WO2022256827A1 - Films adhésifs réversibles activés par voie thermique à durcissement rapide - Google Patents

Films adhésifs réversibles activés par voie thermique à durcissement rapide Download PDF

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WO2022256827A1
WO2022256827A1 PCT/US2022/072730 US2022072730W WO2022256827A1 WO 2022256827 A1 WO2022256827 A1 WO 2022256827A1 US 2022072730 W US2022072730 W US 2022072730W WO 2022256827 A1 WO2022256827 A1 WO 2022256827A1
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polymer composition
polymer
thermoresponsive
lcst
thermoresponsive polymer
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PCT/US2022/072730
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English (en)
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Shu Yang
Mingtao CHEN
Anand Jagota
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The Trustees Of The University Of Pennsylvania
Lehigh University
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Publication of WO2022256827A1 publication Critical patent/WO2022256827A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/20—Polymers characterized by their physical structure
    • C08J2300/208—Interpenetrating networks [IPN]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/10—Homopolymers or copolymers of unsaturated ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides

Definitions

  • the present disclosure relates to the field of thermally-activated adhesive films.
  • Adhesives are ubiquitous in daily life, in construction, automobile manufacture, wound dressing/healing, of medical devices, cosmetics, and in microchip assemblies. Adhesives can generally be divided into two classes: (1) strong but irreversible super glues, such as cyanoacrylate-based adhesives; and (2) weak but reversible adhesives, such as various pressure sensitive adhesives. Both have advantages and disadvantages; strong but irreversible adhesives are often responsible for destructive delamination and thus accumulated waste, while reversible adhesives fail to provide strong enough load transmission for various applications.
  • PSA pressure sensitive adhesive
  • the present disclosure provides polymer compositions, comprising: a polymeric hydrogel; and a thermoresponsive polymer, the polymeric hydrogel and the thermoresponsive polymer being arranged as an interpenetrating network, the thermoresponsive polymer being soluble in water, the thermoresponsive polymer having a lower critical solution temperature (LCST), and the thermoresponsive polymer chains being dispersed within the polymeric hydrogel such that when the thermoresponsive polymer attains a temperature above the LCST, the thermoresponsive polymer becomes insoluble and forms physical crosslinks between chains of the polymeric hydrogel.
  • LCST critical solution temperature
  • articles comprising a polymer composition according to the present disclosure (e.g., any one of Aspects 1-20) disposed on a substrate.
  • articles comprising a polymer composition according to the present disclosure (e.g., any one of Aspects 1-20) disposed so as to bond two portions of a substrate to one another.
  • a polymer composition according to the present disclosure e.g., any one of Aspects 1-20
  • articles comprising a polymer composition according to the present disclosure (e.g., any one of Aspects 1-20) disposed so as to bond two substrates to one another.
  • a polymer composition according to the present disclosure e.g., any one of Aspects 1-20
  • kits comprising an applicator and an amount of a polymer composition according to the present disclosure (e.g., any one of Aspects 1-20), the applicator configured to controllably dispense the polymer composition.
  • thermoresponsive polymer composition comprising: effecting heating of a polymer composition according to the present disclosure (e.g., any one of Aspects 1-20) such that the thermoresponsive polymer attains a temperature above the LCST of the thermoresponsive polymer, or effecting cooling of a polymer composition according to the present disclosure (e.g., any one of Aspects 1-20) such that the thermoresponsive polymer attains a temperature below the LCST of the thermoresponsive polymer.
  • a polymer composition according to the present disclosure e.g., any one of Aspects 1-20
  • the methods can also be performed to bond two portions of a substrate to one another.
  • thermoresponsive polymer comprising: dispersing a thermoresponsive polymer into a hydrogel precursor, the thermoresponsive polymer being soluble in water, the thermoresponsive polymer having a lower critical solution temperature (LCST), and the thermoresponsive polymer chains being dispersed within the polymeric hydrogel such that when the thermoresponsive polymer attains a temperature above the LCST, the thermoresponsive polymer becomes insoluble and forms physical crosslinks between chains of the polymeric hydrogel.
