Biobased monomers and adhesive compositions including the same

Abstract

Provided are monomers represented by the structure where R1 is -H or -CH3 and R2 is derived from an amino acid sidechain selected from the group consisting of -H, an alkyl group, or a heteroalkyl group. Curable compositions, adhesives, and articles including the same are provided.

Description

[0001] BIOBASED MONOMERS AND ADHESIVE COMPOSITIONS INCLUDING THE SAME

[0002] BACKGROUND

[0003] An adhesion promoter typically has an affinity for a particular substrate. Due to this property, an adhesion promoter may be used as an additive or as a primer in compositions such as, for example, coatings, inks, and adhesives, to enhance adhesion of these compositions to a substrate of interest. The specific type of adhesion promoter useful in a given application may vary depending upon the composition of the surface to which it will be adhered.

[0004] SUMMARY

[0005] The present disclosure provides the synthesis of amino-acid derived, biobased (meth)acrylate monomers and the use of such monomers in (meth)acrylic (semi) structural adhesives and (meth)acrylic water-based and solvent-polymerized acrylic compositions that have utility as pressure sensitive adhesives, to improve adhesion to various substrates.

[0006] In one aspect, provided herein are monomers represented by the structure (I) wherein

[0007] R1is -H or -CHs; and

[0008] R2is derived from an amino acid sidechain selected from the group consisting of -H, an alkyl group, or a heteroalkyl group.

[0009] In another aspect, provided herein are monomers represented by the structure (II)

[0010] wherein

[0011] R3is a moiety represented by the structure (III), (IV), or (V)

[0012] In another aspect, provided herein are curable compositions comprising the monomer described above.

[0013] In another aspect, adhesives comprising curable compositions of the present disclosure and articles comprising the same are provided.

[0014] As used herein:

[0015] The term "(meth)acrylate" refers to "methacrylate" and / or "acrylate".

[0016] The term “biobased” refers to compositions that mainly consist of a substance (or substances) derived from living matter (biomass) that either occur naturally or are synthesized; the term may also refer to products made by processes that use biomass. Many common materials, such as, for example, paper, wood, and leather, can be referred to as biobased, but typically, the term refers to modem materials that have undergone more extensive processing. Materials from biomass sources may include, for example, bulk chemicals, platform chemicals, solvents, polymers, and biocomposites, with the understanding that some materials may fall under more than one category.

[0017] The term “pressure-sensitive adhesive” (“PSA”) is used in its conventional manner according to the Pressure-Sensitive Tape Council, which states that pressure-sensitive adhesives are known to possess properties including the following: (1) aggressive and permanent tack, (2) adherence with no more than finger pressure, (3) sufficient ability to hold onto an adherend, and (4) sufficient cohesive strength to be removed cleanly from the adherend. Materials that have been found to function well as PSAs include polymers designed and formulated to exhibit the requisite viscoelastic properties resulting in a desired balance of tack, peel adhesion, and shear holding power. PSAs are characterized by being normally tacky at room temperature (e.g., 20°C). Central to all PSAs is a desired balance of adhesion and cohesion that is often achieved by optimizing the physical properties of the elastomer, such as glass transition temperature and modulus. For example, if the glass transition temperature (Tg) or modulus of the elastomer is too high and above the Dahlquist criterion fortack (storage modulus of 3 x 106dynes / cm2at room temperature and oscillation frequency of 1 Hz), the material will not be tacky and may not useful by itself as a PSA material.

[0018] The term “semi-structural adhesive” refers to compositions that when at least partially cured to at least one substrate can resist forces of approximately at least 1.5 MPa as determined by the Overlap Shear Test. In one example, if the stage before curing includes a film-type form factor and curable composition is applied to the surface in the similar way that PSA is applied to a surface and then post-cured to transform it to have a high modulus with the targeted shear strength, it may be considered as a semi-structural adhesive.

[0019] The term “structural adhesive” refers to compositions that when at least partially cured to at least one substrate can resist forces of approximately at least 3 MPa as determined by the Overlap Shear Test. This high-modulus adhesive typically requires an initial wetting stage and post curing stage to increase modulus to the target range. For example, a curable resin may be applied on a surface and cured to make a structural junction.

