Phenolic polymer antioxidants

Abstract

A polymeric phenolic antioxidant is described. Specifically, the polymeric phenolic antioxidant is the reaction product of hydroxybenzene, dienes, and aldehydes. The invention relates to a stable preparation, a polymer preparation, and a product containing a polymeric phenolic antioxidant. The invention also relates to a method for preparing a polymeric phenolic antioxidant which includes: reacting hydroxybenzene with dienes to obtain the first reaction product; reacting the first reaction product in the presence of hydroxybenzene with aldehydes to obtain the crude reaction product containing the polymeric phenolic antioxidant.

Description

POLYMERIC PHENOLIC ANTIOXIDANT AND USE THEREOFCross-Reference to Related Application

[0001] The present application claims filing benefit of UK Patent Application No. 2315957.7 having a filing date of October 18, 2023, which is incorporated herein by reference in its entirety.Background

[0002] Stabilizer compositions are added to a wide variety of materials, such as polymers, elastomers, and rubbers, during manufacturing and processing for a number of benefits. For instance, these materials may have a tendency to degrade or deteriorate, particularly when exposed to air or oxygen particularly at elevated temperatures, over a period of time. As a result of such thermal and oxidative degradation, these materials can become discolored and / or brittle. Thus, to stabilize against such deleterious effects, antioxidants can be utilized. These antioxidants may be able to protect a material from damage resulting from an oxidizing event and thereby increase the lifetime of the material. Examples of some of these antioxidants may include phenolic, arylamine, phosphite, or sulfide antioxidants alone or in combination. Depending on the specific end-use material and application, certain antioxidants may perform better than others.

[0003] In this regard, there is a desire to provide a new and improved antioxidants.Summary

[0004] In accordance with one embodiment of the present disclosure, a polymeric phenolic antioxidant is disclosed. The polymeric phenolic antioxidant is the reaction product of a hydroxybenzene, a diene, and an aldehyde.

[0005] In accordance with another embodiment of the present disclosure, a polymeric phenolic antioxidant mixture comprising a first aforementioned polymeric phenolic antioxidant and a second aforementioned polymeric phenolic antioxidant is disclosed.

[0006] In accordance with another embodiment of the present disclosure, a stabilizer composition comprising the aforementioned polymeric phenolic antioxidant is disclosed.

[0007] In accordance with another embodiment of the present disclosure, a polymeric composition comprising a polymer and the aforementioned polymeric phenolic antioxidant or stabilizer composition is disclosed.

[0008] In accordance with another embodiment of the present disclosure, an article comprising any of the aforementioned polymeric phenolic antioxidant, stabilizer composition, or polymeric composition is disclosed.

[0009] In accordance with another embodiment of the present disclosure, a method of making a polymeric phenolic antioxidant is disclosed. The method comprises: reacting a hydroxybenzene and a diene to obtain a first reaction product; reacting the first reaction product in the presence of the hydroxybenzene and an aldehyde to obtain a crude reaction product comprising the polymeric phenolic antioxidant.

[0010] In accordance with another embodiment of the present disclosure, a polymeric phenolic antioxidant made according to the aforementioned method is disclosed.Definitions

[0011] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present disclosure.

[0012] “About” means within 5% of the disclosed value.

[0013] “Alkyl” refers to straight chain, branched chain, or cyclic monovalent saturated aliphatic hydrocarbyl groups and “Cq-Cr alkyl” refers to alkyl groups having from q to r carbon atoms. This term includes, by way of example, straight chain, branched chain, or cyclic hydrocarbyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosanyl, henicosanyl, docosanyl, tricosanyl, tetracosanyl, pentacosanyl, hexacosanyl, heptacosanyl, octacosanyl, and the like.

[0014] “Aryl” refers to an aromatic ring, for example phenyl, and includes bicyclic ring systems where at least one of the rings is aromatic, for example naphthyl. An aryl group may be optionally substituted by one or more substituents, for example up to 4, 3 or 2 substituents. Preferably the aryl group is phenyl.

[0015] “Carboxyl” or “carboxy” refers to -COOH or salts thereof.

[0016] “Halo” or “halogen” refers to a fluorine (fluoro, F), chlorine (chloro, Cl), bromine (bromo, Br) or iodine (iodo, I).

[0017] “Hydroxy” refers to -OH.Detailed Description

[0018] It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only and is not intended as limiting the broader aspects of the present disclosure.

[0019] Generally speaking, the present disclosure is directed to a polymeric phenolic antioxidant. The polymeric phenolic antioxidant is the reaction product of a hydroxybenzene and a diene. Further, the polymeric phenolic antioxidant is the reaction product of a hydroxybenzene, a diene, and an aldehyde. Such a polymeric phenolic antioxidant as disclosed herein may have at least an equivalent if not better antioxidant performance than certain conventional antioxidants generally utilized in the industry. In addition, such reaction product may have a reduced level of certain species, such as relatively low molecular weight species.

[0020] For instance, the polymeric phenolic antioxidant may be recognized as a polymer and conform with the widely-accepted Organization for Economic Cooperation and Development (OECD) definition of a polymer. In this regard, in one embodiment, the reaction product and / or the polymeric phenolic antioxidant may have less than 10% by weight of oligomers having a molecular weight of less than 500 Da and less than 25% by weight of oligomers having a molecular weight of less than 1000 Da.I. Polymeric Phenolic Antioxidant

[0021] As indicated herein, the polymeric phenolic antioxidant is formed from a hydroxybenzene and a diene and particularly from a hydroxybenzene, a diene, and an aldehyde. In this regard, depending on the reaction conditions, the polymeric phenolic antioxidant may have a number of configurations, such as a random configuration, a repeating configuration, a block configuration, or a combination thereof. In one embodiment, the polymeric phenolic antioxidant may have a random configuration. In another embodiment, the polymeric phenolic antioxidant may have a repeating configuration. In a particular embodiment, the polymeric phenolic antioxidant may have a block configuration.

[0022] In one embodiment, the polymeric phenolic antioxidant may have a configuration including a first repeating unit structure (I) and a second repeating unit of structure (II):- P — S - L (II) wherein:A is a first hydroxybenzene residue;B is a diene residue;P is a second hydroxybenzene residue;S is an aldehyde residue; n is an integer of 1 or more; and m is an integer of 1 or more.

[0023] In one embodiment, the aforementioned repeating units of structures (I) and (II) may be presented as respective blocks within the polymeric phenolic antioxidant. In another embodiment, the aforementioned repeating units of structures (I) and (II) may be presented within the polymeric phenolic antioxidant in a random configuration.

[0024] As indicated above, “A” and “P” are a respective hydroxybenzene residue. In this regard, upon reacting a respective hydroxybenzene with the respective component(s) that make up a particular unit or block, the residue of such hydroxybenzene is respectively noted by “A” and “P” in the respective structures (I) and (II). In one embodiment, “A” and “P” may be the same.

[0025] It should be understood that the hydroxybenzene may be substituted or unsubstituted. In one embodiment, the hydroxybenzene may be unsubstituted. For instance, it may be phenol. In another embodiment, the hydroxybenzene may be substituted. For instance, the hydroxybenzene may include at least 1 , such as at least 2, such as 3 substitution(s). The hydroxybenzene may include 3 or less, such as 2 or less, such as 1 substitution(s). In this regard, the hydroxybenzene may be mono-, di-, or tri-substituted.

[0026] In one embodiment, the hydroxybenzene may include at least one substituent. In one embodiment, the hydroxybenzene may simply include onesubstituent. In another embodiment, the hydroxybenzene may include at least two substituent. In another embodiment, the hydroxybenzene may simply include two substituents.

[0027] The position of the substitution is not necessarily limited. For instance, regardless of the number of substitutions, in one embodiment, at least one substituent, when present, may be para to the hydroxy group of the hydroxybenzene. In another embodiment, the substituent, when present, may be ortho to the hydroxy group of the hydroxybenzene. In a further embodiment, the substituent, when present, may be meta to the hydroxy group of the hydroxybenzene. If two substituents are present, one substituent may be para to the hydroxy group of the hydroxybenzene while one substituent may be ortho to the hydroxy group of the hydroxybenzene in one embodiment. In another embodiment, one substituent may be para to the hydroxy group of the hydroxybenzene while one substituent may be meta to the hydroxy group of the hydroxybenzene in one embodiment. In a further embodiment, one substituent may be meta to the hydroxy group of the hydroxybenzene while one substituent may be ortho to the hydroxy group of the hydroxybenzene in one embodiment. In another embodiment, both substituents, when present, may be ortho to the hydroxy group of the hydroxybenzene.

[0028] When substituted, the substituent (or functional group) is not necessarily limited and may include, but is not limited to, alkyl, aryl, aralkyl, alkaryl, alkoxy (e.g., Ci-Ce alkoxy), alkylthio (e.g., Ci—Ce alkylthio), alkylsulfonyl (e.g., Ci- Ce alkylsulfonyl), amino, alkylamino (e.g., Ci-Ce alkylamino), aryloxy (e.g., Ce-C aryloxy), arylsulfoxy (e.g., Ce-Cw arylsulfoxy), cyano, carboxyl, halogen, hydroxy, nitro, etc.

[0029] For instance, the substituent may be an alkyl. The alkyl may have 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more, such as 8 or more, such as 10 or more, such as 12 or more, such as 14 or more, such as 16 or more, such as 18 or more, such as 20 or more, such as 22 or more, such as 24 or more, such as 26 or more, such as 28 or more, such as 30 or more carbon atoms. The alkyl may have 50 or less, such as 48 or less, such as 46 or less, such as 44 or less, such as 42 or less, such as 40 or less, such as 38 or less, such as 36 or less, such as 34 or less, such as 32 or less, such as 30 or less,such as 28 or less, such as 26 or less, such as 24 or less, such as 22 or less, such as 20 or less, such as 18 or less, such as 16 or less, such as 14 or less, such as 12 or less, such as 10 or less, such as 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less carbon atoms.

[0030] In one particular embodiment, the alkyl may be a lower alkyl. For instance, the alkyl may be a methyl. In another embodiment, the alkyl may be a long chain alkyl. In this regard, the alkyl may have from 10 to 40 carbon atoms, such as from 14 to 36 carbon atoms, such as from 16 to 34 carbon atoms. For instance, the alkyl may have from 16 to 18 carbon atoms in one embodiment. In another embodiment, the alkyl may have from 24 to 28 carbon atoms. In another embodiment, the alkyl may have from 26 to 28 carbon atoms. In a further embodiment, the alkyl may have 30 or more carbon atoms.

[0031] In one embodiment, the hydroxybenzene may include two alkyl substituents. For instance, the respective alkyl substituents may be ortho and meta to the hydroxy group in one embodiment. In another embodiment, the respective alkyl substituents may be ortho and para to the hydroxy group. In a further embodiment, the respective alkyl substituents may be para and meta to the hydroxy group. In another embodiment, the respective alkyl substituents may both be ortho to the hydroxy group. In an even further embodiment, the respective alkyl substituents may both be meta to the hydroxy group. With two alkyl substituents, the hydroxybenzene may be a xylenol. For instance, the xylenol may be 2,6- xylenol, 2,5-xylenol, 2,4-xylenol, 2,3-xylenol, 3,4-xylenol, 3,5-xylenol, etc., or a mixture thereof.

[0032] The hydroxybenzene may be a monohydroxybenzene. In this regard, the hydroxybenzene may only have one hydroxy group. In one embodiment, the hydroxybenzene may have two hydroxy groups. In this regard, the hydroxybenzene may include a hydroxy substitution such that the hydroxybenzene may be a dihydroxybenzene. The hydroxy groups may be para to one another in one embodiment. In another embodiment, the hydroxy groups may be ortho to one another. In a further embodiment, the hydroxy groups may be meta to one another. Nevertheless, in one embodiment, the hydroxybenzene may be a monohydroxybenzene, a dihydroxybenzene, or a mixture thereof.

[0033] In one embodiment, the hydroxybenzene may be a monohydroxybenzene. The hydroxybenzene, such as the monohydroxybenzene, may be a cresol. For instance, the cresol may be meta-cresol, para-cresol, or a mixture thereof. In one embodiment, the cresol may include meta-cresol. In a further embodiment, the cresol may include para-cresol. The cresol may also include a mixture of cresols, such as a mixture of meta-cresol and para-cresol in one embodiment.

[0034] In one embodiment, the hydroxybenzene may be a dihydroxybenzene. The hydroxybenzene, such as the dihydroxybenzene, may comprise catechol, hydroquinone, resorcinol, or a mixture thereof. In one embodiment, the dihydroxybenzene may include catechol. In another embodiment, the dihydroxybenzene may include hydroquinone. In a further embodiment, the dihydroxybenzene may include resorcinol. The dihydroxybenzene may also include a mixture of at least two, such as at least three of catechol, hydroquinone, and resorcinol.

