Patent Application
20200299302
The present disclosure relates to compounds and/or materials for use as adhesives and coatings for application to surfaces, where the adhesives and coatings may be debonded from the surface without harm to that surface upon the application of an electromotive force. This disclosure also relates to methods for debonding adhesives and coatings from surfaces. More particularly, this disclosure relates to cationic cyclic ammonium compositions and anionic fluorosulfonylimide compositions for use in the adhesives and coatings.
Ionic compositions, such as ionic liquids, may be useful as adhesives, such as adhesives for metal surfaces. However, it is known that compositions including some imidazolium sulfonylimides can be relatively corrosive to an aluminum surface.
Thus, there is a need for a new ionic composition that can be debonded from a surface without displaying the corrosiveness to metallic substrates.
In some embodiments, an ionic composition can include: at least one cyclic ammonium cation of Formula 1 and/or Formula 3:
wherein: R1, R2, and R3 are independently H, optionally substituted C1-5 hydrocarbyl, optionally substituted C1-5 hydrocarbyl-OH, or optionally substituted C1-5 hydrocarbyl-O—C1-5 hydrocarbyl.
The ionic composition can also include at least one fluorosulfonylimide anion or (fluorohydrocarbyl)sulfonylimide anion of Formula 2 and/or Formula 4:
wherein: each R4 is individually a fluorine or C1-3 fluorohydrocarbyl, and each R8 is individually a hydrogen or a fluorine; and n is an integer.
Some embodiments include an adhesive composition comprising an ionic composition described herein.
Some embodiments include a structure comprising: 1) a first electro-conductive surface, 2) a second electro-conductive surface, and 3) the adhesive composition described herein disposed between the first electro-conductive surface and the second electro-conductive surface.
Some embodiments include an adhesive member comprising: the adhesive composition described herein formed into an adhesive layer; and at least one release liner on at least one side of the adhesive layer.
Some embodiments include a method of preparing the adhesive composition described herein. The method comprises combining the fluorosulfonylimide anion with the cyclic ammonium cation.
Some embodiments include a method of adhering the adhesive composition described herein to a substrate, the method comprising: applying the adhesive composition to a first electrically conductive substrate; and applying the adhesive composition to a second electrically conductive substrate such that the adhesive composition is between the first electrically conductive substrate and the second electrically conductive substrate.
A method of adhering the adhesive layer described herein to first surface. In this method, the release liner is removed from the side of the adhesive layer of the adhesive member to expose a surface of the adhesive layer, and adhering the surface of the adhesive layer to the first surface.
The foregoing summary is illustrative only and is not intended to be in any way limiting. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features will become apparent by reference to the drawings and the following detailed description.
The foregoing and following information as well as other features of this disclosure will become more fully apparent from the following description and appended claims, taken in conjunction with the accompanying drawings. Understanding that these drawings depict only several embodiments in accordance with the disclosure and are, therefore, not to be considered limiting of its scope, the disclosure will be described with additional specificity and detail through use of the accompanying drawings.
The elements and components in the figures can be arranged in accordance with at least one of the embodiments described herein, and which arrangement may be modified in accordance with the disclosure provided herein by one of ordinary skill in the art.
In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting.
Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that the aspects of the present disclosure, as generally described herein, and illustrated in the figures, can be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are explicitly contemplated herein.
Generally, the present technology includes compounds and/or materials for use as adhesives and coatings for application to surfaces, where the adhesives and coatings may be debonded from the surface without harm to that surface upon the application of electromotive force. The present technology also includes methods and systems for debonding adhesives and coatings from substrate surfaces. Additionally, the present technology includes cationic cyclic ammonium and anionic sulfonylimide compositions for use in the adhesives and coatings.
In some embodiments, the ionic compositions described herein can be used for bonding to a surface. In some aspects, the ionic compositions can be configured as adhesives or coatings for a surface that when applied bond to the surface, the adhesive or coatings on the surface can be removed therefrom by a debonding procedure. The ionic composition is configured such that after being bonded to the surface, it can be removed without damaging the surface. This can be beneficial to allow for adhesives or coatings to be removed from a surface to retain the surface in pristine condition. The debonding procedure can include applying electricity, such as via an electromotive force, to allow for the adhesive or coating to lift from the surface without damaging the surface.
Additionally, the ionic composition described herein can be configured such that it is substantially less corrosive to metallic substrates than previous ionic compositions. The ionic composition can now be applied to a metallic surface of a substrate without causing the substrate to corrode. This can provide substantial benefit by allowing for more types of surfaces, such as on metallic substrates to receive an ionic composition as an adhesive or coating that are selectively debondable while reducing corrosion compared to prior compositions.
In some embodiments, the ionic composition can include a cyclic ammonium cation which may or may not be substituted. The cyclic ammonium cation of the ionic composition can include an optionally substituted structure under Formula 1 provided as follows:
The structure of Formula 1 can include any substituent R group for R1, R2, or R3. With respect to any relevant structural representation, such as Formula 1, in some embodiments, R1, R2, and R3 are independently H, optionally substituted C1-5 hydrocarbyl (such as C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C2 alkenyl, C3 alkenyl, etc.), optionally substituted C1-5 hydrocarbyl-OH (e.g. —CH2—OH, —C2H4—OH, —C3H4—OH, etc.), or optionally substituted C1-5 hydrocarybyl-O—C1-5 hydrocarbyl (e.g. —C2H4—O—CH3, —C2H4—O—C2H5, —C3H6—O—C2H5, etc.).
