US20060041087A1 - Anti-oxidant macromonomers and polymers and methods of making and using the same - Google Patents

Anti-oxidant macromonomers and polymers and methods of making and using the same Download PDF

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US20060041087A1
US20060041087A1 US11/184,716 US18471605A US2006041087A1 US 20060041087 A1 US20060041087 A1 US 20060041087A1 US 18471605 A US18471605 A US 18471605A US 2006041087 A1 US2006041087 A1 US 2006041087A1
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antioxidant
group
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macromonomer
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Ashok Cholli
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Polnox Corp
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Definitions

  • antioxidants that possess (a) enhanced antioxidant properties, and (b) active and thermally stable at elevated temperatures. Designing of new antioxidants possessing these two desired properties is essential today for the following reasons: The amount of synthetic antioxidant added to some materials, especially in processed food products, is restricted and need to follow Food and Drug Administration (FDA) regulations (for example, 21 CFR 110, 115, 185, 515 and 615, 21 CFR 182.1660, 3169 and 3173, and 21 CFR 184.1660).
  • FDA Food and Drug Administration
  • antioxidants such as BHA (butylated hydroxy anisole) and BHT (butylated hydroxy toluene) are suspected to be carcinogenic beyond certain concentration. It is desirable to design new antioxidants possessing enhanced antioxidant activities so that the materials are protected with lower amount of synthetic antioxidants.
  • thermally stable antioxidants are required to protect the materials at high temperatures. For instance, many polyolefins and thermoplastics are processed at elevated temperatures. At these elevated temperatures, some of the antioxidants used today are themselves prone to degradation at these elevated temperatures. There is a need for antioxidants that are stable and active at elevated temperatures so that the new antioxidants could be used in high temperature material applications.
  • FIG. 1 depicts a) the 1 H NMR spectrum of 4-acetoxy benzoic acid, b) the 1 H NMR spectrum of 3,5-di-tert-butyl-4-hydroxy benzyl alcohol, c) the 1 H NMR spectrum of the macromonomer formed from 4-acetoxy benzoic acid and 3,5-di-tert-butyl-4-hydroxy benzyl alcohol (compound 1), d) the 1 H NMR spectrum of the macromonomer formed from deacetylation of acetylated monomer (compound 1), and e) the 1 H NMR spectrum of macromonomer 6.
  • FIG. 2 depicts a) the 1 H NMR spectrum of poly(macromonomer compound 1) formed from deacetylation of acetylated monomer (compound 1) and b) the 1 H NMR spectrum of poly(macromonomer compound 6).
  • FIG. 3 depicts the comparison of oxidative induction time (OIT) (min) of polypropylene samples containing 200 ppm of polymeric macromonomer antioxidant (polymer 1) (trace two) and Irganox 1010 (trace one).
  • OIT oxidative induction time
  • the present invention relates to methods of preparing an antioxidant polymer comprising polymerizing macromonomers that comprise an antioxidant.
  • an antioxidant By having the antioxidant as part of the macromonomer, a polymer with a higher density of antioxidants is prepared more efficiently than coordinating antioxidants to an already formed polymer.
  • the methods of polymerization of the present invention also encompass methods of copolymerization wherein different macromonomers comprising different antioxidants may be used. Alternatively, the other macromonomer, or monomer, may not include an antioxidant depending on the intended use of the copolymer and desired properties.
  • the macromonomer comprising an antioxidant may comprise more than one antioxidant which may be the same or different. Polymerization may be carried out with a variety of catalysts known to one of ordinary skill in the art.
  • the catalyst selected will depend, in part, upon the nature of the macromonomer polymerized.
  • the macromonomer is benzene or olefin based, wherein the benzene or olefin is substituted with an antioxidant.
  • an element means one element or more than one element.
  • antioxidant is art-recognized and refers to any of various compounds that are added to substances in order to reduce the effect of oxidation and the accompanying degradation of properties.
  • substances that utilize antioxidants include paints, plastics, gasoline, rubber, and food products.
  • Oxidation is art-recognized and refers to any reaction in which one or more electrons are removed from a species, thus increasing its valence (oxidation state).
  • radical is art-recognized and refers to an electrically neutral or ionic group having one or more unpaired electrons.
  • substrate is used herein to mean any physical entity, commonly homogeneous, that occurs in macroscopic amounts.
  • polymer is art-recognized and refers to a macromolecule comprising a repeating monomeric unit.
  • the term “monomer” is art-recognized and refers to a compound that is able to combine in long chains with other like or unlike molecules to produce polymers.
  • the terms “macromonomer” and “monomer” are considered functionally the same.
  • the term “homopolyer” is art-recognized and refers to a polymer derived by a single repeating monomer.
  • copolymer is art-recognized and refers to a polymer that is composed of polymer chains made up of two or more chemically different repeating units that can be in different sequences.
  • the phrase “bulky alkyl group” is used herein to mean an alkyl group branched alpha or beta to a group, such as a benzene ring.
  • the bulky alkyl group may be branched twice alpha to a benzene ring (i.e., to form an alpha-tertiary carbon), such as in a t-butyl group.
  • Other non-limiting examples of a bulky alkyl group include isopropyl, 2-butyl, 3-pentyl, 1,1-dimethlypropyl, 1-ethyl-1-methylpropyl, and 1,1-diethylpropyl.
  • enzyme is art-recognized and refers to a protein that catalyzes reactions without itself being permanently altered or destroyed.
