US20070149660A1 - Stabilized polyolefin compositions - Google Patents

Stabilized polyolefin compositions Download PDF

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US20070149660A1
US20070149660A1 US11/589,319 US58931906A US2007149660A1 US 20070149660 A1 US20070149660 A1 US 20070149660A1 US 58931906 A US58931906 A US 58931906A US 2007149660 A1 US2007149660 A1 US 2007149660A1
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tert
group
butyl
copolymers
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Vijayendra Kumar
Rajesh Kumar
Ashish Dhawan
Suizhou Yang
Ashok Cholli
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Polnox Corp
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Assigned to POLNOX CORPORATION reassignment POLNOX CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KUMAR, RAJESH, CHOLLI, ASHOK L., DHAWAN, ASHISH, KUMAR, VIJAYENDRA, YANG, SUIZHOU
Publication of US20070149660A1 publication Critical patent/US20070149660A1/en
Priority to US12/082,967 priority patent/US7705075B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

Definitions

  • Antioxidants are employed to prevent oxidation in a wide range of materials, for example, plastics, elastomers, lubricants, petroleum based products (lubricants, gasoline, aviation fuels, and engine oils), cooking oil, cosmetics, processed food products, and the like. While many antioxidants exist, there is a continuing need for new antioxidants that have improved properties.
  • the present invention relates to compositions comprising antioxidants and stabilizers, such as, acid scavengers or organic phosphorus stabilizers and optionally further comprising co-stabilizers. These compositions are useful as stabilizers for polyolefins and other polymeric materials.
  • the present invention is a composition comprising an antioxidant, and at least one additive selected from the group consisting of a phosphorus stabilizer (e.g., a phosphate or phosphite stabilizer), an acid stabilizer and a co-stabilizer.
  • a phosphorus stabilizer e.g., a phosphate or phosphite stabilizer
  • an acid stabilizer e.g., a phosphate or phosphite stabilizer
  • co-stabilizer e.g., a co-stabilizer
  • the present invention is a polyolefin composition
  • a polyolefin composition comprising a polyolefin or a mixture of polyolefins, an antioxidant, and at least one additive selected from the group consisting of a phosphorus stabilizer (e.g., a phosphate or phosphite stabilizer), an acid stabilizer and a co-stabilizer.
  • a phosphorus stabilizer e.g., a phosphate or phosphite stabilizer
  • an acid stabilizer e.g., a phosphate or phosphite stabilizer
  • the present invention is a method of preventing oxidation in a polyolefin or a mixture of polyolefins comprising combining the polyolefin or mixture of polyolefins with an antioxidant, and at least one additive selected from the group consisting of a phosphorus stabilizer (e.g., a phosphate or phosphite stabilizer), an acid stabilizer and a co-stabilizer.
  • a phosphorus stabilizer e.g., a phosphate or phosphite stabilizer
  • compositions and methods of the present invention generally provide longer shelf life and better oxidative resistance to materials than currently available antioxidants.
  • FIG. 1 is a comparison of an oxidative induction time (OIT) of polypropylene in combination with one embodiment of the invention, namely, benzenepropanamide, 3, 5-bis(1,1-dimethylethyl)-4-hydroxy-N-(4-hydroxyphenyl): i) alone, ii) in combination with calcium stearate (CasS), iii) in combination with calcium stearate and phosphate (P) and iv) in combination with calcium sulfide, phosphite and zinc oxide (Z).
  • OIT oxidative induction time
  • FIG. 2 is a comparison of the Melt flow Index (MFI) of polypropylene in combination with one embodiment of the invention, namely, benzenepropanamide, 3, 5-bis(1,1-dimethylethyl)-4-hydroxy-N-(4-hydroxyphenyl): i) alone, ii) in combination with calcium stearate (CasS), iii) in combination with calcium stearate and phosphate (P) and iv) in combination with calcium sulfide, phosphite and zinc oxide (Z).
  • MFI Melt flow Index
  • compositions such as, polymer processing formulations involving i) antioxidants described in Provisional Patent Application Nos. 60/853,275, 60/632,893, 60/633,197, 60/633,252, 60/633,196, 60/665,638, 60/731,021, 60/731,125 and 60/655,169, U.S. patent application Ser. Nos.
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include but are not limited to polyalkyl phenol based antioxidants, sterically hindered phenol based antioxidants, sterically hindered phenol based macromolecular antioxidants, nitrogen (amine, imine) and hindered phenol containing dual functional macromolecular antioxidants, alkylated macromolecular antioxidants, sterically hindered phenol and phosphite based macromolecular antioxidants.
