WO2007127225A2 - Compositions polymériques réticulables - Google Patents

Compositions polymériques réticulables Download PDF

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WO2007127225A2
WO2007127225A2 PCT/US2007/009986 US2007009986W WO2007127225A2 WO 2007127225 A2 WO2007127225 A2 WO 2007127225A2 US 2007009986 W US2007009986 W US 2007009986W WO 2007127225 A2 WO2007127225 A2 WO 2007127225A2
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cross
styrene
polymer
linking
group
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PCT/US2007/009986
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WO2007127225A9 (fr
WO2007127225A3 (fr
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Jonathan James Wilker
Glenn Westwood
Trinity Noel Horton
James Donald White
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Purdue Research Foundation
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Publication of WO2007127225A9 publication Critical patent/WO2007127225A9/fr
Publication of WO2007127225A3 publication Critical patent/WO2007127225A3/fr
Priority to US12/106,840 priority Critical patent/US8759465B2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08F212/00—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 aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds

Definitions

  • This invention may have been made with United States government support from the National Science Foundation grant number 0094281 -CHE.
  • Polymers have important and wide-ranging applications. For example, orthopedic repairs, prosthesis implantation, soft tissue healing, sutures, and timed release of drugs all utilize polymers.
  • Polyethylene is often used in joint replacements.
  • Ligament and tendon repairs may employ polytetrafluoroethylene (PTFE, Teflon®) or condensation polymers (Dacron).
  • Catheters may be made of PTFE or polyurethanes.
  • Skin repair templates may use silicone and collagen.
  • Polymethylmethacrylate (PMMA) is used for bone cement and replacement eye lenses.
  • dental cements are made from acrylics polymers (polyacrylic acid, PAA) cross-linked with calcium or zinc.
  • Biological environments tend to be wet, contain large amounts of possible foulants (e.g., proteins, polysaccharides, cells), and may impart large mechanical stresses.
  • a suitable composition may have the following qualities: the ability to set in wet environments, create strong bonds with both soft tissue and hard bone, cure on a reasonable time scale, be convenient to work with, and be biocompatible. At this time, no available composition meets all these requirements well.
  • the two most commonly used surgical adhesives are fibrin and the cyanoacrylates. Fibrin is a two tube sealant comprised of fibrinogen and thrombin, essentially making a blood clot upon mixing.
  • cyanoacrylates ⁇ e.g., ethylcyanoacrylate, "Super Glue"
  • Super Glue ethylcyanoacrylate
  • the oral environment is particularly problematic for adhesion. Mechanical stresses, a changing environment, and high levels of bacteria all challenge adhesion to teeth.
  • Current dental cements are based upon zinc phosphate, zinc polyacrylic acid (PAA), or a glass ionomer consisting of a polycarboxylate (e.g., PAA) with an aluminosilicate. Although the biocompatibility and physical properties of these cements are good, they do not seal sufficiently well to teeth. Microleakage also is common and often leads to secondary caries and cement failure. Similar problems can arise with skeletal hard connective tissue repaired by use of ceramics and glasses (e.g., alumina, silica, hydroxyapatite).
  • Desirable medical adhesives and cements may be either degradable or permanent, depending upon the application.
  • a soft tissue adhesive for example, may be degraded after complete healing.
  • For a bone cement by contrast, permanent attachment is typically required.
  • a modulus mismatch may yield high levels of interfacial stress.
  • a desirable adhesive may provide a gradient of moduli spanning the range from one surface to the next, in order to minimize interfacial stresses.
  • PMMA polymethyl methacrylate
  • Mussels may use iron for protein cross-linking and adhesive formation.
  • iron in mussel adhesive may be bound by three DOPA residues, as shown in Figure 1.
  • Oxygen may then react with this iron center to yield a protein based radical.
  • radical-radical coupling to further cross-link the composition may then follow. Formation of these radicals may proceed by a mechanism similar to that proposed for the intradiol catechol dioxygenase enzymes.
  • An Fe 3+ -DOPA may undergo valence tautomerism to Fe 2+ semiquinone followed by O 2 reaction with the semiquinone ligand.
  • the radical species may be reactive given that it is short lived. Radical species may be present in barnacle cement. Thus radicals may be important intermediates in marine biomaterial generation.
  • Expression of DOPA-containing proteins has proven difficult. Enzymatic oxidation of tyrosine containing synthetic polypeptides may yield DOPA-containing products. Long polypeptides with DOPA may also be directly prepared. In general, however, proteins and polypeptides with DOPA residues may be impractical to products on a large scale and prohibitively expensive. BRIEF SUMMARY
  • a new class of polymer compositions is disclosed.
  • a family of polymers may be prepared in which cross-linking groups are incorporated.
  • the copolymer may comprise pendant dihydroxyphenyl groups; and a cross-linking agent selected from the group consisting of, for example, oxidants, enzymes, metals, and light.
  • the polymer compositions may have varied properties ⁇ e.g., hardness, crystallinity) and may have varied degrees of incorporated cross-linking groups.
  • the polymers may be prepared such that they can be cross-linked with many different reagents ⁇ e.g., oxidants, enzymes, metals, light, etc.) For example but not limited to a series of polystyrene derivatives into which may be incorporated catechol. Catechol groups may serve as a mimic of 3,4- dihydroxyphenylalanine (DOPA), which may be the key cross-linkable group in mussel adhesive proteins.
  • DOPA 3,4- dihydroxyphenylalanine
  • a class of bio-inspired, cross-linking polymers may be prepared by distributing catechol functionalities into the backbone of a bulk polymer. These polymers may cross-link in a manner analogous to that found for mussel adhesive proteins, but without the complexity of a polypeptide backbone or a variety of amino acid side chains. Varied cross-linking groups may be incorporated into different backbones, and subsequently reacted with an array of reagents.
  • the compositions may also have broad applications in diverse areas from industry to consumer products and beyond, for example but not limited to, polymeric membranes forming gas barriers, self healing adhesives, rust-proof coatings, under water adhesives.
  • One method of making a copolymer composition which may be an adhesive, including steps of, for example, anionic polymer synthesis.
  • the method may comprise copolymerizing a first monomer comprising pendant dihydroxy-protected dihydroxyphenyl groups; deprotecting the dihydroxy-protected dihydroxyphenyl groups; cross-linking the dihydroxyphenyl groups with a cross-linking agent.
  • Figure 1 is an exemplary structure of the cross-linking iron-protein in marine mussel adhesives.
  • Figure 2 is a chart of exemplary results of the effect of controlling polymer composition on shear adhesive strength.
  • Figure 3 is an exemplary NMR spectra illustrating the effect of the percentage of 3,4-dimethoxystyrene on the number of methoxy groups in the resulting polymer, under the conditions of Example 1.