  • enzyme mimetic is art-recognized and refers to any substance that mimics the activity of an enzyme.
  • catalyst is art-recognized and refers to any substance that affects the rate of a chemical reaction without itself being consumed ore essentially altered.
  • synthetic is art-recognized and refers to production by in vitro chemical or enzymatic synthesis.
  • the term “instructional material” or “instructions” includes a publication, a recording, a diagram, or any other medium of expression which can be used to communicate the usefulness of a subject composition described herein for a method of treatment or a method of making or using a subject composition.
  • the instructional material may, for example, be affixed to a container which contains the composition or be shipped together with a container which contains the composition or be contained in a kit with the composition. Alternatively, the instructional material may be shipped separately from the container with the intention that the instructional material and the composition be used cooperatively by the recipient.
  • “Small molecule” is an art-recognized term. In certain embodiments, this term refers to a molecule which has a molecular weight of less than about 2000 amu, or less than about 1000 amu, and even less than about 500 amu.
  • aliphatic is an art-recognized term and includes linear, branched, and cyclic alkanes, alkenes, or alkynes.
  • aliphatic groups in the present invention are linear or branched and have from 1 to about 20 carbon atoms.
  • alkyl is art-recognized, and includes saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl substituted cycloalkyl groups, and cycloalkyl substituted alkyl groups.
  • a straight chain or branched chain alkyl has about 30 or fewer carbon atoms in its backbone (e.g., C 1 -C 30 for straight chain, C 3 -C 30 for branched chain), and alternatively, about 20 or fewer.
  • cycloalkyls have from about 3 to about 10 carbon atoms in their ring structure, and alternatively about 5, 6 or 7 carbons in the ring structure.
  • alkyl is also defined to include halosubstituted alkyls.
  • aralkyl is art-recognized, and includes alkyl groups substituted with an aryl group (e.g., an aromatic or heteroaromatic group).
  • alkenyl and alkynyl are art-recognized, and include unsaturated aliphatic groups analogous in length and possible substitution to the alkyls described above, but that contain at least one double or triple bond respectively.
  • lower alkyl refers to an alkyl group, as defined above, but having from one to ten carbons, alternatively from one to about six carbon atoms in its backbone structure. Likewise, “lower alkenyl” and “lower alkynyl” have similar chain lengths.
  • heteroatom is art-recognized, and includes an atom of any element other than carbon or hydrogen.
  • Illustrative heteroatoms include boron, nitrogen, oxygen, phosphorus, sulfur and selenium, and alternatively oxygen, nitrogen or sulfur.
  • aryl is art-recognized, and includes 5-, 6- and 7-membered single-ring aromatic groups that may include from zero to four heteroatoms, for example, benzene, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine and pyrimidine, and the like.
  • aryl groups having heteroatoms in the ring structure may also be referred to as “aryl heterocycles” “heteroaryls,” or “heteroaromatics.”
  • the aromatic ring may be substituted at one or more ring positions with such substituents as described above, for example, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromatic moieties, —CF 3 , —CN, or the like.
  • aryl also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings (the rings are “fused rings”) wherein at least one of the rings is aromatic, e.g., the other cyclic rings may be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls.
  • ortho, meta and para are art-recognized and apply to 1,2-, 1,3- and 1,4-disubstituted benzenes, respectively.
  • 1,2-dimethylbenzene and ortho-dimethylbenzene are synonymous.
  • heterocyclyl and “heterocyclic group” are art-recognized, and include 3- to about 10-membered ring structures, such as 3- to about 7-membered rings, whose ring structures include one to four heteroatoms. Heterocycles may also be polycycles.
  • Heterocyclyl groups include, for example, thiophene, thianthrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxathiin, pyrrole, imidazole, pyrazole, isothiazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine, isoquinoline, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthridine, acridine, pyrimidine, phenanthroline, phenazine, phenarsazine, phenothiazine, furazan, phenoxazine, pyrrolidine, o
  • the heterocyclic ring may be substituted at one or more positions with such substituents as described above, as for example, halogen, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, a heterocyclyl, an aromatic or heteroaromatic moiety, —CF 3 , —CN, or the like.
  • substituents as described above, as for example, halogen, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxy
  • polycyclyl and “polycyclic group” are art-recognized, and include structures with two or more rings (e.g., cycloalkyls, cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls) in which two or more carbons are common to two adjoining rings, e.g., the rings are “fused rings”. Rings that are joined through non-adjacent atoms, e.g., three or more atoms are common to both rings, are termed “bridged” rings.
  • rings e.g., cycloalkyls, cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls
  • Each of the rings of the polycycle may be substituted with such substituents as described above, as for example, halogen, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, a heterocyclyl, an aromatic or heteroaromatic moiety, —CF 3 , —CN, or the like.
  • substituents as described above, as for example, halogen, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, si
  • Carbocycle is art recognized and includes an aromatic or non-aromatic ring in which each atom of the ring is carbon.
  • nitro means —NO 2
  • halogen designates —F, —Cl, —Br or —I
  • sulfhydryl means —SH
  • hydroxyl means —OH
  • sulfonyl means —SO 2 —.