In some embodiments, the ionic composition can include a cyclic ammonium cation which may or may not be substituted. The cyclic ammonium cation of the ionic composition can include a structure under Formula 3 provided as follows:
In some embodiments of Formula 3, R1H, optionally substituted C1-5 hydrocarbyl, optionally substituted C1-5 hydrocarbyl-OH, or optionally substituted C1-5 hydrocarybyl-O—C1-5 hydrocarbyl.
In Formulae 1 and 3, the cation can be described as both an amino group and an ammonium group. The term “amino” refers to the uncharged chemical group:
The term “ammonium” refers to the positively charged chemical group:
In some embodiments, R1, R2, and R3 are independently
In some embodiments, R1 is methyl. In some embodiments, R1 is ethyl.
In some embodiments, R2 is methyl. In some embodiments, R2 is ethyl.
In some embodiments, R3 is methyl. In some embodiments, R3 is ethyl.
As used herein, optionally substituted refers to a group that may be substituted or unsubstituted. A substituted group is derived from an unsubstituted group in that one or more of the hydrogen atoms of an unsubstituted group are replaced by one or more substituent groups. A substituent group may have one or more substituent groups on the parent group structure. The substituent groups are independently selected from optionally substituted alkyl, —O-hydrocarbyl (e.g. —OCH3, —OC2H5, —OC3H7, —OC4H9, etc.), —S-hydrocarbyl (e.g., —SCH3, —SC2H5, —SC3H7, —SC4H9, etc.), —NR′R″, —OH, —SH, —CN, —NO2, or a halogen, wherein R′ and R″ are independently H or optionally substituted hydrocarbyl. Wherever a substituent is descried as “optionally substituted,” that substituent can be substituted with the above substituents.
In some embodiments, the R1, R2, and/or R3 substituents of formulae 1 and 3 can each independently include a hydrophilic functional group. In some embodiments, at least one of R1, R2, and R3 substituents can include hydrophilic functional group. In some embodiments, the hydrophilic functional group can comprise nitrogen, sulfur and/or phosphorous. In some embodiments, the hydrophilic functional group can comprise an amino group. In some aspects, the R2, and/or R3 substituents can each independently include a hydrophilic functional group. In some aspects, the R1 and/or R3 substituents can each independently include a hydrophilic functional group.
In some embodiments, the R1, R2, and/or R3 substituents can each independently include a hydrophilic functional group that includes one or more of the following: amino, mono- and di-(alkyl)-substituted amino, mono- and di-(aryl)-substituted amino, alkylamido, arylamido, imino, alkylimino, arylimino, nitro, nitroso, sulfo, sulfonato, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, phosphono, phosphonato, phosphinato, phospho, phosphino, hydroxyl, and combinations thereof, which may further include at least one C1-C3 alkyl coupled thereto so as to form the hydrophilic functional group. In some embodiments, at least one of the R1, R2, and R3 substituents can include the hydrophilic functional group. In some aspects, the R1, R2, and/or R3 substituents can each independently include a hydrophilic functional group. In some aspects, the R1 and/or R3 substituents can each independently include a hydrophilic functional group.
In some embodiments, the R1, R2, and/or R3 substituents can each independently include a hydrophobic functional group. In some embodiments, at least one of the R1, R2, and R3 substituents can include a hydrophobic functional group. In some embodiments, the hydrophobic functional group can comprise an optionally substituted alkyl group. In some embodiments, the optionally substituted alkyl group can comprise a methyl, ethyl, and/or propyl group. In some aspects, the R1, R2, and/or R3 substituents can each independently include a hydrophobic functional group. In some aspects, the R1 and/or R3 substituents can each independently include a hydrophobic functional group. In some aspects, the R2 substituent can include a hydrophobic functional group.
In some embodiments, R1, R2 and/or R3 can include hydrocarbyl, such as methyl, ethyl, or propyl.
In some embodiments, R1, R2 and/or R3 can include the following substituent: H, —CH3, —CH2CH3, —CH2CH2CH3, —CH2OCH3, —CH2CH2OCH3, —CH2OCH2CH3, —CH2CH2CH2OCH3, —CH2OCH2CH2CH3, —CH2CH2OCH2CH3, —CH2CH2CH2OCH2CH3, —CH2CH2CH2OCH2CH2CH3, or —CH2CH2OCH2CH2CH3, —CH2OH, —CH2CH2OH, —CH2CH2CH2OH, or —CH2CH2CH2CH2OH.
In some embodiments, the cyclic ammonium cation is:
optionally substituted
or optionally substituted
or a combination thereof. Potential substituents for these compounds may be low molecular weight substituents, e.g. having a molecular weight of 15-50 Da, 15-100 Da, or 15-150 Da, such as F, C1, Br, OH, NH2, or C1-6H0-15O0-2N0-2S0-1. In some embodiments, any substituent of these cyclic ammonium cations are C1-3 alkyl, C1-30-alkyl, or OH, or any hydrogen on any of the structures above may be replaced with C1-3 alkyl, C1-3 O-alkyl, or OH.
In some embodiments, the cyclic ammonium cation is:
or a combination thereof.