[0020] The term “amino acid” refers to organic compounds that contain both amino and carboxylic acid functional groups. Amino acid side-chain groups can be classified as aliphatic, acyclic, aromatic, polar, and the like. There are standard and non-standard, or non-canonical, amino acids as well as non-proteinogenic amino acids. See, e.g., Organic Chemistry, Third Edition, Janice Gorzynski Smith, copyright 2011, the McGraw Hill Companies Inc., pages 1076- 1078. The term “cured” refers to at least some of the monomers (e.g., (meth)acrylic) being polymerized.

[0021] The term “solvent-polymerized PSA” refers to a pressure -sensitive adhesive prepared by dissolving monomers (e.g., (meth)acrylate), optionally a chain transfer agent, optionally acidic monomers, optionally high Tg monomers, and a polymerization initiator into solvents such as, for example, toluene, ethyl acetate, isopropyl alcohol, heptane, methyl ethyl ketone, or combinations thereof to form a liquid. The liquid is then coated and evaporated (by e.g., heat) to form a smooth consistent thickness layer of PSA. The monomers may be at least partially polymerized or fully polymerized prior to coating and evaporating. Solvent-polymerized PSAs may comprise crosslinkers and can be additionally crosslinked to provide additional cohesive strength or shear holding performance.

[0022] The term “water-based PSA” (also referred to herein as “waterborne adhesive” and “water-polymerized adhesive”) refers to a pressure-sensitive adhesive prepared by combining components including water, optionally emulsifier(s), (meth)acrylate monomer(s), a chain transfer agent, a crosslinker, and a polymerization initiator. Optionally, acidic monomers, high Tg monomers, and combinations thereof may be added.

[0023] Features and advantages of the present disclosure will be further understood upon consideration of the detailed description as well as the appended claims.

[0024] DETAILED DESCRIPTION

[0025] Polymers are predominantly sourced from crude-oil building blocks. As awareness of implications related to heavily relying on petroleum grow, consumers, manufacturers, and politicians are becoming increasingly interested in using non-petroleum sourced raw materials. Currently, there are few polymerizable, sustainably sourced raw materials that are commercially available. Furthermore, the limited availability of such materials often results in the use of fatty acids or the like as a starting material, which may result in a limited set of properties obtainable when using these monomers in polymerizable resins.

[0026] Biobased (meth)acrylate monomers are predominantly non-polar and generally do not contain functional groups typically associated with adhesion promotion (e.g., -SH, -OH, -NHR). Therefore, polar, biobased monomers could be useful for promoting adhesion in adhesives with high levels of sustainably derived raw materials.

[0027] The present disclosure provides the synthesis of amino-acid derived, biobased (meth)acrylate monomers and the use of such monomers in (meth)acrylic (semi)structural adhesives and (meth)acrylic water-based and solvent-polymerized acrylic compositions that may have utility as pressure sensitive adhesives, to improve adhesion to various substrates.

[0028] In one aspect, provided herein are monomers represented by the structure (I) wherein

[0029] R1is -H or -CHs; and

[0030] R2is derived from an amino acid sidechain selected from the group consisting of -H, an alkyl group, or a heteroalkyl group.

[0031] In another aspect, provided herein are monomers represented by the structure (II)

[0032] wherein

[0033] R3is a moiety represented by the structure (III), (IV), or (V)

[0034] Such monomers may be prepared by methods known to those of ordinary skill in the relevant arts and preparatory methods are provided in the Examples below. Such monomers may be in the neutral state as represented herein, in a zwitterion form, or in a salt form.

[0035] In another aspect, curable compositions comprising the novel monomers described above are disclosed. Such curable compositions may be prepared by methods known to those of ordinary skill in the relevant arts and preparatory methods are provided in the Examples below.

[0036] In some embodiments, the curable composition comprises monomers that are 100 wt.%, at least 99 wt.%, at least 95 wt.%, at least 90 wt.%, at least 80 wt.%, at least 70 wt.%, at least 60 wt.%, at least 50 wt.%, or at least 40 wt.% (meth)acrylate monomers.

[0037] In some embodiments, the curable composition may comprise an adhesive.

[0038] In some embodiments, the adhesive may be a semi-structural adhesive or a structural adhesive. In some embodiments, the adhesive may be a pressure-sensitive adhesive (“PSA”). In some embodiments, the adhesive comprises a solvent-polymerized pressure-sensitive adhesive or a water-based pressure-sensitive adhesive.

[0039] In some embodiments curable compositions of the present disclosure may be biobased compositions. In some embodiments curable compositions of the present disclosure may be at least partially cured.

