Bio-based elastomeric polymer compositions

Abstract

A sealant composition is provided. The composition includes A) at least one carrier including water; B) an elastomeric acrylate polymer; C) at least one surfactant; D) optionally at least one rheology modifier; E) optionally at least one filler; F) optionally at least one freeze-thaw stabilizer; G) optionally at least one adhesion promotor. The elastomeric polymer B) in a form of a dispersion in the carrier A) and includes one or more C6-C10 alkyl(meth)acrylate monomers and one or more C1-C5 alkyl(meth)acrylate monomers. The C6-C10 alkyl(meth)acrylate monomers have a biocarbon content of 40% or more as determined by ASTM 6866-22 Method B. The elastomeric acrylate polymer has a biocarbon content of 22% or more determined by ASTM 6866-22 Method B.

Description

[0001] BIO-BASED ELASTOMERIC POLYMER COMPOSITIONS

[0002] FIELD OF THE INVENTION

[0003] Bio-based acrylate polymers suitable for use in caulk and sealant compositions.

[0004] BACKGROUND

[0005] Caulks and sealants may be used to fill in gaps or create a waterproof or water-resistant barrier between two or more different substrates. Acrylic emulsion polymers are commonly used in this application due to their good balance of water-resistance (hydrophobicity), flexibility, adhesion, durability (e.g., dirt pick up resistance), and cost.

[0006] However, from an environmental standpoint, a downside to acrylic emulsion polymers is that they are made from propylene, which is derived from petroleum. With dwindling supplies of petroleum combined with increased impacts of climate change due to uses of petroleum sourced feedstocks, it is necessary to look for new ways to synthesize acrylic emulsion polymers using monomers derived from renewable sources, particularly, plants and biomass. These monomers are referred to in the art as bio-based, or bio-sourced.

[0007] One way to reduce petroleum-sourced content in acrylic emulsion polymers is to add some bio-based materials via a blending approach. It is well known that most polymer pairs are chemically incompatible. This inherent incompatibility often causes performance deterioration, rather than the synergistic performance benefits hoped for blended polymer systems.

[0008] US 8193278 B2 relates to filled aqueous caulk and sealant compositions made from high solids aqueous binders chosen from copolymers having a mixture of backbone acid and hydroxyl groups.

[0009] US 8642696 B2 relates to copolymer compositions and methods for making these compositions. The copolymers include a vinyl aromatic monomer; a second monomer, and a biobased monomer. US 9593191 B2 relates to the use of a polymer from the polymerization of 2-octyl acrylate of renewable origin and optionally at least one other monomer, as a binding agent in, or for the production of, a coating composition.

[0010] US 10662273 B2 relates to an aqueous copolymer dispersion formed by emulsion polymerization of a monomer mixture including one or more (meth)acrylic acid esters in which at least one has a biorenewable carbon content of at least 50 wt. % of the total carbon content of the ester.

[0011] US 2021 / 0324114 Al relates to an aqueous dispersion as a bio-based binder and an aqueous coating composition including the aqueous dispersion and showing balanced stain resistance, freeze-thaw stability, and anti-clogging properties.

[0012] CN 1 12300343 A relates to a bio-based acrylate emulsion for building interior wall coating and a preparation method thereof. The bio-based content of the bio-based acrylate emulsion exceeds 25% according to the test result of ASTM D6866.

[0013] EP 2626397 Bl relates to polyacrylate-based pressure-sensitive adhesives.

[0014] WO 2022 / 033945 Al relates to an aqueous vinyl polymer dispersion including a hydrophilic vinyl oligomer, a hydrophobic vinyl oligomer and a vinyl polymer obtained by the emulsion polymerization of ethylenically unsaturated monomers from petrochemical or renewable origin.

[0015] In order to increase the percent biocarbon content (BCC) of an acrylic polymer while maintaining or improving the performance of resulting sealant compositions, a better approach is to polymerize acrylic monomers containing a certain degree of bio-renewable content. The challenge lies in producing an acrylic polymer from available bio-based acrylic monomers while simultaneously achieving the performance requirements for the intended application and the added sustainability target of a minimum BCC threshold of 22% as measured according to ASTM-6866-22 Method B.

[0016] SUMMARY

[0017] In this present invention, this problem has been unexpectedly solved by providing an aqueous dispersion formed by polymerizing certain bio-based monomers chosen from available bio-based acrylate monomers. The resulting elastomeric polymer composition is useful as a caulk or a sealant and therefore meets the goal of providing a bio-based acrylic caulk or sealant. This elastomeric polymer based on bio-based monomers surprisingly meets and, in some cases, exceeds, the performance of available petrochemical sourced elastomeric binders presently in use in caulks or sealants.

[0018] As used herein, the terms, “caulk” and “sealant” are interchangeable and refer to a hydrophobic and flexible material used to fill in the seams, gaps, holes, joints, spaces, or surfaces of a substrate or between two or more substrates, and to maintain a watertight, airtight, or steamtight adhesion during its lifetime.

[0019] Accordingly, a bio-based sealant composition is provided. The bio-based sealant meets the necessary physical requirements to be an effective sealant, while at the same time incorporating bio-based monomers in the binder. The sealant composition comprises, consists essentially of, or consists of:

[0020] A) at least one carrier comprising water;

[0021] B) an elastomeric polymer in a form of a dispersion in the carrier A) comprising, as polymerized monomers, based on a total weight of the elastomeric polymer: a) 5-95wt% of one or more C6-C10 alky l(meth)acry late monomers of Structure I: where R1is H or methyl and R2is a non-cyclic C6-C10 alkyl group; b) 5-95wt% of one or more C1-C5 alkyl(meth)acrylate monomers having structure II: where R3is H or methyl and R4is a C1-C5 alkyl group; c) 0.25-10wt% of one or more unsaturated ionic acid monomers; and d) 0.01-10wt% in total of one or more functional monomers each comprising at least one functional group comprising at least one selected from the group consisting of silane, hydroxyl, keto, amide, epoxy, and ureido functional groups; preferably at least one selected from the group consisting of silane, hydroxyl, keto, amide, and epoxy functional groups; more preferably at least one selected from the group consisting of silane, hydroxyl, keto, and amide functional groups, even more preferably at least one selected from the group consisting of silane and hydroxyl functional groups, most preferably silane functional groups; e) optionally from 0.01 to 1% of a monomer comprising two or more unsaturations; wherein: the elastomeric polymer B) has a Tg of from -60°C to 0°C, preferably from -60°C to -15°C, more preferably from -60°C to -25°C, most preferably from -60 to -40°C, calculated using the Fox equation; a homopolymer of the monomer a) has a Tg of 25°C or less; the monomer a) has a biocarbon content of 40% or more as determined by ASTM 6866-22 Method B; the monomer b) optionally has a biocarbon content of 5% or more as determined by ASTM 6866-22 Method B; and the biocarbon content of the elastomeric polymer B) is 22% or more as determined by ASTM 6866-22 Method B; C) at least one surfactant;

[0022] D) optionally at least one rheology modifier in an amount sufficient to raise a viscosity of the sealant to at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T- E-bar spindle;

[0023] E) optionally at least one filler in an amount sufficient to raise the viscosity of the sealant to at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T-E-bar spindle;

[0024] F) optionally at least one freeze-thaw stabilizer; such as polyols, diols, triols, ethylene glycol, propylene glycol, octylphenol ethoxylate, nonylphenol ethoxylate or combinations thereof.

[0025] G) optionally at least one adhesion promotor; such as functionalized silanes, alkoxysilanes, epoxysilanes, trialkoxysilanes, aminoalkylsilanes, aminoalkoxysilanes, organotitanates, or combinations thereof.

[0026] The viscosity of the sealant is at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T-E-bar spindle.

[0027] Also provided is the elastomeric polymer B) useful in a sealant in a form of an aqueous dispersion of the elastomeric polymer, comprising, consisting essentially of, or consisting of, as polymerized monomers, based on a total weight of the elastomeric polymer B): a) 5-95 wt.% of one or more C6-C10 alkyl(meth)acrylate monomers of Structure I: where R1is H or methyl and R2is a non-cyclic C6-C10 alkyl group; b) 5-95 wt.% of one or more C1-C5 alkyl(meth)acrylate monomers having structure II: where RJis H or methyl and R4is a C1-C5 alkyl group; c) 0.25-10 wt.% of one or more unsaturated ionic acid monomers; and d) 0.01-10 wt.% in total of one or more functional monomers each comprising at least one functional group comprising at least one of silane, hydroxyl, keto, amide, epoxy, or ureido functional groups; preferably at least one of silane, hydroxyl, keto, amide, or epoxy functional groups; more preferably silane, hydroxyl, keto, or amide functional groups, even more preferably silane, or hydroxyl functional groups, most preferably silane functional groups; e) optionally from 0.01 to 1% of a monomer comprising two or more unsaturations; wherein: the elastomeric polymer has a Tg of from -60°C to 0°C, preferably from -60°C to 15°C, more preferably from -60°C to -25°C, most preferably from -60 to 40°C, calculated using the Fox equation; a homopolymer of the monomer a) has a Tg of 25°C or less; the monomer a) has a biocarbon content of 40% or more as determined by ASTM 6866 22 Method B; the monomer b) optionally has a biocarbon content of 5% or more as determined by ASTM 6866-22 Method B; the biocarbon content of the elastomeric polymer is 22% or more as determined by ASTM 6866-22 Method B; and a 25 pm thick layer of the elastomeric polymer has a water contact angle of 70 degrees or more, preferably 75 degrees or more, more preferably 80 degrees or more, after drying for 72 hours at 25°C and 50% relative humidity.