  • amine and “amino” are art-recognized and include both unsubstituted and substituted amines, e.g., a moiety that may be represented by the general formulas: wherein R50, R51 and R52 each independently represent a hydrogen, an alkyl, an alkenyl, —(CH 2 ) m —R61, or R50 and R51, taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure; R61 represents an aryl, a cycloalkyl, a cycloalkenyl, a heterocycle or a polycycle; and m is zero or an integer in the range of 1 to 8.
  • R50 or R51 may be a carbonyl, e.g., R50, R51 and the nitrogen together do not form an imide.
  • R50 and R51 each independently represent a hydrogen, an alkyl, an alkenyl, or —(CH 2 ) m —R61.
  • alkylamine includes an amine group, as defined above, having a substituted or unsubstituted alkyl attached thereto, i.e., at least one of R50 and R51 is an alkyl group.
  • acylamino is art-recognized and includes a moiety that may be represented by the general formula: wherein R50 is as defined above, and R54 represents a hydrogen, an alkyl, an alkenyl or —(CH 2 ) m —R61, where m and R61 are as defined above.
  • amide is art recognized as an amino-substituted carbonyl and includes a moiety that may be represented by the general formula: wherein R50 and R51 are as defined above. Certain embodiments of the amide in the present invention will not include imides which may be unstable.
  • alkylthio is art recognized and includes an alkyl group, as defined above, having a sulfur radical attached thereto.
  • the “alkylthio” moiety is represented by one of —S-alkyl, —S-alkenyl, —S-alkynyl, and —S—(CH 2 ) m —R61, wherein m and R61 are defined above.
  • Representative alkylthio groups include methylthio, ethyl thio, and the like.
  • carbonyl is art recognized and includes such moieties as may be represented by the general formulas: wherein X50 is a bond or represents an oxygen or a sulfur, and R55 represents a hydrogen, an alkyl, an alkenyl, —(CH 2 ) m —R61 or a pharmaceutically acceptable salt, R56 represents a hydrogen, an alkyl, an alkenyl or —(CH 2 ) m —R61, where m and R61 are defined above. Where X50 is an oxygen and R55 or R56 is not hydrogen, the formula represents an “ester”.
  • X50 is an oxygen
  • R55 is as defined above
  • the moiety is referred to herein as a carboxyl group, and particularly when R55 is a hydrogen, the formula represents a “carboxylic acid”.
  • X50 is an oxygen
  • R56 is hydrogen
  • the formula represents a “formate”.
  • the oxygen atom of the above formula is replaced by sulfur
  • the formula represents a “thiocarbonyl” group.
  • X50 is a sulfur and R55 or R56 is not hydrogen
  • the formula represents a “thioester.”
  • X50 is a sulfur and R55 is hydrogen
  • the formula represents a “thiocarboxylic acid.”
  • X50 is a sulfur and R56 is hydrogen
  • the formula represents a “thioformate.”
  • X50 is a bond, and R55 is not hydrogen
  • the above formula represents a “ketone” group.
  • X50 is a bond, and R55 is hydrogen
  • the above formula represents an “aldehyde” group.
  • alkoxyl or “alkoxy” are art recognized and include an alkyl group, as defined above, having an oxygen radical attached thereto. Representative alkoxyl groups include methoxy, ethoxy, propyloxy, tert-butoxy and the like.
  • An “ether” is two hydrocarbons covalently linked by an oxygen. Accordingly, the substituent of an alkyl that renders that alkyl an ether is or resembles an alkoxyl, such as may be represented by one of —O-alkyl, —O-alkenyl, —O-alkynyl, —O—(CH 2 ) m —R61, where m and R61 are described above.
  • sulfonate is art recognized and includes a moiety that may be represented by the general formula: in which R57 is an electron pair, hydrogen, alkyl, cycloalkyl, or aryl.
  • sulfonamido is art recognized and includes a moiety that may be represented by the general formula: in which R50 and R56 are as defined above.
  • sulfamoyl is art-recognized and includes a moiety that may be represented by the general formula: in which R50 and R51 are as defined above.
  • sulfonyl is art recognized and includes a moiety that may be represented by the general formula: in which R58 is one of the following: hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl or heteroaryl.
  • sulfoxido is art recognized and includes a moiety that may be represented by the general formula: in which R58 is defined above.
  • phosphonamidite is art recognized and includes moieties represented by the general formulas: wherein Q51, R50, R51 and R59 are as defined above, and R60 represents a lower alkyl or an aryl.
  • Analogous substitutions may be made to alkenyl and alkynyl groups to produce, for example, aminoalkenyls, aminoalkynyls, amidoalkenyls, amidoalkynyls, iminoalkenyls, iminoalkynyls, thioalkenyls, thioalkynyls, carbonyl-substituted alkenyls or alkynyls.
  • selenoalkyl is art recognized and includes an alkyl group having a substituted seleno group attached thereto.
  • exemplary “selenoethers” which may be substituted on the alkyl are selected from one of —Se-alkyl, —Se-alkenyl, —Se-alkynyl, and —Se—(CH 2 ) m —R61, m and R61 being defined above.
  • triflyl, tosyl, mesyl, and nonaflyl are art-recognized and refer to trifluoromethanesulfonyl, p-toluenesulfonyl, methanesulfonyl, and nonafluorobutanesulfonyl groups, respectively.
  • triflate, tosylate, mesylate, and nonaflate are art-recognized and refer to trifluoromethanesulfonate ester, p-toluenesulfonate ester, methanesulfonate ester, and nonafluorobutanesulfonate ester functional groups and molecules that contain said groups, respectively.