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include antioxidant polymers which comprises repeat units that include one or both of Structural Formulas (I) and (II): where:
  • R is —H or a substituted or unsubstituted alkyl, substituted or unsubstituted acyl or substituted or unsubstituted aryl group;
  • Ring A is substituted with at least one tert-butyl group or substituted or unsubstituted n-alkoxycarbonyl group, and optionally one or more groups selected from the group consisting of —OH, —NH, —SH, a substituted or unsubstituted alkyl or aryl group, and a substituted or unsubstituted alkoxycarbonyl group;
  • Ring B is substituted with at least one —H and at least one tert-butyl group or substituted or unsubstituted n-alkoxycarbonyl group and optionally one or more groups selected from the group consisting of —OH, —NH, —SH, a substituted or unsubstituted alkyl or aryl group, and a substituted or unsubstituted alkoxycarbonyl group;
  • n is an integer equal to or greater than 2;
  • p is an integer equal to or greater than 0.
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include polymers with repeat units represented by one or both of Structural Formulas (III) and (IV): where Rings A and B are substituted as described above and n and p are as defined above.
  • Ring A and Ring B in Structural Formulas (I) to (IV) are each substituted with at least one tert-butyl group.
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include polymers with repeat units represented by one or more of Structural Formulas (Va), (Vb), (Vc), (VIa), (VIb) and (VIc):
  • R 1 , R 2 and R 3 are independently selected from the group consisting of —H, —OH, —NH, —SH, a substituted or unsubstituted alkyl or a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkoxycarbonyl group, provided that at least one of R 1 , R 2 and R 3 is a tert-butyl group; and j and k are independently integers of zero or greater, such that the sum of j and k is equal to or greater than 2.
  • R is —H or —CH 3 ;
  • R 2 is —H, —OH, or a substituted or unsubstituted alkyl group; or both.
  • repeat units included in polymers which are suitable for use in the compositions and methods of the present invention are represented by one of the following structural formulas:
  • Antioxidant polymers as described immediately above which are suitable for use in the compositions and methods of the present invention have two or more repeat units, preferably greater than about five repeat units.
  • the molecular weight of the polymers disclosed above is generally selected to be appropriate for the desired application. Typically, the molecular weight is greater than about 500 atomic mass units (amu) and less than about 2,000,000 amu, greater than about 1000 amu and less than about 100,000, greater than about 2,000 amu and less than about 10,000, or greater than about 2,000 amu and less than about 5,000 amu.
  • Antioxidant polymers as described immediately above which are suitable for use in the compositions and methods 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.
  • 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.
  • Antioxidant polymers as described immediately above which are suitable for use in the compositions and methods 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 as described immediately above which are suitable for use in the compositions and methods of the present invention can be branched or linear, but are preferably linear.
  • Branched antioxidant polymers can only be formed from benzene molecules having three or fewer substituents (e.g., three or more hydrogen atoms), as in Structural Formulas (XX), (XXI) and (XXIV).
  • antioxidants which are suitable for use in the compositions and methods of the present invention include polymers with repeat units represented by one or both of Structural Formulas (I) and (II): where:
  • R is —H or a substituted or unsubstituted alkyl, acyl or aryl group
  • Ring A is substituted with at least one tert-butyl group, 1-ethenyl-2-carboxylic acid group or ester thereof, substituted or unsubstituted alkylenedioxy group, or substituted or unsubstituted n-alkoxycarbonyl group and zero, one or more additional functional groups;
  • Ring B is substituted with at least one —H and at least one tert-butyl group, 1-ethenyl-2-carboxylic acid group or ester thereof, substituted or unsubstituted alkylenedioxy group, or substituted or unsubstituted n-alkoxycarbonyl group and zero, one or more additional functional groups;
  • n is an integer equal to or greater than 2;
  • p is an integer equal to or greater than 0,
  • polymer includes two or more repeat units represented by one or both of Structural Formulas (I) and (II) that are directly connected by a C—C or C—O—C bond between benzene rings.
  • Polymers as described immediately above which are suitable for use in the compositions and methods of the present invention that do not include any repeat units represented by Structural Formula (I) are preferably substituted on Ring B with one or more hydroxyl or acyloxy groups.
  • Repeat units of the antioxidant polymers as described immediately above which are suitable for use in the compositions and methods of the present invention include substituted benzene molecules.
  • These benzene molecules are typically based on phenol or a phenol derivative, such that they have at least one hydroxyl, ester or ether functional group.
  • the benzene molecules have a hydroxyl group.
  • the hydroxyl group is not restricted to being a free hydroxyl group, and the hydroxyl group can be protected or have a cleavable group attached to it (e.g., an ester group).
  • Such cleavable groups can be released under certain conditions (e.g., changes in pH), with a desired shelf life or with a time-controlled release (e.g., measured by the half-life), which allows one to control where and/or when an antioxidant polymer is able to exert its antioxidant effect.