[0028] DETAILED DESCRIPTION

[0029] The term “bio-based” as used herein means products or materials that are derived in whole or in part from biomass resources, i.e. biomass-derived. Biomass resources are organic materials that are available on a renewable or recurring basis such as crop residues, wood residues, grasses, and aquatic plants.. Products or materials, monomers, polymers, etc. containing any amount of bio-based content are referred to as “bio-based” or “biobased” Products made entirely from petrochemical resources are referred to as non-bio-based products.

[0030] Percent bio-based carbon content, also referred to herein as “biocarbon content” (BCC) is a measure of the amount of biomass-derived or bio-based carbon in a product as compared to its total organic carbon content (TOC). Percent bio carbon content is measured according to ASTM D6866-22, Method B. A product’s biocarbon content (BCC) is reported as a fraction of total organic carbon content (TOC) and not on its weight according to ASTM D6866-22 Method B.

[0031] Unless otherwise indicated, all percentages herein are weight percentages.

[0032] “Polymer” as used herein, is meant to include organic molecules with a weight average molecular weight higher than 20,000 g / mol, preferably higher than 50,000 g / mol, as measured by gel permeation chromatography.

[0033] As used herein, the terms, “caulk” and “sealant” are interchangeable and refer to a hydrophobic and flexible material / products used to fill in the seams, gaps, holes, joints, spaces, or surfaces of a substrate or between two or more substrates, and to maintain a watertight, airtight, or steamtight adhesion. Sealants (and caulks) are products intended to make airtight, watertight or steamtight seams, fill gaps, holes, joints, or provide a sealed surface between adjoining surfaces or edges of substrates. Desirably, sealants and caulks are water-resistant and flexible over time and do not embrittle upon repeated exposure to water and moist environments that also experience changes in temperature. Therefore, desirable properties are being hydrophobic (low water uptake), having good flexibility at low temperatures, and having good extension recovery. The present sealant composition(s) are unexpectedly water resistant, flexible, and have good adhesion to surfaces such as but not limited to, plastics, glass, wood, stone, ceramic, and / or metal.

[0034] A sealant composition is provided. The sealant composition includes the following components A)-G).

[0035] A) At least one carrier comprising water.

[0036] B) An elastomeric polymer in a form of a dispersion in the carrier A).

[0037] C) At least one surfactant.

[0038] D) Optionally at least one rheology modifier in an amount sufficient to raise a viscosity of the sealant to at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T- E-bar spindle.

[0039] E) Optionally at least one filler in an amount sufficient to raise the viscosity of the sealant to at least about 350,000 cps, preferably about 400,000 cp, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T-E-bar spindle.

[0040] F) Optionally at least one freeze-thaw stabilizer; such as polyols, diols, triols, ethylene glycol, propylene glycol, octylphenol ethoxylate, nonylphenol ethoxylate, or combinations thereof.

[0041] G) Optionally at least one adhesion promotor; such as functionalized silanes, such as alkoxysilanes, epoxysilanes, trialkoxysilanes, aminoalkylsilanes, aminoalkoxysilanes; organotitanates, or combinations thereof.

[0042] The viscosity of the sealant is at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T-E-bar spindle.

[0043] These caulks or sealants may have a pigment to binder ratio (P / B) of up to 8, preferably up to 7, more preferably up to 5.5 according to some embodiments. As used herein, the terms “pigment and filler” are interchangeable. The pigment to binder ratio is defined as the weight ratio of the sum of the weight of the pigments (pigments and fillers) to weight of the binder solids. Thus P / B = Mp / Mb, where Mp is the weight of the pigments and fillers and Mb is the weight of the binder solids. By “binder solids” is meant the weight of the elastomeric polymer B) exclusive of any water, solvent, or other ingredients in the sealant composition. Likewise, the weight of the pigment and filler is exclusive of water, solvent or other ingredients in the sealant composition.

[0044] The sealant may have an elongation of 50-700% measured according to ASTM D2370- 16R21. According to some embodiments, the sealant may have an elongation of at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or at least 100% measured according to ASTM D2370-16R21.

[0045] The sealant passes low temperature flexibility tests according to ASTM C734-15R19.

[0046] The sealant meets the USDA BioPreferred® certification requirement of BCC of 22% or more as measured according to ASTM-D6866-22 Method B. According to some embodiments, the sealant has a BCC of at least 22, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99 or up to 100% as measured according to ASTM-D6866-22 Method B.

[0047] The sealant must have sufficient extension recovery, which means that it is able to extend and then relax back. In other words, it has good stretch recovery, which is the opposite of brittleness which is needed to provide a tight, yet flexible watertight and airtight seal. This property of stretch recovery is measured by extension recovery. According to some embodiments, the sealant may have extension recovery of at least 50% as measured according to ASTM C736. According to some embodiments the sealant may have extension recovery of at least 55, 60, 65, 70, 75, 80, or at least 85%.

[0048] The sealant desirably has low water uptake, measured according to ASTM-D471-16. According to some embodiments, the water uptake is less than 20%. According to some embodiments, the water uptake is less than 19%, less than 18%, less than 17% or less than 10%.

[0049] The sealant may optionally include a plasticizer in some embodiments. If present, the plasticizer may comprise phthalates, benzoates, or bio-based plasticizers. According to some other embodiments, the sealant does not include or includes less than 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, or less than 0.001 wt.% of plasticizer, based on a total weight of the sealant composition. The sealant composition can be clear in some embodiments. This means that it does not include any opacifying pigment or filler, such as titanium dioxide for example. According to some other embodiments, the sealant does include a pigment. According to some other embodiments, the sealant does not include or includes less than 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, or less than 0.001 wt.% of titanium dioxide. According to some embodiments the sealant does not include or includes less than 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, or less than 0.001 wt.% of calcium carbonate, based on a total weight of the sealant composition.

[0050] A) Carrier including water

[0051] The sealant composition includes a carrier that itself includes at least water. At least some of the water may be present because the elastomeric polymer B) may be provided in the form of a waterborne emulsion. However, the sealant composition may include additional carrier components such as solvents and / or additional water. Nonlimiting examples of such additional carriers or solvents include mineral spirits, isopropanol, methanol, ethanol, toluene, or xylene.

[0052] The sealant composition includes from about 5 to about 60 wt%, about 5 to about 50 wt.%, preferably from about 10 to about 45 wt.%, more preferably from about 20 to about 40 wt.% of the carrier including water by weight of the sealant composition.

[0053] B) Elastomeric Polymer

[0054] The polymer B) is present in the sealant composition at from about 5 to about 95 wt.% by weight of the sealant composition. According to some embodiments, the sealant composition includes at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75., 80 or at least about 90 wt.% of polymer B) by weight of the sealant composition. According to some embodiments the sealant composition includes at most about 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 15, or at most about 5 wt.% of polymer B) by weight of the sealant composition.

[0055] The elastomeric polymer B) includes the following monomers as polymerized monomers. The amounts are recited based on a total weight of the elastomeric polymer B), exclusive of water or other solvent or components of the sealant composition. a) 5-95 wt.% of one or more C6-C10 alkyl (meth)acrylate monomers of Structure I: where R1is H or methyl and R2is a non-cyclic C6-C10 alkyl group. A homopolymer of the monomer a) has a Tg of 25°C or less and the monomer a) has a biocarbon content (BCC) of 40% or more as determined by ASTM 6866-22 Method B. b) 5-95 wt.% of one or more C1-C5 alkyl (meth)acrylate monomers having structure II: where R3is H or methyl and R4is a C1-C5 alkyl group.

[0056] The monomer b) optionally has a biocarbon content of 5% or more as determined by ASTM 6866-22 Method B. c) 0.25-10 wt.% of one or more unsaturated ionic acid monomers. d) 0.01-10 wt.% in total of one or more functional monomers each comprising at least one functional group comprising at least one selected from the group consisting of silane, hydroxyl, keto, amide, epoxy, and ureido functional groups; preferably at least one selected from the group consisting of silane, hydroxyl, keto, amide, and epoxy functional groups; more preferably at least one selected from the group consisting of silane, hydroxyl, keto, and amide functional groups, even more preferably at least one selected from the group consisting of silane and hydroxyl functional groups, most preferably silane functional groups. e) optionally from 0.01 to 1 wt.% of a monomer comprising two or more unsaturations. Unsaturations are carbon-carbon double bonds, capable of being free- radical polymerized. Accordingly, monomer e), if present, when polymerized provides crosslinks in the elastomeric polymer B).