In some embodiments, the ionic composition can have one or more different types of cyclic ammonium cations, such as one or both of the aforementioned structures.
In some embodiments, the ionic composition can include a sulfonylsulfonic imide anion. In some embodiments, the sulfonylsulfonic imide anion can include a fluoroalkylsulfonylimide compound (e.g. CH2FSO2NSO2CH2F, CF3SO2NSO2CF3, etc.). In some embodiments, the sulfonylsulfonic imide anion can comprise a fluorosulfonylimide compound. Accordingly, the ionic composition may also include a sulfonylimide anion. The sulfonylimide anion can include a structure under Formula 2 as provided as follows:
In some embodiments of Formula 2, R4 is a fluoro group:
In some embodiments, the ionic composition can include the fluoroalkysulfonylimide compound having a structure as in Formula 4 provided as follows:
The structure of Formula 4 can include any substituent R group for each R8 independently, such as those described herein or otherwise known. Also, each n can be an integer, such as 0, 1, 2, 3, or 4, or other.
In some embodiments of Formula 4, each R8 can individually be H or a halogen. In some embodiments of Formula 4, each R8 can individually be H or a fluorine. In some embodiments, at least one R8 is a halogen, such as fluorine. In some embodiments, for each sulfonyl group, at least one R8 is a halogen, such as fluorine. In some embodiments, for each sulfonyl group, only one R8 is a halogen, such as fluorine.
In some embodiments, the ionic composition can include the cyclic ammonium cation and the sulfonylimide anion:
In some embodiments, ammonium is also described as aminium. In some embodiments of the invention, ammonium is also described as octanium. In some embodiments of the invention ammoniums is also described as piperazinium.
In some embodiments, sulfonylimide is also described as sulfonyl imide, sulfonyl amide and/or sulfonylamide.
In some instances, the ionic composition can include the cyclic ammonium cation with or without the sulfonylimide anion (e.g., bis(fluorosulfonyl)imide). In some instances, the ionic composition can include the sulfonylimide anion with or without the cyclic ammonium cation. In any configuration, the ionic composition can be used as the adhesive layer or coating layer, or other layer.
In some embodiments, the ionic composition can include a cation having an amino group, a linker and an ammonium group, where the amino and ammonium groups bound to each other by the linker to form a cyclic structure. In some embodiments, the cation may be a composition with an anion. In some embodiments, the anion may be bis(fluorosulfonyl)imide.
In some embodiments, the adhesive composition of one of the embodiments can include a polymer containing the cyclic ammonium cation and the fluorosulfonylimide anion. In some aspects, the polymer includes at least one polymer selected from an acrylate polymer, alkylacrylate polymer, an alkyl-alkylacrylate ester polymer, or a combination thereof. In some aspects, the polymer comprises an acrylate polymer, a methacrylate polymer, or a combination of both acrylate and methacrylate polymers. In some aspects, the polymer comprises acrylic acid, C1-14 hydrocarbyl acrylate, C1-14 hydrocarbyl methacrylate monomers, or a combination thereof. In some aspects, the polymer is crosslinked. In some aspects, the polymer is crosslinked with an epoxy crosslinker. In some aspects, the epoxy crosslinker is N,N,N′,N′-tetraglycidyl-m-xylenediamine.
Any suitable amount of ionic liquid may be used in the adhesive composition. In some embodiments, the ionic liquid or ionic compound is about 0.0-1%, about 1-2%, about 2-3%, about 3-4%, about 4-5%, about 5-6%, about 6-7%, about 7-8%, about 8-9%, about 9-10%, about 10-15%, about 15-20%, about 20-25%, about 25-30%, about 30-40%, about 40-50, about 50-100%, about 4.5-5%, or about 5% of the total weight of the ionic liquid plus the polymer.
In some embodiments, the cyclic ammonium cation and the fluorosulfonylimide anion are present in about a 1:1 ratio.
In some embodiments, the adhesive composition is configured to be selectively debondable. In some aspects, the adhesive composition is configured to be selectively debondable under application of an electromotive force.
In some embodiments, a method of preparing the adhesive composition of one of the embodiments can include: combining the fluorosulfonylimide anion with the cyclic ammonium cation. In some aspects, the method can include combining the fluorosulfonylimide anion and the cyclic ammonium cation with a polymer. In some aspects, the method can include crosslinking the polymer before, during or after being combined with the fluorosulfonylimide anion and the cyclic ammonium cation.
In some embodiments, a method of adhering the adhesive composition of one of the embodiments to a substrate can include: applying the adhesive composition to a first electrically conductive substrate. In some aspects, the method can further include applying the adhesive composition to a second electrically conductive substrate such that the adhesive composition is between the first electrically conductive substrate and the second electrically conductive substrate.
In some embodiments, an adhesive member can include: the adhesive composition of one of the embodiments formed into an adhesive layer; and at least one release liner on at least one side of the adhesive layer. In some aspects, the adhesive member can include a release liner on each side of the adhesive layer. The release liner may be removed to expose a side of the adhesive layer so that the adhesive layer can be adhered to another surface.
In some embodiments, a selectively adhesive material can include the adhesive composition of one of the embodiments configured such that application of an electromotive force to the selectively adhesive material reduces the adhesion of the selectively adhesive material.