  • conditions e.g., changes in pH
  • time-controlled release e.g., measured by the half-life
  • Substituted benzene repeat units of an antioxidant polymer as described immediately above which are suitable for use in the compositions and methods of the present invention are also typically substituted with a bulky alkyl group, a 1-ethenyl-2-carboxylic acid group, a substituted or unsubstituted alkylenedioxy group, or an n-alkoxycarbonyl group.
  • the benzene monomers are substituted with a bulky alkyl group. More preferably, the bulky alkyl group is located ortho or meta to a hydroxyl group on the benzene ring.
  • a “bulky alkyl group” is defined herein as an alkyl group that is branched alpha- or beta- to the benzene ring.
  • the alkyl group is branched alpha to the benzene ring. More preferably, the alkyl group is branched twice alpha to the benzene ring (i.e., to form an alpha-tertiary carbon), such as in a tert-butyl group.
  • Other examples of bulky alkyl groups include isopropyl, 2-butyl, 3-pentyl, 1,1-dimethylpropyl, 1-ethyl-1-methylpropyl and 1,1-diethylpropyl.
  • the bulky alkyl groups are preferably unsubstituted, but they can be substituted with a functional group that does not interfere with the antioxidant activity of the molecule or the polymer.
  • Substituted benzene repeat units that are substituted with a substituted or unsubstituted alkylenedioxy group typically have an unsubstituted alkylenedioxy group.
  • Substituted alkylenedioxy groups are also suitable, although the substituents should not interfere with the antioxidant activity of the molecule or the polymer.
  • an alkylenedioxy group is a lower alkylenedioxy group, such as a methylenedioxy group or an ethylenedioxy group.
  • a methylenedioxy group is preferred (as in sesamol).
  • Straight chained alkoxycarbonyl groups typically have an alkyl chain of one to sixteen carbon atoms, and include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl and n-pentoxycarbonyl. n-propoxycarbonyl is a preferred group. Similar to the bulky alkyl groups, n-alkoxycarbonyl groups are optionally substituted with a functional group that does not interfere with the antioxidant activity of the molecule or the polymer. Alkoxycarbonyl groups can also be present in their hydrolyzed form, namely as carboxy groups or carboxylic acid groups.
  • the 1-carbon i.e., the carbon distal from the carboxylic acid moiety
  • the 1-carbon is attached to the benzene ring.
  • substituted benzene repeat units can have additional functional groups as substituents.
  • the additional functional groups can be selected from the group consisting of —OH, —NH, —SH, a substituted or unsubstituted alkyl or aryl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkoxy group and a saturated or unsaturated carboxylic acid group.
  • the additional functional groups are selected from the group consisting of —OH, a substituted or unsubstituted alkoxy group and a saturated or unsaturated carboxylic acid group.
  • Ring A and Ring B in Structural Formulas (I) to (IV) are each substituted with at least one tert-butyl group.
  • repeat units included in polymers which are suitable for use in the compositions and methods of the present invention are represented by one of the following structural formulas:
  • Structural Formulas (XI), (XVI), (XVII) and (XVIII) are represented as having a propoxycarbonyl substituent, this group can generally be replaced with a different C 1 -C 16 n-alkoxycarbonyl group or can be a carboxylate group.
  • a particular polymer suitable for use in the methods and compositions of the present invention is poly(2-tert-butyl-4-hydroxyanisole).
  • Antioxidant polymers as described immediately above which are suitable for use in the methods and compositions of the present invention have two or more repeat units, preferably greater than about five repeat units.
  • the molecular weight of the polymers disclosed herein is generally selected to be appropriate for the desired application. Typically, the molecular weight is greater than about 500 atomic mass units (amu) and less than about 2,000,000 amu, greater than about 1000 amu and less than about 100,000, greater than about 2,000 amu and less than about 10,000 amu, or greater than about 2,000 amu and less than about 5,000 amu.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods and compositions 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.
  • copolymers examples include poly(TBHQ-co-propyl gallate), poly(TBHQ-co-BHA), poly(TBHQ-co-sesamol), poly(BHA-co-sesamol), poly(propyl gallate-co-sesamol) and poly(BHA-co-propyl gallate).
  • the ratio of one monomer to another, on a molar basis is typically about 100:1 to about 1:100, such as about 10:1 to about 1:10, for example, about 2:1 to about 1:2. In one example, the ratio of monomers is about 1:1.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods and compositions of the present invention are typically insoluble in aqueous media, although certain polymers of gallic acid and its esters are water soluble.
  • 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 as described immediately above which are suitable for use in the methods and compositions of the present invention can be branched or linear, but are preferably linear.
  • Branched antioxidant polymers can only be formed from benzene molecules having three or fewer substituents (e.g., three or more hydrogen atoms), as in Structural Formulas (XX), (XXI) and (XXIV).
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include a polyalkylphenol antioxidant represented by Structural Formula U or U′.
  • n is an integer equal or greater than 2.