  • Me, Et, Ph, Tf, Nf, Ts, and Ms are art recognized and represent methyl, ethyl, phenyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl, p-toluenesulfonyl and methanesulfonyl, respectively.
  • a more comprehensive list of the abbreviations utilized by organic chemists of ordinary skill in the art appears in the first issue of each volume of the Journal of Organic Chemistry ; this list is typically presented in a table entitled Standard List of Abbreviations.
  • Certain monomeric subunits of the present invention may exist in particular geometric or stereoisomeric forms.
  • polymers and other compositions of the present invention may also be optically active.
  • the present invention contemplates all such compounds, including cis- and trans-isomers, R- and S-enantiomers, diastereomers, (D)-isomers, (L)-isomers, the racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention.
  • Additional asymmetric carbon atoms may be present in a substituent such as an alkyl group. All such isomers, as well as mixtures thereof, are intended to be included in this invention.
  • a particular enantiomer of a compound of the present invention may be prepared by asymmetric synthesis, or by derivation with a chiral auxiliary, where the resulting diastereomeric mixture is separated and the auxiliary group cleaved to provide the pure desired enantiomers.
  • the molecule contains a basic functional group, such as amino, or an acidic functional group, such as carboxyl, diastereomeric salts are formed with an appropriate optically active acid or base, followed by resolution of the diastereomers thus formed by fractional crystallization or chromatographic means well known in the art, and subsequent recovery of the pure enantiomers.
  • substitution or “substituted with” includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, or other reaction.
  • substituted is also contemplated to include all permissible substituents of organic compounds.
  • the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds.
  • Illustrative substituents include, for example, those described herein above.
  • the permissible substituents may be one or more and the same or different for appropriate organic compounds.
  • the heteroatoms such as nitrogen may have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms. This invention is not intended to be limited in any manner by the permissible substituents of organic compounds.
  • hydrocarbon is art recognized and includes all permissible compounds having at least one hydrogen and one carbon atom.
  • permissible hydrocarbons include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic organic compounds that may be substituted or unsubstituted.
  • protecting group is art recognized and includes temporary substituents that protect a potentially reactive functional group from undesired chemical transformations.
  • Examples of such protecting groups include esters of carboxylic acids, silyl ethers of alcohols, and acetals and ketals of aldehydes and ketones, respectively.
  • the field of protecting group chemistry has been reviewed. Greene et al., Protective Groups in Organic Synthesis 2 nd ed., Wiley, New York, (1991).
  • hydroxyl-protecting group is art recognized and includes those groups intended to protect a hydroxyl group against undesirable reactions during synthetic procedures and includes, for example, benzyl or other suitable esters or ethers groups known in the art.
  • electron-withdrawing group is recognized in the art, and denotes the tendency of a substituent to attract valence electrons from neighboring atoms, i.e., the substituent is electronegative with respect to neighboring atoms.
  • ⁇ Hammett sigma
  • Exemplary electron-withdrawing groups include nitro, acyl, formyl, sulfonyl, trifluoromethyl, cyano, chloride, and the like.
  • Exemplary electron-donating groups include amino, methoxy, and the like.
  • Contemplated equivalents of the polymers, subunits and other compositions described above include such materials which otherwise correspond thereto, and which have the same general properties thereof (e.g., biocompatible), wherein one or more simple variations of substituents are made which do not adversely affect the efficacy of such molecule to achieve its intended purpose.
  • the methods of the present invention may be methods illustrated in the general reaction schemes as, for example, described below, or by modifications thereof, using readily available starting materials, reagents and conventional synthesis procedures. In these reactions, it is also possible to make use of variants which are in themselves known, but are not mentioned here.
  • Polymerization of the macromonomers can be catalyzed by a natural or synthetic enzyme or an enzyme mimetic capable of polymerizing a substituted benzene compound in the presence of hydrogen peroxide, where the enzyme or enzyme mimetic typically has a heme or related group at the active site.
  • a natural or synthetic enzyme or an enzyme mimetic capable of polymerizing a substituted benzene compound in the presence of hydrogen peroxide, where the enzyme or enzyme mimetic typically has a heme or related group at the active site.
  • One general class of enzymes capable of catalyzing this reaction is commonly referred to as the peroxidases. Horseradish peroxidase, soybean peroxidase, Coprinus cinereus peroxidase, and Arthromyces ramosus peroxidase are readily available peroxidases.
  • Other enzymes capable of catalyzing the reaction include laccase, tyrosinase, and lipase.
  • Suitable enzymes are able to catalyze the formation of a carbon-carbon bond and/or a carbon-oxygen-carbon bond between two aryl (e.g., phenol) groups when a peroxide (e.g., hydrogen peroxide or an organic peroxide) is present.
  • a peroxide e.g., hydrogen peroxide or an organic peroxide
  • a subunit or other portion of a peroxidase is acceptable, provided that the active site of the enzyme is still functional.
  • Enzyme mimetics typically correspond to a part of an enzyme, so that they can carry out the same reaction as the parent enzyme but are generally smaller than the parent enzyme. Also, enzyme mimetics can be designed to be more robust than the parent enzyme, such as to be functional under a wider variety of conditions (e.g., different pH range and/or aqueous, partially aqueous and non-aqueous solvents) and are generally less subject to degradation or inactivation. Suitable enzyme mimetics include hematin, tyro sinase-model complexes and metal-salen (e.g., iron-salen) complexes. Hematin, in particular, can be functionalized to allow it to be soluble under a wider variety of conditions is disclosed in U.S. application Ser. No. 09/994,998, filed Nov. 27, 2001, the contents of which are incorporated herein by reference.