[0040] In another aspect, provided are methods of preparing adhesives (e.g., semi-structural adhesives, structural adhesives, pressure-sensitive adhesives), the method including preparing the curable compositions of the present disclosure and curing, at least partially, the curable compositions to provide the adhesives.

[0041] In some embodiments, curing comprises stirring the curable composition, heating the curable composition, exposing the curable composition to radiant energy, or combinations thereof.

[0042] Curable compositions of the present disclosure may be useful in the manufacture of a variety of articles, such as, for example, adhesives, fdms, sealants, coatings, protective coatings, hardcoats, polymers, and composites.

[0043] Objects and advantages of this disclosure are further illustrated by the following nonlimiting examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure.

[0044] EXAMPLES

[0045] Unless otherwise noted or readily apparent from the context, all parts, percentages, ratios, etc. in the Examples and the rest of the specification are by weight.

[0046] Materials Used in the Examples

[0047] Preparation of Monomers

[0048] Synthesis of 3-(lH-indol-3-yl)-2-[2-(2-methylprop-2-enoyloxy)ethylcarbamoylamino]propanoic acid ("lEM-Trp")

[0049] Tryptophan (5.11 g, 25 mmol) was weighed into a 100 mL round-bottomed flask. Sodium hydroxide solution (25 mL of IN NaOH) and deionized water (5 mL) was added to the flask. The mixture was immersed in an ice-water bath and stirred magnetically under a nitrogen purge until dissolved. A solution of 4-hydroxy TEMPO solution (50 uL, 10,000 ppm in DI water) was added as free radical inhibitor. Isocyanatoethylmethacrylate was added by micropipet (1.75 mL). After about 10 minutes reaction time, a second portion of IEM (1.75 mL) was added. The mixture was stirred for an additional 30 minutes. The reaction mixture was acidified by dropwise addition of concentrated HC1, which led to rapid precipitation of a gummy solid. The solid was placed in a crystallizing dish, air dried, then broken up to give a somewhat waxy colorless solid, 7.3 grams. The solid was dissolved in acetone (ca. 25 mL) and a small amount of insoluble material was filtered. The solution was concentrated on a rotary evaporator, diluted with diethylether, and placed in a refrigerator overnight. The colorless solid that had separated was filtered, rinsed with diethylether, and air-dried (5.4 grams). ' H-NMR (dg- Acetone): 5 1.86 (s, 3H), 3.19 (dd, 1H), 3.29 (dd, 1H), 3.42 (m, 2H), 4.11 (t, 2H), 4.68 (m, 1H), 5.57 (s, 1H), 5.93 (br. d, ca. 0.6H), 6.05 (s, 1H), 6.16 (br. M, ca. 0.6H), 6.97 (t, 1H), 7.05 (t, 1H), 7.16 (s, 1H), 7.34 (d, 1H), 7.58 (d, 1H), 10.19 (s, ca. 0.7H).13C-NMR (d6-Acetone): 5 18.4, 28.7, 39.4, 54.7, 65.0, 110.9, 112.0, 119.4, 121.9, 124.3, 124.4, 126.0, 128.8, 137.2, 137.3, 158.9, 167.6, 175.0.

[0050] Synthesis of 5-((diaminomethylene)amino)-2-(3-(2-(methacryloyloxy)ethyl)ureido)pentanoic acid ("lEM-Arg")

[0051] A stirred solution of L-arginine (69.6 g, 400 mmol) dissolved in 400 mL of deionized water was cooled in an ice bath. IEM (63.2 g, 408 mmol) was added dropwise to the stirred solution over a period of 30 minutes. After stirring an additional 30 minutes, the reaction mixture was lyophilized to give 129.4 g of lEM-Arg as a white powder. 'H NMR (500 MHz, DEUTERIUM OXIDE) 5 ppm 6.04 (s, 1 H) 5.63 (s, 1 H) 4.14 (t, J=5.26 Hz, 2 H) 3.86 - 4.01 (m, 1 H) 3.38 - 3.46 (m, 1 H) 3.29 - 3.36 (m, I H) 3.10 (t, J=6.85 Hz, 2 H) 1.83 (s, 3 H) 1.67 - 1.75 (m, 1 H) 1.55 - 1.61 (m, 1 H) 1.47 - 1.55 (m, 2 H)

[0052] Synthesis of ((2-(methacryloyloxy)ethyl)carbamoyl)methionine (“lEM-Met”)