  • R is a C1-C10 alkyl group, an aryl group, or a benzyl group. Typically, R is a tertiary alkyl group, or in preferred embodiments, a tertiary butyl group.
  • X is —O—, —NH— or —S—.
  • Each R 10 is independently an optionally substituted C1-C10 alkyl group, an optionally substituted aryl group, and optionally substituted alkoxy group, an optionally substituted carbonyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, —OH, —SH or —NH 2 ; or two R 10 groups on adjacent carbon atoms join together to form an optionally substituted aromatic ring or an optionally substituted carbocyclic or heterocyclic non-aromatic ring.
  • q is an integer from 0 to 2.
  • Repeat units of the antioxidant polymers as described immediately above which are suitable for use in the compositions and methods of the present invention include substituted benzene molecules.
  • These benzene molecules are typically based on phenol or a phenol derivative, such that they have at least one hydroxyl or ether functional group.
  • the benzene molecules have a hydroxyl group.
  • the hydroxyl group can be a free hydroxyl group and can be protected or have a cleavable group attached to it (e.g., an ester group).
  • Such cleavable groups can be released under certain conditions (e.g., changes in pH), with a desired shelf life or with a time-controlled release (e.g., measured by the half-life), which allows one to control where and/or when an antioxidant polymer can exert its antioxidant effect.
  • the repeat units can also include analogous thiophenol and aniline derivatives, e.g., where the phenol —OH can be replaced by —SH, —NH—, and the like.
  • Substituted benzene repeat units of an antioxidant polymer as described immediately above which are suitable for use in the compositions and methods of the present invention are also typically substituted with a bulky alkyl group or an n-alkoxycarbonyl group.
  • the benzene monomers are substituted with a bulky alkyl group. More preferably, the bulky alkyl group is located ortho or meta to a hydroxyl group on the benzene ring, typically ortho.
  • a “bulky alkyl group” is defined herein as an alkyl group that is branched alpha— or beta- to the benzene ring. Preferably, the alkyl group is branched alpha to the benzene ring.
  • the alkyl group is branched twice alpha to the benzene ring, such as in a tert-butyl group.
  • Other examples of bulky alkyl groups include isopropyl, 2-butyl, 3-pentyl, 1,1-dimethylpropyl, 1-ethyl-1-methylpropyl and 1,1-diethylpropyl.
  • the bulky alkyl groups are preferably unsubstituted, but they can be substituted with a functional group that does not interfere with the antioxidant activity of the molecule or the polymer.
  • Straight chained alkoxylcarbonyl groups include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl and n-pentoxycarbonyl.
  • n-propoxycarbonyl is a preferred group.
  • n-alkoxycarbonyl groups are optionally substituted with a functional group that does not interfere with the antioxidant activity of the molecule or the polymer.
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include a polymer comprising repeat units represented by one or both of Structural Formulas (i) and (ii): where:
  • Ring A is substituted with at least one tert-butyl group, and optionally one or more groups selected from the group consisting of a substituted or unsubstituted alkyl or aryl group, and a substituted or unsubstituted alkoxycarbonyl group;
  • Ring B is substituted with at least one —H and at least one tert-butyl group and optionally one or more groups selected from the group consisting of—a substituted or unsubstituted alkyl or aryl group, and a substituted or unsubstituted alkoxycarbonyl group;
  • n is an integer equal to or greater than 2;
  • p is an integer equal to or greater than 0.
  • the antioxidants which are suitable for use in the compositions and methods of the present invention are polymers represented by one or both of Structural Formulas (iv) and (v): where Ring A is substituted with at least one tert-butyl group, and optionally one or more groups selected from the group consisting of a substituted or unsubstituted alkyl or aryl group, and a substituted or unsubstituted alkoxycarbonyl group; Ring B is substituted with at least one —H and at least one tert-butyl group and optionally one or more groups selected from the group consisting of a substituted or unsubstituted alkyl or aryl group, and a substituted or unsubstituted alkoxycarbonyl group; R is —H, an optionally substituted C1-C10 alkyl group, an aryl group, a benzyl group, or an acyl group n is an integer equal to or greater than 2; and p is an
  • Antioxidant polymers as described immediately above which are suitable for use in the methods of the present invention have two or more repeat units, preferably greater than about five repeat units.
  • the molecular weight of the polymers disclosed herein can be generally selected to be appropriate for the desired application. Typically, the molecular weight can be greater than about 500 atomic mass units (amu) and less than about 2,000,000 amu, greater than about 1,000 amu and less than about 100,000, greater than about 2,000 amu and less than about 10,000, or greater than about 2,000 amu and less than about 5,000 amu.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods 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.
  • 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.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods 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 can be insoluble in a particular medium or substrate, it can be preferably well-mixed with that medium or substrate.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods of the present invention can be branched or linear, but are preferably linear.