  • Figure 4 is an exemplary 1 H-NMR spectra of 5-S-DMS and the deprotected polymer 5-S-DMS, under the conditions of Example 1.
  • Figure 5 is an exemplary differential scanning calorimetry of polystyrene, 5-
  • Figure 6 is an exemplary chart of the effect of various cross-linking agents on ultimate shear strength, under the conditions of Example 2.
  • Figure 7 illustrates exemplary average ultimate shear strengths of various polymers with a dichromate cross-linking agent, under the conditions of Example 3.
  • Figure 8 illustrates exemplary average ultimate shear strength of 10-S-HDS-
  • Figure 9 illustrates exemplary ultimate shear strengths of 10-S-HDS-40 and
  • Figure 10 is a table illustrating exemplary polymer synthesis conditions and characterizations.
  • Figure 11 is a table of exemplary average penetration forces (in mN) for reaction of polymers of varied 3,4-dimethoxystyrene:styrene ratios with different exemplary cross-linking reagents.
  • Figure 12 shows exemplary curing data for the 1:10 3,4- dihydroxystyrene:styrene copolymer reacted with select cross-linkers, after a 1 hour cure at room temperature.
  • Figure 13 shows exemplary penetration forces at 35 mm rod extension found for copolymers of 3,4-dihydroxystyrene and styrene with varied percentages of 3,4- dihydroxystyrene, under the conditions of Example 18.
  • Figure 14 shows exemplary shear adhesive strengths of a 1 : 10 3,4- dihydroxystyrene: styrene copolymer after cross-linking.
  • a class of bio-inspired, cross-linking polymers by incorporating catechol functionalities into the backbone of a bulk polymer is disclosed. These polymers may cross-link in a manner analogous to that found for mussel adhesive proteins.
  • a general approach to designing compositions is disclosed, in which varied cross-linking groups may be incorporated into different polymer backbones, and subsequently reacted with an array of reagents.
  • By combining the approaches of marine biological composition formation with the accessibility of synthetic polymers, a nearly limitless array of new compositions may be developed for tissue engineering platforms, nonfouling compositions, medical adhesives, industrial and consumer products, for example, polymeric membranes-forming gas barriers, self-healing adhesives, rust-proof coatings, underwater adhesives applications.
  • a marine biological composition may be reduced to a polymer, a cross-linkable group, a metal, and oxygen.
  • the disclosed synthetic compositions may be used to create polymer systems for many applications, including but not limited to applications in medicine, dentistry, scientific research, industry, and consumer products.
  • Catechol groups may be incorporated into polystyrene.
  • Cross-linking reactions may transform polystyrene, for example, into an adhesive, which may be modified to a range of strengths.
  • DOPA-proteins, metals, and oxygen may be involved in synthesis of the disclosed compositions. Adhesive formation may begin with the chelation of three DOPA-containing protein strands about an Fe 3+ metal center. Subsequent reaction with oxygen may yield the formation of a protein-based radical. This oxidized protein may then undergo protein-protein coupling to generate covalent cross-links or protein-surface bonding for adhesion. Alternatively, simple oxidation or enzymatic oxidation may be utilized.
  • 3,4-dihydroxystyrene may be incorporated into a polymer backbone.
  • This 3,4-dihydroxystyrene may mimic the catechol sidechain of DOPA and is similar to styrene, with two hydroxyls. Homopolymers of 100% dihydroxystyrene may also be prepared.
  • Data collected from characterizing, for example, marine mussel adhesive may be used to inspire biomaterial design efforts.
  • the complex protein may be reduced to a simple polymer such as polyethylene or polystyrene.
  • a catechol derivative may be incorporated to mimic DOPA.
  • Polystyrene serves as a non-limiting example in this disclosure.
  • 3,4-dihydroxystyrene is a chemical derivative of styrene, with two hydroxyls.
  • the reactivity of this 3,4-dihydroxystyrene monomer may be different from styrene.
  • Polystyrene may also be examined owing to ease of large scale synthesis and tight control of molecular weights (e.g., low polydispersity) when using anionic polymerization methods.
  • the present invention is not limited to the polystyrene polymer backbone; this polymer backbone is utilized in the disclosure because it is convenient for illustrating composition design.
  • Alternative cross-linked polymer materials may be prepared by varying the polymer backbones, cross-linkable groups, and cross-linking agents. For example, the following modifications may be made.
  • Polymer backbones such as, but not limited to polyethyleneglycol (PEG), PMMA/PAA, polylactic acid/polyglycolic acid (PLGA) may be utilized.
  • Possible cross-linking groups include, but are not limited to, catechol, thiol, and the like.
  • Potential cross-linking agents include, but are not limited to, oxidants, metals, and the like.
  • Copolymers of, for example but not limited to, styrene and 3,4- dimethoxystyrene may be prepared by standard methods using H-butyllithium initiator.
  • Copolymer of monomers which mimic other amino acids for example, amino acids capable of cross-linking via metal chelation (e.g., histidine analogs, imidazoles) and oxidation (e.g., cysteine analogs, thiols) may also be incorporated into polymers.
  • metal chelation e.g., histidine analogs, imidazoles
  • oxidation e.g., cysteine analogs, thiols
  • the percentage of each monomer in the final polymer may be varied by altering the ratio of starting monomers.
  • Both monomers may copolymerize with even incorporation, as determined by integrals of each broadened monomer signal in 1 H nuclear magnetic resonance (NMR) spectra.
  • the methoxy groups may be deprotected with BBr 3 to yield the final, catechol- containing polymer.
  • the polymers may be characterized, for example, with gel permeation chromatography (GPC) to provide typical molecular weights and polydispersities.
  • the molecular weights may be varied by altering the initiator: monomer ratios. Typical molecular weights may range between about 3,000 and about 120,000, depending upon this ratio. Polydispersities may typically fall between about 1.1 and about 1.8.
  • GPC gel permeation chromatography
  • DSC Differential scanning calorimetry
  • a 100% polystyrene polymer may yield a glass transition temperature (Tg) of about 97.4 0 C.
  • the homopolymer of, for example, 100% 3,4-dimethoxystyrene provided a Tg of about 68.3 0 C.
  • a 5:1 copolymer of styrene (83%) and 3,4-dimethoxystyrene (17%) may show a single phase transition between these two extremes, with a Tg of about 93.9 0 C.
  • copolymers of styrene may also be prepared with 2,3- dihydroxystyrene, mimics of crosslinkable amino acids, amino acids, PEG, PMAA/PAA, PLGA, and the like.
  • the following examples utilize the 3,4-derivatives for illustration purpose only.
  • Cross-linking reactions of these polymers may be examined with a penetration test.