In some embodiments, a selectively debondable structure can include a selectively debondable layer of the selectively adhesive material of one of the embodiments, wherein the selectively debondable layer is disposed between a first electro-conductive surface and a second electro-conductive surface. In some aspects, the selectively adhesive material adheres to the first electro-conductive surface and the second electro-conductive surface. In some aspects, the selectively debondable structure of one of the embodiments can include a power supply that is in electrical communication with at least one of the first electro-conductive surface and the second electro-conductive surface, creating a closeable electrical circuit therewith. In some aspects, the power supply is a DC power supply, which may provide about 3 volts to about 100 volts. In some aspects, the selectively debondable structure of one of the embodiments, can include the first electro-conductive surface having an electro-conductive material, which can be configured as a substrate. In some aspects, the selectively debondable structure of one of the embodiment can include the second electro-conductive surface having an electro-conductive material, which can be configured as a substrate. In some aspects, the electro-conductive material includes a metal, a mixed metal, an alloy, a metal oxide, a composite metal, a conductive plastic or a conductive polymer. In some aspects, the electro-conductive material includes an electro-conductive metal, a mixed metal, an alloy, a metal oxide, a mixed metal oxide, a conductive plastic, a carbonaceous material, a composite metal, or a conductive polymer. In some aspects, the electro-conductive material includes an electro-conductive metal. In some aspects, the electro-conductive metal includes aluminum. In some aspects, the selectively adhesive material has a reduced corrosive effect upon the first electro-conductive surface and/or second electro-conductive surface.
In some embodiments, a selectively debondable structure can include a selectively debondable layer of the selectively adhesive material of one of the embodiments, wherein the selectively debondable layer is disposed on a first electro-conductive surface. In some aspects, the selectively debondable structure of one of the embodiments can include a power supply that is in electrical communication with the first electro-conductive surface.
In some embodiments, a selectively debondable material can include the ionic compositions and/or adhesive compositions of one of the embodiments. In some aspects, the selectively debondable material can include a polymer. In some aspects, the polymer can include an acrylate polymer, a methacrylate polymer, or a combination of both acrylate and methacrylate polymers. In some aspects, the polymer can include acrylic acid, C1-14 hydrocarbyl acrylate or C1-14 hydrocarbyl methacrylate monomers. In some aspects, the selectively debondable material is an adhesive.
In some embodiments, the ionic composition described herein with the cyclic ammonium cation and the bis(fluorosulfonyl)imide anion can be formulated as follows:
In this formulation, the amino group can include the R groups as defined herein, such as for R1, R2, and/or R3 can be the H or substituents as defined herein.
In some embodiments, the ionic composition described herein with the cyclic ammonium cation and the bis(fluorosulfonyl)imide anion can be formulated as follows:
In some embodiments, the ionic composition described herein with the cyclic ammonium cation and/or the sulfonylimide anion can be formulated with a polymer. The polymer can be selected based on the functionality thereof in view of the desired functionality. In some aspects, the polymer formulated in the ionic composition can include an acrylic polymer.
In some embodiments, the polymer formulated in the ionic composition, such as with the cyclic ammonium cation and/or the sulfonylimide anion can be a polymer suitable for use as the adhesive or coating that is selectively debondable, such as by applying the debonding process to the adhesive or coating. The suitable polymer can include the polymers described in WO2017/064918 and/or JP2017-075289, which are incorporated herein by specific reference in their entirety. In some aspects, the polymer can include a glass transition temperature below 0° C. In some aspects, the polymer can be an acrylic polymer. In some aspects, the acrylic polymer can include a monomer unit derived from a monomer of a formula RaCH═CHCO2Rb, wherein Ra is H or C1-14 alkyl (e.g. methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, etc.), and Rb is H or C1-14 alkyl (e.g. methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, etc.). In some embodiments, the polymer includes repeating units derived from acrylic acid, methyl acrylate, methacrylic acid, methylmethacrylate, or a combination thereof. In some aspects, the acrylic polymer can contain an alkyl-methacrylate ester and a monomer unit derived from a monomer that contains a polar group. In some aspects, the monomer containing the polar group (e.g., polar monomer) can be a monomer that contains a carboxyl group. In some aspects, the C1-C14 alkyl group containing alkyl-methacrylate ester is butyl-methacrylate ester, and may be methylmethacrylate ester, ethyl-methacrylate ester, propyl-methacrylate ester, methyl-ethylacrylate ester, methyl-propylacrylate ester, methyl-butylacrylate ester, or other alkyl-alkylacrylate ester.
In some embodiments, the polymer may be crosslinked. The crosslinked polymer may include the polymer crosslinked with only polymers in the composition. In some aspects, the crosslinked polymer may chemically crosslink with the ammonium cation. In some aspects, the crosslinked polymer may chemically crosslink with the fluorosulfonylimide anion. In some aspects, the crosslinked polymer may chemically crosslink with the cyclic ammonium cation and fluorosulfonylimide anion. Crosslinkers that can crosslink the polymers can be selected based on the desired properties in order to provide the crosslinked polymer. The crosslinkers may be suitable for use with the alkyl-alkylacrylate esters. The crosslinker can be an epoxy crosslinker, such as N,N,N′,N′-tetraglycidyl-m-xylenediamine. However, it should be recognized that any suitable crosslinker may be used to crosslink the polymer. The crosslinker can be selected to retain the selective adhesive properties and selective debonding properties as described herein. The crosslinker can also be selected to retain the anticorrosive properties described herein.