[0035] The hydroxybenzene may comprise a single hydroxybenzene or a mixture of two or more hydroxybenzenes. In one embodiment, the hydroxybenzene may comprise a mixture of two or more monohydroxybenzenes. In one particular embodiment, the hydroxybenzene may comprise a mixture of two or more dihydroxybenzenes. In another embodiment, the hydroxybenzene may comprise a mixture of at least one monohydroxybenzene and at least one dihydroxybenzene. For instance, in one embodiment, the hydroxybenzene may be a mixture of para-cresol and hydroquinone. In another embodiment, the hydroxybenzene may be a mixture of para-cresol and resorcinol.

[0036] In one embodiment, the first hydroxybenzene and the second hydroxybenzene may have a corresponding structure (Illa) and (II lb), respectively, as follows:wherein:Ria, Rib, Ric, Rid, and Rieare each individually hydrogen or a respective functional group; andR2a, R2b, R2C, R2d, and R2e are each individually hydrogen or a respective functional group.

[0037] As indicated above, Ria, Rib, Ric, Rid, and Rie are each individually hydrogen or a respective functional group. In this regard, the functional group may be one as mentioned above. For instance, the functional group may be one of alkyl, aryl, aralkyl, alkaryl, alkoxy (e.g., Ci-Ce alkoxy), alkylthio (e.g., Ci- Ce alkylthio), alkylsulfonyl (e.g., Ci-Ce alkylsulfonyl), amino, alkylamino (e.g., Ci- Ce alkylamino), aryloxy (e.g., Ce-Cw aryloxy), arylsulfoxy (e.g., Ce-Cw arylsulfoxy), cyano, carboxyl, halogen, hydroxy, or nitro. In one embodiment, the functional group may be one of alkyl, aryl, aralkyl, alkaryl, alkoxy (e.g., Ci-Ce alkoxy), aryloxy (e.g., Ce-Cw aryloxy), halogen, or hydroxy. In one particular embodiment, the functional group may be one of alkyl, aryl, alkoxy, or hydroxy. In a particular embodiment, the functional group may be alkyl. The alkyl may be as defined above with respect to the substituents for the hydroxybenzene.

[0038] In one embodiment, at least one of Ria, Rib, Ric, Rid, and Rie is an alkyl. For instance, at least one of Ria, Rib, Ric, Rid, and Rie is an alkyl and the remaining groups may be hydrogen. In one embodiment, at least one of R1a, Rib, Ric, Rid, and Rie is hydroxy. For instance, at least one of Ria, Rib, Ric, Rid, and Rie is hydroxy and the remaining groups may be hydrogen. In one embodiment, at least one of Ria, Rib, Ric, Rid, and Rie is an alkyl and at least one of Ria, Rib, Ric, Rid, and Rie is hydroxy. For instance, at least one of Ria, Rib, Ric, Rid, and Rie is alkyl, at least one of Ria, Rib, Ric, Rid, and Rie is hydroxy, and the remaining groups may be hydrogen.

[0039] As indicated above, R2a, R2b, R2c, R2d, and R2e are each individually hydrogen or a respective functional group. In this regard, the functional group may be one as mentioned above. For instance, the functional group may be one of alkyl, aryl, aralkyl, alkaryl, alkoxy (e.g., Ci-Ce alkoxy), alkylthio (e.g., Ci- Ce alkylthio), alkylsulfonyl (e.g., Ci-Ce alkylsulfonyl), amino, alkylamino (e.g., Ci- Ce alkylamino), aryloxy (e.g., Ce-C aryloxy), arylsulfoxy (e.g., Ce-C arylsulfoxy), cyano, carboxyl, halogen, hydroxy, or nitro. In one embodiment, the functionalgroup may be one of alkyl, aryl, aralkyl, alkaryl, alkoxy (e.g., C1-C6 alkoxy), aryloxy (e.g., C6-C10 aryloxy), halogen, or hydroxy. In one particular embodiment, the functional group may be one of alkyl, aryl, alkoxy, or hydroxy. In a particular embodiment, the functional group may be alkyl. The alkyl may be as defined above with respect to the substituents for the hydroxybenzene.

[0040] In one embodiment, at least one of R2a, R2b, R2c, R2d, and R2e is an alkyl. For instance, at least one of R2a, R2b, R2c, R2d, and R2e is an alkyl and the remaining groups may be hydrogen. In one embodiment, at least one of R2a, R2b, R2C, R2d, and R2e is hydroxy. For instance, at least one of R2a, R2b, R2c, R2d, and R2e is hydroxy and the remaining groups may be hydrogen. In one embodiment, at least one of R2a, R2b, R2c, R2d, and R2e is an alkyl and at least one of R2a, R2b, R2c, R2d, and R2e is hydroxy. For instance, at least one of R2a, R2b, R2c, R2d, and R2e is alkyl, at least one of R2a, R2b, R2c, R2d, and R2e is hydroxy, and the remaining groups may be hydrogen.

[0041] In one particular embodiment, the hydroxybenzene may have an alkyl substituent, particularly para to the hydroxy group. In this regard, the hydroxybenzene may be a cresol. The first hydroxybenzene and the second hydroxybenzene may have a corresponding structure (IVa) and (IVb), respectively, as follows:wherein:Ri and R2 are alkyl.

[0042] As indicated above, in one embodiment, R1 and R2 are alkyl. The alkyl may have 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more carbon atoms. The alkyl may have 20 or less, such as 18 or less, such as 16 or less, such as 14 or less, such as 12 or less, such as 10 or less, such as 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, suchas 3 or less, such as 2 or less carbon atoms. In one particular embodiment, the alkyl may be methyl.

[0043] The hydroxybenzene is not necessarily limited by the present disclosure. In this regard, the hydroxy benzene may include, but is not limited to, phenol, phenol alkylated with one or more alkyl moieties having up to about 10 carbon atoms (e.g., cresol, such as m- and / or p-cresol), xylenol (e.g., 2,6-xylenol, 2,5-xylenol, 2,4-xylenol, 2,3-xylenol, 3,4-xylenol, 3,5-xylenol, etc.), p-tert-3,4,5- trimethylphenol, 3-ethyl phenol, 3,5-diethyl phenol, p-butyl phenol (e.g., o-t- butylphenol, p-t-butylphenol, etc.), 3,5-dibutyl phenol, p-amylphenol, p-octylphenol, p-nonylphenol, etc.) p-cyclohexyl phenol, 3,5-dicyclohexyl phenol, p-phenyl phenol, p-crotyl phenol, 3,5-dimethoxy phenol, 3,4,5-trimethoxy phenol, p-methoxy phenol, p-ethoxy phenol, p-butoxy phenol, 3-methyl-4-m ethoxy phenol, p-phenoxy phenol, resorcinol, catechol, hydroquinone, or p,p’-dihydroxy biphenyl, etc. as well as mixtures thereof.

[0044] As indicated above, “B” is a diene residue. In this regard, upon reacting a diene with the respective component(s) that make up a particular unit or block, the residue of such diene is noted by “B” in structure (I).

[0045] The diene is not necessarily limited by the present disclosure. In this regard, the diene may be an unconjugated diene, a conjugated diene, or a mixture thereof. In one embodiment, the diene may be a conjugated diene. In another embodiment, the diene may be an unconjugated diene. In one embodiment, the diene may not be a cumulated diene.

[0046] The diene may have 4 or more, such as 5 or more, such as 6 or more, such as 7 or more, such as 8 or more, such as 9 or more, such as 10 or more non-hydrogen atoms. The diene may have 20 or less, such as 18 or less, such as 16 or less, such as 14 or less, such as 12 or less, such as 10 or less, such as 8 or less, such as 6 or less non-hydrogen atoms. For instance, the nonhydrogen atoms may include any combination of carbon, oxygen, nitrogen, and / or phosphorus. In one embodiment, the non-hydrogen atoms may simply be carbon atoms. In this regard, the aforementioned number of atoms within the diene may be in reference to the number of carbon atoms.

[0047] The diene may include, but is not limited to, a butadiene (e.g., 1 ,3- butadiene, 2,3-dimethyl-1 ,3-butadiene, 2-ethyl-1 ,3-butadiene, etc.), isoprene, apentadiene (e.g., 1 ,3-pentadiene, 1 ,4-pentadiene, 3-methyl-1 ,3-pentadiene, 2- methyl-1 ,3-pentadiene, 2,4-dimethyl-1 ,3-pentadiene, 3-ethyl-1 ,3-pentadiene, 4- methyl-1 ,3-pentadiene, etc.), a hexadiene (e.g., 1 ,3-hexadiene, 1 ,4-hexadiene,1 .5-hexadiene, 4-hexadiene, 3-methyl-1 ,4-hexadiene, 3-methyl-1 ,5-hexadiene, 3- ethyl-1 ,4-hexadiene, 3-ethyl-1 ,5-hexadiene, 3, 3-dimethyl-1 , 4-hexadiene, 3,3- dimethyl-1 ,5-hexadiene, etc.), a heptadiene (e.g., 1 ,5-heptadiene, 1 ,6-heptadiene, methylheptadiene, etc.), an octadiene (e.g., 1 ,6-octadiene, 1 ,7-octadiene, methyloctadiene, etc.), a nonadiene (e.g., 1 ,7-nonadiene, 1 ,8-nonadiene, methylnonadiene, etc.), a decadiene (e.g., 1 ,8-decadiene, 1 ,9-decadiene, methyldecadiene, etc.), an undecadiene (e.g., 1 ,9-undecadiene, 1 ,10- undecadiene, etc.), a dodecadiene (e.g., 1 ,10-dodecadiene, 1 ,11 -dodecadiene, etc.), a tridecadiene (e.g., 1 ,11 -tridecadiene, 1 ,12-tridecadiene, etc.), tetradecadiene (e.g., 1 ,12-tetradecadiene, 1 ,13-tetradecadiene, etc.), a pentadecadiene, a hexadecadiene, a heptadecadiene, an octadecadiene, a nonadecadiene, a icosadiene, a heneicosadiene, a docosadiene, a tricosadiene, a tetracosadiene, a pentacosadiene, a hexacosadiene, a heptacosadiene, an octacosadiene, a nonacosadiene, a triacontadiene, a vinylcycloalkene (e.g., vinylcyclopentene, vinylcyclohexene, vinylcycloheptene, vinylcyclooctene, vinylcyclononene, etc.), a cyclopentadiene (e.g., 1 ,3-cyclopentadiene, methylcyclopentadiene, etc.), a cyclohexadiene (e.g., 1 ,3-cyclohexadiene, 1 ,4- cyclohexadiene, methylcyclohexadiene, etc.), a cycloheptadiene (e.g., 1 ,3- cycloheptadiene, 1 ,4-cycloheptadiene, etc. or a mixture thereof), a cyclooctadiene, a vinylnorbornene (e.g., 5-vinyl-2-norbornene, etc.), a norbornadiene (e.g., norbornadiene, 2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5- norbornadiene, 7-propyl-2,5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-phenyl-2.5-norbornadiene, 7-hexyl-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene, 7- methyl-7-ethyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene, 7-bromo-2,5- norbornadiene, 7-fluoro-2,5-norbornadiene, 7,7-dichloro-2,5-norbornadiene, 1- methyl-2,5-norbornadiene, 1 -ethyl-2,5-norbornadiene, 1 -propyl-2,5-norbornadiene, 1 -butyl-2,5-norbornadiene, 1 -chloro-2,5-norbornadiene, 1 -bromo-2,5- norbornadiene, etc.), ethylidene norbornene (e.g., 5-ethylidene-2-norbornene), a divinylbenzene, a dicyclopentadiene, dipentene, etc. as well as mixtures thereof.

[0048] In one embodiment, the diene may include a linear or branched diene. In one embodiment, the diene may be linear. In another embodiment, the diene may be branched. The linear or branched diene may include, but is not limited to, a butadiene (e.g., 1 ,3-butadiene, 2,3-dimethyl-1 ,3-butadiene, 2-ethyl-1.3-butadiene, etc.), isoprene, a pentadiene (e.g., 1 ,3-pentadiene, 1 ,4-pentadiene, 3-methyl-1 ,3-pentadiene, 2-methyl-1 ,3-pentadiene, 2,4-dimethyl-1 ,3-pentadiene, 3- ethyl-1 ,3-pentadiene, 4-methyl-1 ,3-pentadiene, etc.), a hexadiene (e.g., 1 ,3- hexadiene, 1 ,4-hexadiene, 1 ,5-hexadiene, 4-hexadiene, 3-methyl-1 ,4-hexadiene, 3-methyl-1 ,5-hexadiene, 3-ethyl-1 , 4-hexadiene, 3-ethyl-1 ,5-hexadiene, 3,3- dimethyl-1 , 4-hexadiene, 3,3-dimethyl-1 ,5-hexadiene, etc.), a heptadiene (e.g., 1 ,5- heptadiene, 1 ,6-heptadiene, methylheptadiene, etc.), an octadiene (e.g., 1 ,6- octadiene, 1 ,7-octadiene, methyloctadiene, etc.), a nonadiene (e.g., 1 ,7- nonadiene, 1 ,8-nonadiene, methylnonadiene, etc.), a decadiene (e.g., 1 ,8- decadiene, 1 ,9-decadiene, methyldecadiene, etc.), an undecadiene (e.g., 1 ,9- undecadiene, 1 ,10-undecadiene, etc.), a dodecadiene (e.g., 1 ,10-dodecadiene, 1 ,11 -dodecadiene, etc.), a tridecadiene (e.g., 1 ,11 -tridecadiene, 1 ,12-tridecadiene, etc.), a tetradecadiene (e.g., 1 ,12-tetradecadiene, 1 ,13-tetradecadiene, etc.), a pentadecadiene, a hexadecadiene, a heptadecadiene, an octadecadiene, a nonadecadiene, a icosadiene, a heneicosadiene, a docosadiene, a tricosadiene, a tetracosadiene, a pentacosadiene, a hexacosadiene, a heptacosadiene, an octacosadiene, a nonacosadiene, a triacontadiene, etc. or a mixture thereof.