  • a polymer may be dissolved in an organic solvent at high concentrations (e.g., 1 g/mL) to yield a viscous solution.
  • Cross-linking agents may then be mixed into the solution and curing, where applicable, may be observed directly by using the penetration test (see Example 13).
  • Potential cross-linking reagents that may be examined may include (but are not limited to) [(C 4 H ⁇ 4 N]IO 4 , ter// ⁇ ry-C 4 H 5 -OOH, Fe(acetonylacetonate) 3 , [(C 4 Hs) 4 N](MnO 4 ), Mn(OOCCH 3 ) 3 , [(C 4 H ⁇ 4 N] 2 (Cr 2 O 7 ), Na 3 VO 4 , Zn(NO 3 ) 2 , Ga(NO 3 ) 2 , Co(NO 3 ) 2 , and [(C 4 H 9 ) ⁇ N] 2 (SO 4 ).
  • oxidizing metallic reagents for example, [(C 4 H 9 ) 4 N](MnO 4 ) and [(C 4 Hg) 4 N] 2 (Cr 2 O 7 ), along with the simple oxidant [(C 4 Hg) 4 N]IO 4 , may bring about the most curing. Some viscosity increase may be observed with Fe(acetonylacetonate) 3 .
  • the other exemplary reagents may exhibit little or no detectable cross- linking. This pattern of effective cross-linkers may be similar to those found when working with the DOPA-containing proteins extracted from mussels. In order to bring about significant curing, ⁇ 2% or higher 3,4-dihydoxystyrene may be required in the polymer.
  • Adhesive properties of these polymers may be examined.
  • a typical test explained briefly, may begin with a polymer (e.g., 10 mg in 15 ⁇ L acetone) and a cross- linking agent (e.g., 2 mg in 10 ⁇ L acetone) mixed on a metal adherend (e.g., aluminum coupon).
  • a second adherend may be added and the sample cured under varied conditions.
  • the adhesive bond may then be pulled to failure and this maximum shear load may be measured on an Instron 5544 Materials Testing Machine.
  • the most effective cross-linking agents may yield the greatest adhesion strength, may include Fe(acetonylacetonate) 3 , [(C 4 Hg) 4 N](MnO 4 ), and [(C 4 Hg) 4 N] 2 (Cr 2 O 7 ). Chromium toxicity may preclude use of this reagent in biomedical compositions, but it may be used in other, non-biomedical applications where toxicity is not an issue. Further, it provides examples of trends in the reagents most effective at bringing about protein and polymer bonding.
  • adhesive bonding strength of Fe 3+ may generally be half that OfMn 7+ and Cr 6+ .
  • cross- linking agents the following may also be changed or varied: cure time, temperature, total quantity of polymer, concentrations, and ratio of catechol groupxross-linker. Polymer molecular weight and composition may also be controlled and varied.
  • Figure 2 illustrates exemplary results of a test of adhesive strength of a series of styrene-3,4-dihydoxystyrene copolymers, each cross-linked with
  • Maximum adhesion may be about 5.0 ( ⁇ 1.7) MPa with the 10:1 polymer.
  • the bio-inspired adhesive at 5.0 ( ⁇ 1.7) MPa may be stronger than typical pressure sensitive (-0.05 MPa), starch ( ⁇ 0.5 MPa), cellulosic ( ⁇ 2 MPa), and polyvinyl alcohol (white glue, —3 MPa) adhesives.
  • An assessment of adhesion to a biologically relevant substrate may be made, for example, with hydroxyapatite blocks of 2.5 x 0.9 x 0.6 cm.
  • a 10:1 styrene:3,4- dihydoxystyrene copolymer may be placed between two hydroxyapatite blocks and cured with [(C 4 H 9 ) 4 N J 2 (Cr 2 O 7 ). Pulling the blocks apart in shear mode may result in the blocks breaking while the adhesive bond remained intact. Substrate failure may occur at the equivalent average force of —2.5 MPa.
  • cross-linkable polymers may also be prepared.
  • soluble or wettable versions terpolymers in which styrene,
  • these terpolymers may be synthesized using nitroxide-mediated radical polymerization with 2,2'-azobis(2-methylpropionitrile) (AlBN) for initiation and the radical 2,2,5,5- tetramethyl-4-diethylphosphono-3-azahexane-3-nitroxide (DEPN) for capping.
  • AlBN 2,2'-azobis(2-methylpropionitrile)
  • DEPN 2,2,5,5- tetramethyl-4-diethylphosphono-3-azahexane-3-nitroxide
  • Water solubility may be found when the styrene sulfonate content of the polymer is over ⁇ 40%. Cross-linking reactions may proceed rapidly with the typical metallic and oxidizing reagents.
  • Examples 1-7 which follow provide one exemplary polymer synthesis and characterization system. Other exemplary systems are provided to illustrate the diversity of the system.
  • Styrene may be inhibited, for example, with approximately 10-15 ppm of 4- tert- butylcatechol.
  • Polymer synthesis may begin with monomer purification.
  • Column chromatography may be used to separate 4-/erf-butylcatechol inhibitor from styrene and the hydroquinone inhibitor from 3,4-dimethoxystyrene.
  • a glass tube may be packed with, for example, 1/8 in. of cotton, 1/8 in. of sand, 3 to 4 inches of oven dried alumina, and 1/8 in. of potassium carbonate.
  • Each monomer may be added to its own column and allowed to elute. Care may be taken to prevent the red color present on the column elute into the collection flask.
  • the inhibitor may be removed within approximately 12 hours prior to polymerization and may be stored at 4°C.
  • Synthesis of poly[styrene-co-(3,4-dihydroxystyrene)] may follow monomer purification. After heating overnight in a glassware oven at, for example, approximately 105 0 C, a 100 mL Schlenk flask fitted with a rubber septum may be placed under vacuum, flame dried until no vapor is visible, and then backfilled with argon. This flame drying procedure may be repeated twice.
  • the flask may be charged with 50 mL of dry toluene under argon, for example, using a gas-tight syringe. While stirring, uninhibited styrene and 3,4-dimethoxystyrene (total of 10 mL of monomer) may be syringed into the solution, and then placed on a dry ice/ isopropanol bath. After cooling to approximately -78°C, an approximately 2.5 M solution of n-butyl lithium (exemplary amounts which may be added are listed in Figure 10) in hexanes may be added by gas- tight syringe to the reaction flask.
  • n-butyl lithium exemplary amounts which may be added are listed in Figure 10
  • the reaction may be kept under a positive argon pressure and at a temperature of approximately -78°C, for example, by the continued addition of dry ice to the dry ice/isopropanol bath. After eight hours, the bath may be topped off with dry ice and transferred to a refrigerator at approximately 4°C.