  • LCST critical solution temperature
  • PHEMA poly (2 -hydroxy ethyl methacrylate) hydrogels that include an additional poly(N-isopropylacrylamide) (PNIPAm) segment, which additional segment introduces thermal response through lower critical solution temperature (LCST) and significantly reduces the adhesion evolution time (from 60 - 90 minutes to 2 minutes) at T > LCST.
  • LCST critical solution temperature
  • PHEMA-PNIPAm poly(N-isopropylacrylamide)
  • FIG. 1 provides an exemplary composition according to the present disclosure
  • FIG. 2 provides exemplary results from an illustrative composition according to the present disclosure.
  • the term “comprising” may include the embodiments “consisting of' and “consisting essentially of.”
  • the terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named ingredients/steps and permit the presence of other ingredients/steps.
  • compositions or processes as “consisting of and “consisting essentially of' the enumerated ingredients/steps, which allows the presence of only the named ingredients/steps, along with any impurities that might result therefrom, and excludes other ingredients/steps.
  • the terms “about” and “at or about” mean that the amount or value in question can be the value designated some other value approximately or about the same. It is generally understood, as used herein, that it is the nominal value indicated ⁇ 10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims.
  • amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art.
  • an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. It is understood that where “about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.
  • approximating language may be applied to modify any quantitative representation that may vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” and “substantially,” may not be limited to the precise value specified, in some cases. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. The modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints.
  • the expression “from about 2 to about 4” also discloses the range “from 2 to 4.”
  • the term “about” may refer to plus or minus 10% of the indicated number. For example, “about 10%” may indicate a range of 9% to 11%, and “about 1” may mean from 0.9-1.1. Other meanings of “about” may be apparent from the context, such as rounding off, so, for example “about 1” may also mean from 0.5 to 1.4.
  • the term “comprising” should be understood as having its open-ended meaning of “including,” but the term also includes the closed meaning of the term “consisting.” For example, a composition that comprises components A and B may be a composition that includes A,
  • the present disclosure relates to hydrogels providing strong and reversible adhesion with a temperature-controlled fast hardening trigger.
  • An example of such a composition is an interpenetrating polymeric precursor based on 2-hydroxy ethyl methacrylate (HEMA) and N-isopropylacrylamide (NIP Am), which composition can optionally include a miscible crosslinker and radical initiator.
  • HEMA 2-hydroxy ethyl methacrylate
  • NIP Am N-isopropylacrylamide
  • PHEMA hydrogel with relatively low modulus (200 kPa) adapts to rough surfaces and guarantees good contact between hydrogel and substrates.
  • modulus of PHEMA gel increases significantly to 2.3 GPa, which increase locks the shape adaption in hydrogel and provides a strong load transition (strong adhesion).
  • strong adhesion strong adhesion
  • the modulus decreases back to 200 kPa, affording easy recycling as an intact adhesive film.
  • PHEMA adhesive without PNIPAm segment can serve as a strong and reversible adhesive, albeit with a relatively slowly evolving adhesion force (60 to 90 minutes to achieve high adhesion).
  • PHEMA/PNIPAm can adhere to substrates within minutes ( ⁇ 2 min) when T > LCST.
  • T > LCST PNIPAm becomes insoluble aggregates in the hydrogel which physically crosslinks the hydrogel (FIG. 1).
  • the additional physical crosslink provides fast hardening to accelerate the soft-hard transition in PHEMA hydrogel.
  • the LCST of PNIPAm is tunable through the molecular weight of NIP Am to meet various working temperatures.
  • One object of this disclosure is providing a new adhesive formula with strong and reversible adhesion, and the time of adhesion can be further decreased to under 2 minutes.
  • PHEMA is used as an illustrative hydrogel polymer
  • other polymers can be used, e.g., other hydroxyl group-rich polymers instead of PHEMA, such as polysaccharides and alginates.
  • PNIPAm is merely an example model thermal responsive polymer with LCST behavior.