[0049] In one embodiment, the diene may include a vinylcycloalkene. For instance, the vinylcycloalkene may include, but is not limited to vinylcyclopentene, vinylcyclohexene, vinylcycloheptene, vinylcyclooctene, vinylcyclononene, etc. or a mixture thereof.

[0050] In one embodiment, the diene may include a cyclic diene. In this regard, the cyclic diene may include, but is not limited to, a cyclopentadiene (e.g.,1.3-cyclopentadiene, methylcyclopentadiene, etc.), a cyclohexadiene (e.g., 1 ,3- cyclohexadiene, 1 ,4-cyclohexadiene, methylcyclohexadiene, etc.), a cycloheptadiene (e.g., 1 ,3-cycloheptadiene, 1 ,4-cycloheptadiene, etc. or a mixture thereof), a cyclooctadiene, a vinylnorbornene (e.g., 5-vinyl-2-norbornene, etc.), a norbornadiene (e.g., norbornadiene, 2,5-norbornadiene, 7-methyl-2,5- norbornadiene, 7-ethyl-2,5-norbornadiene, 7-propyl-2,5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-phenyl-2,5-norbornadiene, 7-hexyl-2,5-norbornadiene, 7,7- dimethyl-2,5-norbornadiene, 7-methyl-7-ethyl-2,5-norbornadiene, 7-chloro-2,5- norbornadiene, 7-bromo-2,5-norbornadiene, 7-fluoro-2,5-norbornadiene, 7,7- dichloro-2,5-norbornadiene, 1 -methyl-2,5-norbornadiene, 1 -ethyl-2,5- norbornadiene, 1-propyl-2,5-norbornadiene, 1-butyl-2,5-norbornadiene, 1-chloro- 2,5-norbornadiene, 1-bromo-2,5-norbornadiene, etc.), an ethylidene norbornene (e.g., 5-ethylidene-2-norbornene), a divinylbenzene, a dicyclopentadiene, dipentene, etc. or a mixture thereof. The cyclic diene may also include higher ring containing diolefins as well as mixtures of any of the aforementioned. In one embodiment, the diene, such as the cyclic diene, may be cyclopentadiene. In one particular embodiment, the diene, such as the cyclic diene, may be dicyclopentadiene.

[0051] In one embodiment, the diene, such as the cyclic diene, may include a bicyclic diene. For instance, the bicyclic diene may be a norbornadiene, dicyclopentadiene, vinyl norbornene, etc. or a mixture thereof. In one embodiment, the diene, such as the bicyclic diene, may be dicyclopentadiene.

[0052] In addition to the above, it should be understood that these dienes may be with or without substituents. For instance, for the cyclic dienes, it should be understood that they may be with or without substituents at various ring positions.

[0053] As indicated above, “S” is an aldehyde residue. In this regard, upon reacting an aldehyde with the respective component(s) that make up a particular unit or block, the residue of such aldehyde is noted by “S” in structure (II).

[0054] In one embodiment, the aldehyde may have a general structure (V) as follows:OR3^^H(V) wherein:Rs is hydrogen or methyl.

[0055] As indicated above, Rs is hydrogen or methyl. In one embodiment, Rs is hydrogen. In another embodiment, Rs is methyl.

[0056] The aldehyde is not necessarily limited by the present disclosure. In this regard, the aldehyde may be formaldehyde, acetaldehyde, or a mixture thereof. In one embodiment, the aldehyde comprises acetaldehyde. In another embodiment, the aldehyde comprises formaldehyde. In forming the formaldehyde residue, the synthesis may utilize paraformaldehyde, which may be converted to formaldehyde during the reaction. Similarly, in forming the acetaldehyde residue, the synthesis may utilize paraldehyde, which may be converted to acetaldehyde during the reaction. In other embodiments, the aldehyde source may include trioxane which may be converted to formaldehyde in situ.

[0057] As indicated above, “n” is an integer of 1 or more. For instance, “n” may be 1 or more, such as 2 or more, such as 3 or more, such as 5 or more, such as 8 or more, such as 10 or more, such as 20 or more, such as 25 or more, such as 30 or more, such as 40 or more, such as 50 or more, such as 75 or more. In addition, “n” may be 200 or less, such as 175 or less, such as 150 or less, such as 125 or less, such as 100 or less, such as 90 or less, such as 80 or less, such as 75 or less, such as 50 or less, such as 40 or less, such as 30 or less, such as 25 or less, such as 20 or less, such as 15 or less, such as 12 or less, such as 10 or less, such as 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less.

[0058] As indicated above, “m” is an integer of 1 or more. For instance, “m” may be 1 or more, such as 2 or more, such as 3 or more, such as 5 or more, such as 8 or more, such as 10 or more, such as 20 or more, such as 25 or more, such as 30 or more, such as 40 or more, such as 50 or more, such as 75 or more. In addition, “m” may be 200 or less, such as 175 or less, such as 150 or less, such as 125 or less, such as 100 or less, such as 90 or less, such as 80 or less, such as 75 or less, such as 50 or less, such as 40 or less, such as 30 or less, such as 25 or less, such as 20 or less, such as 15 or less, such as 12 or less, such as 10 or less, such as 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less.

[0059] In one embodiment, the polymeric phenolic antioxidant may have a structure (VI) as follows:wherein:Ri, R2, R3, n, and m are as defined above;R4 is hydrogen, methyl, or hydroxy; and Rs is hydrogen, methyl, or hydroxy.

[0060] As indicated above, the respective polymeric phenolic antioxidant may include certain terminations based on the combinations of R3 and R4 as well as R3 and Rs. As indicated above, Rs is hydrogen, methyl, or hydroxy. In one embodiment, R4 is hydrogen. In a further embodiment, R4 is methyl. In another embodiment, R4 is hydroxy. Also, as indicated above, Rs is hydrogen, methyl, or hydroxy. In one embodiment, Rs is hydrogen. In a further embodiment, Rs is methyl. In another embodiment, Rs is hydroxy. In one embodiment, both R4 and Rs may be the same. In another embodiment, R4 and Rs may be different.

[0061] Furthermore, with respect to the above structure (VI), the respective bonds between the diene residue, in particular the dicyclopentadiene residue, and the adjacent hydroxybenzene residue would be with a respective carbon atom that participated in an unsaturated carbon-carbon double bond within the dicyclopentadiene. In particular, at least one carbon from each of the respective unsaturated carbon-carbon double bonds within the dicyclopentadiene would be bonded with an adjacent hydroxybenzene residue.

[0062] In one embodiment, R1 and R2 may be methyl, R3 may be hydrogen, R4 may be hydroxy, and Rs may be hydroxy. In this regard, the polymeric phenolic antioxidant may have a structure (Via) as follows:wherein: n and m are as defined above.

[0063] In one embodiment, Ri and R2 may be methyl, R3 may be methyl, R4 may be hydroxy, and Rs may be hydroxy. In this regard, the polymeric phenolic antioxidant may have a structure (VI b) as follows:wherein: n and m are as defined above.

[0064] In one embodiment, the polymeric phenolic antioxidant may be a solid. Particularly, the polymeric phenolic antioxidant may be a solid at a temperature of about 25°C and about 1 atmosphere pressure (i.e. , 101 .325 kPa).

[0065] The melting temperature of the polymeric phenolic antioxidant may be a particular temperature. For instance, the melting temperature may be 100°C or more, such as 110°C or more, such as 120°C or more, such as 130°C or more, such as 140°C or more, such as 150°C or more, such as 160°C or more, such as 170°C or more, such as 180°C or more, such as 190°C or more, such as 200°C or more, such as 210°C or more, such as 220°C or more, such as 230°C or more, such as 240°C or more. The melting temperature may be 300°C or less, such as 290°C or less, such as 280°C or less, such as 270°C or less, such as 260°C or less, such as 250°C or less, such as 240°C or less, such as 230°C or less, such as 220°C or less, such as 210°C or less, such as 200°C or less, such as 190°C orless, such as 180°C or less, such as 170°C or less, such as 160°C or less, such as 150°C or less, such as 140°C or less, such as 130°C or less, such as 120°C or less. The melting temperature may be determined using means generally known in the art, such as dynamic scanning calorimetry.

[0066] The polymeric phenolic antioxidant may also have a particular color. For instance, the Gardner color may be 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more. The Gardner color may be 9 or less, such as 8 or less, such as 7 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less. The Gardner color can be determined using a LOVIBOND™ Comparator 3000 based on a 10% solution in toluene.

[0067] The polymeric phenolic antioxidant may have a particular number average molecular weight of 400 g / mol or more, such as 500 g / mol or more, such as 600 g / mol or more, such as 700 g / mol or more, such as 800 g / mol or more, such as 900 g / mol or more, such as 1 ,000 g / mol or more, such as 1 ,200 g / mol or more, such as 1 ,400 g / mol or more, such as 1 ,600 g / mol or more, such as 1 ,800 g / mol or more, such as 2,000 g / mol or more, such as 2,400 g / mol or more, such as 2,800 g / mol or more, such as 3,000 g / mol or more, such as 3,400 g / mol or more, such as 3,800 g / mol or more, such as 4,000 g / mol or more, such as 4,400 g / mol or more, such as 4,800 g / mol or more, such as 5,000 g / mol or more, such as 5,500 g / mol or more, such as 6,000 g / mol or more, such as 6,500 g / mol or more, such as 7,000 g / mol or more, such as 7,500 g / mol or more, such as 8,000 g / mol or more, such as 8,500 g / mol or more, such as 9,000 g / mol or more, such as 9,500 g / mol or more, such as 10,000 g / mol or more. The number average molecular weight may be 30,000 g / mol or less, such as 26,000 g / mol or less, such as 22,000 g / mol or less, such as 20,000 g / mol or less, such as 18,000 g / mol or less, such as 16,000 g / mol or less, such as 14,000 g / mol or less, such as 12,000 g / mol or less, such as 10,000 g / mol or less, such as 8,000 g / mol or less, such as 6,000 g / mol or less, such as 5,000 g / mol or less, such as 4,000 g / mol or less, such as 3,000 g / mol or less. The number average molecular weight may be determined using means known in the art, such as gel-permeation chromatography.

[0068] The polymeric phenolic antioxidant may have a particular weight average molecular weight of 400 g / mol or more, such as 500 g / mol or more, such as 600 g / mol or more, such as 700 g / mol or more, such as 800 g / mol or more,such as 900 g / mol or more, such as 1 ,000 g / mol or more, such as 1 ,200 g / mol or more, such as 1 ,400 g / mol or more, such as 1 ,600 g / mol or more, such as 1 ,800 g / mol or more, such as 2,000 g / mol or more, such as 2,400 g / mol or more, such as 2,800 g / mol or more, such as 3,000 g / mol or more, such as 3,400 g / mol or more, such as 3,800 g / mol or more, such as 4,000 g / mol or more, such as 4,400 g / mol or more, such as 4,800 g / mol or more, such as 5,000 g / mol or more, such as 5,500 g / mol or more, such as 6,000 g / mol or more, such as 6,500 g / mol or more, such as 7,000 g / mol or more, such as 7,500 g / mol or more, such as 8,000 g / mol or more, such as 8,500 g / mol or more, such as 9,000 g / mol or more, such as 9,500 g / mol or more, such as 10,000 g / mol or more. The weight average molecular weight may be 30,000 g / mol or less, such as 26,000 g / mol or less, such as 22,000 g / mol or less, such as 20,000 g / mol or less, such as 18,000 g / mol or less, such as 16,000 g / mol or less, such as 14,000 g / mol or less, such as 12,000 g / mol or less, such as 10,000 g / mol or less, such as 8,000 g / mol or less, such as 6,000 g / mol or less, such as 5,000 g / mol or less, such as 4,000 g / mol or less, such as 3,000 g / mol or less. The weight average molecular weight may be determined using means known in the art, such as gel-permeation chromatography.II. Method of Making a Polymeric Phenolic Antioxidant

[0069] The present disclosure is also directed to a method of making a polymeric phenolic antioxidant as disclosed herein. In this regard, the general method may include a step of reacting a hydroxybenzene, a diene, and an aldehyde to form the polymeric phenolic antioxidant.