[0057] Properties of the elastomeric polymer B):

[0058] The elastomeric polymer B) is a binder for the sealant. The polymer has the following properties.

[0059] The elastomeric polymer has a Tg of from -60°C to 0°C, preferably from -60°C to -15°C, more preferably from -60°C to -25°C, most preferably from -60 to -40°C, calculated using the Fox equation.

[0060] Biocarbon content (BCC) of the elastomeric polymer B) is 22% or more as determined by ASTM 6866-22 Method B. Desirably, the biocarbon content of the polymer B) is higher. According to some embodiments, the bio-carbon content of the polymer B) is at least 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or 100% as measured according to ASTM 6866- 22 Method B.

[0061] According to an embodiment, a 91pm thick layer of the elastomeric polymer B) has a water contact angle of 55 degrees or more, preferably 60 degrees or more, more preferably 65 degrees or more, after drying for 72 hours at 25°C and 50% relative humidity.

[0062] The elastomeric polymer B) is prepared in the form of an emulsion. Emulsion polymers and monomers useful to prepare polymeric emulsions or dispersions are known in the art (as described in texts on the subject such as “Emulsion Polymerization: Theory and Practice” by D. C. Blackley published by Wiley in 1975, “Emulsion Polymerization” by F. A. Bovey et al. published by Interscience Publishers in 1965, and “Emulsion Polymerization and Emulsion Polymers” by P.A. Lovell et al. published by Wiley Science in 1997).

[0063] The aqueous dispersion of the present invention comprises one or more emulsion polymers prepared by emulsion polymerization as is well known in the art.

[0064] The emulsion polymer may be prepared by emulsion polymerization of a mixture of monomers comprising the monomers a, b, c, d described above. The mixture of monomers may be added neat or as an emulsion in water; or added in one or more additions or continuously, linearly or nonlinearly, over the reaction period of preparing the emulsion polymer. A monomer emulsion containing all or some portion of the monomers to be polymerized may be prepared using the monomers, water and surfactants.

[0065] One or more surfactants surfactant may be added prior to, during, or after the polymerization of the monomer mixture, or combinations thereof. These surfactants may include anionic and / or nonionic emulsifiers. Examples of suitable nonionic emulsifiers include acyl, alkyl, oleyl, alkylaryl ethoxylates, and copolymers of ethylene oxide and propylene oxide. These products are commercially available, for example, under the name Genapol®, Lutensol® or Emulan®, Rhodasurf®, Tergitol™, and Pluronic™. They include, for example, C4 to C12 mono-, di-, and tri-alkylphenols ethopxylates (EO range 3 to 70), C8 to C18 fatty alcohol ethoxylates, Cl 1-C15 oxo-process alcohol ethoxylates, C16 to C18 fatty alcohol ethoxylates, Cl 1 oxoprocess alcohol ethylates, C13 Oxo-process alcohol ethoxylates, Some of commercially available anionic surfactants include sodium, potassium, and ammonium salts of linear and branched alcohol sulfates (e.g., Polystep® B-5, B-7 available from Stepan), alcohol ether sulfates (e.g., Disponil® FES 32, FES77 and FES993 available from BASF and Polystep® B-l 1, B-12, B- 19, B-20, B-22, B-23, B-40, B-41, etc. available from Stepan), linear and branched alkylbenzene sulfonates (e.g., Polystep® A-15 and A-16 available from Stepan), alpha olefin sulfonates (e.g., Polystep® A- 18 from Stepan and Rhodacal® DS-4 from Solvay), linear and branched alkyldiphenyloxide disulfonates (e.g., Dowfax™ 2A-1 available from The Dow Chemical Company and Calfax® DB-45 and Calfax® 16L-35 from Pilot Chemical); sulfosuccinates (e.g., Aerosol® A- 102, OTPG-75, MA-80I, etc. available from Solvay), alcohol phosphate esters (e.g., Rhodafac® RS-610 from Solvay and Polystep® P-11, P-12, P-13 from Stepan), di- and tristyrylphenol sulfates and phosphates (e.g., Polystep® TSP-16S and TSP-16S from Stepan). The amount of surfactants used can typically range from 0 to about 5%, from 0.1% to 3%, from 0.5 to 2%, by weight based on the total weight of monomer quantity.

[0066] Also suitable as stabilizers for the present dispersions are copolymerizable nonionic and anionic surfactants such as those disclosed in US2014 / 0243552. Other suitable copolmerizable surfactants are sold under the trade names Hitenol ® BC, Hitenol® KH, Hitenol® AR, Adeka Reasoap SR and Adeka Reasoap ER, Oximulsion® React.

[0067] The polymerization process may be thermally initiated or redox initiated emulsion polymerization. Examples of suitable free radical initiators include hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, ammonium and / or alkali metal persulfates, sodium perborate, perphosphoric acid, and salts thereof; potassium permanganate, and ammonium or alkali metal salts of peroxydisulfuric acid. The free radical initiators may be used typically at a level of 0.01 % to 3.0 % by weight, based on the total weight of monomers. Redox systems comprising the above described initiators coupled with a suitable reductant may be used in the polymerization process. Examples of suitable reductants include sodium sulfoxylate formaldehyde, ascorbic acid, isoascorbic acid, alkali metal and ammonium salts of sulfur containing acids, such as sodium sulfite, bisulfite, thiosulfate, hydrosulfite, sulfide, hydrosulfide or dithionite, formadinesulfinic acid, acetone bisulfite, glycolic acid, hydroxymethanesulfonic acid, glyoxylic acid hydrate, lactic acid, glyceric acid, malic acid, tartaric acid and salts of the proceeding acids. Metal salts of iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium, or cobalt may be used to catalyze the redox reaction. Chelating agents for the metals may optionally be used.

[0068] Chain transfer agents such as mercaptans, polymercaptan, polyhalogeno, and allyl compounds in the polymerization mixture may be used to regulate the molecular weight of the polymer. Examples of suitable chain transfer agents include 3 -mercaptopropionic acid, n-dodecyl mercaptan, t-dodecyl mercaptan, methyl 3-mercaptopropionate, butyl 3 -mercaptopropionate, Isooctyl 3-mercaptopropionate, benzenethiol, azelaic alkylmercaptan, or mixtures thereof. The chain transfer agent may be used in an effective amount to control the molecular weight of the emulsion polymer, for example, from zero to 1%, from 0.1% to 0.5 %, or from 0.15% to 0.4%, by weight based on the total weight of monomers used for preparing the emulsion polymer.

[0069] The temperature suitable for polymerization process may be lower than 100°C, in the range of from 30°C to 95°C, or in the range of from 50°C to 90°C. Emulsion polymerization may be seeded or unseeded. In another aspect of the present invention the aqueous acrylic emulsion polymer may be prepared by a multistage emulsion polymerization process, in which at least two stages differing in composition are polymerized in sequential fashion.

[0070] Monomers a) C6-C10 alkyl(meth)acrylate bio-based monomers

[0071] Monomer a) is one or more monomers of Structure I:

[0072] where R1is H or methyl and R2is a non-cyclic C6-C10 alkyl group. A homopolymer of the monomer a) has a Tg of 25°C or less. If a mixture of monomers a) is used in the polymer B), the Tg of the resulting copolymer of monomers a) is less than 25°C as calculated by the Fox equation. According to some embodiments the Tg of a homopolymer [or copolymer if more than one such monomer a) is present in polymer B)] is less than 25, 20, 15, 10, 5, 0, -5, -10, -20, -25, - 30, -35, -40, -45, -50, or less than -55°C.

[0073] The monomer a) or mixture of monomers a) has a biocarbon content (BCC) of 40% or more as determined by ASTM 6866-22 Method B. According to some embodiments, the monomer a) or mixture of monomers a) has a biocarbon content (BCC) of at least 45, 50, 55, 60, 65, 70, 75, 80 85, 90 95, 99, or up to 100% as determined by ASTM 6866-22 Method B.

[0074] The monomer a) or mixture of monomers a) are present in the polymer B) at 5-95 wt.% by dry weight of the polymer B). According to some embodiments, the polymer B) includes at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or at least 90 wt.% of monomer(s) a) by weight of the polymer B). According to some embodiments, the polymer B) includes at most 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 15, or at most 5 wt.% of monomer(s) a) by weight of the polymer B).

