems, in some embodiments, ionic liquids with relatively very low vapor pressures can be used as a new class of plasticizers. This use can take advantage of better solvency, osmotic pressure, and low volatility. Some ionic liquids used as plasticizers are Figures 16A-16F and they can all be used as the second ionic liquid in the ionic liquid epoxide system.

[0204] Figures 17A-17DVarious examples of ionic liquid epoxy compounds according to each of the corresponding epoxy systems of the embodiments are shown, for example as shown in Scheme 1. In recent years, the presence of bisphenol A (BPA) in various polymer formulations has been found to cause health problems. BPA is associated with reproductive system problems in women and men, birth defects in children, metabolic diseases and immune system effects. For these and / or other reasons, it is important for manufacturers to choose BPA-free options in polymer production. Since the solvent-free ionic liquid epoxy systems according to various embodiments have low inherent vapor pressures and the risk of volatile BPA is relatively low, they are important for mitigating the possibility of BPA contamination in polymer products intended for human use. Aliphatic systems are an example of an embodiment that can alleviate BPA problems. Figures 17A-17D Some proposed structures are shown to mitigate the potential for BPA byproducts.

[0205] Figures 18A-18B Examples of devices each including a corresponding epoxy material according to an embodiment are shown. For example, Fig.18A and 18B The devices may each include the corresponding epoxy material formed by such reactions as shown in Scheme 1.

[0206] Solid electrolytes and electrochemical actuators are closely related - for example, both systems are usually affected by a polymer matrix containing an electrolyte (organic or inorganic salt) between two electronic conductors (electrodes). The main difference is that in solid electrolytes, the corresponding chemistry is usually designed to minimize the volume change of the electrodes due to the applied potential ( Fig.18A ) due to ion migration, where the electrolyte concentration is constant during the charge and discharge cycles. On the other hand, in an electrochemical actuator, a different effect is desired—for example, where both the electrode volume and the electrolyte concentration vary. Therefore, different chemistries may be needed to induce different volume changes in the electrode ( Fig.18B ), resulting in compression on one side of the battery and expansion on the other side, a phenomenon used to create a potential difference with that applied to the battery.

[0207] Ionic liquid epoxide systems according to different embodiments can be used in different ways to produce corresponding solid electrolytes and electrochemical actuators. Such epoxide systems can promote the synthesis of polymeric matrices (epoxide polymers) while producing second ionic liquids as a byproduct of the polymerization reaction. The conversion between electrochemical cells with solid electrolytes and electrochemical actuators can be based on the design time selection of the second ionic liquid ions and the composition of the electrodes. In addition, the presence of these electromechanical properties can enable ionic liquid epoxide systems to provide improved piezoelectric material design and development-for example, due to the strong correspondence between the mechanical stress in the polymer and the applied electrochemical potential. One possible use of this technology is to construct various sensors.

[0208] Self-healing polymers

[0209] Fig.19 Examples of self-healing polymers are shown that include epoxy materials according to the disclosed embodiments, such as epoxy materials formed by reactions of the type shown in Scheme 1. Self-healing polymers are materials that are able to self-heal mechanical damage, such as scratches, punctures, or cracks. There are several mechanisms that can provide self-healing properties to polymers, the most common being the formation of microcapsules filled with monomeric materials and catalysts that react after mechanical damage is inflicted. However, there are also polymeric materials composed of ionomer chains where the healing process drives the electrostatic attraction of charges present in the polymer structure. Fig.19 A cross-sectional diagram showing the repair process of such a system.

[0210] The properties of the ionic liquid epoxide system according to some embodiments may enable polymer chains with fixed charges to be suitable in various ways to promote the self-healing properties of the material, for example, where the second ionic liquid produced during the polymerization reaction will act as a plasticizer to improve the mechanical properties of the final product.

[0211] Polymer film

[0212] Fig. 20 Examples of films including epoxy materials according to disclosed embodiments, such as those formed by the type shown in Scheme 1, are shown.