[0070] In one particular embodiment, the method may include certain steps to form a polymeric phenolic antioxidant having a desired configuration. For instance, generally, this may include a step of: (a) reacting a hydroxybenzene and a diene to obtain a first reaction product; (b) reacting a hydroxybenzene and an aldehyde to obtain a second reaction product; (c) reacting the first reaction product and the second reaction product to obtain the polymeric phenolic antioxidant. In particular, this may include a step of: (a) reacting a first hydroxybenzene and a diene to obtain a first reaction product; (b) reacting a second hydroxybenzene and an aldehyde to obtain a second reaction product; (c) reacting the first reaction product and the second reaction product to obtain the polymeric phenolic antioxidant. In one embodiment, such reactions may result in a crude reactionproduct comprising the polymeric phenolic antioxidant. In this regard, such crude product may undergo neuralization and / or purification steps as described herein.

[0071] Alternatively, generally, this may include a step of: (a) reacting a hydroxybenzene and a diene to obtain a first reaction product; (b) reacting the first reaction product in the presence of a hydroxybenzene and an aldehyde to obtain the polymeric phenolic antioxidant. In particular, this may include a step of: (a) reacting a first hydroxybenzene and a diene to obtain a first reaction product; (b) reacting the first reaction product in the presence of a second hydroxybenzene and an aldehyde to obtain the polymeric phenolic antioxidant. In one embodiment, such reactions may result in a crude reaction product comprising the polymeric phenolic antioxidant. In this regard, such crude product may undergo neuralization and / or purification steps as described herein.

[0072] In the aforementioned reactions, the first hydroxybenzene and the second hydroxybenzene may be different in one embodiment. In another embodiment, the first hydroxybenzene and the second hydroxybenzene may be the same.

[0073] In addition, in one embodiment, the aldehyde may be provided as an aldehyde to the reaction. In this regard, the aldehyde may be as defined herein. In one embodiment, when the aldehyde is formaldehyde, it may be provided as an aqueous formaldehyde. In one embodiment, the aldehyde may be provided as trioxane initially. For instance, the trioxane may be converted to formaldehyde in situ.

[0074] In general, the molar ratio of hydroxybenzene to diene may be 0.5 or more, such as 0.6 or more, such as 0.7 or more, such as 0.8 or more, such as 0.9 or more, such as 1 or more, such as 1 .1 or more, such as 1 .2 or more, such as 1 .3 or more, such as 1 .4 or more, such as 1 .5 or more, such as 1 .6 or more, such as 1 .7 or more, such as 1 .8 or more, such as 1 .9 or more, such as 2 or more. The molar ratio may be 5 or less, such as 4.5 or less, such as 4 or less, such as 3.5 or less, such as 3 or less, such as 2.8 or less, such as 2.6 or less, such as 2.4 or less, such as 2.2 or less, such as 2 or less, such as 1 .8 or less, such as 1 .6 or less, such as 1 .5 or less, such as 1 .4 or less, such as 1 .3 or less, such as 1 .2 or less, such as 1.1 or less. In one embodiment, the hydroxybenzene may be used in an excess. In this regard, more moles of hydroxybenzene may be utilized than thediene. In one embodiment, the aforementioned molar ratio may refer to the entire moles of hydroxybenzene (i.e. , the first hydroxybenzene and the second hydroxybenzene) utilized in the reaction.

[0075] The addition of the diene to the hydroxybenzene may be conducted stepwise or continuously such that the diene is gradually added to a bulk quantity of the hydroxybenzene, catalyst, and optionally the solvent. The addition of the diene may be performed over a period of time to obtain the desired result and reaction product. Thus, the time period is not necessarily limited but may be 0.2 hours or more, such as 0.4 hours or more, such as 0.6 hours or more, such as 0.8 hours or more, such as 1 hour or more, such as 1 .2 hours or more, such as 1 .4 hours or more, such as 1 .6 hours or more, such as 1 .8 hours or more, such as 2 hours or more. The time period may be 4 hours or less, such as 3.6 hours or less, such as 3.2 hours or less, such as 2.8 hours or less, such as 2.4 hours or less, such as 2.2 hours or less, such as 2 hours or less, such as 1 .8 hours or less, such as 1 .6 hours or less, such as 1 .4 hours or less, such as 1 .2 hours or less.

[0076] In one embodiment, a respective reaction may be conducted in the presence of a catalyst. For instance, the reaction of the hydroxybenzene and the diene may be conducted in the presence of a catalyst in one embodiment. In one embodiment, the reaction including the hydroxybenzene and the aldehyde may be conducted in the presence of a catalyst. In a further embodiment, both reactions may be conducted in the presence of a catalyst. The catalyst may be an acid catalyst or a base catalyst for a respective reaction. In one embodiment, the catalyst may be an acid catalyst. In addition, the catalyst may comprise a Lewis acid and / or a Bronsted acid.

[0077] The catalyst may comprise boron trifluoride, a sulfonic acid (e.g., p- toluene sulfonic acid, dodecylbenzenesulfonic acid, an alkane sulfonic acid such as trifluoromethane sulfonic acid, etc.), a mineral acid (e.g., sulfuric acid, hydrochloric acid, phosphoric acid, or nitric acid), an organic acid (e.g., a haloacetic acid such as trifluoroacetic acid, etc.), and / or phosphotungstic acid.

[0078] In one embodiment, the catalyst may be boron trifluoride. The boron trifluoride may be in gaseous form or may be part of a complex, such as a phenol complex, an acetic acid complex, a methanol methyl etherate complex, or a tetrahydrofuran complex. In one embodiment, the catalyst may be a mineral acid.In another embodiment, the catalyst may be an organic acid, such as a haloacetic acid and in particular trifluoroacetic acid. In one particular embodiment, the catalyst may be a sulfonic acid. For instance, the sulfonic acid may be p-toluene sulfonic acid, dodecylbenzenesulfonic acid, an alkane sulfonic acid, or a mixture thereof. The catalyst may be an alkane sulfonic acid, such as trifluoromethane sulfonic acid, in one embodiment.

[0079] Examples of base catalysts include, but are not limited to, sodium hydroxide, barium hydroxide, potassium hydroxide, calcium hydroxide, organic amines, sodium carbonate, and combinations thereof.

[0080] The catalyst may be present in an amount of 0.001 wt.% or more, such as 0.005 wt.% or more, such as 0.01 wt.% or more, such as 0.05 wt.% or more, such as 0.1 wt.% or more, such as 0.15 wt.% or more, such as 0.2 wt.% or more, such as 0.25 wt.% or more, such as 0.3 wt.% or more, such as 0.35 wt.% or more, such as 0.4 wt.% or more, such as 0.45 wt.% or more, such as 0.5 wt.% or more based on the weight of the hydroxybenzene. The catalyst may be present in an amount of 5 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2.5 wt.% or less, such as 2 wt.% or less, such as 1 .8 wt.% or less, such as 1 .6 wt.% or less, such as 1 .4 wt.% or less, such as 1 .3 wt.% or less, such as 1 .2 wt.% or less, such as 1 .1 wt.% or less, such as 1 wt.% or less, such as 0.9 wt.% or less, such as 0.8 wt.% or less, such as 0.7 wt.% or less, such as 0.6 wt.% or less, such as 0.5 wt.% or less, such as 0.4 wt.% or less, such as 0.3 wt.% or less based on the weight of the hydroxybenzene.

[0081] The respective reaction may be performed in a solvent. The respective component(s) (e.g., hydroxybenzene) may be mixed in the solvent prior to addition of another component (e.g., diene, aldehyde). For instance, the reaction of the hydroxybenzene and the diene may be conducted in a solvent in one embodiment. In one embodiment, the reaction including the hydroxybenzene and the aldehyde may be conducted in a solvent. In a further embodiment, both reactions may be conducted in a solvent. The solvent may be a hydrocarbon solvent in one embodiment. In this regard, the solvent may be an organic solvent. In particular, the solvent may be an aromatic hydrocarbon solvent. In this regard, the solvent may be toluene, xylene, or a mixture thereof. In one particular embodiment, the solvent may be toluene.

[0082] The solvent for a respective reaction may be present in an amount of about 1 wt.% or more, such as 2 wt.% or more, such as 3 wt.% or more, such as 5 wt.% or more, such as 10 wt.% or more, such as 20 wt.% or more, such as 30 wt.% or more, such as 40 wt.% or more, such as 50 wt.% or more, such as 70 wt.% or more, such as 100 wt.% or more, such as 150 wt.% or more based on the weight of the hydroxybenzene. The solvent for a respective reaction may be present in an amount of 300 wt.% or less, such as 250 wt.% or less, such as 200 wt.% or less, such as 170 wt.% or less, such as 150 wt.% or less, such as 120 wt.% or less, such as 100 wt.% or less, such as 90 wt.% or less, such as 80 wt.% or less, such as 70 wt.% or less, such as 60 wt.% or less, such as 50 wt.% or less based on the weight of the hydroxybenzene.

[0083] The respective reaction may be conducted at conditions that promote the formation of the respective reaction product. In this regard, in one embodiment, the respective reaction may be performed at an absolute pressure of from 0 bar to about 2 bar. In one embodiment, the respective reaction may be performed under vacuum. For instance, without intending to be limited, sealing the reaction vessel may prevent loss of a respective component, such as a diene, that may otherwise occur in an open reaction vessel. As a result, this may result in a more efficient reaction. Accordingly, the respective reaction may be performed at an absolute pressure of from 0 bar to about 1 bar, such as from 0 bar to about 0.5 bar, such as from 0 bar to about 0.2 bar.

[0084] The respective reaction may be conducted at a reaction temperature of 40°C or greater, such as 45°C or greater, such as 50°C or greater, such as 55°C or greater, such as 60°C or greater, such as 65°C or greater, such as 70°C or greater. The reaction temperature for a respective reaction may be 150°C or less, such as 140°C or less, such as 130°C or less, such as 120°C or less, such as 110°C or less, such as 100°C or less, such as 90°C or less, such as 80°C or less, such as 70°C or less, such as 60°C or less. For example, an addition of a diene to a hydroxybenzene may be conducted at a reaction temperature of 30°C or greater, such as 35°C or greater, such as 40°C or greater, such as 45°C or greater, such as 50°C or greater, and / or 90°C or less, such as 80°C or less, such as 70°C or less, such as 60°C or less, or approximately 55°C. A reaction of a hydroxybenzene and a diene may be heated to and conducted at a reaction temperature of 100°Cor greater, such as 110°C or greater, such as 120°C or greater, and / or 160°C or less, such as 150°C or less, such as 145°C or less, such as 140°C or less, such as 135°C or less, such as 130°C or less, or approximately 135°C. A subsequent addition of an aldehyde may be conducted at a reaction temperature of 80°C or greater, such as 85°C or greater, such as 90°C or greater, such as 95°C or greater, such as 100°C or greater, and / or 130°C or less, such as 120°C or less, such as 110°C or less, such as 100°C or less, or approximately 100°C.

[0085] The respective reaction may be conducted for a time sufficient to form a respective reaction product. For instance, the reaction time may be 0.2 hours or more, such as 0.4 hours or more, such as 0.6 hours or more, such as 0.8 hours or more, such as 1 hour or more, such as 1 .5 hours or more, such as 2 hours or more, such as 2.5 hours or more, such as 3 hours or more, such as 3.5 hours or more, such as 4 hours or more. The reaction time may be 10 hours or less, such as 9 hours or less, such as 8 hours or less, such as 7 hours or less, such as 6 hours or less, such as 5 hours or less, such as 4 hours or less, such as 3 hours or less, such as 2 hours or less, such as 1 hour or less.

[0086] Upon completion of the reaction, the method may include a neutralization step. In this regard, the method may include a step of neutralizing a respective reaction product and / or the polymeric phenolic antioxidant with a neutralizing agent. For instance, upon reacting with the aldehyde, the reaction may result in a crude reaction product or crude polymeric phenolic antioxidant. Such neutralization step may be conducted prior to a purification step. The neutralizing agent is not necessarily limited by the present disclosure.

[0087] The neutralizing agent may include a single compound or a mixture of two or more compounds. In one embodiment, the neutralizing agent may comprise an organic base, such as an amine. For instance, the amine may be triethanolamine. In another embodiment, the neutralizing agent may comprise a metal hydroxide and / or a metal carbonate. In one embodiment, the neutralizing agent may comprise a metal hydroxide. In another embodiment, the neutralizing agent may comprise a metal carbonate. The metal may be an alkali metal, such as sodium or potassium. In this regard, the neutralizing agent may comprise sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, or a mixture thereof. In one embodiment, the neutralizing agent may comprisesodium carbonate. In another embodiment, the neutralizing agent may comprise a mixture of sodium hydroxide and sodium carbonate. In another embodiment, the neutralizing agent may comprise a mixture of potassium hydroxide and potassium carbonate.