In some embodiments, a device is described comprising any of the aforementioned compounds. A suitable example of such a device can be as described in JP 2017-075289 and/or WO2017/064925, which are incorporated herein by specific reference in their entirety. Accordingly, the device can be an electronic device that includes an electro-conductive substrate having the selectively adhesive compositions described herein. In some aspects, the device can include a battery.
The ionic composition can be used as a selectively debondable layer on a surface of a substrate, such as the adhesive layer or coating layer as described herein. In some aspects, the ionic composition configured as a selectively debondable layer can be positioned or otherwise located between two electro-conductive surfaces, such as between a first electro-conductive surface and a second electro-conductive surface. The selectively debondable layer formed from the ionic composition can be applied as an adhesive layer (e.g., selectively adhesive) between the first electro-conductive surface and the second electro-conductive surface, so as to adhere a first substrate having the first electro-conductive surface to a second substrate having the second electro-conductive surface. The adhesive layer may be considered to be selectively adhesive due to the debonding procedure that can be implemented to debond the adhesive layer from the first electro-conductive surface and/or the second electro-conductive surface. The debonding procedure can include applying electricity, such as via an electromotive force, to the first electro-conductive substrate and/or the second electro-conductive substrate to debond the adhesive layer therefrom. The debonding procedure can cause a reduction of adhesiveness in the adhesive layer so as to be less adhesive to the first electro-conductive surface and/or the second electro-conductive surface, which allows separating the adhesive layer therefrom. This also allows for the first electro-conductive surface to be separated from the second electro-conductive surface. Due to the ionic composition being less corrosive and the debonding procedure allowing for removal from the surfaces without damage, the surfaces can be retained in significantly improved conditions compared to prior adhesives. The improved condition can be beneficial for reuse of the substrates having the surfaces.
In some embodiments, the ionic composition can be configured to have reduced corrosion or no corrosion (e.g., unmeasurable or undetectable) for metal substrates, such as electro-conductive metal substrates.
In some embodiments, the ionic composition can be provided with the ingredients as described herein. In some aspects, the ionic composition has a reduced Lewis acidity. In some aspects, the ionic composition can include a suitable pH. In some aspects, the ionic composition can include a pH that is not overly acidic or overly basic. In some examples, the pH can range from about 5 to about 9, or about 6 to about 8 or about 7. When alkaline, the pH can range from about 7 to about 9, about 7.5 to about 8.5, or about 8.
The selectively debondable layer can be used in a selectively debondable structure that used to adhere two non-conductive materials to one another, and then release the bonding so that the debonded materials do not contain any conductive materials or layers. This type of structure comprises an electro-conductive layer with a selectively debondable layer adhered to each side. Each of these adhesive layers can then be adhered to a nonconductive material, thus providing adhesion between two nonconductive structures. An electromotive force can then be applied to the electro-conductive layer to reduce the adhesion in both adhesive layers. Thus, the two nonconductive structures can be adhered to one another, and then separated, without needing to first be bonded or attached to a conductive layer or material.
In some embodiments, the ionic composition can be provided with various ratios of the cyclic ammonium cation with respect to the sulfonylimide anion. In some aspects, the molar ratios of the cyclic ammonium cation:sulfonylimide anion can be 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 1:10-1:9, 1:9-1:8. 1:8-1:7, 1:7-1:6, 1:6-1:5, 1:5-1:4, 1:4-1:3, 1:3-1:2, 1:2-1:1, 1:1-2:1, 2:1-3:1, 3:1-4:1, 4:1-5:1, 5:1-6:1, 6:1-7:1, 7:1-8:1, 8:1-9:1, or 9:1-10:1. In one aspect, the ratio of the cyclic ammonium cation:sulfonylimide anion can be 1:1, or substantially equivalent, such as being 0.1%, 0.5%, 0.75%, 1%, 2%, or 5% from being equivalent.
In some embodiments, the ionic composition can be provided so that the molecular weight is reduced. For example, the molecular weight may be less than 160 g/mole. This molecular weight can be for a substance formed from the cyclic ammonium cation and/or sulfonylimide anion.
As shown in
The selectively adhesive material 203 can include the compounds of the ionic compositions described herein. As such, the selectively adhesive material 203 can be a selectively debondable layer or coating disposed between the first electro-conductive substrate 206 and the second electro-conductive substrate 207. The first electro-conductive substrate 206 having an electro-conductive surface 208 and the second electro-conductive substrate 207 having an electro-conductive surface 210, can respectively be each individually disposed upon two non-metal (non-electro-conductive) substrates or layers, 201 and 202.