[0213] Ionic liquids can be used to modify epoxide polymers to change the curing reaction conditions, such as temperature, time, hardener / resin ratio, etc. For example, when used as a modifier, the ionic liquid content in the epoxy system can be in the range of 2 to 5 parts per hundred parts of rubber (phr). During the curing process, ionic liquids in the range of 5 to 10 phr can be used to change the viscosity of some epoxide components. However, at higher levels of ionic liquid (approximately 30% to 70% w / w of the total mass), the ionic liquid tends to create void spaces in the final material. After washing away this ionic liquid, the resulting material is a highly porous solid with a pore size of approximately 10-20 μm (see Fig. 20 SEM image of Jeffamine-BPA system with 50% tetrabutylphosphonium TFSI ionic liquid).

[0214] Ionic liquid epoxide systems according to some embodiments can produce similar results, and the final product can be used as a filter structure with highly regular pore size. By varying the ionic liquid content, the resulting pore size and selectivity of the filtration system can be selectively designed ("tuned").

[0215] Solvent-free ionic liquid epoxy resin battery separator (SILER)

[0216] In an embodiment, the disclosed ionic liquid is used as an ionothermal crosslinking agent. For example, in some embodiments, a molecule having the structure provided in Table 1 is used as an IT-crosslinking agent. It is expected that the disclosed ionic liquid can be used as an ionothermal crosslinking agent for various industrial applications. In some specific embodiments, the IT-crosslinking agent is used with a solvent-free ionic liquid epoxy resin (SILER) to construct a battery separator. Ionic conductivity is a fundamental property of those materials. Figure 21A-23 Shows a study demonstrating the ability of the disclosed composition to act as an IT-crosslinking agent. First, several SILER polymer samples modified with an IT-crosslinking agent and containing additional ionic liquid were tested by electrochemical impedance spectroscopy. The all-polymer samples were placed between two zinc plates, and a custom-made hand press was used to control the thickness and connect to a GAMRY potentiostat. The polymer samples had the same basic formulation (imidazolium BF4 resin, imidazolium bromide hardener, and tetramimidazolium bromide crosslinker, in a molar ratio of 10:9:1 respectively) and were modified with 20% m / m of additional ionic liquid to improve the conductivity of the material. The polymer samples were cured overnight at 60 °C to ensure complete polymerization. Diethylmethylammonium trifluoromethanesulfonate (DEMATF) was added to one sample to determine the proton conductivity; another contained zinc chloride, 0.2 M in tributyloctylphosphonium bromide, simulating a typical concentration in a commercial zinc battery. Three samples were modified with different lithium compounds used in lithium batteries: lithium bis(trifluoromethane)sulfonimide (LiTFSI, 0.2 M), lithium carbonate (LiCO3, 1 M), and lithium hexafluorophosphate (LiPF6, 1 M) in tributyloctylphosphonium bromide. The resulting electrochemical impedance spectra are shown in Figures 21A-21E The conductivity of the following ionothermal polymer samples increases in the order of DEMATF < ZnCl2 < LiTFSI < LiCO3 < LiPF6. The Z' value at the intercept was estimated by the best-fit semicircle equation, and the corresponding conductivity was calculated using the specific geometric dimensions of each sample and is shown in Table 2 below. The conductivity of the polymer containing 1 M LiPF6 is three orders of magnitude higher than that of the polymer containing DEMATF (see Table 2). It is worth noting that traditional epoxy polymers require an ionic liquid content of 40% to 60% to have a similar conductivity. The reduction from 60 wt% to 20 wt% indicates the superiority of the IT structure over non-ionic epoxy materials in terms of ionic conductivity.

[0217] Table 2. Conductivity values of SILER polymer samples containing 20% m / m additional ionic liquid, in μS / m. An electrochemical cell was assembled using two zinc plates and connected to a Gamry potentiostat. Estimated based on the electrochemical impedance Z' at the intercept and the respective geometric dimensions.