  • the flask may be removed from the refrigerator, and ⁇ 1 mL of room temperature methanol may be added to the reaction flask.
  • the solution may then be poured into a 1 L round-bottom flask charged with 200 mL of methanol. This may result in the immediate precipitation of a white polymer.
  • the flask may then be immediately dried, for example by rotovapping.
  • the resulting poly[styrene-co-(3,4-dimethoxystyrene)] may be re-dissolved in dichloromethane, transferred to a 100 mL round-bottom flask, and rotovapped to dryness again.
  • the polymer may then be placed under vacuum overnight to remove any residual solvent.
  • Conversion of poly[styrene-co-(3,4-dimethoxystyrene)] to poly[styrene- co-(3,4-dihydroxystyrene)] may be accomplished by the use of, for example, boron tribromide.
  • a 100 mL Schlenk flask (flame dried as previously described) may be charged with a stir bar and 3-4 grams of poly[styrene-co-(3,4-dimethoxystyrene)].
  • 50 mL of dry dichloromethane may be added by gas-tight syringe, and stirred until all polymer is dissolved and the solution is clear.
  • the flask may be cooled to 0 0 C, for example, by immersion in an ice water bath for 30 minutes. A 3-fold molar excess of boron tribromide to 3,4- dimethoxystyrene (as pure liquid or solution in hexanes) may then be added to the reaction flask by gas-tight syringe, affording a brown solution. The flask may be allowed to gradually warm to room temperature and to stir overnight under a positive pressure of argon.
  • the reaction mixture may be poured into 300 mL of an aqueous 0.1 M HCl solution in a 500 mL Ehrlenmeyer flask at approximately 4°C and stirred for approximately 15 minutes at 4°C.
  • the aqueous layer may be removed and poured through a filter, leaving a white suspension in the dichloromethane phase.
  • 300 mL of an aqueous 0.1 M HCl solution may then be added to the white suspension and stirred for 15 minutes at 4°C, and then the aqueous layer may again be removed.
  • the resulting white composition may then be washed twice by stirring in 300 mL of nanopure water and the aqueous phase may then be removed.
  • the polymer may be washed into a 1 L round- bottom flask with dichloromethane, and rotovapped (e.g., cold trap filled with ice and vacuum provided by a water aspirator) to near dryness. Some water may then be poured out of the flask, and significant amounts of water may further be removed by drying on a rotovap using a water aspirator and a cold trap filled with dry ice/isopropanol. The last traces of water may then be removed, for example, by drying on a rotovap using a pump and a liquid nitrogen trap. Care may be taken not to heat the flasks higher than 35°C while rotovapping. The resulting poly[styrene-co-(3,4-dihydroxystyrene)] may be placed under vacuum overnight.
  • rotovapped e.g., cold trap filled with ice and vacuum provided by a water aspirator
  • the general identification of the different poly[styrene-co-(3,4- dihydroxystyrene)] and poly[styrene-co-(3,4-dimethoxystyrene)] polymers may be done as follows: An example identification is carried out with 10-S-DMS-35, where 10 stands for the ratio of styrene to 3,4-dihydroxystyrene monomers used in the polymerization; S, DMS, or DHS stands for the polymerized monomers styrene (S), 3,4-dimethoxystyrene (DMS), or 3,4-dihydroxystyrene (DHS); and 35 stands for the volume ratio (mL:mL) of monomer to n-butyllithium initiator used in the polymerization.
  • 1 H-NMR Spectroscopic Characterization of Polymers may be performed as illustrated in the following exemplary description.
  • 1 H-NMR spectra may be collected, for example, using a Gemini 200 MHz spectrometer and all samples may be prepared, for example, in deuterated chloroform.
  • Figures 3 and 4 provide exemplary NMR spectra for the polymers of the present example. These exemplary spectra display a broad group of peaks between about 6 to about 8 ppm for the aromatic hydrogens, a broad group of peaks between about 0.5 to about 3 ppm, and two broad peaks between about 3.5 to about 4.0 ppm for the methoxy peaks.
  • Figure 3 shows that as the percentage of 3,4-dimethoxystyrene is increased in the polymerization, more methoxy groups may be observed in the resulting polymer.
  • Figure 4 shows an exemplary 1 H-NMR spectra of 5-S-DMS and the deprotected polymer, 5-S-DHS.
  • the methoxy peaks may disappear between about 3.5 to about 4 ppm under the conditions of this Example. The disappearance of the methoxy peaks may indicate the completion of the methoxy deprotection reaction.
  • This example illustrates how differential scanning calorimetery may be used to determine the glass transition temperatures (Tg) of the synthesized polymers, using, for example, a TA Instruments 2920 modulated differential scanning calorimeter. Prior to testing, all polymer samples may be baked in an oven at 1 10 0 C for 1 week.
  • Approximately 7.0 mg of polymer may be weighed out into a hermetically sealed aluminum pans. The pans may be held at 10 0 C for 5 min and then heated to 200 0 C at
  • Figure 5 illustrates exemplary DSC thermographs for polystyrene, 5-S-
  • DMS-35 DMS-I. Glass transition temperatures may be observed as endothermic shifts in the DSC thermograph. The observed Tg for the polymers in this illustration are - 97.4°C, ⁇ 93.9°C, and ⁇ 0.3 0 C, respectively.
  • Homogeneous and random copolymers may display sharp steplike features, while block copolymers may display either multiple steps or very broad transitions. The sharp step displayed by 5-S-DMS-35 in the thermograph may indicate that the synthesized copolymers are random, not block, copolymers.
  • cross-linking agent The effect of cross-linking agents may be tested, for example but not limited to, using Fe(acetonylacetonate) 3 , (TBA) 3 V 3 O 9 , (TBA)MnO 4 , and (TBA) 2 Cr 2 O 7 as the cross-linking agents.
  • the number of agents used may be limited due to the solubility of the polymers.
  • the polymers of this example may be soluble only in nonaqueous solutions.
  • Initial shear tests may be performed on 10-S-DHS-1 , using cross-linking agent concentrations that may afford a metal to 3,4-dihydroxystyrene monomer ratio of approximately 0.66: 1.
  • polystyrene (S-I) may also be measured with these cross-linking agents.
  • Lap shear strength tests may be performed using, for example, aluminum adherends ⁇ e.g., 4" x 1" x 1/5") with a hole placed near one of the ends (e.g., 1/2" diameter).
  • the adherends may be polished with, for example, a Craftsman 8" Polishing Wheel, first with Mibro #3 Cleaning & Polishing compound followed by Mibro #5 Cleaning and polishing compound.
  • the adherends may be suspended by a glass bar in a beaker and washed in stirring hexanes for approximately 15 min., stirring acetone for approximately 15 min., stirring ethanol for approximately 15 min., and stirring water for approximately 15 min.