[0075] Suitable examples of monomer a) are non-cyclic C6-C10 (meth)acrylates or mixtures thereof in which the mono-or homopolymer has the Tg range recited above. For example, the monomer a) may be at least one of 2 octyl(meth)acrylate, 2-ethylhexyl(meth) acrylate, 2- propylheptyl (meth) acrylate, ethylbutyl(meth)acrylate, isomers of heptyl(meth)acrylate such as n-hepyl(meth)acrylate, isomers of hexyl(meth)acrylate, isomers of octyl(meth) acrylate, isomers of nonyl(meth)acylate, isomers of decyl(meth) acrylate or combinations thereof. Isomers of heptyl(meth)acrylate such as n-hepyl(meth)acrylate and isomers of octyl(meth) acrylate such as 2 octyl(meth)acrylate are preferred. More preferred are n-hepyl(meth)acrylate or 2- octyl(meth)acrylate. Still more preferred are n-hepyl acrylate or 2 octyl acrylate. Most preferred is 2-octyl acrylate. b) C1-C5 alkyl(meth)acrylate monomers

[0076] The C1-C5 alkyl (meth)monomers have structure II: where R3is H or methyl and R4is a C1-C5 alkyl group.

[0077] The monomer b) optionally has a biocarbon content of 5% or more as determined by ASTM 6866-22 Method B.

[0078] According to some embodiments, the monomer b) includes at least 5% biocarbon content as measured according to ASTM-D6866-22 Method B. Desirably, if the monomer b) is biobased, the biocarbon content of the monomer a) is higher. According to some embodiments the biocarbon content of the monomer b) is at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or 100% as measured according to ASTM 6866-22 Method B.

[0079] The polymer B) may include one of these monomers b), or more than one as a mixture. Non-limiting examples include the following, which may be bio-based or not, but are preferably bio-based. Non limiting examples of monomer b) are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl (meth) acrylate, butyl (meth)acrylates such as n-butyl(acrylate), sec-butyl (meth)acrylate, tert-butyl(meth)acrylate, isomers of pentyl(meth)acrylate, or combinations thereof. C1-C4 (meth)acrylates are preferred, more preferred are n-butyl (meth)acrylate, isobutyl(meth)acrylate, t-butyl (meth)acrylate, 2-methyl butyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, or a combination thereof, most preferred are ethyl(meth)acrylate, n-butyl (meth)acrylate, 2-methyl butyl(meth) acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, or combinations thereof. Especially preferred are bio- based versions of these monomers derived from bio-based (meth)acrylic acid and / or bio-based alcohols.

[0080] The monomer b) or mixture of monomers b) are present in the polymer B) at 5-95 wt.% by dry weight of the polymer B). According to some embodiments, the polymer B) includes at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or at least 90 wt.% of monomer / s) b) by weight of the polymer B). According to some embodiments the polymer B) includes at most 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 15, or at most 5 wt.% of monomer(s) b) by weight of the polymer B). c) Unsaturated ionic acid monomers

[0081] The polymer B) includes one or more unsaturated ionic acid monomers c). As used herein, “unsaturated” means the monomer includes at least one free-radical polymerizable carbon-carbon double bond.

[0082] Polymer B) may include from 0.25-10 wt.% by dry weight of polymer B) of the one or more unsaturated ionic acid monomers c). For example, the polymer B) may include at least 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.5, 1.75, 2, 2.25, 2.75, 3, 3.25, 3.5, 3.75, 4, 4.25, 4.5, 4.75, 5 ,5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, or at least 9.5 wt.% by dry weight of polymer B) of the one or more unsaturated ionic acid monomers c). The polymer may include at most 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 4.5, 4, 3.75, 3.5, 3.25, 3, 2.75, 2.5, 2.25, 2, 1.75, 1.5, 1, or at most 0.5 wt.% by dry weight of polymer B) of the one or more unsaturated ionic acid monomers c).

[0083] Acid-functionalized co-monomers c) may include but are not limited to carboxylic acid- functionalized co-monomers such as (meth)acrylic acid, beta-carboxyethyl acrylate, maleic acid, fumaric acid, itaconic acid, ethacrylic acid, crotonic acid, citraconic acid, cinnamic acid, and / or 1 ,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid.

[0084] A strong acid-functionalized co-monomer selected from phosphorus-based or sulfurbased acid-functionalized monomers or phosphate co-monomers may be used, including nonlimiting examples such as: phosphoalkyl (meth)acrylates or acrylates; phospho alkyl (meth)acrylamides or acrylamides; phosphoalkyl crotonates, phosphoalkyl maleates, phosphoalkyl fumarates, phosphodialkyl (meth)acrylates, phosphodialkyl crotonates, vinyl phosphates or (meth)allyl phosphate; phosphate esters of polypropylene glycol mono(meth)acrylate or polyethylene glycol mono(meth)acrylate; polyoxyethylene allyl ether phosphate, or vinyl phosphonic acid.

[0085] Sulfur-based co-monomers include, without limitation, vinyl- and allyl- sulfonic or sulfuric acids; sulfoethyl (meth)acrylate, aryl- sulfonic or sulfuric acids;

[0086] (meth)acrylamidoethane- sulfonic or sulfuric acids; methacrylamido-2-methyl propane- sulfonic or sulfuric acids; and the alkali metal salts of sulfonic and sulfuric acids.

[0087] Preferred acid monomers are (meth)acrylic acid, itaconic acid, methacrylamido-2-methyl propane sulfonic or sulfuric acid, more preferred are acrylic acid and methacrylic acid. d) Functional monomers

[0088] The polymer B) may include one or more functional monomers d). The total amount of functional monomer(s) d) present in the elastomeric polymer B) is from 0.01-10 wt.% by dry weight of the polymer B). According to some embodiments the elastomeric polymer B) includes at least 0.02, 0.03, 0.04, 0.0.5, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 1 , 2, 3, 4, 5, 6, 7, 8 or at least 9 wt.% of functional monomer(s) d). According to some embodiments, the polymer B) may include at most 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 4.5, 4, 3.75, 3.5, 3.25, 3, 2.75, 2.5, 2.25, 2, 1.75, 1.5, 1.25, 1, 0.75, 0.5, 0.25, 0.2, 0.15, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, or at most 0.05 wt.% by dry weight of polymer B) of the one or more functional monomer(s) d).

[0089] The functional monomer(s) d) include at least one functional group including at least one selected from the group consisting of silane, hydroxyl, keto, amide, epoxy, and ureido functional groups; preferably at least one selected from the group consisting of silane, hydroxyl, keto, amide, and epoxy functional groups; more preferably at least one selected from the group consisting of silane, hydroxyl, keto, and amide functional groups, even more preferably at least one selected from the group consisting of silane and hydroxyl functional groups, most preferably silane functional groups.

[0090] Non-limiting examples of suitable such functional monomers are nitrogen-containing comonomers which include but are not limited to: ureido (meth)acrylates, (meth)acrylates with at least one of urea and thiourea in the side chains; acrylic allophanes, aminoethyl acrylate and methacrylate; dimethylaminoethyl acrylate and methacrylate; diethylaminoethyl acrylate and methacrylate, dimethylaminopropyl acrylate and methacrylate; 3-dimethylamino-2,2- dimethylpropyl acrylate and methacrylate; aminoethyl methacrylate, N-(2- aminoethyl)(meth)acrylamide, N-(3-aminopropyl)(meth)acrylamide, 2-(diethylamino)ethyl (meth)acrylate, 2-(diisopropylamino)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, N- [2-(Diethylamino)ethyl](meth)acrylamide, 2-morpholinoethyl (meth)acrylate, N morpholinoethyl acrylate and methacrylate; 2-N-piperidinoethyl acrylate and methacrylate; N-(3- dimethylaminopropyl)acrylamide and -methacrylamide; N-dimethylaminoethylacrylamide and - methacrylamide; N-diethylaminoethylacrylamide and methacrylamide; N- (4morpholinomethyl)acrylamide and methacrylamide; vinylimidazole and also monoethylenically unsaturated derivatives of ethyleneurea, such as N (2 (meth)acryloyloxyethyl)ethyleneurea, N-(P-acrylamidoethyl)ethyleneurea, N-2 (allylcarbamato)aminoethylimidazolidinone, N-vinylethyleneurea, N-(3 allyloxy-2- hydroxypropyl)aminoethylethyleneurea, N-vinyloxyethyleneurea, N- methacryloyloxyacetoxyethylethyleneurea, N-(acrylamidoethylene)ethyleneurea, N- (methacrylamidoethylene)-ethyleneurea, 1 -(2-methacryloyloxyethyl)-2-imidazolidone, N- (methacrylamidoethyl)ethyleneurea, N-(2 methacrloyloxyethyl) ethylene urea, N-(2 methacryloxyacetamidoethyl)-N, N' ethyleneurea, allylalkyl ethylene urea, N- methacrylamidomethyl urea, N-methacryoyl urea, N-[3-(l,3-diazacryclohexan)-2-on- propyl]methacrylamide, 2-( 1 -imidazolyl)ethyl methacrylate, 2 (l-imidazolidin-2- on)ethylmethacrylate, and N-(methacrylamido)ethyl urea.