  • Other thermally-responsive polymers with LOST behavior can provide similar fast adhesion.
  • Additives can optionally be used to modulate the properties of the disclosed compositions; example additives include (but are not limited to) cellulose nanocrystals (CNCs), salts, cellulose ether, and ionic liquids.
  • compositions that comprise an interpenetrating polymeric precursor based on 2- hydroxyethyl methacrylate (HEMA) and N-isopropylacrylamide (NIP Am, optional).
  • HEMA 2- hydroxyethyl methacrylate
  • NIP Am N-isopropylacrylamide
  • the compositions can also include a miscible crosslinker and a radical initiator.
  • HEMA and NIP Am monomer are both commercially available and can be used without any pre-treatment.
  • PNIPAm with a particular molecular weight can be synthesized through radical polymerization and dissolved in HEMA monomer.
  • the mixture can be further oligomerized with the addition of radical polymerization.
  • crosslinker and more radical initiator are introduced to the mixture.
  • a cured gel is then submerged in water to form soft hydrogel.
  • the formed hydrogel undergoes shape adaption to targeted surfaces and formed strong adhesion upon dehydration. The adhesion emerges significantly faster when T > LCST of PNIPAm.
  • the choice of the molecular weight of PNIPAm can depend on the selected application.
  • the molecular weight of PNIPAm is chosen so that the LSCT is close to body temperature (37 °C).
  • a longer PNIPAm is preferred as LCST decreases with increasing PNIPAm molecular weight; however, increasing molecular weight of PNIPAm leads to higher viscosity for the hydrogel precursor.
  • the PNIPAm (or other therm oresponsive polymer) can have a molecular weight (and LCST) that is based on the application of interest.
  • the ratio of HEMA/NIPAm can dictate adhesion strength.
  • the modulus of PNIPAm is significantly lower than PHEMA (both wet and dry modulus)
  • the final adhesion can benefit from a high HEMA/NIPAm ratio.
  • PNIPAm as physical crosslinker, enhanced the gel modulus through increased crosslinking density.
  • a fast adhesion favors low HEMA/NIPAm ratio.
  • an intermediate HEMA/NIPAm ratio can provide the optimized fast and strong adhesion.
  • the intermediate HEMA/NIPAm ratio also varies with the molecular weight of PNIPAm.
  • a crosslinker can be selected on the basis of good miscibility with the polymer mixture.
  • the crosslinker concentration can vary form 2 vol% to 8 vol% without significant influence on the adhesion performance.
  • An initiator can also be selected on the basis of good miscibility with the polymer mixture. The initiator concentration can vary form 2 v% to 8 v% without significant influence on the adhesion performance.
  • example adhesion tests consisted of crosslinking a square PHEMA/PNIPAm film under UV (with photo-induced radical initiator). The cured film is submerged in water overnight to reach full hydration (hydrogel).
  • hydrogel was directly sandwiched between two glass slides with two clippers to ensure good contact. After a certain amount of time at a specific temperature, the clippers were removed, and the glass slides were tested in a lap shear set-up: one glass slide was fixed on a clamp while various weights were attached to the other glass slide.
  • This example illustrates the slow adhesion evolution from a PHEMA hydrogel without a NIP Am segment.
  • HEMA monomers with 1.5 v% Darocure 1173 were exposed to 3000 J/cm 2 UV (365 nm) with 30 S vortex after every 1000 J/cm 2 .
  • the mixture was settled for 1 h in dark before the addition of 2 v% ethylene glycol dimethacrylate (EGDMA, crosslinker) and 1 v% of Darocure 1173.
  • the mixture was homogenized using ultrasoni cation for 20 min.
  • the resulting precursor was directly poured into square mold with PDMS lid on top to ensure flat top surface before exposure to 365 nm UV for 20000 J/cm 2 dose.
  • the cured film was soaked in deionized (DI) water overnight for complete hydration, although complete hydration is not a requirement.