The first electro-conductive substrate 206 and second electro-conductive substrate 207 may be in electrical communication with a power supply 204 (e.g., DC, but may be AC) to complete a closeable electrical circuit with an intervening switch 205, or may be attached to the power supply when debonding is desired. When the switch 205 is open, as shown in
In some embodiments, the selectively adhesive material 203 can also be referred to as a selectively debondable layer due to the ability to have selective bonding without an electrical current or selective debonding with an electrical current. The material 203 can comprise a selectively adhesive material, which can be formed from the ionic compositions described herein. In some aspects, the material 203 can bind and connect the first electro-conductive surface 208 and the second electro-conductive surface 210 together, wherein the application of an electromotive force to the electro-conductive materials of the first electro-conductive substrate 206 or second electro-conductive substrate 207 reduces the adhesion of the material 203. In some aspects, the material 203 can include an ionic composition having a compound of at least Formula 1. In some embodiments, the material 203 can include an ionic composition having a compound of Formula 1 and a compound of Formula 2. In some instances, the ionic composition can include a compound of Formula 3 in place of the compound of Formula 1 or in addition thereto. In some instances, the ionic composition can include a compound of Formula 4 in place of the compound of Formula 2 or in addition thereto. As such, the ionic composition can include a cation of at least one of Formula 1 or Formula 3, with or without an anion of at least one of Formula 2 or Formula 4.
While not wanting to be bound by theory, it is believed that a movement of ions within the material 203 formed by the ionic composition may be effected by application of the electrical potential thereto. Upon a sufficient amount of movement being effected, such as sufficient ionic components being adjacent to the electro-conductive surface (e.g., 208 and/or 210), the adhesive qualities of the material 203 formed from the ionic composition is reduced, enabling separation of one or both of the electro-conductive surfaces 208, 210 from the material 203.
The selectively adhesive material 203 (e.g., also selectively debondable layer) incorporating the compounds of Formula 1 and/or Formula 3, with or without an anion of at least one of Formula 2 and/or Formula 4, can be a selectively debondable layer or coating disposed between the first electro-conductive substrate 206 and second electro-conductive substrate 207.
The first electro-conductive substrate 206 and second electro-conductive substrate 207 can be any electrically conductive material, such as a metal. An example of an electro-conductive metal that can be used for a first electro-conductive substrate 206 and second electro-conductive substrate 207 is aluminum. The electro-conductive material may include a conventional material such as a metal, mixed metal, alloy, metal oxide, mixed-metal oxide, a conductive polymer, a conductive plastic, or a conductive carbonaceous material. Examples of suitable metals include the Group 1 metals and Groups 4-15 metals. Examples of suitable metals include, but are not limited to, stainless steel, Al, Ag, Mg, Ca, Cu, Mg/Ag, LiF/AI, CsF, CsF/AI and/or alloys thereof. In some embodiments, the electro-conductive layers (e.g., first electro-conductive substrate 206 and second electro-conductive substrate 207) and/or the adhesive layer can each have a thickness in the range of about 1 nm to about 1000 μm, or 1 nm to about 100 μm, or 1 nm to about 10 μm, or 1 nm to about 1 μm, or 1 nm to about 0.1 μm, or 10 nm to about 1000 μm, or 100 nm to about 1000 μm, or 1 μm to about 1000 μm, or 10 μm to about 1000 μm, or 100 μm to about 1000 μm. In some aspects, the thickness can be from 20 nm to about 200 μm, or 100 nm to about 100 μm, or 200 nm to about 500 μm.
The two non-electro-conductive substrates or layers 201 and 202 can be any non-conducting material. Some examples can include non-conducting wood, cardboard, fiberglass density fiberboard, or plastic, as well as any other non-conducting material. In some aspects, the layers 201 and 202 can be electrical insulators. In some aspects, the layers 201 and 202 may be semiconductors. Any of the non-electro-conductive substrates 201 or 202 or semiconductor substrate (e.g., printed circuit board, PCB) can have any thickness and may be coupled to other substrates, materials or devices.
In some embodiments, the ionic composition, whether configured as an adhesive or a coating, of the selectively adhesive material 203 can have a reduced corrosive effect on the electro-conductive layers of the first electro-conductive substrate 206 or second electro-conductive substrate 207. The reduced corrosive effect can be comparable to the corrosive effect of other ionic compositions. Suitable protocols to assess the corrosive effect of the material 203 on the electro-conductive materials can include the procedures described in ASTM G69-12 (Standard Test Method for Measurement of Corrosion Potentials of Aluminum Alloys), which is incorporated herein by specific reference. Suitable alternative protocols to assess the corrosive effect of the ionic composition material 203 upon the electro-conductive materials of the first electro-conductive substrate 206 or second electro-conductive substrate 207 can be achieved by visually examining interface between the material 203 (e.g., adhesive) and the electro-conductive substrate (e.g., aluminum foil) for any indication of corrosive degradation of the substrate and/or dissolution of the material from the electro-conductive substrate (e.g., metal) into the material 203 and/or pitting of the surface of the electro-conductive substrate. If corrosiveness was observed, the time was recorded and the sample was indicated as corrosive, as shown in Table 1 below.
In some embodiments, the selectively adhesive material can be chemically stable with an electrically conductive electrode or electro-conductive materials. That is, the selectively adhesive material can avoid chemical degradation when applied to an electrically conductive electrode or electro-conductive materials, whether in the bonding stage with no electrical current, or in the debonding stage with electrical current. As such, the selectively adhesive material can be considered to have chemical stability during use. The stability of the selectively adhesive material can be maintained when located on aluminum, stainless steel, and/or combinations and/or mixtures thereof. In some aspects, the chemical stability of the selectively adhesive material is defined as lack of (or minimal presence) of undesired reactions between the electrically conductive material and the selectively adhesive material. Undesired reactions may include, for example, corrosive degradation of the electrically conductive material, dissolution of the electrically conductive material into the selectively adhesive material and/or pitting of the electrically conductive material.