[0091] Other functional co-monomers include, but are not limited to, urethane methacrylate, acrylamide, methacrylamide, acrylonitrile, and vinyl cyanides, vinylpyrrolidone; polypropylene glycol mono(meth)acrylate or polyethylene glycol mono(meth)acrylate; silane-functionalized comonomers such as methacryloxypropyl trimethoxysilane, methacryloxypropyl triethoxysilane, methacryloxypropyl tripropoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Keto functional monomers include but are not limited to aceto acetoxy ethyl methacrylate (AAEM) and diacetone acrylamide (DAAM). Non-limiting examples of epoxy functional monomers are glycidyl(meth)acrylates, or epoxy (meth)acrylate. Preferred such functional monomers d) are those including at least one hydroxyl and / or silane group. Preferred examples are 2-hydroxy-3-phenoxypropyl methacrylate, (meth)acryloxyalkyl trialkyloxysilanes, vinyltrialkoxysilanes, hydroxyalkyl (meth)acrylates or combination thereof; preferably, 4-hydroxybutyl acrylate, methacryloxypropyl trimethoxysilane, methacryloxypropyl triethoxysilane, acryloxypropyl trimethoxysilane, acryloxypropyl triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and combinations thereof, more preferably, 2-hydroxyethyl acrylate, 2 -hydroxy ethyl methacrylate, 3 -hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl(meth)acrylate, or combinations thereof. e) Monomer including two or more unsaturations

[0092] The polymer B) may optionally include from 0.01 to 1% of a monomer e) including two or more unsaturations. As is known in the art, unsaturations are carbon-carbon double bonds, capable of being free- radical polymerized. Accordingly, monomer e), if present, when polymerized, provides crosslinks in the elastomeric polymer B). Nonlimiting examples are crosslinkers with two or more sites of ethylenic unsaturation, such as tripropylene glycol diacrylate, 1,3 -butylene glycol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane tri(meth)acrylate, 1,3-butyleneglycol dimethacrylate, 1,4- butyleneglycol dimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, 1,10-decanediol diacrylate, ethoxylated (2) bisphenol A diacrylate, 1,3 -propanediol dimethacrylate, 1 ,4-butanediol diacrylate, 1 ,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol dimethacrylate, dially phthalate, ally methacrylate, divinylbenzene, or combinations thereof.

[0093] Preferably ethylene glycol dimethacrylate, 1 ,6-hexandiol diacrylate, diethylene glycol dimethacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, more preferably ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, trimethylpropane triacrylate or combinations thereof.

[0094] According to some embodiments the elastomeric polymer B) includes at least 0.02, 0.03, 0.04, 0.0.5, 0.06, 0.07, 0.08, or at least 0.09 wt.% of the one or more monomer(s) including two or more unsaturations e). According to some embodiments, the polymer B) may include at most 0.08, 0.07, 0.06, 0.05, or at most 0.04 wt.% by dry weight of polymer B) of the one or more monomer(s) including two or more unsaturations e).

[0095] C) Surfactant

[0096] The sealant composition may include at least one surfactant or dispersant. Non- limiting examples include any known surfactants, such as ammonium, alkali metal, alkaline earth metal, and lower alkyl quaternary ammonium salts of sulfosuccinates, salts of fatty rosin and naphthenic acids, condensation products of sulfonic acid and formaldehyde, carboxylic polymers, higher fatty alcohol sulfates, aryl sulfonates, alkyl sulfonates, alkylaryl sulfonates, alkylphenoxy polyethoxyethanols or ethylene oxide derivatives of long chain carboxylic acids, as well as polyacid dispersants, such as polyacrylic acid or polymethylacrylic acid or salts thereof, and hydrophobic co-polymeric dispersants, such as co-polymers of acrylic acid, methacrylic acid, or maleic acid with hydrophobic monomers. Other surfactants may be sodium sulfonate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, potassium stearate, sodium dioctyl sulfosuccinate, sodium dodecyldiphenyloxide disulfonate, onylphenoxyethylpolyethoxyethyl sulfate ammonium salt, sodium styrene sulfonate, sodium dodecyl allyl sulfosuccinate, sodium or ammonium salts of phosphate esters of ethoxylated nonylphenol, sodium octoxynol-3-sulfonate, sodium cocoyl sarcocinate, sodium 1 -alkoxy-2 -hydroxypropyl sulfonate, sodium a-olefin (Cl 4- C16)sulfonate, sulfates of hydroxyalkanols, tetrasodium N-(l,2-dicarboxy ethyl)-N- octadecylsulfosuccinamate, disodium N-octadecylsulfosuccinamate, disodium alkylamido polyethoxy sulfosuccinate, disodium ethoxylated nonylphenol half ester of sulfosuccinic acid and the sodium salt of tert-octylphenoxyethoxypolyethoxyethyl sulfate and combinations thereof. Also suitable are acyl, alkyl, oleyl, and alkylaryl ethoxylates. These products are commercially available, for example, under the tradename Genapol™, Lutensol™ or Emulan™. They include, for example, ethoxylated mono-, di-, and tri-alkylphenols (EO degree: 3 to 80, alkyl substituent radical: C4 to C12) and also ethoxylated fatty alcohols (EO degree: 3 to 80; alkyl radical: C8 to C36), especially Cl 0-C 14 fatty alcohol (EO 3-80) ethoxylates, Cl 1-C15 oxo-process alcohol (EO 3-80) ethoxylates, C16-C18 fatty alcohol (EO 3-80) ethoxylates, Cl l oxo-process alcohol (EO 3-80) ethoxylates, Cl 3 oxo-process alcohol (EO 3-80) ethoxylates, polyoxyethylenesorbitan monooleate with 20 ethylene oxide groups, copolymers of ethylene oxide and propylene oxide having a minimum ethylene oxide content of 10% by weight, the polyethylene oxide (EO 3-80) ethers of oleyl alcohol, and the polyethene oxide (EO 3-80) ethers of nonylphenol. Particularly suitable are the polyethylene oxide (EO 3-80) ethers of fatty alcohols, more particularly of oleyl alcohol, stearyl alcohol or Cl 1 alkyl alcohols. Preferred surfactants are salts of sulfosuccinates, alkylaryl sulfonates, and alkyl alcohol ethoxylates (EO 5-40). More preferred surfactants are dihexyl sulfosuccinate, dioctyl sulfosuccinate, dodecylbenzene sulfonate, tridecyl alcohol ethoxylates (EO 10-40).

[0097] D) Rheology modifier

[0098] The sealant composition may optionally include at least one rheology modifier. The rheology modifier is intended to raise the viscosity of the sealant. Although pigments or particulate additives can also increase the viscosity of the sealant, these rheology modifiers D) are understood not to include pigments, particulates, or fibers.

[0099] The amount of the rheology modifier, if present, is effective, either alone, or in combination with a filler, to raise the viscosity of the sealant composition to at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T-E-bar spindle. According to some embodiments, the sealant composition may include from 0 to 2 wt. %, preferably from 0 to 1.5 wt.%, more preferably from 0 to 0.5 wt.%. of rheology modifier based on a total weight of the composition.

[0100] Several illustrative examples of the rheology modifier may include, without limitation, celluloses, gums, associative and non- associative polymers, polyamides, calcium sulfonate derivatives, modified polyureas, castor oil derivatives, hydroxyethylcellulose, carboxymethylcellulose, hydrophobically-modified ethylene oxide urethane (HEUR) polymers, hydrophobically-modified alkali soluble or swellable emulsion (HASE) polymers, hydrophobically-modified hydroxyethyl celluloses (HMHECs), hydrophobically-modified polyacrylamide, alkali soluble emulsions (ASE), and combinations thereof.

[0101] E) Filler

[0102] The sealant composition may optionally include at least one filler in an amount, either alone or together with the rheology modifier (if present), sufficient to raise the viscosity of the sealant to at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T- E-bar spindle.

[0103] If present, the sealant composition includes 5-95 wt.% of fillers and / or pigments by weight of the sealant composition. According to some embodiments, the sealant composition includes at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or at least 90 wt.% of fillers and / or pigments by weight of the sealant composition. According to some embodiments the sealant composition includes at most 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20 15, or at most 5 wt.% of fillers and / or pigments by weight of the sealant composition.