[0088] When utilized, the neutralizing agent may be provided in a particular amount. For instance, the neutralizing agent may be present in an amount of 0.001 wt.% or more, such as 0.005 wt.% or more, such as 0.01 wt.% or more, such as 0.05 wt.% or more, such as 0.1 wt.% or more, such as 0.2 wt.% or more, such as 0.3 wt.% or more, such as 0.4 wt.% or more, such as 0.5 wt.% or more, such as 0.6 wt.% or more, such as 0.7 wt.% or more, such as 0.8 wt.% or more, such as 0.9 wt.% or more, such as 1 wt.% or more, such as 1 .2 wt.% or more, such as 1 .4 wt.% or more, such as 1 .6 wt.% or more, such as 1 .8 wt.% or more, such as 2 wt.% or more based on the weight of the polymeric phenolic antioxidant. The neutralizing agent may be provided in an amount of 5 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2.8 wt.% or less, such as 2.6 wt.% or less, such as 2.4 wt.% or less, such as 2.2 wt.% or less, such as 2 wt.% or less, such as 1 .8 wt.% or less, such as 1 .6 wt.% or less, such as 1 .4 wt.% or less, such as 1 .2 wt.% or less, such as 1 wt.% or less, such as 0.9 wt.% or less, such as 0.8 wt.% or less, such as 0.7 wt.% or less, such as 0.6 wt.% or less, such as 0.5 wt.% or less, such as 0.4 wt.% or less, such as 0.3 wt.% or less, such as 0.2 wt.% or less based on the weight of the polymeric phenolic antioxidant.

[0089] The method may also include one or more purification steps. In this regard, the method may include a step of purifying the reaction product and / or the polymeric phenolic antioxidant. The purification is not necessarily limited. For instance, in one embodiment, purification may be via distillation, evaporation, or a combination. In one embodiment, purification may include distillation. In another embodiment, purification may include evaporation. In a further embodiment, purification may include distillation and evaporation. In general, also, it should be understood that the specific conditions for purification may be dependent upon the particular evaporation technique(s) utilized.

[0090] When utilizing distillation, it may be performed using standard vacuum distillation techniques as known in the art. For instance, the distillation temperature may be from about 180°C to about 230°C. The distillation may beperformed under vacuum with an absolute pressure of no greater than about 100 mbar, such as no greater than about 10 mbar.

[0091] When utilizing evaporation, it may be performed using standard techniques including, but not limited to, falling film evaporation, wiped film evaporation, or short path evaporation.

[0092] The purification may provide a polymeric phenolic antioxidant having a particular molecular weight distribution. For instance, the polymeric phenolic antioxidant may comprise less than about 10% by weight of reaction products having a molecular weight of less than about 500 Da and less than about 25% by weight of reaction products having a molecular weight of less than about 1000 Da.

[0093] Furthermore, once purified, the purified product may comprise trace amounts of butylated hydroxytoluene (BHT). By “trace amounts,” it is preferably meant less than about 1 %, such as less than about 0.9%, such as less than about 0.8%, such as less than about 0.7%, such as less than about 0.6%, such as less than about 0.5% by weight of the purified reaction product. The purified reaction product may therefore be further purified to reduce the amount of BHT present in said purified reaction product. The purified reaction product may be heated at a temperature of at least about 200°C, such as at least about 210°C, such as at least about 220°C. The purified reaction product may be heated under vacuum, with an absolute pressure of no greater than about 50 mbar, such as no greater than about 30 mbar, such as no greater than about 10 mbar, such as no greater than about 5 mbar, such as about 0 mbar. The purified reaction product may be heated for a time period for about 10 minutes or more, such as about 20 minutes or more, such as about 30 minutes or more, such as about 50 minutes or more, such as about 100 minutes or more, such as about 150 minutes or more, such as about 200 minutes or more, such as about 250 minutes or more, such as about 300 minutes or more to about 500 minutes or less, such as about 450 minutes or less, such as about 400 minutes or less, such as about 350 minutes or less, such as about 300 minutes or less, such as about 250 minutes or less, such as about 200 minutes or less. Following this further purification, the purified reaction product may comprise BHT in an amount less than 0.6%, such as less than 0.5%, such as less than 0.4%, such as less than 0.3%, such as less than 0.2%, such as less than 0.1 %, such as less than 0.05%, such as less than 0.01 % by weight of the purifiedreaction product. In some instances, the purified reaction product may comprise BHT in an amount of less than 100 ppm, such as less than 50 ppm, such as less than 10 ppm.III. Mixtures of Polymeric Phenolic Antioxidants

[0094] In addition to a polymeric phenolic antioxidant, the present disclosure may also be directed to mixtures of the polymeric phenolic antioxidant as disclosed herein. In this regard, a mixture may include two or more polymeric phenolic antioxidants as defined herein. In this regard, each polymeric phenolic antioxidant may be made utilizing a hydroxybenzene, a diene, and an aldehyde as disclosed herein. Further, each polymeric phenolic antioxidant may have a structure including a first repeating unit structure (I) and a second repeating unit of structure (II) as defined herein.

[0095] When multiple polymeric phenolic antioxidants are utilized, they may be provided in respective amounts. For instance, a first polymeric phenolic antioxidant may be provided in an amount of greater than 0 wt.%, such as 0.1 wt.% or more, such as 0.3 wt.% or more, such as 0.5 wt.% or more, such as 1 wt.% or more, such as 2 wt.% or more, such as 3 wt.% or more, such as 5 wt.% or more, such as 8 wt.% or more, such as 10 wt.% or more, such as 15 wt.% or more, such as 20 wt.% or more, such as 25 wt.% or more, such as 30 wt.% or more, such as 35 wt.% or more, such as 40 wt.% or more, such as 45 wt.% or more, such as 50 wt.% or more, such as 55 wt.% or more, such as 60 wt.% or more, such as 65 wt.% or more, such as 70 wt.% or more, such as 75 wt.% or more, such as 80 wt.% or more, such as 85 wt.% or more, such as 90 wt.% or more, such as 95 wt.% or more. The first polymeric phenolic antioxidant may be provided in an amount of less than 100 wt.%, such as 99 wt.% or less, such as 98 wt.% or less, such as 97 wt.% or less, such as 95 wt.% or less, such as 93 wt.% or less, such as 90 wt.% or less, such as 85 wt.% or less, such as 80 wt.% or less, such as 75 wt.% or less, such as 70 wt.% or less, such as 65 wt.% or less, such as 60 wt.% or less, such as 55 wt.% or less, such as 50 wt.% or less, such as 45 wt.% or less, such as 40 wt.% or less, such as 35 wt.% or less, such as 30 wt.% or less, such as 25 wt.% or less, such as 20 wt.% or less, such as 15 wt.% or less, such as 10 wt.% or less, such as 5 wt.% or less. In one embodiment, the aforementioned weight percentages may be based on the combined weight of thefirst polymeric phenolic antioxidant and the second polymeric phenolic antioxidant. In another embodiment, the aforementioned weight percentages may be based on the total weight of all the polymeric phenolic antioxidants.

[0096] Similarly, a second polymeric phenolic antioxidant may be provided in an amount of greater than 0 wt.%, such as 0.1 wt.% or more, such as 0.3 wt.% or more, such as 0.5 wt.% or more, such as 1 wt.% or more, such as 2 wt.% or more, such as 3 wt.% or more, such as 5 wt.% or more, such as 8 wt.% or more, such as 10 wt.% or more, such as 15 wt.% or more, such as 20 wt.% or more, such as 25 wt.% or more, such as 30 wt.% or more, such as 35 wt.% or more, such as 40 wt.% or more, such as 45 wt.% or more, such as 50 wt.% or more, such as 55 wt.% or more, such as 60 wt.% or more, such as 65 wt.% or more, such as 70 wt.% or more, such as 75 wt.% or more, such as 80 wt.% or more, such as 85 wt.% or more, such as 90 wt.% or more, such as 95 wt.% or more. The second polymeric phenolic antioxidant may be provided in an amount of less than 100 wt.%, such as 99 wt.% or less, such as 98 wt.% or less, such as 97 wt.% or less, such as 95 wt.% or less, such as 93 wt.% or less, such as 90 wt.% or less, such as 85 wt.% or less, such as 80 wt.% or less, such as 75 wt.% or less, such as 70 wt.% or less, such as 65 wt.% or less, such as 60 wt.% or less, such as 55 wt.% or less, such as 50 wt.% or less, such as 45 wt.% or less, such as 40 wt.% or less, such as 35 wt.% or less, such as 30 wt.% or less, such as 25 wt.% or less, such as 20 wt.% or less, such as 15 wt.% or less, such as 10 wt.% or less, such as 5 wt.% or less. In one embodiment, the aforementioned weight percentages may be based on the combined weight of the first polymeric phenolic antioxidant and the second polymeric phenolic antioxidant. In another embodiment, the aforementioned weight percentages may be based on the total weight of all the polymeric phenolic antioxidants.IV. Stabilizer Composition

[0097] In one embodiment, the polymeric phenolic antioxidant (or mixture thereof) may be provided within a stabilizer composition. For instance, the stabilizer composition may include a combination of components for providing a stabilizing effect to a material for a particular application. In this regard, the stabilizer composition may comprise the polymeric phenolic antioxidant (or mixture thereof) as disclosed herein. In one particular embodiment, the stabilizercomposition may comprise the polymeric phenolic antioxidant (or mixture thereof) as disclosed herein and one or more additives. The one or more additives may be additives generally known in the art. For instance, the one or more additives may include a further antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, an acid scavenger, a clarifying agent, a nucleating agent, etc. or a mixture thereof.

[0098] The stabilizer composition may comprise a further antioxidant. For instance, the further antioxidant may comprise one or more of a further phenolic antioxidant, an organic phosphite antioxidant, a sulfur-containing antioxidant, an aminic antioxidant, or a mixture thereof.

[0099] In one embodiment, the further antioxidant may comprise a further phenolic antioxidant. Such phenolic antioxidant may be a fully hindered phenolic antioxidant, a partially hindered phenolic antioxidant, a low-hindered phenolic antioxidant, a non-hindered phenolic antioxidant, or a mixture thereof. Such terms “fully hindered,” “partially hindered,” “low-hindered,” and “non-hindered” are generally understood by one skilled in the art.

[0100] In this context, by “fully hindered” it is preferably meant that the phenolic antioxidant comprises substituent hydrocarbyl groups on both positions ortho to the phenolic -OH group, each of those substituent groups being branched at the Ci and / or C2 position, preferably at the Ci position, with respect to the aromatic ring.

[0101] The fully hindered phenolic antioxidant, if present, may comprise tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane (ANOX™ 20- CAS 6683-19-8); 2,2'thiodiethylene bis[3(3,5-di-t-butyl hydroxyphenyl)propionate] (ANOX™ 70-CAS 41484-35-9); octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl) propionate (ANOX™ PP18-CAS 2082-79-3); 1 ,3,5-tris(3,5-di-t-butyl-4- hydroxybenzyl) isocyanurate (ANOX™ IC14-CAS 27676-62-6); 1 ,3,5-trimethyl- 2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene (ANOX™ 330 CAS 1709-70-2); N,N'-hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide] (LOWINOX™ HD98-CAS 23128-74-7); 1 ,2-bis(3,5-di-t-butyl-4- hydroxyhydrocinnamoyl)hydrazine (LOWINOX™ MD24-CAS 32687-78-8); 2,2'- ethylidenebis[4,6-di-t-butylphenol] (ANOX™ 29-CAS 35958-30-6); butylated hydroxytoluene (BHT-CAS 128-37-0); and / or compatible mixtures of two or more thereof. In one embodiment, the fully hindered phenolic antioxidant may compriseoctadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl) propionate (ANOX™ PP18-CAS 2082-79-3).

[0102] In this context, by “partially hindered” it is preferably meant that the phenolic antioxidant comprises at least one substituent hydrocarbyl group ortho to the phenolic -OH group, only one of the or each substituent group being branched at the Ci and / or C2 position, preferably at the Ci position, with respect to the aromatic ring.

[0103] The partially hindered phenolic antioxidant, if present, may comprise1 .3.5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1 , 3,5-triazine-2 ,4,6-( 1 H, 3H, 5H)-trione (LOWINOX™ 1790-CAS 40601-76-1); triethyleneglycol-bis-[3-(3-t-butyl- 4-hydroxy-5-methylphenyl)propionate] (LOWINOX™ GP45-CAS 36443-68-2); the butylated reaction product of p-cresol and dicyclopentadiene (LOWINOX™ CPL- CAS 68610-51-5); 2,2'-methylenebis(6-t-butyl methylphenol) (LOWINOX™ 22M46- CAS 119-47-1); ethylene bis[3,3-bis[3-(1 , 1 -dimethylethyl)-4- hydroxyphenyl]butanoate] (CAS 32509-66-3); and / or compatible mixtures of two or more thereof.

[0104] In this context, by “low hindered” it is preferably meant that the phenolic antioxidant comprises at least one substituent hydrocarbyl group ortho to the phenolic -OH group, none of those substituent groups being branched at the Ci or C2 position, preferably at the Ci position, with respect to the aromatic ring.

[0105] In this context, by “non-hindered” it is preferably meant that the phenolic antioxidant comprises no substituent hydrocarbyl groups ortho to the phenolic -OH group.