  • DI deionized
  • hydrogel (0.9 c 0.9 inch) was sandwiched between two glass slides and dried at 40 °C for 2 minutes and demonstrates essentially no adhesion; however, the completely dried hydrogel between glass slides shows strong adhesion comparable to super glue. Rehydration of the poly(HEMA) gel leads to the detachment of the adhesive as an intact film.
  • the hydrogel (0.9 c 0.9 inch) was sandwiched between two glass slides and dried at 40 °C for 2 minutes and demonstrates different adhesion strengths (FIG. 2).
  • a PHEMA/PNIPAm hydrogel with 5000 g/mol and 1250 g/mol PNIPAm exhibits weak adhesion (> 5 g) after 2 minutes heating at 40 °C, while a 2500 g/mol PNIPAm provides strong adhesion (> 300 g). In all three cases, the adhesion continued to increase until the hydrogel is fully dehydrated. If the drying temperature is raised to 65 °C for 5 minutes, the above three composition all showed strong adhesion (> 300 g).
  • PNIPAm with number average molecular weight (M n ) of 2500 g/mol was synthesized following the procedures in Example 2.
  • M n number average molecular weight
  • HEMA/NIPAm molar ratios were targeted: 96/4, 92/8, and 87.5/12.5.
  • the hydrogel films fabricated through the procedures in Example 2 demonstrated different adhesive properties (FIG. 2). After drying at 40 °C for 2 minutes, low HEMA/NIPAm ratios showed limited adhesion ( > 5 g) while high HEMA/NIPAm ratio (96/4) adhered strongly to the glass surfaces (> 300 g).
  • Example 4 illustrates water resistance of the PHEMA/PNIPAm adhesive after the fully development of the adhesion force.
  • a hydrogel composed of 12.5 mol% 2500 g/mol PNIPAm was fabricated through the procedures in Example 2. The hydrogel was sandwiched between two glass slides and allowed to be fully developed for 2 h. The resulting adhesive was exposed to DI water, and its adhesion was tested every 15 minutes. After 120 minutes, the adhesive fails, thus showing significant water resistance.
  • PHEMA hydrated for 30 minutes can be applied as an adhesive film directly; increasing the film thickness from 45 pm to 210 pm improved the adhesion from 12.7 N/cm 2 to 17.9 N/cm 2 after 2 min of adhering (FIG. 3 A). Extending the hydration time from 30 min to 45 and 60 min (for a 210 pm thick film), the lap shear adhesion firstly increased to 27.0 N/cm 2 and then declined to 10.4 N/cm 2 , demonstrating an optimized hydration time for fast adhesion (e.g., 2 min) of 45 min (FIG. 3B).
  • adhesion in a partial hydrated films relies on the balance between surface softening (to conform easily to the surface of the adherend) and fast water evaporation (to more quickly complete the adhesion process).
  • PNIPAm (or other thermoresponsive polymers) can also be added into a PHEMA system to further enhance adhesion speed, e.g., with temperature response (37 °C). Such a system need not be fully hydrated and can instead be partially hydrated.
  • a polymer composition comprising: a polymeric hydrogel; and a thermoresponsive polymer, the polymeric hydrogel and the thermoresponsive polymer being arranged as an interpenetrating network, the thermoresponsive polymer being soluble in water, the thermoresponsive polymer having a lower critical solution temperature (LCST), and the thermoresponsive polymer chains being dispersed within the polymeric hydrogel such that when the thermoresponsive polymer attains a temperature above the LCST, the thermoresponsive polymer becomes insoluble and forms physical crosslinks between chains of the polymeric hydrogel.
  • LCST critical solution temperature
  • the composition can be present as, e.g., a film.
  • a film can have a thickness of, e.g., from about 10 to about 1000 pm, or from about 20 to about 500 pm, or from about 50 to about 300 pm, or even from about 100 to about 200 pm.
  • the composition can be incorporated into a bandage (e.g., a bandage with a removable/peelable backing), as one example use.