In some embodiments, the presently described ionic composition formed as the selectively adhesive material when deposited on or in contact with the electro-conductive material may result in reduced or absence of corrosive degradation thereof. In some embodiments, direct contact of the neat ionic compound (e.g., cyclic ammonium cation and/or sulfonylimide anion) or ionic composition or the selectively adhesive material formed from the ionic composition on the electro-conductive material may show an absence of or minimize any corrosive degradation thereof for a period of at least or greater than 15 minutes, 30 minutes, 1 hour, 3 hours, 5 hours, 7 hours, 24 hours, 50 hours, 100 hours, 125 hours, 200 hours, and/or 300 hours. In some aspects, direct contact of the neat ionic compound or ionic composition or selectively adhesive material on the electro-conductive material may minimize and/or prevent corrosive degradation thereof for one of the time periods described above. In some aspects, direct contact of the neat ionic compound or ionic composition or selectively adhesive material upon the electro-conductive material may minimize and/or prevent corrosive degradation thereof for periods described above in a 60° C./90% relative humidity (RH), 85° C./85% RH, or 90° C./80% RH environment, or any range therebetween for humidity and/or for temperature. In some aspects, a suitable protocol to exemplify an absence of any corrosive degradation can be by demonstrating a lack of total penetration into a surface of the electro-conductive material. In an example, the electro-conductive material can be an about 50 nm thick electro-conductive sheet of aluminum foil and the corrosive test can be performed for the above described time periods and/or environmental conditions.
In some embodiments, the selectively adhesive materials formed from the ionic compositions described herein can be formulated to minimize corrosion of the above described electro-conductive substrates under conditions of prolonged high humidity and high temperature. In particular, the adhesive composition is capable of maintaining two such electro-conductive substrates in fixed relation to each other during and after being subjected to aging. This resistance to corrosion has been validated by Accelerated Aging Test Method II, described herein, which can include exposure to 90° C./80% RH for a period of time described herein. The selectively adhesive materials can be fabricated using techniques known in the art, as informed by the guidance provided herein.
It has been discovered that embodiments of ionic compositions and the selectively adhesive materials described herein can reduce the deterioration and/or corrosion of the electro-conductive materials (e.g., conductive metal layers) described herein. These benefits are further shown by the following examples, which are intended to be illustrative of the embodiments of the disclosure, but are not intended to limit the scope or underlying principles in any way.
1,4-diazabicyclo[2.2.2]octane (20 g, 178 mmol) in ethyl acetate (150 mL) was placed in a 3-neck round-bottomed flask. Ethyl bromide (13.2 mL, 178 mmol) was added dropwise by syringe and the reaction mixture was stirred at room temperature for 24 hours under nitrogen atmosphere. The white solid was filtered off, washed with ethyl acetate (2×100 mL) and dried in a vacuum oven for 5 hours at 40° C. to give 1-ethyl-1,4-diazabicyclo[2.2.2]octan-1-ium bromide (35.0 g. 89% yield).
A mixture of 1-ethyl-1,4-diazabicyclo[2.2.2]octan-1-ium bromide (8.0 g. 36.2 mmol), bis(fluorosulfonyl)imide potassium salt [KFSI] (7.93 g, 36.2 mmol) and dry acetone (120 mL) was stirred under nitrogen at 50° C. for 2 h. After cooling to room temperature, the solid was filtered off, and the solvent was removed under reduced pressure to give a crude product. Dichloromethane (100 mL) was added onto the crude product and let it sit overnight. The white precipitates were filtered and the filtrate was concentrated under reduced pressure to give pure 1-ethyl-1,4-diazabicyclo[2.2.2]octan-1-ium bis(fluorosulfonyl)amide (11.06 g, 95% yield). 1H NMR (400 MHz, DMSO-d6) δ 3.29-3.17 (m, 8H), 3.11-2.92 (m, 6H), 1.31-1.13 (m, 3H).
Iodoethane (3.50 mL, 43.8 mmol) in ethyl acetate (45 mL) was placed in a round-bottomed flask. Using an addition funnel, 1,4-dimethylpiperazine (5.0 g, 43.8 mmol) in ethyl acetate (45 mL) was added dropwise into the reaction mixture and was stirred at room temperature under nitrogen atmosphere for 24 hours. The white precipitates were filtered off, washed with ethyl acetate (50 mL) and dried in a vacuum oven for 3 hours at 40° C. to give 1-ethyl-1,4-dimethylpiperazin-1-ium iodide (4.5 g. 38% yield).
A mixture of 1-ethyl-1,4-dimethylpiperazin-1-ium iodide (4.5 g. 16.6 mmol), KFSI (3.65 g, 16.6 mmol) and dry acetone (60 mL) was stirred under nitrogen at 50° C. for 2 h. After cooling to room temperature, the solid was filtered off, and the solvent was removed under reduced pressure to give a crude product. A solution of the crude product in ethyl acetate (150 mL) was washed with water (80 mL), dried over sodium sulfate and concentrated under reduced pressure to give pure 1-ethyl-1,4-dimethylpiperazin-1-ium bis(fluorosulfonyl)amide (3.12 g, 58% yield). 1H NMR (400 MHz, DMSO-d6) δ 3.42 (q, J=7.3 Hz, 2H), 3.38-3.33 (m, 4H), 2.98 (s, 3H), 2.74-2.66 (m, 2H), 2.65-2.59 (m, 2H), 2.28 (s, 3H), 1.24 (t, J=8.2, 6.5 Hz, 3H).