  • the enzymes and enzyme mimetics described above can be immobilized on a solid.
  • the enzymes and enzyme mimetics can be dispersed in a solution or suspension.
  • the macromonomers described herein can also be polymerized by non-enzymatic chemical methods.
  • polymerization can be catalyzed by metal compounds such as iron chloride or a metallocene.
  • polymerization can be catalyzed by cationic, anionic or free radical initiators such as N,N-azobisisobutyromtrile (AIBN), acetylacetone and peroxides (e.g., tert-butyl hydroxide, benzyl peroxide).
  • AIBN N,N-azobisisobutyromtrile
  • acetylacetone and peroxides e.g., tert-butyl hydroxide, benzyl peroxide.
  • Polymerizations of the present invention can be carried out under a wide variety of conditions.
  • the pH is often between about pH 1.0 and about pH 12.0, typically between about pH 6.0 and about pH 11.0.
  • the temperature is generally above about 0° C., such as between about 0° C. and about 45° C. or between about 15° C. and about 30° C. (e.g., room temperature).
  • the solvent can be aqueous (preferably buffered), organic, or a combination thereof.
  • Organic solvents are typically polar solvents such as ethanol, methanol, isopropanol, dimethylformamide (DMF), dioxane, acetonitrile, dimethylsulfoxide (DMSO) and tetrahydrofuran (THF).
  • the concentration of macromonomer or comacromonomers is typically 0.001 M or greater.
  • the concentration of buffer is typically 0.001 M or greater.
  • the enzyme or enzyme mimetic is added to the solution after addition of the antioxidant macromonomer or comacromonomers.
  • a peroxide is then added incrementally to the reaction mixture, such as not to de-activate the enzyme or enzyme mimetic, until an amount approximately stoichiometric with the amount of antioxidant marcromonomer or cocacromonomers has been added.
  • Polymerization preferably results in the formation of C—C bonds between substituted benzene repeat units (i.e., the benzene rings are directly attached to each other in a chain).
  • Preferred polymers will contain at least about 99% C—C bonds, at least about 98% C—C bonds, at least about 95% C—C bonds, at least about 90% C—C bonds, at least about 80% C—C bonds, at least about 70% C—C bonds, at least about 60% C—C bonds or at least about 50% C—C bonds.
  • Especially preferred polymers contain about 100% C—C bonds.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer comprising an antioxidant moiety.
  • polymerization is carried out with a catalyst selected from the group consisting of a peroxidase, laccase, tyosinase, lipase, hematin, metal-salen complex, metallocene, a cationic initiator, an anionic initiator, a radical initiator, or metal halide.
  • the catalyst is horse radish peroxidase (HRP).
  • the catalyst is a Fe-salen complex.
  • the catalyst is AIBN.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer comprising an antioxidant moiety, wherein the macromonomer comprises a benzene ring substituted with an antioxidant moiety.
  • the macromonomer is an alkene substituted with an antioxidant moiety.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer comprising an antioxidant moiety, wherein the antioxidant moiety comprises a hydroxy substituted benzene ring.
  • the benzene ring is substituted with at least one bulky alkyl group.
  • the bulky alkyl group is a t-butyl group.
  • the t-butyl group is adjacent to the hydroxy group.
  • the benzene ring is substituted with 2 t-butyl groups adjacent to the hydroxy group.
  • the present invention relates to a method of preparing an antioxidant polymer comprising reacting a catalyst with a macromonomer having formula I: wherein, independently for each occurrence,
  • the present invention relates to a method of preparing an antioxidant polymer comprising reacting a catalyst with a macromonomer of formula I and the attendant definitions, wherein the catalyst is selected from the group consisting of a peroxidase, laccase, tyosinase, lipase, hematin, metal-salen complex, metallocene, a cationic initiator, an anionic initiator, a radical initiator, or metal halide.
  • the catalyst is horse radish peroxidase (HRP).
  • the catalyst is a Fe-salen complex.
  • the catalyst is AIBN.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein Z is —OC(O)—.
  • Z is —C(O)O—.
  • Z is —C(O)NH—.
  • Z is —NHC(O)—.
  • Z is —NH—.
  • Z is —CH ⁇ N—.
  • Z is —N ⁇ CH—.
  • Z is —C(O)—.
  • Z is —O—.
  • Z is —C(O)OC(O)—.
  • Z is —S—.
  • Z is —S—S—. In another embodiment, Z is —N ⁇ S—. In another embodiment, Z is —S ⁇ N—. In another embodiment, Z is —C(S)O—. In another embodiment, Z is —OC(S). In another embodiment, Z is —OP(O)(OR 4 )O—. In another embodiment, Z is —OP(OR 4 )O—. In another embodiment, Z is a bond.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein both R groups adjacent to —OH are bulky alkyl groups. In a further embodiment, both R groups are t-butyl.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein M is
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein M is
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein at least one R is
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein n is 0.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein m is 1.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein n is 0 and m is 1.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein n is 0, m is 1, and Z is —C(O)O—.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein n is 0, m is 1, Z is —C(O)O—, and the two R groups adjacent to the OH are t-butyl.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein n is 0, m is 1, Z is —C(O)O—, the two R groups adjacent to the OH are t-butyl, and M is
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein n is 0, m is 1, Z is —C(O)O—, the two R groups adjacent to the OH are t-butyl, M is and the R 2 in the para position is OH.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein n is 0, m is 1, Z is —C(O)O—, the two R groups adjacent to the OH are t-butyl, M is the R 2 in the para position is OH, and an adjacent R 2 is OH.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein n is 0, m is 1, Z is —C(O)O—, the two R groups adjacent to the OH are t-butyl, M is the R 2 in the para position is OH, and the two adjacent R 2 's are OH.