  • Aspect 2 The polymer composition of Aspect 1, wherein the hydrogel matrix comprises a polymer having one or more of -ML, -COOH, -OH, -CONH 2 , - CONH -, and -SO 3 H as a side group and/or end group.
  • Aspect 3 The polymer composition of Aspect 2, wherein the polymeric hydrogel comprises a polymer having -OH as a side group in repeat units of the polymer, having -OH at terminations of the polymer (e.g., as an end group), or both.
  • Aspect 4 The polymer composition of Aspect 2, wherein the polymeric hydrogel comprises a polysaccharide or an alginate.
  • a polysaccharide can be, e.g., a starch, a cellulose, or chitin.
  • An alginate can include various cations, e.g., sodium and/or calcium.
  • Aspect 5 The polymer composition of Aspect 1, wherein the polymeric hydrogel comprises poly(2-hydroxyethyl methacrylate) (PHEMA).
  • PHEMA poly(2-hydroxyethyl methacrylate)
  • Aspect 6 The polymer composition of any one of Aspects 1-5, wherein the LCST of the thermoresponsive polymer is about 37 °C.
  • Aspect 6 The polymer composition of any one of Aspects 1-5, wherein the LCST of the thermoresponsive polymer is below 37 °C.
  • thermoresponsive polymer comprises poly(N-isopropylacrylamide) (PNIiPAmM), polyvinyl methyl ether, poly(vinylcaprolactam), a poloxamer, or any combination thereof.
  • Aspect 9 The polymer composition of any one of Aspects 1-8, further comprising a crosslinker that chemically crosslinks chains of the polymeric hydrogel.
  • Aspect 10 The polymer composition of Aspect 9, wherein the crosslinker comprises ethylene glycol dimethacrylate (EGDMA).
  • the crosslinker comprises ethylene glycol dimethacrylate (EGDMA).
  • Aspect 11 The polymer composition of any one of Aspects 1-10, further comprising cellulose nanocrystals, salt, cellulose ether, an ionic liquid, anisotropic bodies, or any combination thereof.
  • Aspect 12 The polymer composition of Aspect 11, wherein an anisotropic body comprises cellulose nanocrystals, cellulose nanofibers, cellulose microfibers, hydrogels, or any combination thereof.
  • a cellulose nanocrystal can have a diameter in the range of tens of nanometers and a length in the range of from about 1 to about 100 microns, e.g., from about 1 to about 100 microns, from about 5 to about 90 microns, from about 10 to about 80 microns, from about 20 to about 70 microns, from about 30 to about 60 microns, or even from about 40 to about 50 microns.
  • a cellulose nanofiber can have a diameter in the range of tens of nanometers, and a length in the range of from about 1 to about 10 microns.
  • a cellulose microfiber can have a diameter in the range of from about 1 to about 10 microns and a length of from about 10 to about 1000 microns.
  • a hydrogel can include one or more anisotropic nanofillers such as cellulose nanocrystals, cellulose nanofibers, cellulose microfibers, gold or silver nanorods (e.g., 1-20 nanometers in diameter and 10- 100 nm in length), or any combination thereof.
  • anisotropic nanofillers such as cellulose nanocrystals, cellulose nanofibers, cellulose microfibers, gold or silver nanorods (e.g., 1-20 nanometers in diameter and 10- 100 nm in length), or any combination thereof.
  • Aspect 13 The polymer composition of any one of Aspects 1-12, wherein the polymer composition has a modulus of from about 10 kPa to about 100 kPA and/or an adhesion strength of from about 0.05 N/cm 2 to about 0.1 N/cm 2 , one or both of which can optionally be achieved within about 2 minutes from when the polymer composition is hydrated and the thermoresponsive polymer is at a temperature below the LCST.
  • the modulus can be, e.g., from about 10 kPa to about 100 kPa, from about 15 kPa to about 95 kPa, from about 20 kPa to about 90 kPa, from about 30 kPa to about 85 kPa, from about 35 kPa to about 80 kPa, from about 40 kPa to about 75 kPa, from about 45 kPa to about 70 kPa, or from about 50 to about 60 kPa.