Preparation of a Polymer Solution
Preparation of a polymer solution was performed as follows. Accordingly, 95 mass parts n-butyl acrylate, 5 mass parts acrylic acid and 125 mass parts ethyl acetate were introduced into a stirring flask attached to a condenser that was equipped with a nitrogen gas inlet. The mixture was stirred at room temperature while introducing the nitrogen gas, for about 1 hour to remove oxygen from the reaction system. Then, 0.2 mass parts azobisisobutyronitrile (AIBN) were added, which increased the temperature of the resulting mixture to about 63°±2° C., and mixed/stirred for about 5-6 hours for polymerization. After stopping the reaction, an acrylic polymer-containing solution resulted, having a solid content of about 30%. The apparent molecular weight of the polymer solution (P1) was determined to be about 800,000 with a Tg (glass transition temperature) of about −50° C.
Preparation of Adhesive Sheet
An adhesive sheet was prepared by mixing the polymer solution described above with 0.01 gram of an epoxy crosslinking agent, such as N,N,N′,N′-tetraglycidyl-m-xylenediamine, per 100 gram of solid polymer solution, and combined with at least one of the ionic liquid compounds (e.g., 5.0 wt %, of the solid polymer, of cyclic ammonium cation and/or bis(fluorosulfonyl)imide), described above, to obtain an electrically debondable adhesive compositions. The prepared compositions were coated/deposited upon a surface treated PET separator (release liner) [MRF38, made by Mitsubishi Chemical Corp., Japan], forming an adhesive composite layer at a thickness of about 150 μm (microns). The coated film was then heat dried at 130° C. for about 3 minutes. A second PET (Polyethylene terephthalate) separator (release liner) was then aligned over the exposed adhesive coating to obtain a layered sheet (PET separator/adhesive coating/PET separator) which was then aged/dried at 50° C. for about 20-24 hours and then stored under ambient conditions until needed.
Adhesive Ionic Composition Corrosive Test
Just prior to the application of the adhesive sheet to an aluminum film, the aforementioned release liner was removed. The adhesive sheet, as previously described above, was applied to the metallic surface of the aluminum film (50 nm-thick aluminum coated PET film [Toray Advanced Film, Tokyo, Japan]). The prepared adhesive-aluminum film was placed in a temperature and humidity benchtop chamber, set at 60° C./85% Relative Humidity (RH), 85° C./85% RH or 80° C./90% RH (ESPEC North America, [Hudsonville, Mich., USA], Criterion Temperature & Humidity Benchtop Model BTL-433) and were periodically checked at selected times (initially hourly). The interface between the adhesive and the aluminum foil was visually examined for an indication of corrosive degradation of the aluminum foil and/or dissolution of the metal in the selectively adherent adhesive and/or pitting of the aluminum foil. If corrosiveness was observed, the time was recorded and the sample was indicated as corrosive. The results are shown in Table 1, below. Here: no IL is the aluminum film without any ionic liquid; AS 110 is a prior ionic liquid; S1 is the composition from Example 1; and S2 is the composition from Example 2. Accordingly, the data shows the ionic compositions of S1 and S2 have superior resistance to corrosion.
Adhesion Test
The testing for adhesion was done in the manner as described in Japanese Patent Publication No. JP 2017-095590 and/or WO2017/064918 and shown in
As shown in
The bonding/de-bonding tester (Mark-10, Copiague, New York, USA, model ESM303 motorized tension/compression stand) was equipped with a Mark-10 force gauge (Series 7-1000) and had lower and upper clamps. The conductive substrate 301 was fixed onto the lower clamp and then electrically connected to the positive pole of a power supply 304 (Protek DC Power Supply 3006B). The top layer 302 was fixed to the upper clamp which is connected with the negative pole of the same DC power supply. This resulted in a configuration similar to
In a dynamic test, the voltage was applied a few seconds after the peeling or separation starts and the time and peeling strength readings from the force gauge are recorded by the data acquisition system (Mark-10 MESURgauge Plus).
In a static de-bonding test, the sample was fixed on to the tester and connected to the power supply in the same way. The initial 180 deg. peeling was measured at the same peeling speed. Then peeling was stopped. A DC voltage (10 VDC for example) was applied for some time (10 second for example). And then the peeling strength was measured at the same peeling speed of 300 mm/min. For the same adhesive sample from the S2 composition of Example 2, the initial peeling strength is 9.5 N/cm; while the residual adhesion peeling strength is ˜4.7 after applying 10 VDC for 10 second.
From the foregoing, it will be appreciated that various embodiments of the present disclosure have been described herein for purposes of illustration, and that various modifications may be made without departing from the scope and spirit of the present disclosure. Accordingly, the various embodiments disclosed herein are not intended to be limiting, with the true scope and spirit being indicated by the following claims.
All references recited herein are incorporated herein by specific reference in their entirety.
This patent application claims priority to U.S. Provisional Application No. 62/589,416 filed Nov. 21, 2017, which provisional is incorporated herein by specific reference in its entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2018/061917 | 11/20/2018 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62589416 | Nov 2017 | US |