  • the adherends may be dried overnight in air at room temperature. [0080] After drying, the adherends may be placed on a plastic sheet. Four 15 ⁇ L aliquots of polymer solution ⁇ e.g., Ig polymer / mL acetone) may be placed within an approximately 1 " x 1 " area at the end of one of the adherends.
  • Two 15 ⁇ L aliquots of cross-linking agent ⁇ e.g., 1 M metal concentration in acetone
  • cross-linking agent ⁇ e.g. 1 M metal concentration in acetone
  • Approximately 30 minutes after setting the samples they may be placed in an incubator at ⁇ 55°C for ⁇ 22 hrs.
  • the shear strength of these samples may then be measured after a total set time of ⁇ 24 hrs.
  • the measurements may be made, for example, using an Instron Materials Testing Instrument.
  • Figure 6 illustrates exemplary results of these measurements as well as the exemplary standard reduction potentials of the cross-linking agent.
  • the ultimate shear strength was measured ten times for each sample and averaged.
  • the use of a transition metal cross-linking agents may result in a greater increase in shear adhesive strength for polymers containing dihydroxystyrene than for just polystyrene.
  • An increase in the standard reduction potential of the cross-linking agent may also results in an increase in the ultimate shear strength of the adhesive.
  • (TBA) 2 Cr 2 O 7 is the cross-linking agent that gave the highest ultimate shear strengths, therefore it may be used in further studies to optimize the ultimate shear strength of this adhesive system.
  • (TBA)MnO 4 may afford ultimate shear strengths comparable to those observed with (TBA) 2 Cr 2 O 7 . Solutions Of(TBA)MnO 4 in acetone may have a tendency to react violently within 10 to 30 minutes of preparation.
  • a new method of mixing polymer and cross-linking solutions may be used that does not involve mechanical mixing with a pipette tip.
  • Polymers with a high percentage of 3,4-dimethoxystyrene may react too quickly upon exposure to the cross- linking agent, possibly resulting in a large mass stuck to the pipette tip or a solid mass that prevents the two adherends from being adhered together.
  • Shear adhesive strength tests may be performed using aluminum adherends ⁇ e.g., 3" x 1/2" x 1/10") with a hole placed near one of the ends ⁇ e.g., 1/4" diameter).
  • the adherends may first be polished, for example, with a Craftsman 8" Polishing Wheel, first with Mibro #3 Cleaning & Polishing compound followed by Mibro #5 Cleaning and polishing compound.
  • the adherends may be suspended by a glass bar in a beaker and washed, for example, in stirring hexanes for ⁇ 15 min., stirring acetone for ⁇ 15 min., stirring ethanol for —15 min., and stirring water for ⁇ 15 min.
  • the adherends may dry overnight in air at room temperature. [0086] After drying the adherends, they may be laid next to each other on a plastic sheet.
  • a polymer solution ⁇ e.g., 0.3 g polymer / 1.0 mL solvent
  • Approximately 15 ⁇ L of crossl inker solution may then be pipetted on top of the polymer solution on one of the adherends.
  • the crosslinked adherend may be placed on top of the other adherend with an overlap area of approximately 1/2" x 1/2".
  • the back end of the top adherend may be supported with a - 1/10" thick sheet of aluminum.
  • they may be placed in an incubator at ⁇ 55°C for — 22 hrs. The shear strength of these samples may then be measured after a total set time of— 24 hrs.
  • An lnstron Materials Testing Instrument may be used to make these measurements at a speed of approximately 2.0 mm/min.
  • Figure 7 shows exemplary average ultimate shear strengths of all polymers with a dichromate cross-linking agent ⁇ e.g., 0.33 CrDMS, lOmg (TBA) 2 Cr 2 O ? per adherend, and 20 mg (TBA) 2 Cr 2 O 7 per adherend).
  • a dichromate cross-linking agent ⁇ e.g. 0.33 CrDMS, lOmg (TBA) 2 Cr 2 O ? per adherend, and 20 mg (TBA) 2 Cr 2 O 7 per adherend.
  • 20 mg was the maximum mass allowed by solubility in 15 ⁇ L of solvent.
  • Shear strength may not be directly related to the percentage of 3,4-dihydroxystyrene. Shear strength may increase with the increase in dihydroxystyrene, for example, up to 10% 3,4-dihydroxystyrene under the conditions of this example. Above 10% 3,4-dihydroxystyrene, shear strengths of the cross-linked adhesive may no longer increase with increasing dihydroxystyrene percentage under the conditions of this example.
  • the adhesive systems that displayed the highest ultimate shear strengths under these conditions were 10-S-DHS-35 (TBA) 2 Cr 2 O 7 cross-linking agent.
  • This example illustrates the effect of cure time and temperature using an exemplary adhesive system.
  • the effect of cure time and temperature on this exemplary adhesive system may be determined using 10-S-DHS-40 and a (TBA) 2 Cr 2 O 7 cross- linking agent (e.g., CnDHS ⁇ 0.9).
  • Shear measurements may be made as described in the previous section; but the temperature may be varied between, for example, room temperature, 55°C, and 77°C. Cure times for each temperature may also be varied between, for example, 30 minutes and 96 hours.
  • the results of this exemplary experiment are shown in Figure 8. For example, at all exemplary cure temperatures, a maximum shear strength may be reached, but a decrease in shear strength may be observed after extensive curing.
  • a room temperature cure may reach a maximum of ⁇ 1 MPa after 48 hrs.
  • the highest ultimate shear strengths under these experimental conditions may be obtained by curing at approximately 55°C from about 24 to about 48 hours or at approximately 77°C from about 8 to about 24 hrs. Under these experimental conditions, curing at higher temperatures, up to about 100 0 C may not result in significant increases in ultimate shear strength.
  • This example further illustrates how varying elements of the system, such as polymer concentration, may affect the properties of the polymers.
  • the effect of polymer concentration on ultimate shear strength may be tested with, for example, 10-S-DHS-40 and a (TBA) 2 Cr 2 O 7 cross-linking agent (CnDHS ⁇ 0.9).
  • Samples may be prepared as in Example 3. The volume of solvent may be kept constant for this experiment, but the mass of polymer may be varied, and the concentration Of (TBA) 2 Cr 2 O 7 may be varied to keep CrDHS « 0.9.
  • Figure 9 illustrates that, under these conditions, the mass of polymer per adherend that provided the highest ultimate shear strength may be about 0.0015 g/adherend.
  • This example further illustrates how varying elements of the system, such as concentration of adhesive, may affect the properties of the polymers.
  • concentration of adhesive may affect the properties of the polymers.
  • the effect of water exposure on adhesive strength may be tested on 10-S-HDS-55 with a CnDMS ratio of, for example, 0.45 using the testing method described above in Example 5.