[0104] Non-limiting examples of fillers include fibers, such as glass, aramid or polyester fibers; carbon black; colored organic pigments; metal oxides, such as titanium dioxide, zinc oxide, or iron oxide; as well as organic dyes; or combinations thereof. Examples of fillers may include, but not be limited to, zinc oxide, zinc hydroxide, magnesium silicate, calcium silicate, fumed silica, amorphous silica, vapor phase silica, colloidal silica, alumina, aluminum hydroxide, zirconium oxide, cerium oxide, calcium sulfate, barium sulfate, zinc carbonate, calcium carbonate, nepheline syenite, feldspar, diatomaceous earth, talc, aluminosilicates, silica, alumina, clay, kaolin, mica, pyrophyllite, perlite, baryte, Wollastonite, triphenyl phosphate, and combinations thereof. The terms “filler” and “pigment” are used interchangeably herein.

[0105] F) Freeze-thaw stabilizer

[0106] The sealant composition may optionally include at least one freeze-thaw stabilizer. A freeze-thaw stabilizer is an additive intended to depress the freezing point of the components in the sealant composition and therefore increase the sealant’s resistance to freezing. It also allows the sealant to remain fluid upon thawing. Non-limiting examples are polyols, diols, triols, ethylene glycol, propylene glycol, octylphenol ethoxylate, nonylphenol ethoxylate, or combinations thereof.

[0107] According to some embodiments, the sealant composition includes from 0 to 5 wt.%, preferably from 0 to 3 wt.%, more preferably from 0 to 1 wt.% of a freeze-thaw stabilizer, based on a total weight of the composition. G) Adhesion promotor

[0108] The sealant composition may optionally include at least one adhesion promotor; such as functionalized silanes, alkoxysilanes, epoxysilanes, trialkoxysilanes, aminoalkylsilanes, aminoalkoxysilanes, organotitanates; or combinations thereof.

[0109] As used herein, an adhesion promotor is an additive that is used to enhance the bonding between a substrate and the sealant. These are also referred to as coupling agents. Such additives work by providing a reactive surface for an adhesive material, i.e., the sealant composition, to attach to, thereby increasing the strength and durability of the bond between the sealant composition and a substrate. Non-limiting examples of suitable adhesion promotors are hydrolysable silanes, epoxy silanes, functional silanes bearing aminoalkyl, mercaptoalkyl, epoxyalkyl, ureido (meth)acrylate and isocyanurate groups. Within these classes, the preferred adhesion promoters are glycidal epoxy functional silanes, and amino alkoxysilanes, such as but not limited to aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, or combinations thereof.

[0110] According to some embodiments, the sealant composition includes from 0 to 1 wt.%, preferably from 0 to 0.5 wt.%, more preferably from 0 to 0.1 wt.% of an adhesion promotor, based on a total weight of the composition.

[0111] Non-limiting Aspects of the invention are summarized as follows.

[0112] Aspect 1 : A sealant composition comprising:

[0113] A) at least one carrier comprising water;

[0114] B) an elastomeric polymer in a form of a dispersion in the carrier A) comprising, as polymerized monomers, based on a total weight of the elastomeric polymer:

[0115] a) 5-95 wt.% of one or more C6-C10 alkyl(meth)acrylate monomers of Structure where R1is H or methyl and R2is a non-cyclic C6-C10 alkyl group; b) 5-95 wt.% of one or more C1-C5 alkyl(meth)acrylate monomers having structure II: where R3is H or methyl and R4is a C1-C5 alkyl group; c) 0.25-10 wt.% of one or more unsaturated ionic acid monomers; d) 0.01-10 wt.% in total of one or more functional monomers each comprising at least one functional group selected from the group consisting of silane, hydroxyl, amide, ureido, amine, epoxy, keto functional groups, or combinations thereof; and e) optionally from 0.01 to 1% of a monomer comprising two or more unsaturations; wherein: a homopolymer of the monomer a) has a Tg of 25°C or less; the monomer a) has a biocarbon content of 40% or more as determined by ASTM 6866- 22 Method B; the monomer b) optionally has a biocarbon content of 5% or more as determined by ASTM 6866-22 Method B; and the elastomeric polymer B) has a Tg of from -60°C to 0°C, preferably from -60°C to -15°C, more preferably from -60°C to -25°C, most preferably from -60 to -40°C, calculated using the Fox equation; the biocarbon content of the elastomeric polymer B) is 22% or more as determined by ASTM 6866-22 Method B;

[0116] C) at least one surfactant;

[0117] D) optionally at least one rheology modifier in an amount sufficient to raise a viscosity of the sealant to at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T- E-bar spindle;

[0118] E) optionally at least one filler in an amount sufficient to raise the viscosity of the sealant to at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T-E-bar spindle;

[0119] F) optionally at least one freeze-thaw stabilizer;

[0120] G) optionally at least one adhesion promotor; wherein the viscosity of the sealant composition is at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T-E-bar spindle.

[0121] Aspect 2: The sealant composition of Aspect 1, wherein the sealant composition has a biocarbon content of about 20% or more, preferably about 22% or more, more preferably about 25% or more, most preferably about 40% or more, as determined by ASTM 6866-22 Method B. Aspect 3: The sealant composition of Aspect 1 or Aspect 2, wherein a 91 m thick layer of the elastomeric polymer B) has a water contact angle of 55 degrees or more, preferably 60 degrees or more, more preferably 65 degrees or more, after drying for 72 hours at 25°C and 50% relative humidity.

[0122] Aspect 4: The sealant composition of any of Aspects 1-3, wherein the sealant composition has a water uptake of 20 wt.% or less, preferably of 19 wt.% or less, more preferably of 18 wt.% or less, as determined by ASTM D471-16.

[0123] Aspect 5: The sealant composition of any of Aspects 1-4, comprising from 5 to 95 wt.% of at least one filler.

[0124] Aspect 6: The sealant composition of any of Aspects 1-5, wherein the monomer a) comprises C6-C8 (meth) acrylates, preferably C6-C8 acrylates, most preferably, C7 acrylates, C8 acrylates, or combinations thereof.

[0125] Aspect 7: The sealant composition of any of Aspects 1-6, wherein the monomer b) comprises at least one of C1 -C4 (meth)acrylates, preferably C1-C4 acrylates, more preferably n- butyl acrylate, 2-isobutyl acrylate, t-butyl acrylate, 2-methyl butyl acrylate, ethyl acrylate, methyl acrylate, or a combination thereof.

[0126] Aspect 8: The sealant composition of any of Aspects 1-7, wherein the unsaturated ionic acid monomer c) comprises at least one of monocarboxylic acids, dicarboxylic acids, sulfur acids, phosphate acids, (meth)acrylic acids, or combinations thereof, preferably monocarboxylic acids, (meth) acrylic acids or combinations thereof, more preferably (meth)acrylic acids.

[0127] Aspect 9: The sealant composition of any of Aspects 1-8, wherein the functional monomer d) comprises at least one functional group selected from the group consisting of silane, hydroxyl, keto, amide, epoxy functional groups, or combinations thereof; preferably at least one selected from the group consisting of silane, hydroxyl, keto, amide functional groups, or combinations thereof; more preferably at least one selected from the group consisting of silane and hydroxyl functional groups, or a combination thereof; most preferably silane functional groups. Aspect 10: The sealant composition of any of Aspects 1-9, wherein the functional monomer d) comprises at least one of (meth)acryloxyalkyl trialkyloxysilanes, vinyltrialkoxysilanes, hydroxyalkyl (meth)acrylates or combination thereof; preferably methacryloxypropyl trimethoxysilane, methacryloxypropyl triethoxysilane, acryloxypropyl trimethoxysilane, acryloxypropyl triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or combinations thereof, more preferably, 2-hydroxyethyl acrylate, 2 -hydroxy ethyl methacrylate, 3- hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl(meth)acrylate, or combinations thereof.

[0128] Aspect 11: The sealant composition of any of Aspects 1-10, wherein the elastomeric polymer B) comprises the monomer e) comprising two or more unsaturations, preferably comprising two or more (meth)acrylate groups.

[0129] Aspect 12: The sealant composition of any of Aspects 1-11, comprising the at least one rheology modifier.

[0130] Aspect 13: The sealant composition of any of Aspects 1-12, comprising the at least one freeze-thaw stabilizer, the freeze-thaw stabilizer comprising at least one of polyols, diols, triols, ethylene glycol, propylene glycol, octylphenol ethoxylate, or combination thereof, more preferably ethylene glycol, propylene glycol, octylphenol ethoxylate, or combinations thereof.

[0131] Aspect 14: The sealant composition of any of Aspects 1-13, comprising the at least one adhesion promotor, preferably at least one of functionalized silanes, alkoxy silanes, epoxysilanes, trialkoxysilanes, aminoalkylsilanes, aminoalkoxysilanes, organotitanates, or combinations thereof, more preferably epoxysilanes, trialkoxysilanes, glycidal epoxy functional silane, or combinations thereof, most preferably aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, or combinations thereof.

[0132] Aspect 15: The sealant composition of any of Aspects 1-14, comprising the at least one filler.