[0053] Methionine (22.38 grams, 0.15 mole) was charged into a 250 mb round bottomed flask and dissolved in a mixture of deionized water (45 mb) and 5N NaOH solution (30 mb). The mixture was stirred magnetically and cooled in an ice-water bath under a slow stream of nitrogen gas for 15 minutes. 4-Hydroxy TEMPO solution (300 pL of a 10,000 ppm mixture in deionized water) was added to the stirring mixture. Isocyanatoethylmethacrylate (23.25 grams, 0.15mole) was added dropwise over 10 minutes. The mixture was stirred rapidly for an additional 10 minutes to give the desired adduct. The mixture was titrated to pH 7-8 as measured by pH paper, % solids = 39.75%. Tf-NMR (D2O): 5 2.01 (m, 1H), 2.05 (s, 3H), 2.17 (m, 1H), 2.22 (s, 3H), 2.65 (t, 2H), 3.54 (m, 1H), 3.63 (m, 1H), 4.24 (m, 1H), 4.35 (t, 2H), 5.84 (s, 1H), 6.26 (s, 1H).

[0054] Testing Methods for Examples 1 to 4

[0055] Test Method 1A: 2K Overlap Shear Testing Procedure (Aluminum ("Al"), Nylon, or Polycarbonate (PC) Substrates) for Structural Adhesive Examples: Substrates (e.g., Nylon substrates (1 inch x 4 inches x 0.25 inch, (2.5 cm x 10 cm x 1.3 cm)), Aluminum ((1 inch x 4 inches x 0.064 inch, (2.5 cm x 10 cm x 0.16 cm))) or Polycarbonate (3.18 x 25.4 x 101.6 mm (1 / 8 x 1 x 4in))) to be tested were washed with isopropyl alcohol and air dried for at least 10 minutes. Base formulations and accelerator PM-16664 were loaded into a 10 / 1 cartridge, spun using a centrifuge for 1 min at 1500 rpm and sealed with the appropriate cap. The adhesives were dispensed with a mixing nozzle and sprinkled with at least one glass bead 5-50 mils (Thomas Scientific, Swedesboro, NJ) over the substrate. Within one minute, a second substrate was applied to the sample, thus closing the bond (bond area = 0.5 inches x 1 inch (1.3 cm x 2.5 cm) for aluminum and 0.25 inch x 1 inch (0.65 cm x 2.5 cm) for nylon). The bond was clamped with binder clips and allowed to sit at room temperature for 24 hr prior to testing. Dynamic overlap shear testing was performed at ambient temperature using an MTS Sintech Tensile Tester, specimens were loaded into the grips and the crosshead was operated at 2 inches per minute (5 cm / min) for Nylon and Polycarbonate substrates, the crosshead was operated at 0.2 inches per minute (0.5 cm / min) for Aluminum substrates loading the specimen to failure. Stress at break was recorded in units of pounds per square inch (psi) or megapascals.

[0056] Test Method IB: Dynamic Mechanical Analysis (DMA) Test Method Temperature Ramp for Structural Adhesive Formulation Examples: The thickness of each film was measured. The films were mounted in the tensile grips of an DMA850 (TA Instruments, New Castle, DE, USA) with an initial grip separation of 12-16 mm. The measurement procedure was done to determine the precise grip separation with an initial / preload force of 0. 1 N with a “Use Force Track” set to 150%. The samples were then tested at an oscillation of 0.2% strain and 1 Hz throughout a temperature ramp from at least -20 °C to 60 °C at a rate of 3 °C per minute. The temperatures at which the tan delta signal reached a maximum were recorded as the glass transition temperature (Tg).

[0057] Structural Adhesive Formulation Preparation for Structural Adhesive Formulation Examples: Formulations were prepared by combining components as listed in Tables 1,3, 5, and 7 below into polypropylene mixing cups (from FlackTek, Inc., Eandrum, SC). The cups were sealed with a polypropylene lid and the mixtures were high shear mixed at ambient temperature and pressure using a SPEEDMIXER (Hauschild SpeedMixer inc., Dallas Texas) for at least 30 s at 2000 revolutions per minute (rpm).

[0058] Solvent-Polymerized Adhesives Preparation for Solvent-Polymerized Adhesive Examples: Linear polymers were synthesized in MEK by monomer compositions as indicated in Table 2. All monomers and initiators are loaded into a glass jar. This mixture was sparged for 2 minutes with N2. The reaction mixture then was mixed over 20 hours while heating at 60C in a Launder- O-Meter. The resulting polymer solution was coated on RF12N release liners with target thickness of 10 mil. The coated solution was dried at 70C for 20 min. Additional release liner (RF02) was laminated on the dried film and UV cured by exposing the adhesive film using a Fusion UV Processor (Fusion UV Systems Inc., Gaithersburg, MD) with D-bulb fixture with a dose of 3,000 mJ / cm2 of UVA as measured by a UVI Cure Power Puck 2 (EIT, Sterling, Virginia).