  • the samples may display average ultimate shear strength of approximately 3.91 +/- 0.74 MPa.
  • another set of samples may be exposed to boiling water for about two hours prior to measurement. These samples may display average ultimate shear strength of approximately 4.07 +/- 0.47 MPa. Under these experimental conditions, exposure of these samples to boiling water may not result in decreased adhesive strength of these adhesive systems.
  • all synthesis may be carried out under an argon atmosphere using, for example, standard Schlenk techniques.
  • Gel permeation chromatography may be performed, for example, on a Waters gel permeation chromatography system with a refractive index detector (2414).
  • Data may be collected on a personal computer using software, such as but not limited to, BreezeTM software.
  • Differential scanning calorimetry may be performed on, for example, a TA Instruments 2920 modulated differential scanning calorimeter.
  • Aldrich may be inhibited with 10-15 ppm of 4-terf-butylcatechol.
  • Column chromatography may be used to separate this inhibitor from the monomer.
  • a 25 mL glass pipette may be cut at the tip and top to afford a functional column for monomer purification.
  • the glass pipette may be oven dried for ⁇ 8 hr. prior to use.
  • the column may be packed with, for example, about 0.6 cm of cotton, about 0.6 cm of oven dried sand, about 15-25 cm of oven-dried alumina, and about 0.6 cm of potassium carbonate.
  • Styrene may be added, for example, to the top of the packed column and allowed to elute.
  • 3,4- dimethoxystyrene may be purchased from Sigma Aldrich, and may also contain an inhibitor, e.g., 1% hydroquinone. Column chromatography may be used to separate hydroquinone from the monomer in a manner analogous to that for styrene.
  • Polystyrene may be synthesized as follows. The preparation of polystyrene may be based on modification of literature procedures for the polymerization of vinyl monomers.(J: Pol. Sci.: Pot. Symp. 1986, 74, 227-242).
  • Anhydrous toluene (235 mL) may be added by syringe to a degassed 500 mL Schlenk flask.
  • the purified styrene (47 mL, 0.41 mol) may be added by syringe to the flask.
  • Vacuum may be applied to the flask for 1 second and then back filled with argon.
  • the flask may be placed into a dry ice/isopropanol bath, allowed to cool to ⁇ -78°C for 15 min., and n-butyllithium (e.g., 1.34 mL, 2.6 M in hexanes) may be added dropwise by syringe.
  • n-butyllithium e.g., 1.34 mL, 2.6 M in hexanes
  • This example further illustrates polymer synthesis.
  • Poly[ (3,4-dimethoxystyrene)-co-styrene] with varied percentages of 3,4-dimethoxystyrene and styrene, may be prepared by modification of the method described above in Example 8.
  • the procedure described here is an exemplary polymerization of 1:1000 3,4-dimethoxystyrene:styrene poly[(3 ,4- dimethoxystyrene)-co-styrene].
  • Polymers containing about 1 :5, 1:10, 1 :15, and 1:50 ratios of 3,4-dimethoxystyrene:styrene may be prepared in a similar manner.
  • Anhydrous toluene ⁇ e.g., 242 mL) may be added by syringe to a degassed 500 mL Schlehk flask and purified styrene ⁇ e.g., 47 mL, 0.41 mol) may be added by syringe.
  • Purified 3,4 dimethoxystyrene (0.06ImL, 0.4 mmol) may be added to the flask by syringe.
  • Vacuum may be applied to the flask for 1 second and then the flask may be back filled with argon.
  • the flask may be placed into a dry ice/isopropanol bath, and may be allowed to cool to ⁇ -78°C for 15 min.
  • n-butyllithium ⁇ e.g., 1.34 mL, 2.6 M in hexanes
  • the solution may turn from colorless to yellow to dark orange.
  • the reaction flask may be kept at ⁇ -78°C for at least about 8 hr.
  • the solution may be allowed to gradually warm to room temperature. Warming may result in a color change, for example, from dark orange to light yellow.
  • the reaction may be quenched, for example, by addition of methanol ⁇ e.g., 2 mL, 25°C), affording a colorless solution.
  • the reaction mixture may be vented and poured into a 1 ,000 mL round bottom flask containing 500 mL of ice cold methanol. A cloudy white precipitate may form.
  • a white solid may be obtained after solvent removal in vacuo ⁇ e.g., 27 ' .1.6 g, 64% yield).
  • 1 H NMR (CDCl 3 ) ⁇ 0.6-2.3 ppm ⁇ e.g., broad, polymer backbone), 3.4-3.8 ppm (e.g., broad, methoxy peaks), 6.0-7.4 ppm (e.g., broad, aromatic).
  • Figure 10 provides exemplary synthetic details and exemplary characterization data for each polymer.
  • This example further illustrates polymer synthesis.
  • Poly(3,4-dimethoxystyrene) may be prepared by modification of the method described above in Example 8.
  • Anhydrous toluene e.g., 45 raL
  • the purified 3,4- dimethoxystyrene styrene e.g., 6.0 mL, 0.041 mol
  • Vacuum may be applied to the flask for about 1 second and then the flask may be back filled with argon.
  • n-butyllithium e.g. 0.17 mL, 2.6 M in hexanes
  • solution may turn from colorless to yellow to dark orange.
  • the reaction flask may be kept at ⁇ -78°C for at least about 8 hr.
  • the solution may be allowed to gradually warm to room temperature. Warming may result in a color change, for example, from dark orange to light yellow.
  • the reaction may be quenched, for example, by addition of methanol (e.g., 2 mL, 25°C), affording a colorless solution.
  • methanol e.g., 2 mL, 25°C
  • the reaction mixture may be vented and poured into a 500 mL round bottom flask containing 200 mL of ice cold methanol. A cloudy white precipitate may form.
  • a white solid may be obtained after solvent removal in vacuo (e.g., 5.8 g, 87% yield).
  • 1 H NMR (CDCl 3 ) ⁇ 0.6-2.8 ppm (e.g., broad, polymer backbone), about 3.1-4.0 ppm (e.g., broad, methoxy peaks), about 5.5-7.1 ppm (e.g., broad, aromatic).
  • Figure 10 provides exemplary synthetic details and exemplary characterization data for each polymer.
  • This example further illustrates polymer synthesis.
  • the methoxy groups of the poly[(3,4- dimethoxystyrene)-c ⁇ -styrene] copolymer may be removed according to standard methods to reveal the deprotected, catechol-containing po ⁇ ymers.(Macromolecular Rapid Comm. 1998, 19, 241-246; J. Pol. ScL: Pol. Symp. 1986. 74, 227-242; J. Org. Chem. 1979, 44, 4444-4446)
  • Anhydrous dichloromethane (e.g., 100 mL) may be added to the flask by syringe, and the flask may be placed into an ice bath and allowed to cool for ⁇ I5 min.