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein n is 0, m is 1, Z is —C(O)O—, the two R groups adjacent to the OH are t-butyl, and M is
  • the present invention relates to a method of preparing an antioxidant polymer comprising polymerizing a macromonomer of formula I and the attendant definitions, wherein n is 0, m is 1, Z is —C(O)O—, the two R groups adjacent to the OH are t-butyl, M is and R 3 is H.
  • HRP horse radish peroxidase
  • the enzymatically synthesized polymer chain may contain both C—C and C—O—C couplings in the backbone.
  • these polymeric materials may differ in color from that of starting monomeric antioxidants as a result of partial delocalization of electrons through C—C bonds between the phenolic repeating units. If the color of the polymeric antioxidant is due to its inherent nature arising from the C—C couplings and delocalization of electrons, it is possible to circumvent such color problem by using acrylate functionalized phenolic macromonomers in the formation of polymeric antioxidants.
  • Macromonomer antioxidant compound 6 was polymerized using an initiator, ⁇ , ⁇ ′-azobis(isobtyronitrile) (AIBN) to obtain polymeric macromonomer antioxidants. Polymerization reaction was performed in THF solution. The structure of the polymer was confirmed by high resolution NMR ( FIG. 2 b ). The disappearance of the signals corresponding to olefinic protons indicated the polymerization reaction.
  • AIBN ⁇ , ⁇ ′-azobis(isobtyronitrile)
  • the ASTM D3895 method was used to evaluate the performance of antioxidants in polyolefins. This is an accelerated ageing test at elevated temperatures under oxygen atmosphere.
  • a differential scanning calorimetry (DSC) instrument is used to detect the degradation by exothermic behavior of the polymeric materials containing antioxidants.
  • the typical experimental conditions were as follows: the sample was heated at 20° C./min to reach 200° C. in the nitrogen atmosphere. At this temperature, the sample was held at constant 200° C. for 3 minutes in nitrogen atmosphere. At the end of this 3 minutes period, gas was changed to oxygen (20 ml/min flow rate). The sample was continued to hold at 200° C. till the sample starts degrading. This is indicated by sudden increase in the exothermic heat flow as presented in the DSC curve (See FIG. 3 ).
  • the isothermal oxidative induction time is used to compare the performance polymeric antioxidants in polyolefins.
  • the polypropylene samples were extruded into small pellets by mixing with 200 ppm by weight of antioxidants.
  • FIG. 3 shows the OIT plots for these materials.
  • the performance of polymeric macromonomer antioxidant is ca. 385% better compared to Irgonox 1010.
  • the polymeric macromonomer antioxidant of the subject compositions e.g., which include repetitive elements shown in any of the macromonomer formulas, have molecular weights ranging from about 2000 or less to about 1,000,000 or more daltons, or alternatively about 10,000, 20,000, 30,000, 40,000, or 50,000 daltons, more particularly at least about 100,000 daltons, and even more specifically at least about 250,000 daltons or even at least 500,000 daltons.
  • Number-average molecular weight (Mn) may also vary widely, but generally fall in the range of about 1,000 to about 200,000 daltons, or even from about 1,000 to about 100,000 daltons or even from about 1,000 to about 50,000 daltons.
  • Mn varies between about 8,000 and 45,000 daltons.
  • a wide range of molecular weights may be present.
  • molecules within the sample may have molecular weights which differ by a factor of 2, 5, 10, 20, 50, 100, or more, or which differ from the average molecular weight by a factor of 2, 5, 10, 20, 50, 100, or more.
  • the molecular weight is advantageously selected to be large enough so that an antioxidant polymer cannot be absorbed by the gastrointestinal tract, such as greater than 1000 amu.
  • the molecule weight is advantageously selected such that the rate of diffusion of the antioxidant polymer through the polymeric material is slow relative to the expected lifetime of the polymeric material.
  • GPC gel permeation chromatography
  • the intrinsic viscosities of the polymers generally vary from about 0.01 to about 2.0 dL/g in chloroform at 40° C., alternatively from about 0.01 to about 1.0 dL/g and, occasionally, from about 0.01 to about 0.5 dL/g.
  • the glass transition temperature (Tg) of the subject polymers may vary widely, and depend on a variety of factors, such as the degree of branching in the polymer components, and the like.
  • the Tg is often within the range of from about ⁇ 10° C. to about 80° C., particularly between about 0 and 50° C. and, even more particularly between about 25° C. to about 35° C. In other embodiments, the Tg is low enough to keep the composition of the invention flowable at ambient temperatures.
  • the glass transition temperature of the polymeric macromonomer antioxidant used in the invention is usually about 0 to about 37° C., or alternatively from about 0 to about 25° C.
  • Antioxidant polymers of the present invention can be either homopolymers or copolymers.