  • Aspect 14 The polymer composition of any one of Aspects 1-12, wherein the polymer composition has a modulus of from about 10 MPa to about 100 MPa and/or an adhesion strength of from about 8 N/cm 2 to about 50 N/cm 2 , one or both of which can optionally be achieved within about 2 minutes from when the polymer composition is hydrated and the thermoresponsive polymer is at a temperature above the LCST.
  • the modulus can be, e.g., from about 10 kPa to about 100 kPa, from about 15 kPa to about 95 kPa, from about 20 kPa to about 90 kPa, from about 30 kPa to about 85 kPa, from about 35 kPa to about 80 kPa, from about 40 kPa to about 75 kPa, from about 45 kPa to about 70 kPa, or from about 50 to about 60 kPa.
  • the adhesion strength can be, e.g., from about 8 to about 50 N/m 2 , from about 10 to about 45 N/m 2 , from about 15 to about 40 N/m 2 , from about 20 to about 35 N/m 2 , or even about 25 N/m 2 .
  • Aspect 15 The polymer composition of any one of Aspects 1-12, wherein the polymer composition has a modulus of from about 100 MPa to about 5 GPa and/or an adhesion strength of from about 100 N/cm 2 to about 1000 N/cm 2 , one or both of which can optionally be attained within 2 hours from when the polymer composition is dried and the thermoresponsive polymer is at a temperature above the LCST.
  • the modulus can be, e.g., from about 100 MPa to about 5 GPa, or from about 200 MPa to about 4 GPa, or from about 300 MPa to about 3 GPa, or from about 500 MPa to about 2 GPa, or even from about 750 MPa to about 1.2 GPa.
  • the adhesion strength can be from about 100 to about 1000 N/cm 2 , from about 200 to about 750 N/cm 2 , from about 300 to about 600 N/cm 2 , or from about 200 to about 500 N/cm 2 .
  • Aspect 16 The polymer composition of any one of Aspects 1-15, wherein the polymer composition’s modulus increases through an order of magnitude when the thermoresponsive polymer attains a temperature above the LCST.
  • Aspect 17 The polymer composition of any one of Aspects 1-16, wherein the polymer composition’s modulus increases by from 10% to 1000% (e.g., from 10 to 1000%, from 20 to 800%, from 50 to 750 %, from 75 to 500 %, from 100 to 300%) within 5 minutes of the thermoresponsive polymer reaching a temperature above the LCST.
  • Aspect 18 The polymer composition of Aspect 17, wherein the polymer composition’s modulus increases by from 10% to 1000% (e.g., from 10 to 1000%, from 20 to 800%, from 50 to 750 %, from 75 to 500 %, from 100 to 300%) within 2 minutes of the thermoresponsive polymer reaching a temperature above the LCST.
  • Aspect 19 The polymer composition of any one of Aspects 1-16, wherein the polymer composition’s adhesion strength increases by from 10% to 1000% (e.g., from 10 to 1000%, from 20 to 800%, from 50 to 750 %, from 75 to 500 %, from 100 to 300%) within 5 minutes of the thermoresponsive polymer reaching a temperature above the LCST.
  • Aspect 20 The polymer composition of Aspect 19, wherein the polymer composition’s adhesion strength increases by from 10% to 10,000% (e.g., from 10 to 1000%, from 20 to 800%, from 50 to 750 %, from 75 to 500 %, from 100 to 300%) within 2 hours of the thermoresponsive polymer reaching a temperature above the LCST.
  • Aspect 21 An article, comprising a polymer composition according to any one of Aspects 1-20 disposed on a substrate.
  • Aspect 22 The article of Aspect 21, wherein the substrate is characterized as removable from the polymer composition.
  • Aspect 23 An article, the article comprising a polymer composition according to any one of Aspects 1-20 disposed so as to bond two portions of a substrate to one another.
  • Aspect 24 An article, the article comprising a polymer composition according to any one of Aspects 1-20 disposed so as to bond two substrates to one another.