[0059] Water-based Adhesive Example Preparation for Water-based Adhesive Examples: Step 1: Aqueous phase preparation: To a plastic beaker were added DS-4 surfactant (16.52g), DDI water (211 .93g), and lEM-Met (4.78g) to prepare the aqueous solution (39.75% solid) the contents were agitated to mix.

[0060] Step 2: Oil phase preparation: To a separate plastic beaker were added IOA (172.90g), MMA (5.70g), AA (9.50g), CBn (0.17g) and then mixed well.

[0061] Step 3: Emulsion polymerization: The polymerization reaction was carried out with a IL glass reactor, which is equipped with a condenser, a N2 purge line, two addition ports, and one agitator. First, the aqueous phase was added into the reactor. Then, the oil phase was slowly added into the reactor under mixing (200 rpm). The mixture was then purged with N2 at room temperature for 30 min to Ih. After that, the temperature was increased to 30 °C with heating lamps, then redox initiators (0.5g of Fe2SO4*7H2O aqueous solution with 0.22% solid, 0.10g Na2S2O5 in 5 g of water solution, and 0.40g KPS with 3 g water for flushing into reactor) were added into the reactor. The polymerization started exotherm shortly. After the exotherm peak, the emulsion was increased to 70 °C, and the polymerization was continued for Ih. Then the emulsion was cooled to room temperature and neutralized with LiOH aqueous solution (17.75g of 7.41% in DDI water). Subsequently, the emulsion was filtered through a cheese cloth.

[0062] Step 4: Making a “handspread”: The emulsion was coated on a 2 mil plasma treated PET with a knife coater, then dried at 70 °C for 20 min. The dried PSA thickness is 2 mil. The PSA was then covered with a LSE300 paper liner from 3M Company.

[0063] Example 1: Base Formulations for Structural Adhesives Including EPXIEM Crosslinker and Testing Results for Comparative Examples 1-3 and Example 1

[0064] Table 2. Testing Results for Example 1

[0065] Example 2: Base Formulations for Structural Adhesives Including EPXIEM Crosslinker and Testing Results for Comparative Examples 4-10 and Examples 2A and 2B

[0066] Table 3. Formulations for Structural Adhesives Including a Urethane Dimethacrylate Crosslinker

[0067] Example 3: Base Formulations for Structural Adhesives Including EPXIEM Crosslinker and Testing Results for Comparative Examples 11 and 12 and Examples 3A and 3B

[0068] Table 6. Testing Results for Example 3. Results acquired using Test Method 1A Example 4: Base Formulations for Structural Adhesives Including PU3701 Crosslinker and Testing Results for Comparative Examples 13-15 and Examples 4A-4F

[0069] Table 7. Base Formulations for Structural Adhesives Including PU3701 Crosslinker

[0070] Table 8. Testing Results for Example 4. Results acquired using Test Method 1A

[0071] Example 5: Base Formulations for Solvent and Waterborne Adhesives Including lEM / Methionine and Testing Results

[0072] Testing Methods for Example 5

[0073] Test Method 1 : Rheology by dynamic mechanical analysis for solvent-polymerized adhesives A TA Instrument rheometer (TA Instruments, New Castle, DE) was used to measure G’, Tg and tan delta values in oscillatory shear mode. OCA films were stacked to have thickness of 1 mm and located between parallel plates with a diameter of 8 mm and angular frequency of 1 rad / sec.

[0074] Test Method 2: Peel Test by 180 degree peel test analysis for solvent-polymerized adhesives Spatially controlled peel adhesion performance was characterized using a standard 180 degree peel test and IMass apparatus (model TL-2300 from IMASS Inc., Strongsville, Ohio). First, OCA films were hand-laminated using rubber rollers onto prime-treated side of PET films (thickness of 2 mil) to make release liner / OCA / PET tri -layer constructions. The film was further cut into 0.5 in width strips and laminated down to a glass substrate. After 24 hours of aging at room temperature-50 RH% condition, a peel test was conducted with a speed of 12 in / min with a 180 peel angle.