  • Branched antioxidant polymers can only be formed from benzene molecules having three or fewer substituents (e.g., three or more hydrogen atoms), as in Structural Formulas (XX), (XXI) and (XXIV).
  • the antioxidant polymers which are suitable for use in the compositions and methods of the present invention includes a macromolecule which can be represented by one or both of Structural Formulas R and S:
  • n is an integer equal to or greater than 2.
  • variable X is 0, NH, or S.
  • the variable Z is H.
  • Each variable K is independently —H or —OH, with at least one —OH adjacent to a —H; or K is a bond when that position is involved in the polymer chain.
  • the antioxidants which are suitable for use in the compositions and methods of the present invention includes a macromolecular antioxidant polymer represented by one or both of Structural Formulas T, T′, V and V′:
  • n is an integer equal to or greater than 2.
  • variable X is O, NH, or S.
  • the variable Z is H.
  • Each variable R is independently —H, —OH, a C1-C10 alkyl group, or a bond when that position is involved in the polymer chain wherein at least one —OH is adjacent to a C1-C10 alkyl group, e.g., a tertiary butyl group.
  • Each R 10 is independently an optionally substituted C1-C10 alkyl group, an optionally substituted aryl group, and optionally substituted alkoxy group, an optionally substituted carbonyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, —OH, —SH or —NH 2 or two R 10 groups on adjacent carbon atoms join together to form an optionally substituted aromatic ring or an optionally substituted carbocyclic or heterocyclic non-aromatic ring.
  • q is an integer from 0 to 2.
  • R 12 is a bulky alkyl group substituent bonded to a ring carbon atom adjacent (ortho) to a ring carbon atom substituted with an —OH group.
  • n is an integer equal to or greater than 2.
  • macromolecular antioxidant polymers can contain, for example, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, BHT type repeat units and their combinations.
  • macromolecular antioxidants described immedialtey above can be homopolymers, copolymers, terpolymers, and the like
  • Substituted benzene repeat units of an antioxidant polymer as described immediately above which are suitable for use in the methods and compositions of the present invention are typically substituted with a bulky alkyl group or an n-alkoxycarbonyl group.
  • the benzene monomers are substituted with a bulky alkyl group.
  • the bulky alkyl group is located ortho or meta to a hydroxyl group on the benzene ring, typically ortho.
  • a “bulky alkyl group” is defined herein as an alkyl group that is branched alpha— or beta- to the benzene ring.
  • the alkyl group is branched alpha to the benzene ring.
  • the alkyl group is branched twice alpha to the benzene ring, such as in a tert-butyl group.
  • Other examples of bulky alkyl groups include isopropyl, 2-butyl, 3-pentyl, 1,1-dimethylpropyl, 1-ethyl-1-methylpropyl and 1,1-diethylpropyl.
  • the bulky alkyl groups are preferably unsubstituted, but they can be substituted with a functional group that does not interfere with the antioxidant activity of the molecule or the polymer.
  • Straight chained alkoxylcarbonyl groups include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl and n-pentoxycarbonyl.
  • n-propoxycarbonyl is a preferred group.
  • n-alkoxycarbonyl groups are optionally substituted with a functional group that does not interfere with the antioxidant activity of the molecule or the polymer.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods and compositions of the present invention have two or more repeat units, preferably greater than about five repeat units.
  • the molecular weight of the polymers disclosed herein can be generally selected to be appropriate for the desired application. Typically, the molecular weight can be greater than about 500 atomic mass units (amu) and less than about 2,000,000 amu, greater than about 1,000 amu and less than about 100,000, greater than about 2,000 amu and less than about 10,000, or greater than about 2,000 amu and less than about 5,000 amu.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods and compositions 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.
  • 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.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods and compositions 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 can be insoluble in a particular medium or substrate, it can be preferably well-mixed with that medium or substrate.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods and compositions of the present invention can be branched or linear, but are preferably linear.
  • Branched antioxidant polymers can only be formed from benzene molecules having three or fewer substituents (e.g., three or more hydrogen atoms), as in Structural Formulas (XX), (XXI) and (XXIV).
  • repeat units included in polymers which are suitable for use in the compositions and methods of the present invention are represented by one of the following structural formulas:
  • examples of sterically hindered polymeric macromolecular antioxidant produced by the methods of the present invention comprises at least one repeat unit selected from: n is an integer equal to or greater than 2.
  • the antioxidants which are suitable for use in the compositions and methods of the present invention includes an antioxidant polymer represented by Structural Formula M.