  • Aspect 25 A kit, the kit comprising an applicator and an amount of a polymer composition according to any one of Aspects 1-20, the applicator configured to controllably dispense the polymer composition.
  • An applicator can be, e.g., a nozzle, a brush, and the like.
  • Aspect 26 A method, comprising: effecting heating of a polymer composition according to any one of Aspects 1-20 such that the thermoresponsive polymer attains a temperature above the LCST of the thermoresponsive polymer, or effecting cooling of a polymer composition according to any one of Aspects 1-20 such that the thermoresponsive polymer attains a temperature below the LCST of the thermoresponsive polymer.
  • Aspect 27 A method, comprising using a polymer composition according to any one of Aspects 1-20 to bond a first substrate to a second substrate.
  • Aspect 28 The method of Aspect 27, further comprising: (a) wetting the polymer composition so as to reduce the modulus of the polymer composition, (b) wetting the polymer composition so as to de-adhere the polymer composition from at least one of the first substrate and the second substrate, (c) cooling the polymer composition so as to reduce the modulus of the polymer composition, (d) cooling the polymer composition so as to de-adhere the polymer composition from at least one of the first substrate and the second substrate, or any combination of (a), (b), (c), or (d).
  • thermoresponsive polymer comprising: dispersing a thermoresponsive polymer into a hydrogel precursor, the thermoresponsive polymer being soluble in water, the thermoresponsive polymer having a lower critical solution temperature (LCST), and the thermoresponsive polymer chains being dispersed within the polymeric hydrogel such that when the thermoresponsive polymer attains a temperature above the LCST, the thermoresponsive polymer becomes insoluble and forms physical crosslinks between chains of the polymeric hydrogel.
  • LCST critical solution temperature
  • Aspect 30 The method of Aspect 29, wherein the method is performed so as to give rise to a polymer composition according to any one of Aspects 1-20.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des matériaux adhésifs réversibles thermosensibles. Les matériaux peuvent comprendre une composition polymère, comprenant : un hydrogel polymère; et un polymère thermosensible, l'hydrogel polymère et le polymère thermosensible étant agencés sous la forme d'un réseau interpénétrant, le polymère thermosensible étant soluble dans l'eau, le polymère thermosensible ayant une température inférieure critique de solubilité (LCST) et les chaînes polymères thermosensibles étant dispersées à l'intérieur de l'hydrogel polymère de telle sorte que, lorsque le polymère thermosensible atteint une température au-dessus de la LCST, le polymère thermosensible devient insoluble et forme des réticulations physiques entre les chaînes de l'hydrogel polymère.
PCT/US2022/072730 2021-06-03 2022-06-02 Films adhésifs réversibles activés par voie thermique à durcissement rapide WO2022256827A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1021447C (zh) * 1988-11-25 1993-06-30 维斯塔肯有限公司 制备包括接触透镜的成型水凝胶制品的方法
US9387276B2 (en) * 2012-01-05 2016-07-12 President And Fellows Of Harvard College Interpenetrating networks with covalent and Ionic Crosslinks
US20180360743A1 (en) * 2017-06-16 2018-12-20 AesculaTech, Inc. Thermoresponsive polymers and uses thereof
WO2020160463A1 (fr) * 2019-02-01 2020-08-06 The Trustees of the University of Pennsylvania Penn Center for Innovation Supercolles intrinsèquement réversibles

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CN1021447C (zh) * 1988-11-25 1993-06-30 维斯塔肯有限公司 制备包括接触透镜的成型水凝胶制品的方法
US9387276B2 (en) * 2012-01-05 2016-07-12 President And Fellows Of Harvard College Interpenetrating networks with covalent and Ionic Crosslinks
US20180360743A1 (en) * 2017-06-16 2018-12-20 AesculaTech, Inc. Thermoresponsive polymers and uses thereof
WO2020160463A1 (fr) * 2019-02-01 2020-08-06 The Trustees of the University of Pennsylvania Penn Center for Innovation Supercolles intrinsèquement réversibles

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