[0133] Aspect 16: An elastomeric polymer useful in a sealant in a form of an aqueous dispersion of the elastomeric polymer, comprising, as polymerized monomers, based on a total weight of the elastomeric polymer: a) 5-95 wt.% of one or more C6-C10 alkyl(meth)acrylate monomers of Structure where R1is H or methyl and R2is a non-cyclic C6-C10 alkyl group; b) 5-95 wt.% of one or more C1-C5 alkyl(meth)acrylate monomers having structure II: where R3is H or methyl and R4is a C1-C5 alkyl group; c) 0.25-10 wt.% of one or more unsaturated ionic acid monomers; and d) 0.01-10 wt.% in total of one or more functional monomers each comprising at least one functional group comprising at least one of silane, hydroxyl, keto, amide, epoxy, or ureido functional groups; preferably at least one of silane, hydroxyl, keto, amide, or epoxy functional groups; more preferably silane, hydroxyl, keto, or amide functional groups, even more preferably silane, or hydroxyl functional groups, most preferably silane functional groups; e) optionally from 0.01 to 1% of a monomer comprising 2 or more unsaturations; wherein; the elastomeric polymer has a Tg of from -60°C to 0°C, preferably from -60°C to -15°C, more preferably from -60°C to -25°C, most preferably from -60 to -40°C, calculated using the Fox equation; a homopolymer of the monomer a) has a Tg of 25°C or less; the monomer a) has a biocarbon content of 40% or more as determined by ASTM 6866-22 Method B; the monomer b) optionally has a biocarbon content of 5% or more as determined by ASTM 6866-22 Method B; the biocarbon content of the elastomeric polymer is 22% or more as determined by ASTM 6866-22 Method B; and a 25pm thick layer of the elastomeric polymer has a water contact angle of 70 degrees or more, preferably 75 degrees or more, more preferably 80 degrees or more, after drying for 72 hours at 25°C and 50% relative humidity.

[0134] Aspect 17: The elastomeric polymer of Aspect 16, wherein: monomer a) comprises a C7-C8 (meth)acrylate or combination thereof; monomer b) comprises a C2-C4 (meth)acrylate, or a combination thereof; monomer c) comprises (meth) acrylic acid; monomer d) comprises silane-functional monomer, a hydroxy functional monomer, or a combination thereof; and monomer e) comprises at least one di(meth) acrylate.

[0135] Aspect 18: Use of the elastomeric polymer according to Aspect 16 or Aspect 17 as a sealant. EXAMPLES

[0136] Methods:

[0137] Water contact angle measurement procedure

[0138] A microscope slide measuring 1 x 3 inches was coated with a latex approximately 6 mils thick. After drying at room temperature for 3 days, the static contact angle was measured with a Rame-hart 250 goniometer.

[0139] Glass transition temperature:

[0140] Glass transition temperature of homopolymers may be measured using differential scanning calorimetry as described in ASTM D3418-21. Glass transition temperatures of copolymers are determined with the Fox equation.

[0141] Low temperature flex testing procedure:

[0142] Following exactly ASTM C734-15R19 procedures, a sealant sample with dimensions 0P / 2 x 5 x 1 / 8 inches was laid out on an aluminum panel. The sealant was cured for 2 days at room temperature, and then placed in a Weatherometer for 53 hours. The sealant was then placed in a -17°C freezer for 4 hours. Afterwards, the sealant is bent over a 1 inch mandrel at 90° in one second. Any cracks or adhesion loss were rated as a “Fail”. If the sample had no cracks or adhesion loss, then it was rated as a “Pass”.

[0143] Extension recovery testing procedure

[0144] Following exactly ASTM C736-12R22 procedures, a sealant sample with dimensions of 0.5 inches X 0.5 inches X 2 inches was laid out between two parallel plates of glass and aluminum. The sealant was cured at room temperature for 7 days, and then at 50°C for 7 days. The sealant was then extended 25% and held at that distance for 5 minutes. Any adhesive or cohesive failure was observed. Then the sealant was relaxed and placed on the benchtop for 2 hours. The distance between the parallel glass and aluminum plates was measured. If this distance measured is greater than or equal to 75% of the original sample length, then it passes ASTM C736-12R22 specifications. Elongation testing procedure

[0145] Following exactly ASTM D2370-16R21 procedures, sealant sample with a wet thickness of 40 mils was dried at room temperature for 2 weeks. The dried sealant sample was stretched with an Instron 3366 tensile tester until it ruptures. The resulting stress-strain curve was evaluated, and the elongation reported is the maximum strain from the curve as a percentage of the original sample length.

[0146] Water uptake testing procedure

[0147] Following exactly ASTM D0471 AR21 procedures, a sealant sample with a wet thickness of 40 mils was dried at room temperature for 2 weeks. A small portion of the sealant sample, with dimensions of 1 inch by 1 inch, was submerged into deionized water for 1 week at room temperature. The change in mass before and after water submersion was reported as water uptake (as a percentage of the initial mass).

[0148] The following latex binders were prepared.

[0149] Example 1 : (Comparative - petroleum based, not of the invention)

[0150] 392 grams of deionized water and 1.8 grams of sodium dihexyl sulfosuccinate were charged into a reactor equipped with a stirrer, reflux condensers, thermocouples, and stainless steel feed lines. The reaction mixture was heated to 81 °C. Then, a 30% solution of ammonium persulfate (19.7 grams) was then added to the reactor in one portion, and then stirred for 5 minutes. A monomer emulsion consisting of 126.7 grams of water, 24.4 grams of disodium succinate alkyl polyoxyethylene ether monoester sulfonate, , 0.6 grams of methacryl oxypropyl trimethoxysilane, 12.4 grams of 2-hydroxyethyl acrylate, 24 grams of methacrylic acid, 245 grams of 2-ethylhexyl acrylate, 943 grams of ethyl acrylate, and 0.6 grams of 1,6 -hexanediol diacrylate, was added over the course of 300 minutes. Seventy minutes after the start of the monomer emulsion addition, a solution of ammonium persulfate (1.7 grams) and sodium bicarbonate (4 grams) in water was added over the course of 230 minutes. After adding 60% of the monomer emulsion, a polystyrene seed latex (Arkema) was added in one portion. After adding all of the monomer emulsion, the reaction mixture was stirred for another 40 minutes at 81 °C and then cooled to 70°C. A solution of tert-butyl hydroperoxide in water and a solution of sodium metabisulfite in water was fed concurrently over the course of 120 minutes. Then the reaction mixture was cooled to room temperature. The solids content of the dispersion was 62.8%.

[0151] Example 2 (Bio-based of the invention)

[0152] Procedures similar to Example 1 were followed, except the following monomer levels were used instead: 245 grams of 2-ethylhexyl acrylate, 477 grams of ethyl acrylate, and 465 grams of bio-based 2-octyl acrylate.

[0153] Example 3 (Bio-based - comparative, not of the invention)

[0154] Procedures similar to Example 2 was followed, except the amount of methacryloxypropyl trimeth oxy silane and 1,6- hexanediol diacrylate was reduced to 0 grams.

[0155] Example 4 (Bio-based - comparative, not of the invention):

[0156] Procedures similar to Example 2 is followed, except the amount of methacryloxypropyl trimethoxysilane and 1,6- hexanediol diacrylate was increased to 5.9 grams each.

[0157] Example 5 (Bio-based, lauryl methacrylate - comparative, not of the invention):

[0158] Procedures similar to Example 1 is followed, except the following monomer levels were used instead: 245 grams of 2-ethylhexyl acrylate, 514 grams of ethyl acrylate, and 428 grams of bio-based lauryl methacrylate. Lauryl methacrylate monomer residuals could not be brought down to levels safe for handling despite multiple treatments of tert-butyl hydroperoxide and sodium metabisulfite. Therefore, it was discarded as hazardous waste.

[0159] The compositions of Examples 1-5 are shown in Table 1 below.

[0160]

[0161] Example 6: Sealant / caulk formulation preparation (ASTM C834-17)

[0162] To a 1 quart double planetary mixer were added the components in Table 2, in the sequence listed. Agitation was adjusted manually to achieve good mixing. After the addition of Ti-Pure, the mixture was stirred for 30 minutes before adding the rest of the components. The properties of the caulks made with Examples 1-5 latex binders were measured and are shown in Table 3.

[0163] The above results show that silane functional monomer and crosslinker (diacrylate) appear to provide improved properties for water uptake (lower), and better extension recovery (higher). The improvement in extension recovery was evident at from 0.049wt% to less than 0.48wt% of each of the silane and the crosslinking monomer. However, excessive amounts of these comonomers provided reduced elongation above those amounts and may have contributed to cracking during cure. Example 2, which contains bio-based monomers, had similar performance as Comparative Example 1, which contained only petroleum-derived monomers. Surprisingly, the samples with the bio-based monomer had lower water uptake and improved low temperature flex than the petroleum based sample.