  • n is an integer equal to or greater than 2;
  • R 1 is O, S, or NH
  • R 4 , R 5 , R 7 and R 8 are independently —H, —OH, —NH, —SH, a substituted or unsubstituted alkyl or aryl group, or a substituted or unsubstituted alkoxycarbonyl group, or a bond when part of the polymer chain, provided that:
  • R 4 , R 5 , R 7 and R 8 is a tert-butyl group or a substituted or unsubstituted alkoxycarbonyl group, and at least two of R 4 , R 5 , R 7 and R 8 are —H; or
  • R 4 , R 5 , R 7 and R 8 is a tert-butyl group or a substituted or unsubstituted alkoxycarbonyl group, at least one of R 4 , R 5 , R 7 and R 8 is a hydroxyl, alkoxy, alkoxycarbonyl or aryloxycarbonyl group, and at least one of R 4 , R 5 , R 7 and R 8 is —H.
  • each X is independently —O—, —NH— or —S—.
  • Each R 10 is independently an optionally substituted C1-C10 alkyl group, an optionally substituted aryl group, and optionally substituted alkoxy group, an optionally substituted carbonyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, —OH, —SH or —NH 2 ; and/or two R 10 groups on adjacent carbon atoms join together to form an optionally substituted aromatic ring or an optionally substituted carbocyclic or heterocyclic non-aromatic ring.
  • q is an integer from 0 to 2.
  • n is an integer greater than or equal to 2.
  • Substituted benzene repeat units of an antioxidant polymer as described immediately above which are suitable for use in the methods and compositions of the present invention are also typically substituted with a bulky alkyl group or an n-alkoxycarbonyl group.
  • the benzene monomers are substituted with a bulky alkyl group. More preferably, the bulky alkyl group is located ortho or meta to a hydroxyl group on the benzene ring, typically ortho.
  • a “bulky alkyl group” is defined herein as an alkyl group that is branched alpha- or beta- to the benzene ring. Preferably, the alkyl group is branched alpha to the benzene ring.
  • the alkyl group is branched twice alpha to the benzene ring, such as in a tert-butyl group.
  • Other examples of bulky alkyl groups include isopropyl, 2-butyl, 3-pentyl, 1,1-dimethylpropyl, 1-ethyl-1-methylpropyl and 1,1-diethylpropyl.
  • the bulky alkyl groups are preferably unsubstituted, but they can be substituted with a functional group that does not interfere with the antioxidant activity of the molecule or the polymer.
  • Straight chained alkoxylcarbonyl groups include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl and n-pentoxycarbonyl.
  • n-propoxycarbonyl is a preferred group.
  • n-alkoxycarbonyl groups are optionally substituted with a functional group that does not interfere with the antioxidant activity of the molecule or the polymer.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods and compositions of the present invention have two or more repeat units, preferably greater than about five repeat units.
  • the molecular weight of the polymers disclosed herein can be generally selected to be appropriate for the desired application. Typically, the molecular weight can be greater than about 500 atomic mass units (amu) and less than about 2,000,000 amu, greater than about 1,000 amu and less than about 100,000, greater than about 2,000 amu and less than about 10,000, or greater than about 2,000 amu and less than about 5,000 amu.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods and compositions 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.
  • 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.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods and compositions 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 can be insoluble in a particular medium or substrate, it can be preferably well-mixed with that medium or substrate.
  • Antioxidant polymers as described immediately above which are suitable for use in the methods and compositions of the present invention can be branched or linear, but are preferably linear.
  • Branched antioxidant polymers can only be formed from benzene molecules having three or fewer substituents (e.g., three or more hydrogen atoms), as in Structural Formulas (XX), (XXI) and (XXIV).
  • R′ is a covalent bond, —O—, —C(O)O—, —C(O)N—, —C(O)—, —CH ⁇ CH—, —S— or —N—.
  • R 1 is —H or an alkyl group, or —(CH 2 ) k —O—X-Z. Typically, R 1 is —H or alkyl.
  • Each X is independently a covalent bond, —C(O)—, —C(O)O— or —C(O)N—.
  • Y is —O—, —N— or —S—.
  • Each Z is an independently selected antioxidant.
  • a is an integer from 0 to 12.
  • Each k is independently an integer from 0 to 12.
  • n is an integer from 0 to 6.
  • n 0 or 1.
  • p is an integer from 0 to 6.
  • the polymer does not include cyclic anhydride repeat units.
  • An antioxidant can be attached to the polymer by one or more linkages or bonds.
  • suitable linkages include acetal, amide, amine, carbamate, carbonate, ester, ether and thioether linkage. Carbon-carbon bonds can be also suitable.
  • an amide is distinguished from a diacyl hydrazide.
  • polymers that can be derivatized with an antioxidant.
  • One type of such polymer has pendant hydroxyl groups, such as poly(vinyl alcohol) and copolymers thereof (e.g., poly(ethylene-co-vinyl alcohol)).
  • the hydroxyl groups of poly(vinyl alcohol), a polyhydroxyalkyl methacrylate (e.g., polyhydroxy methyl methacrylate), and poly(ethylene-co-vinyl alcohol) react with an antioxidant to form the derivatized antioxidant polymer.