[0106] The stabilizer composition may include a phosphite antioxidant. In particular, the phosphite antioxidant may be an organic phosphite antioxidant. The phosphite antioxidant may include, but is not limited to, bis(2,4,di-t- butylphenyl)pentaerythritol diphosphite (ULTRANOX™ 626 — CAS 26741-53-7);2.4.6-tri-tert-buty lphenyl-2-butyl-2-ethy I- 1 ,3-propanediol phosphite (ULTRANOX™ 641— CAS 161717-32-4); tris(2,4-di-t-butylphenyl)phosphite (ALKANOX™ 240— CAS 31570-04-4); tetrakis (2,4-di-t-butylphenyl)4,4'-biphenylene diphosphonite (ALKANOX™ 24-44— CAS 38613-77-3); tris(4-n-nonylphenyl)phosphite (WESTON™ TNPP — CAS 26523-78-4); distearylpentaerythritol diphosphite (WESTON™ 618 — CAS 3806-34-6); bis(2,4-dicumylphenyl) pentaerythritoldiphosphite (DOVERPHOS™ 9228— CAS 154862-43-8, available from Dover Chemical Corporation); WESTON™ 705— CAS 939402-02-5; tris(dipropyleneglycol) phosphite, C18H3909P (WESTON™ 430— CAS 36788-39-3); poly(dipropylene glycol) phenyl phosphite (WESTON™ DHOP — CAS 80584- 86-7); diphenyl isodecyl phosphite, C22H31 O3P (WESTON™ DPDP— CAS 26544- 23-0); phenyl diisodecyl phosphite (WESTON™ PDDP— CAS 25550-98-5); heptakis (dipropyleneglycol) triphosphite (WESTON™ PTP — CAS 13474-96-9); bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (PEP 36 — CAS 80693-00-1 , available from Adeka Polymer Additives); tris(2-t- butylphenyl)phosphite (CAS 31502-36-0); trisphenyl phosphite; and / or compatible mixtures of two or more thereof.

[0107] The stabilizer composition may include a sulfur-containing antioxidant. The sulfur-containing antioxidant may comprise one or more thioether groups. Without intending to be limited, the sulfur-containing antioxidant may have a sulfur group with the formula -CH2-(S)x-CH2-, wherein x=1 or 2. In one embodiment, one or both of the -CH2- groups is directly bonded to an aromatic group. In another embodiment, neither of the -CH2- groups is directly bonded to an aromatic group. Particularly, in one embodiment, the sulfur-containing antioxidant may have the formula V-CH2-(S)x-CH2-W, wherein x=1 or 2 and wherein V and W respectively may be the same or different and may be or contain an aliphatic group.

[0108] The sulfur-containing antioxidant may include, but is not limited to, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1 ,3,5-triazine (CAS 991 - 84-4); 4,6-bis(octylthiomethyl)-o-cresol (LOWINOX™ 520— CAS 110553-27-0); 2,2'thiodiethylene bis[3(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (ANOX™70 — CAS 41484-35-9); dilauryl thiodipropionate (NAUGARD™ DLTDP— CAS 123-28-4); distearyl thiodipropionate (NAUGARD™ DSTSP— CAS 693-36-7); ditridecylthiodipropionate (NAUGARD™ DTDTDP— CAS 10595-72-9); pentaerythritol tetrakis (p-laurylthiopropionate) (NAUGARD™ 412S — CAS 29598- 76-3); 2,4-bis(dodecylthiomethyl)-6-methylphenol (IRGANOX™ 1726— CAS 110675-26-8, available from BASF); distearyl-disulfide (CAS 2500-88-1 ); 4,4'- thiobis(2-tert-butyl-5-methylphenol) (LOWINOX™ TBM-6-CAS 96-69-5); 2,2'-thiobis(6-t-butyl-4-methylphenol) (LOWINOX™ TBP-6-CAS 90-66-4); and / or compatible mixtures of two or more thereof.

[0109] The stabilizer composition may include an aminic antioxidant. The aminic antioxidant may include, but is not limited to, acetone diphenylamine (AMINOX™-CAS 68412-48-6); reaction products of diphenylamine and acetone (BLE™-CAS 112-39-4); N,N'-diphenyl-p-phenylenediamine (FLEXAMINE™-CAS 74-31-7); benzeneamine, bis[4-(2-phenyl-2-propyl)phenyl]amine (NAUGARD™ 445-CAS 10081-67-1); poly(1 ,2-dihydro-2,2,4-trimethylquinoline) (NAUGARD™ Q- CAS 26780-96-1); dioctyldiphenylamine (OCTAMI NE™-CAS 101-67-7); 1 ,4- benzenediamine, N,N'-mixed phenyl and tolyl derivatives (NOVAZONE™ AS-CAS 68953-84-4); N , N', N"-tris[4-[(1 ,4-dimethylpentyl)amino]phenyl]-1 ,3,5-triazine-2,4,6- triamine (DURAZONE™ 37-CAS 121246-28-4); N-isopropyl-N'-phenyl-1 ,4- phenylenediamine (FLEXZONE™ 3C-CAS 101-72-4); N-phenyl-, reaction products with 2,4,4-trimethylpentene (NAUGARD™ PS30-CAS 68411-46-1 ); N,N-bis-(1 ,4- dimethylpentyl)-p-phenylenediamine (FLEXZONE™ 4L-CAS 3081-14-9); diphenylamine (CAS 122-39-4); (1 ,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (CAS 793-24-8); and / or compatible mixtures of two or more thereof.

[0110] The stabilizer composition may include a UV stabilizer. The UV stabilizer may include a hindered amine light stabilizer and / or a UV absorber. The UV stabilizer may include, but is not limited to, butanedioic acid, 1 ,4-dimethyl ester, polymer with 4-hydroxy-2, 2, 6, 6-tetramethyl-1 -piperidineethanol (LOWILITE™ 62- CAS 65447-77-0); bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (LOWILITE™ 77- CAS 52829-07-9); poly[[6-[(1 , 1 ,3,3-tetramethylbutyl)amino]-1 ,3,5-triazine-2,4- diyl][2,2,6,6-tetramethyl-4-piperidiyl)imino]-1 ,6-hexanediyl[(2,2,6,6-tetramethyl-4- piperidiyl)imino]]) (LOWILITE™ 94-CAS 70624-18-9); 1 ,5,8, 12-tetrakis[4,6-bis(N- butyl-N-1 ,2,2,6,6-pentamethyl piperidylamino)-1 ,3,5-triazin-2-yl]-1 ,5,8,12- tetraazadodecane (LOWILITE™ 19-CAS 106990-43-6); bis(1 ,2,2,6, 6-pentamethyl- 4-piperidyl) sebacate (LOWILITE™ 92-CAS 41556-26-7); and / or compatible mixtures of two or more thereof.

[0111] The stabilizer composition may include an acid scavenger. The acid scavenger may include one or more of a metal oxide, a metal hydroxide, a metal carbonate, a metal carboxylate, and / or a metal salt. In one embodiment, the acid scavenger may comprise a metal carboxylate. The metal carboxylate may includea metal stearate and / or a metal lactate. In one embodiment, the metal carboxylate comprises a metal stearate. The metal stearate may include, but is not limited to, calcium stearate, zinc stearate, aluminum stearate, magnesium stearate, lithium stearate, sodium stearate, cadmium stearate, barium stearate and / or a mixture of two or more thereof. The metal lactate may include, but is not limited to, sodium lactate, magnesium lactate, calcium lactate, zinc lactate and / or a mixture of two or more thereof. In one embodiment, the acid scavenger may include a metal oxide. The metal oxide may include, but is not limited to, zinc oxide, magnesium oxide, titanium dioxide, etc. or a mixture thereof. In one embodiment, the acid scavenger may include a metal carbonate. The metal carbonate may include, but is not limited to, calcium carbonate, hydrotalcite, a hydrotalcite-like compound, or a mixture thereof.

[0112] The stabilizer composition may include a clarifying agent and / or a nucleating agent. In one embodiment, the stabilizer composition may include a clarifying agent. In another embodiment, the stabilizer composition may include a nucleating agent. In a further embodiment, the stabilizer composition may include a clarifying agent and a nucleating agent. These agents may include a metal benzoate and / or a sorbitol derivative. The metal benzoate, if present, may comprise sodium benzoate, magnesium benzoate, calcium benzoate, zinc benzoate and / or a mixture of two or more thereof. These agents may include bis(3,4-dimethylbenzylidene) sorbitol (CAS 135861-56-2); bis(4-propylbenzylidene) sorbitol (CAS 882073-43-0); 2,4,8, 10-tetra(tert-butyl)-6-hydroxy-12H- dibenzo[d,g][1 ,3,2]dioxaphosphocin 6-oxide, sodium salt (CAS 85209-91-2); and / or compatible mixtures of two or more thereof.

[0113] The melting temperature of a stabilizer composition, such as one including the polymeric phenolic antioxidant (or mixture thereof) and one or more antioxidants, may be a particular temperature. For instance, the melting temperature may be 50°C or more, such as 60°C or more, such as 70°C or more, such as 80°C or more, such as 90°C or more, such as 100°C or more, such as 110°C or more, such as 120°C or more, such as 130°C or more, such as 140°C or more, such as 150°C or more, such as 160°C or more, such as 170°C or more, such as 180°C or more, such as 190°C or more. The melting temperature may be 250°C or less, such as 240°C or less, such as 230°C or less, such as 220°C orless, such as 210°C or less, such as 200°C or less, 190°C or less, such as 180°C or less, such as 170°C or less, such as 160°C or less, such as 150°C or less, such as 140°C or less, such as 130°C or less, such as 120°C or less, such as 110°C or less, such as 100°C or less, such as 90°C or less, such as 80°C or less, such as 70°C or less. The melting temperature may be determined using means generally known in the art, such as dynamic scanning calorimetry.V. Use / Application

[0114] The polymeric phenolic antioxidant (or mixture thereof) and / or the stabilizer composition as disclosed herein may be utilized in a number of applications. For instance, as one example, the polymeric phenolic antioxidant (or mixture thereof) and / or the stabilizer composition as disclosed herein may be utilized to stabilize a polymer. In this regard, the present disclosure may also be directed to use of the polymeric phenolic antioxidant (or mixture thereof) and / or the stabilizer composition as disclosed herein for stabilizing a polymer.

[0115] In this regard, in one embodiment, the present disclosure is directed to a polymeric composition comprising a polymer and the polymeric phenolic antioxidant (or mixture thereof) as disclosed herein. The polymer is not necessarily limited by the present disclosure. For instance, the polymer may be a thermoplastic polymer, a thermoset polymer, or a mixture thereof. In one embodiment, the polymer may be a thermoset polymer. In another embodiment, the polymer may be a thermoplastic polymer.

[0116] The polymer, in particular the thermoplastic polymer, is not necessarily limited. For instance, the polymer may be a polyolefin, a polystyrene, a polyacrylonitrile, a polyacrylate, a polyurethane, a polyamide, a polyester, a polycarbonate, a polyvinyl chloride, a polyoxyarylene, a polyoxyalkylene, an elastomer, a rubber and / or suitable mixtures, blends or copolymers thereof. In addition, the polymer may be a homopolymer or a copolymer. In one embodiment, the polymer may be a homopolymer. In another embodiment, the polymer may be a copolymer.

[0117] In one embodiment, the polymer may be a polyolefin. For instance, the polyolefin may comprise polyethylene, polypropylene, polybutylene, a higher polyalkene, or a mixture thereof. In one embodiment, the polyolefin may comprise polyethylene and / or polypropylene. The polyethylene may comprise low densitypolyethylene (LDPE), linear low-density polyethylene (LLDPE), medium density polyethylene (MDPE) and / or high density polyethylene (HDPE). The polypropylene may be isotactic, syndiotactic or atactic. The polyolefin may comprise a copolymer (or terpolymer), such as a random copolymer (or terpolymer) or a block copolymer (or terpolymer). For instance, the polyolefin may comprise a copolymer of ethylene, propylene, butylene, and / or a higher alkene. The copolymer may be a random copolymer or a block copolymer. For example, the polyolefin may comprise an ethylene / propylene block copolymer, an ethylene / propylene random copolymer, an ethylene / propylene / butylene random terpolymer or an ethylene / propylene / butylene block terpolymer. In addition, such polyolefin may be synthesized using means generally known in the art. For instance, such polyolefin may be catalyzed by a Ziegler-Natta catalyst, a metallocene catalyst, a single-site catalyst, a chromium-based catalyst, and / or suitable combinations thereof.