  • a copolymer preferably contains two or more or three or more different repeating monomer units, each of which has varying or identical antioxidant properties (including monomers having no antioxidant activity).
  • the identity of the repeat units in a copolymer can be chosen to modify the antioxidant properties of the polymer as a whole, thereby giving a polymer with tunable properties.
  • the second, third and/or further repeat units in a copolymer can be either a synthetic or natural antioxidant.
  • a composition of the invention includes one or more homopolymers and one or more copolymers (e.g., in a blend).
  • both homopolymers and copolymers include two or more substituted benzene repeat units that are directly connected by a C—C or C—O—C bond.
  • at least 50%, such as at least 70%, for example, at least 80%, but preferably about 100% of the repeat units in a copolymer are substituted benzene repeat units directly connected by a C—C or C—O—C bond.
  • Antioxidant polymers of the present invention are typically insoluble in aqueous media.
  • the solubility of the antioxidant polymers in non-aqueous media depends upon the molecular weight of the polymer, such that high molecular weight polymers are typically sparingly soluble in non-aqueous media.
  • an antioxidant polymer of the invention is insoluble in a particular medium or substrate, it is preferably well-mixed with that medium or substrate.
  • Antioxidant polymers of the present invention can be branched or linear, but are preferably linear.
  • the macromonomer antioxidants of the present invention may be prepared by several different methods and starting materials. The following are synthetic routes to formation of the macromonomer antioxidants: 1) esterification, 2) amidification, 3) ketone formation, 4) alkylation, and 5) anhydride formation.
  • antioxidant-acid type molecule and/or antioxidant-alcohol type molecule are coupled to form an ester linkage by one of the following methods: a) chemical routes b) enzymatic routes, and c) chemoenzymatic routes.
  • Scheme 3 depicts the chemical coupling of acid chloride with antioxidant-alcohol in the presence of base like triethyl amine followed by deacetylation to form a macromonomer of the present invention.
  • FIGS. 1 a - 1 c 1 H NMR characterization is depicted in FIGS. 1 a - 1 c . Formation of an ester linkage is clearly evident from the shift of benzylic protons from 4.6 ppm in alcohol to 5.35 ppm in the acetylated ester product and disappearance of acidic proton of 4-acetoxy benzoic acid at 10 ppm in the product ( FIG. 1 a ). The disappearance of acetoxy peaks at 2.3 ppm in FIG. 1 b is the indication of deacetylation of the final product.
  • macromonomer compound 1 and analogs thereof could be prepared by refluxing the mixture of 4-hydroxy benzoic acid and 3,5 di-tert-butyl-4-hydroxy-benzyl alcohol in toluene in presence of anhydrous para-toluene sulponic acid. Journal of Natural Products, 2003, Vol. 66, No. 5.
  • Analogs of compound 1 can be prepared by the above methods starting with 3,4-dihydroxy benzoic acid and 3,4,5-trihydroxybenzoic acid (Gallic acid) and are depicted below as compounds 2 and 3, respectively, or by coupling 4-hydroxy-benzyl alcohol and 3,5-di-tert-butyl-4-hydroxy-propionyl chloride to yield compound 4.
  • the macromonomer antioxidants of the present invention may also comprise an acrylate moiety as depicted in Scheme 8.
  • Scheme 9 represents a chemoenzymatic route for the formation of macromonomer antioxidant compound 1.
  • 2,6-di-tert butyl phenol can be acylated with 4-hydroxy-benzoyl chloride in presence of Lewis acids like aluminum trichloride, boron trifluoride, or zinc chloride, etc. to produce Compound 10 as depicted in Scheme 12.
  • Lewis acids like aluminum trichloride, boron trifluoride, or zinc chloride, etc.
  • Resorcinol can be acylated with 3,5-di-tert-butyl-4-hydroxy-propionyl chloride, 3,5-di-tert-butyl-4-hydroxy acetyl chloride, or 3,5 di-tert-butyl-4-hydroxy-benzoyl chloride etc. in the presence of a Lewis acid like aluminum trichloride, boron trifluoride, zinc chloride etc. to form antioxidant macromonomers (Compound 11) as depicted in Scheme 13.
  • a Lewis acid like aluminum trichloride, boron trifluoride, zinc chloride etc.
  • pyragallol can also be acylated with 3,5-di-tert-butyl-4-hydroxy-propionyl chloride, 3,5-di-tert-butyl-4-hydroxy acetyl chloride, or 3,5-di-tert-butyl-4-hydroxy-benzoyl chloride etc. in the presence of a Lewis acid like aluminum trichloride, boron trifluoride, zinc chloride, etc. to produce antioxidant monomers (Compound 12) as depicted in Scheme 14. 4) Alkylation
  • antioxidant polymers of the present invention can be used in a variety of applications.
  • Antioxidant polymers of the present invention can be present in a wide variety of compositions where free radical mediated oxidation leads to deterioration of the quality of the composition, including edible products such as oils, foods (e.g., meat products, dairy products, cereals, beverages, crackers, potato flakes, bakery products and mixes, dessert mixes, nuts, candies, etc.), and other products containing fats or other compounds subject to oxidation (e.g., chewing gum, flavorings, yeast, etc.).
  • edible products such as oils, foods (e.g., meat products, dairy products, cereals, beverages, crackers, potato flakes, bakery products and mixes, dessert mixes, nuts, candies, etc.), and other products containing fats or other compounds subject to oxidation (e.g., chewing gum, flavorings, yeast, etc.).