  • Another type of derivatizable polymer contains pendant carboxylic acid groups or esters thereof, such as poly(acrylic acid), poly(alkylacrylic acid) and esters thereof.
  • Poly(acrylic acid) is a preferred polymer; the carboxylic acid groups of poly(acrylic acid) can be derivatized, although carboxylic acid groups generally require activation before derivatization can occur.
  • An additional type of derivatizable polymer can be a poly(substituted phenol), where the substituted phenol has a substituent with a nucleophilic or electrophilic moiety.
  • Such poly(substituted phenols) can include repeat units represented by the following structural formulas: where a is an integer from 0 to 12; R is —OH, —COOH, —NH 2 , —SH or a halogen; and R 10 , R 11 and R 12 are each independently —H, —OH, —NH 2 or —SH, provided that at least one of R 10 , R 11 and R 12 is —OH, —NH 2 or —SH.
  • one of R 10 , R 11 and R 12 is —OH and the remaining two are optionally —H. More preferably, R 11 , is —OH and R 10 and R 12 are —H.
  • the derivatizable polymers can be homopolymers or copolymers. Copolymers include, for example, block, star, hyperbranched, random, gradient block, and alternate copolymers.
  • the derivatizable polymers can be branched or linear, but are preferably linear.
  • Second and further repeat units of a copolymer can optionally include a pendant reactive group.
  • a pendant reactive group For example, about 1% to 100%, such as 10% to 50% or 50% to 100%, of the repeat units of a polymer include pendant functional groups.
  • All or a fraction of the pendant reactive groups of a derivatizable polymer can be derivatized with an antioxidant. In one example, about 100% of the pendant reactive groups can be derivatized. In another example, about 5% to about 90%, such as about 20% to about 80% (e.g., about 50% to about 80%) of the pendant reactive groups can be derivatized.
  • These polymers can be minimally derivatized with a single type of antioxidant, but can be derivatized with two or more antioxidants (e.g., chemically distinct antioxidants). When there can be two or more antioxidants, they can be in the same class, as described below, or can be in different classes.
  • the ratio of antioxidants can be varied in order to obtain a polymer having a desired set of properties. For example, when a polymer can be derivatized with two antioxidants, the ratio of a first antioxidant to a second antioxidant can be from about 20:1 to about 1:20, such as from about 5:1 to about 1:5 (e.g., about 1:1).
  • antioxidants can be suitable, provided that they can be attached to a polymer and retain their antioxidant activity.
  • One class of suitable antioxidants can be phenolic antioxidants.
  • Phenolic antioxidants typically have one or more bulky alkyl groups (alkyl groups having a secondary or tertiary carbon alpha to the phenol ring) ortho or meta, preferably ortho, to the phenol hydroxyl group.
  • Phenolic antioxidants can alternatively have an alkylenedioxy substituent, an alkoxycarbonyl substituent, a 1-propenyl-3-carboxylic acid substituent or an ester thereof.
  • a preferred bulky alkyl group is a tert-butyl group.
  • Phenolic antioxidants for use in the present invention also generally have a substituent that can react with the pendant reactive group of one of the polymers described above to form a covalent bond between the antioxidant and the polymer.
  • R 9 is —H or a substituted or unsubstituted alkyl, acyl or aryl group, preferably —H or an acyl group.
  • R 4 , R 5 , R 6 , R 7 and R 8 are independently chosen substituent groups, such that at least one substituent can be a substituted or unsubstituted alkyl or aryl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkylenedioxy group, a 1-propenyl-3-carboxylic acid group or an ester thereof. Also, at least one of R 4 , R 5 , R 6 , R 7 and R 8 must be a substituent capable of reacting with the pendant reactive group of the polymers described above, such as a substituent having a nucleophilic or electrophilic moiety.
  • Other suitable substituents include, for example, —H, —OH, —NH and —SH.
  • a substituent should not decrease the antioxidant activity more than two-fold, instead, substituents preferably increase the antioxidant activity of the molecule.
  • antioxidants that can be attached to one of the polymers described immediately above can be ascorbic acid or a molecule that contains an ascorbic acid moiety.
  • ascorbic acid attached to a polymer has the following configuration: where this moiety can be attached to the polymer by an ether or ester linkage.
  • Polymers described immediately above which are suitable for use in the compositions and methods of the present invention can be homopolymers or copolymers.
  • One type of copolymer includes ethylene repeat units, particularly in a copolymer containing repeat units represented by Structural Formula (A) and/or Structural Formula (B).
  • a polymer comprises repeat units represented by Structural Formula (A).
  • A Structural Formula (A).
  • the sum of m and p is typically two or greater.
  • Z is typically a phenolic antioxidant, as described above.
  • One preferred phenolic antioxidant is a 3,5-di-tert-butyl-4-hydroxyphenyl group, particularly when X is —C(O)—.
  • m is preferably 2 and n and p are each 0.