[0164] Within this specification embodiments have been described in a way which enables a clear and concise specification to be written, but it is intended and will be appreciated that embodiments may be variously combined or separated without departing from the invention. For example, it will be appreciated that all preferred features described herein are applicable to all aspects of the invention described herein.

[0165] The foregoing description of various forms of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Numerous modifications or variations are possible in light of the above teachings. The forms discussed were chosen and described to provide the best illustration of the principles of the invention and its practical application to thereby enable one of ordinary skill in the art to utilize the invention in various forms and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.

Claims

What is claimed is:

1. A sealant composition comprising:A) at least one carrier comprising water;B) an elastomeric polymer in a form of a dispersion in the carrier A) comprising, as polymerized monomers, based on a total weight of the elastomeric polymer: a) 5-95 wt.% of one or more C6-C10 alkyl(meth)acrylate monomers of Structure I:where R1is H or methyl and R2is a non-cyclic C6-C10 alkyl group; b) 5-95 wt.% of one or more C1-C5 alkyl(meth)acrylate monomers having structure II:where R3is H or methyl and R4is a C1-C5 alkyl group; c) 0.25-10 wt.% of one or more unsaturated ionic acid monomers; d) 0.01-10 wt.% in total of one or more functional monomers each comprising at least one functional group selected from the group consisting of silane, hydroxyl, amide, ureido, amine, epoxy, keto functional groups, or combinations thereof; and e) optionally from 0.01 to 1% of a monomer comprising two or more unsaturations;wherein; a homopolymer of the monomer a) has a Tg of 25°C or less; the monomer a) has a biocarbon content of 40% or more as determined by ASTM 6866- 22 Method B; the monomer b) optionally has a biocarbon content of 5% or more as determined by ASTM 6866-22 Method B; and the elastomeric polymer B) has a Tg of from -60°C to 0°C, preferably from -60°C to -15°C, more preferably from -60°C to -25°C, most preferably from -60 to - 40°C, calculated using the Fox equation; the biocarbon content of the elastomeric polymer B) is 22% or more as determined by ASTM 6866-22 Method B;C) at least one surfactant;D) optionally at least one rheology modifier in an amount sufficient to raise a viscosity of the sealant to at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T- E-bar spindle;E) optionally at least one filler in an amount sufficient to raise the viscosity of the sealant to at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T-E-bar spindle;F) optionally at least one freeze-thaw stabilizer;G) optionally at least one adhesion promotor; wherein the viscosity of the sealant composition is at least about 350,000 cps, preferably about 400,000 cps, more preferably about 450,000 cps, most preferably about 500,000 cps, as measured by a Helipath viscometer using T-E-bar spindle.

2. The sealant composition of claim 1, wherein the sealant composition has a biocarbon content of about 20% or more, preferably about 22% or more, more preferably about 25% or more, most preferably about 40% or more, as determined by ASTM 6866-22 Method B.

3. The sealant composition of claim 1 or claim 2, wherein a 91pm thick layer of the elastomeric polymer B) has a water contact angle of 55 degrees or more, preferably 60 degrees or more, more preferably 65 degrees or more, after drying for 72 hours at 25°C and 50% relative humidity.

4. The sealant composition of any of claims 1-3, wherein the sealant composition has a water uptake of 20 wt.% or less, preferably of 19 wt.% or less, more preferably of 18 wt.% or less, as determined by ASTM D471-16.

5. The sealant composition of any of claims 1-4, comprising from 5 to 95 wt.% of at least one filler.

6. The sealant composition of any of claims 1-5, wherein the monomer a) comprises C6-C8 (meth) acrylates, preferably C6-C8 acrylates, most preferably, C7 acrylates, C8 acrylates, or combinations thereof.

7. The sealant composition of any of claims 1-6, wherein the monomer b) comprises at least one of C1-C4 (meth)acrylates, preferably C1-C4 acrylates, more preferably n-butyl acrylate, 2- isobutyl acrylate, t-butyl acrylate, 2-methyl butyl acrylate, ethyl acrylate, methyl acrylate, or a combination thereof.

8. The sealant composition of any of claims 1-7, wherein the unsaturated ionic acid monomer c) comprises at least one of monocarboxylic acids, dicarboxylic acids, sulfur acids, phosphate acids, (meth)acrylic acids, or combinations thereof, preferably monocarboxylic acids, (meth) acrylic acids or combinations thereof, more preferably (meth)acrylic acids.

9. The sealant composition of any of claims 1-8, wherein the functional monomer d) comprises at least one functional group selected from the group consisting of silane, hydroxyl, keto, amide, epoxy functional groups, or combinations thereof; preferably at least one selected from the group consisting of silane, hydroxyl, keto, amide functional groups, or combinations thereof; more preferably at least one selected from the group consisting of silane and hydroxyl functional groups, or a combination thereof; most preferably silane functional groups.

10. The sealant composition of any of claims 1-9, wherein the functional monomer d) comprises at least one of (meth)acryloxyalkyl trialkyloxysilanes, vinyltrialkoxysilanes, hydroxyalkyl (meth)acrylates or combination thereof; preferably methacryloxypropyl trimethoxysilane, methacryloxypropyl triethoxysilane, acryloxypropyl trimethoxysilane, acryloxypropyl triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or combinations thereof, more preferably, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3 -hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl(meth)acrylate, or combinations thereof.

11. The sealant composition of any of claims 1-10, wherein the elastomeric polymer B) comprises the monomer e) comprising two or more unsaturations, preferably comprising two or more (meth)acrylate groups.

12. The sealant composition of any of claims 1-11, comprising the at least one rheology modifier.

13. The sealant composition of any of claims 1-12, comprising the at least one freeze-thaw stabilizer, the freeze-thaw stabilizer comprising at least one of polyols, diols, triols, ethylene glycol, propylene glycol, octylphenol ethoxylate, or combination thereof, more preferably ethylene glycol, propylene glycol, octylphenol ethoxylate, or combinations thereof.

14. The sealant composition of any of claims 1-13, comprising the at least one adhesion promotor, preferably at least one of functionalized silanes, alkoxysilanes, epoxysilanes, trialkoxysilanes, aminoalkylsilanes, aminoalkoxysilanes, organo titanates, or combinations thereof, more preferably epoxysilanes, trialkoxysilanes, glycidal epoxy functional silane, or combinations thereof, most preferably aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, or combinations thereof.

15. The sealant composition of any of claims 1-14, comprising the at least one filler.

16. An elastomeric polymer useful in a sealant in a form of an aqueous dispersion of the elastomeric polymer, comprising, as polymerized monomers, based on a total weight of the elastomeric polymer: a) 5-95 wt.% of one or more C6-C10 alkyl(meth)acrylate monomers of Structure I:where R1is H or methyl and R2is a non-cyclic C6-C10 alkyl group;b) 5-95 wt.% of one or more C1-C5 alkyl(meth)acrylate monomers having structure II:where R3is H or methyl and R4is a C1-C5 alkyl group; c) 0.25-10 wt.% of one or more unsaturated ionic acid monomers; and d) 0.01-10 wt.% in total of one or more functional monomers each comprising at least one functional group comprising at least one of silane, hydroxyl, keto, amide, epoxy, or ureido functional groups; preferably at least one of silane, hydroxyl, keto, amide, or epoxy functional groups; more preferably silane, hydroxyl, keto, or amide functional groups, even more preferably silane, or hydroxyl functional groups, most preferably silane functional groups; e) optionally from 0.01 to 1% of a monomer comprising 2 or more unsaturations; wherein: the elastomeric polymer has a Tg of from -60°C to 0°C, preferably from -60°C to -15°C, more preferably from -60°C to -25°C, most preferably from -60 to -40°C, calculated using the Fox equation; a homopolymer of the monomer a) has a Tg of 25°C or less; the monomer a) has a biocarbon content of 40% or more as determined by ASTM 6866-22 Method B; the monomer b) optionally has a biocarbon content of 5% or more as determined by ASTM 6866-22 Method B; the biocarbon content of the elastomeric polymer is 22% or more as determined by ASTM 6866-22 Method B; anda 25 pm thick layer of the elastomeric polymer has a water contact angle of 70 degrees or more, preferably 75 degrees or more, more preferably 80 degrees or more, after drying for 72 hours at 25°C and 50% relative humidity.

17. The elastomeric polymer of claim 16, wherein: monomer a) comprises a C7-C8 (meth)acrylate or combination thereof; monomer b) comprises a C2-C4 (meth)acrylate, or a combination thereof; monomer c) comprises (meth) acrylic acid; monomer d) comprises silane-functional monomer, a hydroxy functional monomer, or a combination thereof; and monomer e) comprises at least one di(meth) acrylate.

18. Use of the elastomeric polymer according to claim 16 or claim 17 as a sealant.

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