  • Boron tribromide (1.3 mL, 1 M in dichloromethane) may be added to the flask drop-wise by syringe. Upon addition of boron tribromide, the reaction mixture may become dark red. The flask may be left under a positive pressure of argon and may be allowed to gradually warm to room temperature.
  • acidic water e.g.
  • reaction mixture may be poured into the flask and a cloudy pink solution may form.
  • the solution may be stirred at, for example, about 4°C for about 15 min.
  • the reaction mixture may be allowed to separate into organic and aqueous layers.
  • the aqueous layer may be decanted into a filter flask.
  • the organic layer may be washed with acidic water (e.g., 1,000 mL, 0.12 M HCl) for 15 min at 4°C and the aqueous layer may be decanted into the filter flask. This washing step may be repeated approximately twice.
  • Dichloromethane (e.g., 300 mL) may be added to the resulting organic layer and the mixture may be transferred to a 2,000 mL separatory funnel.
  • Fresh acidic water (e.g., 100 mL, 0.12 M HCl) may be added to the separatory funnel.
  • the funnel may be capped, shaken, and allowed to separate into organic and aqueous layers for approximately 12 h.
  • a white solid may be obtained by solvent removal of the resulting organic layer in vacuo (e.g., 23.35 g, 86% yield).
  • 1 H NMR (CDCl 3 ) ⁇ 0.3-2.7 ppm (e.g., broad, polymer backbone), 6.0-8.0 ppm (e.g., broad, aromatic).
  • this procedure may afford about 98% and about 95% deprotection of the 1:10 and 1 :5 polymers, respectively.
  • Methoxy peaks ⁇ e.g., 3.1 -4.9 ppm) may not be observable for polymers of higher styrene content. See Figure 10 for further exemplary characterization.
  • Poly(3,4-dihydroxystyrene) may be prepared by the deprotection of poly[(3 ,4-dimethoxystyrene)-co-styrene] with BBr 3 .
  • Poly(3,4-di methoxystyrene) e.g., 5.5 g
  • Anhydrous dichloromethane e.g., 42 mL
  • Boron tribromide (e.g., 10.5 mL) may be added to the flask drop-wise by syringe. Upon addition Of BBr 3 , the reaction mixture may become cloudy and pink. The flask may be left under positive pressure argon flow and allowed to gradually warm to room temperature.
  • Acidic water e.g., 1 ,000 mL, 0.12 M HCl
  • a viscous, cloudy, dark pink solution may form.
  • Additional dichloromethane e.g., 300 mL
  • the solution may be stirred at 4°C for 15 min.
  • the reaction mixture may then be allowed to separate into organic and aqueous layers.
  • the aqueous layer may be decanted into a filter flask.
  • the organic layer may be washed by addition of acidic water (e.g., 1 ,000 mL, 0.12 M HCI) for 15 min at 4°C, and the aqueous layer may be decanted into an Erlenmeyer flask. This washing step may be repeated twice more.
  • Dichloromethane e.g., 500 mL
  • the mixture may be transferred, for example, to a 2,000 mL separatory funnel.
  • Fresh acidic water (e.g. , 200 mL, 0.12 M HCl) may be added to the separatory funnel.
  • the funnel may be capped, shaken, vented, and allowed to separate into organic and aqueous layers for approximately 12 h.
  • a maroon solid may be obtained after solvent removal of the resultant organic layer in vacuo (e.g., 4.98 g, 90.5% yield).
  • eagent solutions may be prepared in order to test the cross-linking ability of, for example, various metal salts and oxidants.
  • Metal salts and oxidants may be weighed out the day of testing, and solutions may be mixed, for example, 5-10 min prior to reaction with a polymer. Due to the hydrophobicity of the copolymers, all metal salt and oxidant solutions may be prepared in spectroscopy grade acetone, at a concentration of approximately 400 mM, with a final concentration after mixing with polymer of approximately 40 mM. Examples of reagents that can be tested are found in Figure 1 1, this figure is merely illustrative and not limiting.
  • Samples may be prepared by dissolving, for example, 1.20 ⁇ 0.01 g of polymer in ⁇ 1.2 mL of acetone in a glass test tube. Each solution may be agitated, for example, on a mini-vortex machine for 30 seconds and added to a plastic microcentrifuge tube (e.g., 2 mL volume, 9 mm i.d. x 35 mm).
  • a plastic microcentrifuge tube e.g., 2 mL volume, 9 mm i.d. x 35 mm.
  • An lnstron 5544 Materials Testing Machine may be used to drive a steel rod into the cross-linked sample at a constant velocity.
  • a 4.0 mm blank drill bit may penetrate the sample mixture at 20 mm/min.
  • Sample microcentrifuge tubes may be secured in a drill chuck, specifically designed for the lnstron instrument. For each run, the average total penetration depth may be 25-30 mm for each exemplary sample.
  • a 100 N load cell may be used to monitor the resistive force of the sample against the rod, and data may be recorded every 0.5 mm using MerlinTM software on a personal computer.
  • a sample with extensive cross- linking may generate a higher resistive force against penetration than one with limited cross-linking, and thus may require an increased force to lower the rod at a constant velocity.
  • Lap-shear testing for example, of the 10: 1 copolymer may be performed with, for example, an Instron materials testing machine. Polished aluminum adherends (e.g., about 10 cm x 1.2S cm) may be used for these tests.
  • polymer and cross-linking agent concentrations may be diluted to 1/3 that of the concentration used for penetration testing.
  • a ⁇ 22.5 mL aliquot of the polymer solution may be spread over a ⁇ 1.25 x 1.25 cm area on both adherends.
  • An —15 mL aliquot of cross-linking agent may be spread on top of the polymer solution on one adherend.
  • the adherends may be overlapped with a ⁇ 1.25 x 1.25 cm area and may be cured in the same fashion as the penetration tests, for example, 1 h at room temperature.
  • 5 samples may be measured. Each sample may be loaded to failure at, for example, about 2 mm/min and the ultimate shear loads may be recorded and averaged. Under the instant experimental conditions, all samples may display cohesive failure.
  • Examples 16 — 18 provide experimental data characterizing an exemplary system of the disclosed bio-inspired cross-linking polymers. The following data is merely illustrative and is not limiting of the disclosed system.
  • a family of poly[(3,4-dihydroxystyrene)-co-styrene] polymers may be synthesized with differing percentages of 3,4-dihydroxystyrene (0%, 0.001%, 2%, 6%, 9%, 17%, and 100%), for example, by varying the ratio of starting monomers (e.g., 3,4- dimethoxystyrene:styrene ratios of about 1:1000, 1:50, 1:15, 1:10, and 1 :5).