[0118] In one embodiment, the polymer may be a rubber. The rubber is not necessarily limited. The rubber may be a natural rubber, a synthetic rubber, or a mixture thereof. In one embodiment, the rubber may be a natural rubber. In another embodiment, the rubber may be a synthetic rubber. The rubber may be a styrenic block copolymer in one embodiment. The styrenic block copolymer may be selected from styrene-butadiene-styrene (SBS); styrene-isoprene-styrene (SIS); styrene-ethylene / butylene-styrene (SEBS); styrene-ethylene / propylene (SEP); styrene-butadiene rubber (SBR); or suitable mixtures or blends thereof. The rubber may be an ethylene vinyl acetate polymer. Additionally or alternatively, the rubber may comprise polybutadiene rubber (BR); polyisoprene; acrylonitrile butadiene styrene (ABS) copolymer; acrylonitrile butadiene rubber (NBR); or suitable mixtures or blends thereof. In one embodiment, the rubber may comprise a mixture of a polybutadiene rubber, a styrene-butadiene rubber, and a natural rubber. In one embodiment, the rubber may be a natural rubber latex. In addition, it should be understood that the rubber may comprise any combination of the aforementioned rubbers. In this regard, the rubber may comprise one or more rubbers.

[0119] In one embodiment, the polymer may be an elastomer. The elastomer is not necessarily limited. The elastomer may include, but is not limitedto, polyolefin copolymer elastomers (e.g., EPDM), butyl rubber, natural rubber, styrene-butadiene copolymer rubber, butadiene rubber, acrylonitrile rubber, halogenated rubber such as brominated and chlorinated isobutylene-isoprene copolymer rubber, butadiene-styrene-vinyl pyridine rubber, urethane rubber, polyisoprene rubber, epichlorohydrin terpolymer rubber, polychloroprene, etc. as well as suitable mixtures or blends thereof. The elastomer may be a thermoplastic elastomer. For instance, the thermoplastic elastomer may be a thermoplastic polyolefin elastomer, a thermoplastic vulcanizate, a thermoplastic polyurethane, a thermoplastic copolyester, etc. as well as suitable mixtures or blends thereof.

[0120] The polymeric phenolic antioxidant (or mixture thereof) and / or the stabilizing composition as described herein may be used in emulsion polymerization. For instance, it may be utilized or provided during emulsion polymerization of a polymer, such as a rubber or elastomer as described herein. In one embodiment, the polymeric phenolic antioxidant (or mixture thereof) and / or the stabilizing composition may be provided during emulsion polymerization of acrylonitrile butadiene styrene (ABS) copolymer, styrene-butadiene rubber (SBR), or acrylonitrile butadiene rubber (NBR). In one embodiment, it may be provided during emulsion polymerization of acrylonitrile butadiene styrene (ABS) copolymer. In another embodiment, it may be provided during emulsion polymerization of styrene-butadiene rubber (SBR). In a further embodiment, it may be provided during emulsion polymerization of acrylonitrile butadiene rubber (NBR).

[0121] In addition, the polymer may be in virgin form, in the form of industrial recycle, in the form of post-consumer recycle, and / or any suitable combinations thereof. Accordingly, the polymer may be a virgin form or a recycled form.

[0122] In the aforementioned polymeric composition, the polymeric phenolic antioxidant (or mixture thereof) may be provided in a particular amount. For instance, the polymeric phenolic antioxidant (or mixture thereof) may be provided in an amount of 0.001 wt.% or more, such as 0.005 wt.% or more, such as 0.01 wt.% or more, such as 0.05 wt.% or more, such as 0.1 wt.% or more, such as 0.2 wt.% or more, such as 0.3 wt.% or more, such as 0.4 wt.% or more, such as 0.5 wt.% or more, such as 0.6 wt.% or more, such as 0.7 wt.% or more, such as 0.8 wt.% or more, such as 0.9 wt.% or more, such as 1 wt.% or more, such as 1 .2 wt.% or more, such as 1 .4 wt.% or more, such as 1 .6 wt.% or more, such as 1 .8wt.% or more, such as 2 wt.% or more based on the weight of the composition. The polymeric phenolic antioxidant (or mixture thereof) may be provided in an amount of 10 wt.% or less, such as 9 wt.% or less, such as 8 wt.% or less, such as 7 wt.% or less, such as 6 wt.% or less, such as 5 wt.% or less, such as 4.5 wt.% or less, such as 4 wt.% or less, such as 3.5 wt.% or less, such as 3 wt.% or less, such as 2.8 wt.% or less, such as 2.6 wt.% or less, such as 2.4 wt.% or less, such as 2.2 wt.% or less, such as 2 wt.% or less, such as 1 .8 wt.% or less, such as 1 .6 wt.% or less, such as 1 .4 wt.% or less, such as 1 .2 wt.% or less, such as 1 wt.% or less, such as 0.9 wt.% or less, such as 0.8 wt.% or less, such as 0.7 wt.% or less, such as 0.6 wt.% or less, such as 0.5 wt.% or less, such as 0.4 wt.% or less, such as 0.3 wt.% or less, such as 0.2 wt.% or less based on the weight of the composition.

[0123] In the aforementioned polymeric composition, the polymeric phenolic antioxidant (or mixture thereof) may be provided in a particular amount. For instance, the polymeric phenolic antioxidant (or mixture thereof) may be provided in an amount of 0.001 wt.% or more, such as 0.005 wt.% or more, such as 0.01 wt.% or more, such as 0.05 wt.% or more, such as 0.1 wt.% or more, such as 0.2 wt.% or more, such as 0.3 wt.% or more, such as 0.4 wt.% or more, such as 0.5 wt.% or more, such as 0.6 wt.% or more, such as 0.7 wt.% or more, such as 0.8 wt.% or more, such as 0.9 wt.% or more, such as 1 wt.% or more, such as 1 .2 wt.% or more, such as 1 .4 wt.% or more, such as 1 .6 wt.% or more, such as 1 .8 wt.% or more, such as 2 wt.% or more based on the weight of the polymer. The polymeric phenolic antioxidant (or mixture thereof) may be provided in an amount of 10 wt.% or less, such as 9 wt.% or less, such as 8 wt.% or less, such as 7 wt.% or less, such as 6 wt.% or less, such as 5 wt.% or less, such as 4.5 wt.% or less, such as 4 wt.% or less, such as 3.5 wt.% or less, such as 3 wt.% or less, such as 2.8 wt.% or less, such as 2.6 wt.% or less, such as 2.4 wt.% or less, such as 2.2 wt.% or less, such as 2 wt.% or less, such as 1 .8 wt.% or less, such as 1 .6 wt.% or less, such as 1 .4 wt.% or less, such as 1 .2 wt.% or less, such as 1 wt.% or less, such as 0.9 wt.% or less, such as 0.8 wt.% or less, such as 0.7 wt.% or less, such as 0.6 wt.% or less, such as 0.5 wt.% or less, such as 0.4 wt.% or less, such as 0.3 wt.% or less, such as 0.2 wt.% or less based on the weight of the polymer.

[0124] In the aforementioned polymeric composition, the stabilizer composition may be provided in a particular amount. For instance, the stabilizer composition may be provided in an amount of 0.001 wt.% or more, such as 0.005 wt.% or more, such as 0.01 wt.% or more, such as 0.05 wt.% or more, such as 0.1 wt.% or more, such as 0.2 wt.% or more, such as 0.3 wt.% or more, such as 0.4 wt.% or more, such as 0.5 wt.% or more, such as 0.6 wt.% or more, such as 0.7 wt.% or more, such as 0.8 wt.% or more, such as 0.9 wt.% or more, such as 1 wt.% or more, such as 1 .2 wt.% or more, such as 1 .4 wt.% or more, such as 1 .6 wt.% or more, such as 1 .8 wt.% or more, such as 2 wt.% or more based on the weight of the composition. The stabilizer composition may be provided in an amount of 10 wt.% or less, such as 9 wt.% or less, such as 8 wt.% or less, such as 7 wt.% or less, such as 6 wt.% or less, such as 5 wt.% or less, such as 4.5 wt.% or less, such as 4 wt.% or less, such as 3.5 wt.% or less, such as 3 wt.% or less, such as 2.8 wt.% or less, such as 2.6 wt.% or less, such as 2.4 wt.% or less, such as 2.2 wt.% or less, such as 2 wt.% or less, such as 1 .8 wt.% or less, such as 1 .6 wt.% or less, such as 1 .4 wt.% or less, such as 1 .2 wt.% or less, such as 1 wt.% or less, such as 0.9 wt.% or less, such as 0.8 wt.% or less, such as 0.7 wt.% or less, such as 0.6 wt.% or less, such as 0.5 wt.% or less, such as 0.4 wt.% or less, such as 0.3 wt.% or less, such as 0.2 wt.% or less based on the weight of the composition.

[0125] In the aforementioned polymeric composition, the stabilizer composition may be provided in a particular amount. For instance, the stabilizer composition may be provided in an amount of 0.001 wt.% or more, such as 0.005 wt.% or more, such as 0.01 wt.% or more, such as 0.05 wt.% or more, such as 0.1 wt.% or more, such as 0.2 wt.% or more, such as 0.3 wt.% or more, such as 0.4 wt.% or more, such as 0.5 wt.% or more, such as 0.6 wt.% or more, such as 0.7 wt.% or more, such as 0.8 wt.% or more, such as 0.9 wt.% or more, such as 1 wt.% or more, such as 1 .2 wt.% or more, such as 1 .4 wt.% or more, such as 1 .6 wt.% or more, such as 1 .8 wt.% or more, such as 2 wt.% or more based on the weight of the polymer. The stabilizer composition may be provided in an amount of 10 wt.% or less, such as 9 wt.% or less, such as 8 wt.% or less, such as 7 wt.% or less, such as 6 wt.% or less, such as 5 wt.% or less, such as 4.5 wt.% or less, such as 4 wt.% or less, such as 3.5 wt.% or less, such as 3 wt.% or less, such as2.8 wt.% or less, such as 2.6 wt.% or less, such as 2.4 wt.% or less, such as 2.2 wt.% or less, such as 2 wt.% or less, such as 1 .8 wt.% or less, such as 1 .6 wt.% or less, such as 1 .4 wt.% or less, such as 1 .2 wt.% or less, such as 1 wt.% or less, such as 0.9 wt.% or less, such as 0.8 wt.% or less, such as 0.7 wt.% or less, such as 0.6 wt.% or less, such as 0.5 wt.% or less, such as 0.4 wt.% or less, such as 0.3 wt.% or less, such as 0.2 wt.% or less based on the weight of the polymer.

[0126] When providing for purposes of stabilizing a polymer, the polymeric phenolic antioxidant (or mixture thereof) may be provided in any form. For instance, the polymeric phenolic antioxidant (or mixture thereof) may be provided as individual components (or mixture thereof). In this regard, simply the one or more polymeric phenolic antioxidants may be provided. In another embodiment, they may be provided in the form of a dispersion. In this regard, the present disclosure may also be directed to a dispersion comprising the polymeric phenolic antioxidant (or mixture thereof).

[0127] The dispersion may include a disperse phase and a continuous phase. For instance, the polymeric phenolic antioxidant (or mixture thereof) may be present as particles in the dispersion. Such particles may constitute a disperse phase. In addition, the continuous phase may be a liquid. For instance, the liquid may be water in one embodiment. In another embodiment, the liquid may be an organic solvent.

[0128] In addition to the above, the dispersion may also include any other components as necessary. These other components may include those that may be utilized for stabilizing the dispersion. In one embodiment, the dispersion may include any other stabilizing additives, such as those mentioned in Section IV herein.

[0129] The present disclosure is also directed to an article including the polymeric phenolic antioxidant (or mixture thereof) and / or the stabilizing composition as described herein. In particular, the article may be manufactured from the polymeric composition as described herein. Accordingly, the article may comprise the polymeric phenolic antioxidant(or mixture thereof), the stabilizing composition, and / or the polymeric composition as described herein.

[0130] The article is not necessarily limited by the present disclosure. For instance, the article may comprise an extruded nonwoven material (such as ameltspun, spunbond, or meltblown fabric), an extruded or blown film, or a molded article. Regarding the latter, the molded article may be molded using means generally known in the art. For instance, the molded article may be formed from injection molding, blow molding, compression molding, rotational molding, or extrusion molding.

[0131] The article is not necessarily limited and may include a number of articles in various industries. For instance, the article may include a latex article or articles typically formed from a latex. In general, the article may include, but is not limited to, tires, surgical supplies, personal hygiene products (e.g., gloves, condoms, caps), catheters, tires, balloons, foamed articles, etc. In one embodiment, the article may be a tire. In another embodiment, the article may be a personal hygiene product. In particular, the article may be a glove. The foamed articles may include, but are not limited to, mattresses, pillows, neck rests, toppers, shock absorbers, shaped parts of shoes, shoe soles, garment padding, sportswear, athletic implements, saddles, furniture upholstery, bumpers, automotive dashboards, and carpets / carpet backing.

[0132] The invention will now be more particularly described with reference to the following examples.ExamplesExample 1

[0133] A polymeric phenolic antioxidant according to the present disclosure was synthesized in accordance with the below procedure. In particular, the hydroxybenzenes were p-cresol, the diene was dicyclopentadiene, and the aldehyde was paraformaldehyde (which converted to formaldehyde, thereby rendering R4 in the structures above as hydrogen). The below table provides the specific amounts of the reagents utilized in the synthesis.