[0075] Test Method 3: Pressure-Sensitive Adhesive (“PSA”) peel testing for water-based adhesives PSA strips (0.5in by 8in) were cut from the sample PSA tape, followed by removing the LSE300 paper liner, and then laminated on a clean stainless steel (SS) panel with a 2kg roller. The 180° peel adhesion was tested with a peel testing instrument (model TL-2300 from IMASS Inc., Strongsville, Ohio) using a peel speed of 12 in / min. Peel values are reported in ounces / in.

[0076] Test Method 4: PSA shear testing for water-based adhesives

[0077] PSA strips (tin by Win) were cut from the sample PSA tape, followed by removing the LSE300 paper liner, and then laminated on a clean stainless steel (SS) panel with a contact area of lin by lin with a 2kg roller. After 20min dwell at room temperature of the PSA on the SS panel, the panel was put on a shear station together with a weight (1kg). The shear result is the time that PSA failed from the SS panel. If the shear is more than 10K min, the shear testing will be manually stopped.

[0078] Table 9. Composition of the Solvent-Polymerized Adhesive Samples

[0079] Table 10. Rheology Properties and Solvent-Polymerized Adhesive Performances

[0080] As demonstrated by the data in Table 10, the solvent-coated PSAs comprising the novel IEM-TRP demonstrated consistent (Example 5A) or increased peel values (Example 5B and Example 5C) relative to the control sample Example 5A. Table 11. Water-Polymerized Adhesive Performances

[0081] As demonstrated by the data in Table 11, lEM-Met may be utilized as a monomer in preparing an emulsion adhesive with acceptable peel values and long-lasting RT shear values.

[0082] All cited references, patents, and patent applications in the above application for letters patent are herein incorporated by reference in their entirety in a consistent manner. In the event of inconsistencies or contradictions between portions of the incorporated references and this application, the information in the preceding description shall control. The preceding description, given in order to enable one of ordinary skill in the art to practice the claimed disclosure, is not to be construed as limiting the scope of the disclosure, which is defined by the claims and all equivalents thereto.

Claims

What is claimed is:

1. A monomer represented by the structure (I)whereinR1is -H or -CHs; andR2is derived from an amino acid sidechain selected from the group consisting of -H, an alkyl group, or a heteroalkyl group.

2. A curable composition comprising the monomer of claim 1.

3. A monomer represented by the structure (II)whereinR3is a moiety represented by the structure (III), (IV), or (V)4. A curable composition comprising the monomer of claim 3.

5. The curable composition of claim 2 or claim 4, where in the curable monomers are 100 wt.%, at least 99 wt.%, at least 95 wt.%, at least 90 wt.%, at least 80 wt.%, at least 70 wt.%, at least 60 wt.%, at least 50 wt.%, or at least 40 wt.% (meth)acrylate monomers.

6. The curable composition of claim 2 or claim 4, wherein the curable composition comprises an adhesive.

7. The curable composition of claim 6, wherein the adhesive comprises a semi-structural adhesive.

8. The curable composition of claim 6, wherein the adhesive comprises a structural adhesive.

9. The curable composition of claim 6, wherein the adhesive comprises a pressure-sensitive adhesive.

10. The curable composition of claim 9, wherein the adhesive comprises a solvent- polymerized pressure-sensitive adhesive.

11. The curable composition of claim 9, wherein the adhesive comprises a water-based pressure-sensitive adhesive.

12. The curable composition of any one of claims 2 or 4 to 11 wherein the curable composition is a biobased composition.

13. The curable composition of any one of claims 2 or 4 to 12 wherein the curable composition is at least partially cured.

14. An article comprising the curable composition of any one of claims 2 or 4 to 13.

15. The article of claim 14, wherein the article is selected from the group consisting of a film, a sealant, a coating, a protective coating, a hardcoat, a polymer, a composite, and combinations thereof.

16. A method of preparing an adhesive, the method comprising: preparing the curable composition of any one of claims 2, 4, or 5; and curing at least partially the curable composition to provide the adhesive.

17. The method of claim 16, wherein curing comprises stirring the curable composition, heating the curable composition, exposing the curable composition to radiant energy, or combinations thereof.

18. The method of claim 16 or claim 17, wherein the adhesive comprises a semi-structural adhesive.

19. The method of claim 16 or claim 17, wherein the adhesive comprises a structural adhesive.

20. The method of claim 16 or claim 17, wherein the adhesive comprises a pressure -sensitive adhesive.

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