[0218] Compound Conductivity (uS / m) DEMATF 8.27 <![CDATA[ZnCl2(0.2M)]]> 37.47 LiTFSI(0.2M) 52.5 <![CDATA[LiCO3(1M)]]> 1274.5 <![CDATA[LiPF6(1M)]]> 6208.09

[0219] The tensile strength of different SILER polymers modified with IT crosslinkers in various compositions was studied and compared with fully formulated commercial polymers (see Fig.22A and 22B ). Fig.22A and 22B Typical tensile strength versus strain for commercial epoxy polymers alone and IT-crosslinker polymers are shown; all polymers were molded into dog-bone shapes (46 mm x 10 mm x 2 mm). When the polymers were cured with 40% m / m tributyloctylphosphonium bromide, the maximum strength of the commercial polymer was 46 MPa, which is required for adequate ionic conductivity in battery separators; the maximum tensile strength dropped to 8 MPa. In addition, significant viscoelastic properties were observed before the sample broke, which is believed to be related to the plasticizing effect of the additional ionic liquid.

[0220] SILER / IT crosslinker polymer samples (either one with a 10:9:1 molar ratio of imidazolium BF4 resin, imidazolium bromide hardener, and triethylmethylammonium bromide crosslinker ( Fig. 22B , triangle) or tetraimidazolium amine bromide crosslinker ( Fig. 22B , oval) containing 20% ​​additional ionic liquid. The ultimate tensile strength value for the SILER polymer using a linear triamine crosslinker is 15.4 MPa, and the value corresponding to the tetraimidazolium amine crosslinker is 28.2 MPa. In both cases, no obvious viscoelastic region exists. It is expected that the SILER / IT-crosslinker polymers may include an additive balance to match that of commercial epoxy resins to impart improved cure and maximum strength. Thus, the disclosed polymers provide improved mechanical strength properties that are not sacrificed by increased ionic conductivity.

[0221] Another property tested is the ability of the SILER components and polymers to absorb water vapor. To measure this property, samples of imidazolium BF4 resin, imidazolium bromide hardener linear triethylmethylammonium crosslinker, and two SILER polymers (resin:hardener:crosslinker ratio 10:9:1, one using BF4 resin and the other using its PF6 version) were stabilized at different relative humidities: 10%, 30%, 50%, 70%, and 90% until minimal mass change was detected. A typical isotherm, plotted as Δm / m0 versus RH at Fig.23The linear crosslinker and the imidazolium bromide hardener showed high water absorption at all relative humidities, with maximum values ​​of 127% and 120%, respectively. The SILER imidazolium BF4 resin showed negligible water absorption at all relative humidities. The performance of the polymer depends on the resin anion. The polymer with the most hydrophobic anion (PF6) has a maximum Δm / m0 value of 27% (90% RH), and the less hydrophobic (BF4) is nearly three times higher, at 76% at the same relative humidity. When the RH scan direction is reversed, there is no obvious hysteresis in the performance of the Δm / m0 vs. RH plots for all samples, indicating a reversible water absorption / desorption process.

[0222] Although certain embodiments have been shown and described herein, it will be appreciated by those of ordinary skill in the art that a variety of alternative and / or equivalent embodiments or implementations that achieve the same purpose may be substituted for the embodiments shown and described without departing from the scope. It will be readily appreciated by those of skill in the art that embodiments may be implemented in a variety of ways. The present application is intended to encompass any modifications or variations of the embodiments discussed herein. Therefore, it is clearly intended that the embodiments be limited only by the claims and their equivalents.

Claims

1. An epoxy system comprising: A hardener compound H comprising: Molecular structure (R1-(Y 1 ) n ), wherein R1 is an ionic part, Y 1 is a nucleophilic group, n is an integer between 3 and 10; and an ionic portion A that acts as a counter ion for R1; and An epoxy compound E comprising: Molecular structure (R2-(Z 1 ) n ), wherein R2 is an ionic moiety, Z 1 comprising an epoxy group, n being an integer between 2 and 10, and an ionic portion B acting as a counter ion of R2, The hardener compound H is 1,3,5-tris[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-iummethylene]benzene tribromide or tetrakis[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-iummethyl]methane tetrabromide.