[0134] Table I. Reagents for Example 1

[0135] Under a nitrogen purge, a reactor was heated to 55°C. P-cresol and toluene (1 ) were charged under nitrogen and heated to 140°C. Azeotropic distillation was started. The reaction mixture was cooled to 55°C and trifluoromethanesulfonic acid was charged. With a temperature hold of from 55°C- 63°C, dicyclopentadiene was added dropwise. After the addition, the temperature was increased to 131 °C and held for 150 minutes. The mixture was cooled to 100°C and toluene (2) was charged. The paraformaldehyde was added in 10 portions over 5-minute intervals. From the fourth addition, water was collected in a Dean-Stark apparatus. The temperature was maintained at 100°C for 60 minutes. The reaction mixture was cooled to 75°C and toluene (3) was charged along with triethanolamine. The aqueous phase was separated and the organic phase was dripped into heptane (1). The solid was collected via filtration and washed with heptane (2). The solid was dried under vacuum. The polymeric phenolic antioxidant had a melting point of approximately 215°C, a pH (aqueous dispersion) of 8.0-8.5, and a Gardner Color (10% solution in toluene) of 1-3.Example 2

[0136] A polymeric phenolic antioxidant according to the present disclosure was synthesized in accordance with the below procedure. In particular, the hydroxybenzenes were p-cresol, the diene was dicyclopentadiene, and the aldehyde was paraldehyde (which converted to acetaldehyde, thereby rendering R4 in the structures above as methyl). The below table provides the specific amounts of the reagents utilized in the synthesis.

[0137] Table II. Reagents for Example 2

[0138] Under a nitrogen purge, a reactor was heated to 55°C. P-cresol and toluene (1 ) were charged under nitrogen and heated to 140°C. Azeotropic distillation was started. The reaction mixture was cooled to 55°C and trifluoromethanesulfonic acid was charged. With a temperature hold of from 55°C- 63°C, dicyclopentadiene was added dropwise. After the addition, the temperature was increased to 131 °C and held for 150 minutes. The mixture was cooled to 100°C and toluene (2) was charged. The paraldehyde was added in 10 portions over 5-minute intervals. From the fourth addition, water was collected in a Dean- Stark apparatus. The temperature was maintained at 100°C for 60 minutes. The reaction mixture was cooled to 75°C and toluene (3) was charged along with triethanolamine. The aqueous phase was separated and the organic phase was dripped into heptane (1). The solid was collected via filtration and washed with heptane (2). The solid was dried under vacuum. The polymeric phenolic antioxidant had a melting point of approximately 230°C, a pH (aqueous dispersion) of 8.0-8.5, and a Gardner Color (10% solution in toluene) of 2-4Example 3

[0139] A latex polymer including the polymeric phenolic antioxidant of Examples 1 and 2 was formed and tested. In particular, the latex polymer was a low ammonia natural rubber latex and the polymeric phenolic antioxidant was provided in an amount of 1 pph. In particular, various properties were determined after forming the polymer composition, after heat-aging (i.e., exposure to 70°C for 336 hours), and after exposure to ozone (i.e., 100 pphm of ozone at 40°C for 166 hours). The tensile properties were determined in accordance with ASTM D412- 16 (2016), the tear die was determined in accordance with ASTM D62400 (2020), and the yellowing index was determined in accordance with ASTM E313-20(2020). For the averages, at least three samples were measured and the average result was recorded.

[0140] Table 3: Polymer Tensile and Tear Die Properties

[0141] Table 4: Polymer Yellowing Index Properties

[0142] As indicated by the data, the samples formed from the polymeric phenolic antioxidant of Examples 1 and 2 exhibit equivalent if not better properties than certain conventional antioxidants. For instance, the elongation at break strength of the inventive examples was comparable to the conventionalantioxidants. Meanwhile, the initial tensile strength and modulus were greater for the inventive examples compared to at least one conventional antioxidant and equivalent to another conventional antioxidant. Also, the tear die values for the inventive examples were relatively comparable to the conventional antioxidants. In addition, the inventive examples exhibited comparable yellowing index compared to the conventional antioxidants.Example 4

[0143] A latex polymer including the polymeric phenolic antioxidant of Examples 1 and 2 was formed and tested. In particular, the latex polymer was a low ammonia natural rubber latex. In addition, the polymeric phenolic antioxidant was compared against two other conventional antioxidants. In particular, various properties were determined after forming the polymer composition, after heataging (i.e., exposure to 70°C for 336 hours), after exposure to ozone (i.e. , 100 pphm of ozone at 40°C for 166 hours) and after exposure to UV (i.e., Xenon Arc Weathering at 340 nm and irradiance of 0.35 W / (m2nm) for 500 hours). The tensile properties were determined in accordance with ASTM D412-16 (2016) and the tear die was determined in accordance with ASTM D62400 (2020). For the averages, at least three samples were measured and the average result was recorded.

[0144] Table 5: Formulation Information

[0145] T able 6: Polymer T ensile and T ear Die Properties

[0146] As indicated by the data, the samples formed from the polymeric phenolic antioxidant of Examples 1 and 2 exhibit equivalent if not better properties than certain conventional antioxidants. For instance, the elongation at break of the inventive examples was comparable to the conventional antioxidants. Depending on the conditions, the stress at break, M100, and M300 of the inventive examples was comparable to the conventional antioxidants. Also, the tear die values for the inventive examples at certain conditions were relatively comparable to the conventional antioxidants.Example 5

[0147] A rubber mixture including the polymeric phenolic antioxidant ofExamples 1 and 2 was formed and tested. In addition, the polymeric phenolicantioxidant was compared against other conventional antioxidants. The tensile properties of these compositions were determined at various conditions.

[0148] Table ?: Formulation Information

[0149] The tensile properties were measured in accordance with ASTM D412-16 (2016) (500 mm / min) and the durometer was measured in accordance with ASTM D2240-15 (2021). The original properties were determined as well as properties of specimens after heat-aging for 72 hours at 100°C in a forced air oven and after heat-aging for 504 hours at 100°C in a forced air oven.

[0150] Table 8: Testing Results for Original Samples

[0151] Table 9: Testing Results for Heat-Aged (72 hours) Samples

[0152] Table 10: Testing Results for Heat-Aged (504 hours) Samples

[0153] These and other modifications and variations of the present disclosure may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present disclosure. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only and is not intended to limit the disclosure so further described in such appended claims.

Claims

Claims1 . A polymeric phenolic antioxidant which is the reaction product of a hydroxybenzene, a diene, and an aldehyde.

2. The polymeric phenolic antioxidant of claim 1 , wherein the polymeric phenolic antioxidant has a first repeating unit structure (I) and a second repeating unit of structure (II):wherein:A is a first hydroxybenzene residue;B is a diene residue;P is a second hydroxybenzene residue;S is an aldehyde residue; n is an integer of 1 or more; and m is an integer of 1 or more.

3. The polymeric phenolic antioxidant of any preceding claim, wherein the hydroxybenzene comprises a substituted hydroxybenzene.

4. The polymeric phenolic antioxidant of any one of claims 1 -3, wherein the hydroxybenzene is substituted with an aryl, an alkoxy, an aryloxy, a carboxyl, a halogen, or a hydroxy.

5. The polymeric phenolic antioxidant of any one of claims 1 -3, wherein the hydroxybenzene is substituted with an alkyl.

6. The polymeric phenolic antioxidant of claim 5, wherein the alkyl has 1 or more to 20 or less carbon atoms; wherein optionally the alkyl has 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more carbon atoms, and 20 or less, optionally 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less carbon atoms; or wherein the alkyl is methyl.

7. The polymeric phenolic antioxidant of any one of claims 1 -3 or 5-6, wherein the hydroxybenzene comprises a cresol, optionally meta-cresol or paracresol.

8. The polymeric phenolic antioxidant of any preceding claim, wherein the hydroxybenzene comprises a monohydroxybenzene.

9. The polymeric phenolic antioxidant of any one of claims 1-7, wherein the hydroxybenzene comprises a dihydroxybenzene comprising catechol, hydroquinone, resorcinol, or a mixture thereof.

10. The polymeric phenolic antioxidant of any one of claims 1 -9, wherein the diene comprises a conjugated diene.11 . The polymeric phenolic antioxidant of any one of claims 1 -9, wherein the diene comprises an unconjugated diene.

12. The polymeric phenolic antioxidant of any preceding claim, wherein the diene comprises from 4 or more to 20 or less non-hydrogen atoms; wherein optionally the diene has 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more or 10 or more non-hydrogen atoms and 20 or less, optionally 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, or 6 or less non-hydrogen atoms; wherein optionally the non-hydrogen atoms include any combination of carbon, oxygen, nitrogen, and phosphorus.

13. The polymeric phenolic antioxidant of any preceding claim, wherein the diene comprises a linear or branched diene.

14. The polymeric phenolic antioxidant of any one of claims 1-12, wherein the diene comprises a cyclic diene.

15. The polymeric phenolic antioxidant of any one of claims 1 -12, wherein the diene comprises a cyclopentadiene, a cyclohexadiene, a cycloheptadiene, a cyclooctadiene, a vinylnorbornene, a norbornadiene, an ethylidene norbornene, a divinylbenzene, dipentene, or a mixture thereof.

16. The polymeric phenolic antioxidant of any one of claims 1-12, wherein the diene comprises dicyclopentadiene.

17. The polymeric phenolic antioxidant of any one of claims 1 -16, wherein the aldehyde comprises acetaldehyde and / or formaldehyde.

18. The polymeric phenolic antioxidant of any preceding claim, wherein the polymeric phenolic antioxidant comprises less than about 10% by weight of reaction product having a molecular weight of less than about 500 Da and comprises less than about 25% by weight of reaction product having a molecular weight of less than about 1000 Da.

19. The polymeric phenolic antioxidant of any preceding claim, wherein the polymeric phenolic antioxidant has a number average molecular weight of from 400 g / mol or more to 30,000 g / mol or less and / or a weight average molecular weight of from 400 g / mol or more to 30,000 g / mol or less; wherein optionally the polymeric phenolic antioxidant has a number average molecular weight and / or a weight average molecular weight of 400 g / mol or more, 500 g / mol or more, 600 g / mol or more, 700 g / mol or more, 800 g / mol or more, 900 g / mol or more, 1 ,000 g / mol or more, 1 ,200 g / mol or more, 1 ,400 g / mol or more, 1 ,600 g / mol or more,1 ,800 g / mol or more, 2,000 g / mol or more, 2,400 g / mol or more, 2,800 g / mol or more, 3,000 g / mol or more, 3,400 g / mol or more, 3,800 g / mol or more, 4,000 g / mol or more, 4,400 g / mol or more, 4,800 g / mol or more, 5,000 g / mol or more, 5,500 g / mol or more, 6,000 g / mol or more, 6,500 g / mol or more, 7,000 g / mol or more, 7,500 g / mol or more, 8,000 g / mol or more, 8,500 g / mol or more, 9,000 g / mol or more, 9,500 g / mol or more or 10,000 g / mol or more; and / or a number average molecular weight and / or a weight average molecular weight of 30,000 g / mol or less, 26,000 g / mol or less, 22,000 g / mol or less, 20,000 g / mol or less, 18,000 g / mol or less, 16,000 g / mol or less, 14,000 g / mol or less, 12,000 g / mol or less, 10,000 g / mol or less, 8,000 g / mol or less, 6,000 g / mol or less, 5,000 g / mol or less, 4,000 g / mol or less, or 3,000 g / mol or less.

20. The polymeric phenolic antioxidant of any preceding claim, wherein the polymeric phenolic antioxidant has a melting temperature of from 100°C or more to 300°C or less and / or a Gardner color of 1 or more to 9 or less.21 . A polymeric phenolic antioxidant mixture comprising a first polymeric phenolic antioxidant of any preceding claim and a second polymeric phenolic antioxidant of any preceding claim.

22. A stabilizer composition comprising the polymeric phenolic antioxidant of any one of claims 1 to 20 or the polymeric phenolic antioxidant mixture of claim 21 , wherein the stabilizer composition further comprises a further antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, an acid scavenger, a clarifying agent, a nucleating agent, or a mixture thereof.

23. A polymeric composition comprising a polymer and the polymeric phenolic antioxidant of any one of claims 1 to 20 or the polymeric phenolic antioxidant mixture of claim 21 .

24. A polymeric composition comprising a polymer and the stabilizer composition of claim 22.

25. A polymeric composition of claim 23 or 24, wherein the polymer comprises a rubber.

26. An article comprising the polymeric phenolic antioxidant of any one of claims 1 to 20, the polymeric phenolic antioxidant mixture of claim 21 , the stabilizer composition of claim 22, or the polymeric composition of any one of claims 23-25.

27. The article of claim 26, wherein the article comprises a glove.

28. A method of making the polymeric phenolic antioxidant of any one of claims 1-20, the method comprising: reacting a hydroxybenzene and a diene to obtain a first reaction product; reacting the first reaction product in the presence of the hydroxybenzene and an aldehyde to obtain a crude reaction product comprising the polymeric phenolic antioxidant.