  • Antioxidant polymers can also be present in plastics and other polymers, elastomers (e.g., natural or synthetic rubber), petroleum products (e.g., mineral oil, fossil fuels such as gasoline, kerosene, diesel oil, heating oil, propane, jet fuel), adhesives, lubricants, paints, pigments or other colored items, soaps and cosmetics (e.g., creams, lotions, hair products). Soaps and cosmetics, in particular, benefit from the addition of a large proportion of one or more antioxidant polymers of the invention. Soaps and cosmetics can contain, for example, about 1% to about 20% (e.g., about 5% to about 15%) by weight of antioxidant polymer.
  • the antioxidant polymers can be used to coat a metal as a rust and corrosion inhibitor.
  • Antioxidant polymers additionally can protect antioxidant vitamins (Vitamin A, Vitamin C, Vitamin E) and pharmaceutical products (i.e., those containing a pharmaceutically active agent) from degradation.
  • antioxidant polymers is particularly advantageous when the vitamin or pharmaceutically active agent is present in a liquid composition, although the antioxidant polymers is expected also to have a benefit in solid compositions.
  • the antioxidant polymers will prevent rancidity. In plastics, the antioxidant polymers will prevent the plastic from becoming brittle and cracking.
  • Antioxidant polymers of the present invention can be added to oils to prolong their shelf life and properties. These oils can be formulated as vegetable shortening or margarine. Oils generally come from plant sources and include cottonseed oil, linseed oil, olive oil, palm oil, corn oil, peanut oil, soybean oil, castor oil, coconut oil, safflower oil, sunflower oil, canola (rapeseed) oil and sesame oil.
  • oils contain one or more unsaturated fatty acids such as caproleic acid, palmitoleic acid, oleic acid, vaccenic acid, elaidic acid, brassidic acid, erucic acid, nervomc acid, linoleic acid, eleosteric acid, alpha-linolenic acid, gamma-linolenic acid, and arachidonic acid, or partially hydrogenated or trans-hydrogenated variants thereof.
  • Antioxidant polymers of the present invention are also advantageously added to food or other consumable products containing one or more of these fatty acids.
  • a packaging material can be coated with an antioxidant polymer (e.g., by spraying the antioxidant polymer or by applying as a thin film coating), blended with or mixed with an antioxidant polymer (particularly for polymers), or otherwise have an antioxidant polymer present within it.
  • thermoplastic polymer such as polyethylene, polypropylene or polystyrene is melted in the presence of an antioxidant polymer in order to minimize its degradation during the polymer processing.
  • An antioxidant polymer can also be co-extruded with a polymeric material.
  • Smart packaging is designed, for example, such that it controls gas exchange through the packaging. Examples of smart packaging are described in U.S. Pat. Nos. 5,911,937, 5,320,889 and 4,977,004, the contents of which are incorporated herein in their entirety.
  • One conventional type of smart packaging involves a layer of an oxygen barrier such as nylon or poly(ethylene-co-vinyl alcohol) that is typically sandwiched between one or more layers of a moisture-resistant polymer or polymer blend such as polyethylene terephthalate, poly(vinylidene chloride), poly(vinyl chloride), poly(ethylene) or poly(propylene).
  • the layers of moisture-resistant polymer can be either the same or different.
  • one or more of the antioxidant polymers described herein can be added as an additional layer or can be blended with a layer of the packaging material.
  • compositions that are particularly suitable as a packaging material includes polyethylene and polymer 1, typically where the two polymers are blended together.
  • the proportion of polymer 1 in the composition is typically about 1 ppm to about 1,000 ppm, such as about 10 ppm to about 100 ppm.
  • the composition can be, for example, in the form of a film or a pellet.
  • the composition can also include a macromonomeric antioxidant, such as compounds 1-15. When the macromonomeric antioxidant is present, the concentration is typically about 1 ppm to about 1,000 ppm.
  • the concept of having a mixture of an antioxidant polymer and another antioxidant or polymer can generally be applied to combinations of one or more antioxidant polymers described herein and one or more synthetic and/or natural monomeric and/or oligomeric antioxidants and/or preservatives. Such compositions are expected to have both short-term and long-term antioxidant activity.
  • the ratio of polymer to macromonomer and/or oligomer in a composition can be selected so that the composition has the desired set of properties.
  • the ratio of polymer to macromonomer and/or oligomer can be about 1:100 to about 100:1, such as about 1:10 to about 10:1.
  • the absolute concentration of antioxidant polymers in such compositions ranges from about 0.1 ppm to about 10,000 ppm.
  • Macromonomer antioxidant was prepared using lipase (Novozyme 435) to couple 3,5-di-tert-butyl-4-hydroxybenzyl alcohol to the vinyl ester monomer of methacrylic acid.
  • the enzymatic reaction was carried out at 40° C. for 8 hours in toluene.
  • the reaction product was separated and the structure of the macromonomer product was confirmed by high resolution proton NMR.
  • Fe-salen biomimetic polymerization of macromonomer antioxidant Compound 1 (4 g) was dissolved in THF (20 ml) and 80 mg of Fe-Salen was added to it. To the reaction mixture 25% hydrogen peroxide solution was added incrementally over the period of 1 hour. After completion of addition, the reaction mixture was stirred for additional 24 hours. After completion of reaction THF was removed, product washed with water and dried.
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