2. The epoxy system according to claim 1, wherein the epoxy compound E is a solvent-free ionic liquid.

3. The epoxy system according to any one of claims 1 to 2, wherein the hardener compound H is a solvent-free ionic liquid.

4. The epoxy system according to claim 3, wherein the molecular structure (R2-(Z 1 ) n ) is selected from one or more of the following: in: R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is any suitable chain, and B + It is the cationic part.

5. The epoxy system according to claim 3, wherein the molecular structure (R2-(Z 1 ) n ) is selected from one or more of the following:

6. The epoxy system according to any one of claims 1 to 2, further comprising one or more of an accelerator, a crosslinker, a plasticizer or an inhibitor.

7. The epoxy system according to claim 6, wherein the accelerator is one or more of the following:

8. The epoxy system of claim 6, wherein the crosslinking agent is one or more of:

9. The epoxy system of claim 6, wherein the plasticizer is one or more of:

10. The epoxy system according to any one of claims 1 to 2, further comprising an ionic hydrophobic and / or superhydrophobic compound.

11. The epoxy system according to claim 10, wherein after polymerization of the hardener compound H and the epoxy compound E, the ionic hydrophobic and / or superhydrophobic compound is released as an ionic liquid to modify the properties of the resulting polymer.

12. The epoxy system according to any one of claims 1 to 2, further comprising an ionic hydrophilic compound.

13. The epoxy system according to claim 12, wherein after polymerization of the hardener compound H and the epoxy compound E, the ionic hydrophilic compound is released as an ionic liquid to modify the properties of the resulting polymer.

14. The epoxy system of any one of claims 1 to 2, further comprising an ionic transitional hydrophobic / hydrophilic compound, wherein the ionic transitional hydrophobic / hydrophilic compound is a compound composed of a positive and negative ion pair whose hydrophobic or hydrophilic character can be changed from one to another based on chemical or environmental input.

15. The epoxy system according to claim 14, wherein after polymerization of the hardener compound H and the epoxy compound E, the ionic transitional hydrophobic / hydrophilic compound is released as an ionic liquid to modify the properties of the resulting polymer.

16. The epoxy system according to any one of claims 1 to 2, further comprising a biologically active compound.

17. The epoxy system of claim 16, wherein after polymerization of the hardener compound H and the epoxy compound E, the biologically active compound is released as an ionic liquid to modify the properties of the resulting polymer.

18. The epoxy system of claim 16, wherein the biologically active compound is one or more of the following biologically active compounds: wherein the group R is an alkyl group.

19. The epoxy system according to any one of claims 1 to 2, further comprising a plasticizer compound.

20. The epoxy system according to claim 19, wherein after polymerization of the hardener compound H and the epoxy compound E, the plasticizer compound is released as an ionic liquid to modify the properties of the resulting polymer.

21. The epoxy system of claim 19, wherein the plasticizer compound is one or more of the following plasticizer compounds:

22. The epoxy system of claim 19, wherein the plasticizer compound has low to zero volatility.

23. The epoxy system according to any one of claims 1 to 2, wherein the polymer produced after polymerization of the hardener compound H and the epoxy compound E comprises self-healing properties due to the presence of stable charges along the polymeric chain, driving the healing process by electrostatic attraction.

24. The epoxy system according to any one of claims 1 to 2, wherein the polymer produced after polymerization of the hardener compound H and the epoxy compound E forms a highly regular porous system.

25. The epoxy system of claim 24, wherein the produced polymer is a filter membrane, a solid electrolyte or an exchange membrane.