  • Styrene and 3,4-dimethoxystyrene may be copolymerized by anionic methods, and deprotected to yield poly[(3,4-dihydroxystyrene)-co-styrene] products.
  • Glass transition temperatures of the protected polymers may be obtained by differential scanning calorimetry (DSC), or any other suitable method.
  • DSC differential scanning calorimetry
  • the following results may be obtained. These results are not limiting.
  • 100% styrene may display a T g of about 106.3 0 C.
  • the 100% poly(3,4-dihydroxystyrene) may provide T g of about 53.1 0 C.
  • intermediate T g values may be obtained, such as T g of about 90.6 0 C for a 17% 3,4-dimethoxystyrene and about 87% styrene copolymer.
  • the single, sharp thermal transitions found for each copolymer may indicate distribution of the two monomers throughout the chain, rather than formation of block copolymers.
  • GPC Gel permeation chromatography
  • the 1 :50 copolymer may display M n of about 9,460 and PDl of about 1.38.
  • Further data obtained may include: 1 : 15 copolymer, M n of about 14,726, PDI of about 1.71; 1 : 10 copolymer, M n of about 16,149, PDI of about 1.92; 1 :5 copolymer, M n of about 14,641, PDI of about 1.84.
  • longer chains lengths may be found (e.g., 100% styrene, M n of about 126,000, PDI of about 1.26; 100% 3,4-dimethoxystyrene, M n of about 43,894, PDI of about 1.37).
  • Polymers may also be characterized by 1 H NMR spectroscopy (see Examples 8-15 above).
  • cross linking reactions of exemplary bio- inspired cross-linking polymers.
  • Cross-linking reactions may be explored, for example, by using an Instron 5544 materials testing system.
  • An about 4.0 mm diameter rod may be driven into a viscous solution (e.g., 1 g polymer in 1 mL acetone) at constant velocity (20 mm/min), while the resistive penetration force may be recorded.
  • High resistive forces may indicate a hardened composition while low forces may show a lack of curing.
  • Figure 12 shows exemplary curing data for the 1 :10 3,4- dihydroxystyrene:styrene copolymer reacted with select cross-linkers, after a 1 hour cure at room temperature.
  • the results are exemplary of those obtained under the present experimental conditions; results may vary with varied conditions.
  • Dichromate (Cr 2 O 7 2' ) may display the highest penetration forces, thereby indicating the greatest amount of polymer cross-linking. Under the conditions of the present experiment, Fe 3+ , 1O 4 " , and MnO 4 " may not exhibit the effectiveness Of(Cr 2 O 7 2' ) , they may also show penetration forces significantly greater than those obtained for an uncrosslinked control sample.
  • Reactions with Zn(NO 3 ) 2 , Ga(NO 3 ) 3 , Co(NO 3 ) 2 , t- C 4 H 9 OOH, and (C 4 Hg) 4 N) 2 SO 4 may not afford any observable cross-linking. Likewise, no reactions may be observed between a 100% polystyrene homopolymer and any of these reagents mentioned. A trend similar to cross-linking mussel adhesive proteins, may be observed in the present system, in which oxidizing metal ions were most effective at curing.
  • FIG. 13 shows exemplary penetration forces at 35 mm rod extension found for copolymers with varied percentages of 3,4-dihydroxystyrene distributed amongst styrene, under the conditions of this experiment. As indicated, each polymer may be reacted with four reagents. Penetration tests may also be performed on about 100% poly(3,4-dihydroxystyrene), cross-linked by Cr 2 O 7 2' (75 ⁇ 3 N) and 1O 4 " (38 ⁇ 4 N).
  • Both a polymer e.g., 13.5 tng in 45 ⁇ L acetone.
  • a cross-linking agent e.g., 1 :3 cross-linker:3,4-dihydroxystyrene monomer ratio, in 15 ⁇ L acetone
  • the exemplary data on the table in Figure 14 indicate that cross-linking enhances the adhesive characteristics of the polymers.
  • the exemplary polymer synthesized by the disclosed method exhibited a maximum force just over about 1 MPa.
  • the adhesive properties of this polymer may therefore be stronger than starch-based glues ( ⁇ 0.4 MPa) and weaker than polyvinyl acetate "white” glues ( ⁇ 4 MPa).

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Abstract

L'invention concerne une classe de polymères réticulables inspirés de biopolymères, créée en travaillant les fonctionnalités du catéchol dans le squelette d'un polymère volumineux. On peut incorporer différents groupes de réticulation dans différents squelettes de polymères et les faire à la suite de cela réagir avec un ensemble de réactifs. L'invention concerne également une composition d'adhésif comprenant un copolymère, le copolymère comprenant des groupes dihydroxyphényles pendants ; et un agent de réticulation sélectionné dans le groupe constitué, par exemple, d'oxydants, d'enzymes, de métaux et de la lumière. L'invention concerne également un procédé de préparation d'une composition d'adhésif consistant à copolymériser un premier monomère comprenant des groupes dihydroxyphényles dont les deux groupes hydroxy sont protégés ; déprotéger les groupes dihydroxyphényles dont les deux groupes hydroxy sont protégés ; réticuler les groupes dihydroxyphényles avec un agent de réticulation.
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WO2015129846A1 (fr) * 2014-02-28 2015-09-03 独立行政法人科学技術振興機構 Copolymère séquencé contenant un segment catéchol, nanoparticules inorganiques revêtues dudit copolymère séquencé, procédé d'obtention du copolymère séquencé contenant le segment catéchol et procédé d'obtention de nanoparticules inorganiques revêtues dudit copolymère séquencé
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WO2017004174A1 (fr) * 2015-06-30 2017-01-05 Purdue Research Foundation Adhésifs et leurs procédés de fabrication
WO2018089078A3 (fr) * 2016-08-22 2018-06-21 Purdue Research Foundation Méthodes associées à l'adhérence dans un environnement aqueux
CN109266086A (zh) * 2018-09-11 2019-01-25 徐昊 水性涂料附着力促进剂及其制备方法
RU2698315C2 (ru) * 2013-02-04 2019-08-26 В.Л. Гор Энд Ассошиейтс, Инк. Покрытие для подложки
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US11260146B2 (en) 2019-11-27 2022-03-01 Terumo Medical Corporation Seal-healing valve for a medical instrument
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JPWO2015129846A1 (ja) * 2014-02-28 2017-03-30 国立研究開発法人科学技術振興機構 カテコールセグメントを含むブロック共重合体及び該ブロック共重合体で被覆された無機ナノ粒子、並びに、カテコールセグメントを含むブロック共重合体の製造方法及び該ブロック共重合体で被覆された無機ナノ粒子の製造方法
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