26. A polymer produced by polymerization of an epoxy system according to any one of claims 1 to 25.

27. The polymer of claim 26, wherein the polymer comprises a solid electrolyte.

28. An electronic component comprising the polymer according to claim 27.

29. The electronic component according to claim 28, wherein the electronic component is a component of a battery, a capacitor, a piezoelectric material and / or an electric actuator.

30. An ionic thermosetting epoxy system comprising: Hardener crosslinker compound H; and An epoxy crosslinker compound E comprising: Molecular structure (R2-(Z 1,2,3 )3), wherein R2 is an ionic part, Z 1 Contains epoxy groups, Z 2 Contains epoxy groups and Z 3 comprising an epoxy group; and an ionic portion B acting as a counter ion of R2, The hardener crosslinker compound H is 1,3,5-tris[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-iummethylene]benzene tribromide or tetrakis[1-(2'-aminoethyl)-2-methyl-1H-imidazol-3-iummethyl]methane tetrabromide.

31. The epoxy system according to claim 30, wherein the epoxy crosslinker compound E is a solvent-free ionic thermosetting crosslinker resin.

32. The epoxy system according to any one of claims 30 to 31, wherein the hardener crosslinker compound H is a solvent-free ionic thermosetting crosslinker hardener.

33. The epoxy system according to any one of claims 30 to 31, wherein the molecular structure (R2-(Z 1,2,3 )3) is: in: R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is any suitable chain, and B + It is the cationic part.

34. The epoxy system according to any one of claims 30 to 31 further comprising an ionic hydrophobic and / or superhydrophobic compound.

35. The epoxy system of claim 34, wherein after polymerization of the hardener crosslinker compound H, the epoxy crosslinker compound E, the ionic hydrophobic and / or superhydrophobic compound is released as an ionic liquid to modify the properties of the resulting polymer.

36. The epoxy system of any one of claims 30 to 31 further comprising an ionic hydrophilic compound.

37. The epoxy system of claim 36, wherein after polymerization of the hardener crosslinker compound H and the epoxy crosslinker compound E, the ionic hydrophilic compound is released as an ionic liquid to modify the properties of the resulting polymer.

38. The epoxy system of any one of claims 30 to 31 further comprising an ionic transitional hydrophobic / hydrophilic compound, wherein the ionic transitional hydrophobic / hydrophilic compound is a compound composed of a positive and negative ion pair whose hydrophobic or hydrophilic character can be changed from one to the other based on chemical or environmental input.

39. The epoxy system of claim 38, wherein after polymerization of the hardener crosslinker compound H and the epoxy crosslinker compound E, the ionic transitional hydrophobic / hydrophilic compound is released as an ionic liquid to modify the properties of the resulting polymer.

40. The epoxy system of any one of claims 30 to 31 further comprising a biologically active compound.

41. The epoxy system of claim 40, wherein after polymerization of the hardener crosslinker compound H and the epoxy crosslinker compound E, the biologically active compound is released as an ionic liquid to modify the properties of the resulting polymer.

42. The epoxy system of claim 40, wherein the biologically active compound is one or more of the following: wherein the group R is an alkyl group.

43. The epoxy system of any one of claims 30 to 31, wherein the polymer produced after polymerization of the hardener crosslinker compound H and the epoxy crosslinker compound E comprises self-healing properties due to the presence of stable charges along the polymeric chain, driving the healing process by electrostatic attraction.

44. The epoxy system according to any one of claims 30 to 31, wherein the polymer produced after polymerization of the hardener crosslinker compound H and the epoxy crosslinker compound E forms a highly regular porous system.

45. The epoxy system of claim 44, wherein the produced polymer is a filter membrane, a solid electrolyte, or an exchange membrane.

46. ​​A polymer produced by polymerisation of an epoxy system according to any one of claims 30 to 45.

47. The polymer of claim 46, wherein the polymer comprises a solid electrolyte.

48. An electronic component comprising the polymer according to claim 47.

49. The electronic component according to claim 48, wherein the electronic component is a component of a battery, a capacitor, a piezoelectric material and / or an electric actuator.

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