  • a second preferred antioxidant is a 3,4,5-trihydroxyphenyl group, particularly when X is —C(O)—.
  • antioxidants are mono and di-tert-butylated-4-hydroxyphenyl groups, 4-acetoxy-3-tert-butylphenyl groups and 3-alkoxycarbonyl-2,6-dihydroxyphenyl groups (e.g., 3-propoxycarbonyl-2,6-dihydroxyphenyl groups), particularly when X is a covalent bond.
  • m and p are each 0.
  • n is also typically 0.
  • Z is typically ascorbic acid.
  • X is typically a covalent bond.
  • Z is a 3,4,5-trihydroxyphenyl group or a 4-acetoxy-3-tert-butylphenyl group, particularly when X is —C(O)—.
  • an antioxidant polymer has repeat units represented by Structural Formula (B).
  • m, n and p are each typically 0.
  • Z is preferably a phenolic antioxidant, specifically a 3,4,5-trihydroxyphenyl, 3,5-di-tert-butyl-4-hydroxyphenyl group or a 3,5-di-tert-butyl-2-hydroxyphenyl group.
  • a further embodiment of the invention involves polymers that include repeat units represented by Structural Formula (C).
  • Y is —O— and Z is preferably ascorbic acid, particularly when k is 0.
  • Y is —O— and Z is a phenolic antioxidant, particularly when k is 0 to 3; more preferably, k is 1.
  • a preferred phenolic antioxidant is a 3,5-di-tert-butyl-4-hydroxyphenyl group.
  • phenolic antioxidants include 4-acetoxy-3-tert-butylphenyl, 3-tert-butyl-4-hydroxyphenyl, 2,6-di-tert-butyl-4-mercaptophenyl and 2,6-di-tert-butyl-4-hydroxyphenyl groups.
  • a polymer in yet another embodiment of the invention, includes repeat units represented by Structural Formula (D).
  • R′ is a covalent bond or —OH in such polymers.
  • Other typical values of R′ are amide and ester linkages.
  • Preferred Z groups can be phenolic antioxidants, as described above. For these polymers, the phenol hydroxyl group is typically para or meta to the group containing Z, more typically para.
  • Antioxidant polymers described immediately above which are suitable for use in the methods of the present invention have two or more repeat units, preferably greater than about five repeat units.
  • the molecular weight of the polymers disclosed herein can be generally selected to be appropriate for the desired application. Typically, the molecular weight can be greater than about 500 atomic mass units (amu) and less than about 2,000,000 amu, greater than about 1000 amu and less than about 1,000,000 amu, greater than about 1000 amu and less than about 100,000 amu, greater than about 2,000 amu and less than about 10,000 amu, or greater than about 2,000 amu and less than about 5,000 amu.
  • Antioxidant polymers described immediately above which are suitable for use in the methods of the present invention can be 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 can be typically sparingly soluble in non-aqueous media.
  • an antioxidant polymer of the invention can be insoluble in a particular medium or substrate, it can be preferably well-mixed with that medium or substrate.
  • antioxidants which are suitable for use in the compositions and methods of the present invention are represented by the following structural formula:
  • n and m in each occurrence independently is 0 or a positive integer. Preferably 0 to 18 inclusive.
  • j in each occurrence independently is 0, 1, 2, 3 or 4.
  • Z′ in each occurrence independently is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —N ⁇ CH—, —C(O)—, —O—, —S—, —S—S—, —S ⁇ N—, —N ⁇ S—, —C(S)O—, —OC(S), —OP(O)(OR 4 )O—, OP(OR 4 )O—, —C(O)OC(O)— or a bond.
  • Z′ is —C(O)O—.
  • R′ in each occurrence independently is C1-C6 alkyl, —OH, —NH 2 , —SH, an optionally substituted aryl, an optionally substituted ester or
  • R′ adjacent to the —OH group is an optionally substituted bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
  • bulky alkyl group e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like.
  • R′ 1 in each occurrence independently is C1-C6 alkyl, an optionally substituted aryl, an optionally substituted aralkyl, —OH, —NH 2 , —SH, or C1-C6 alkyl ester wherein at least one R 1 adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).).
  • a bulky alkyl group e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like.
  • M′ is H, an optionally substituted aryl, C1-C20 linear or branched alkyl chain with or without any functional group anywhere in the chain,
  • o 0 or a positive integer
  • R′ 2 in each occurrence independently is —H, C1-C6 alkyl, —OH, —NH 2 , —SH, optionally substituted aryl, ester, or
  • R′ 2 is —OH
  • R′ 3 in each occurrence independently is —H, C1-C6 alkyl, optionally substituted aryl, optionally substituted aralkyl —OH, —NH 2 , —SH or ester.
  • antioxidants which are suitable for use in the compositions and methods of the present invention are represented by the following structural formula:
  • X′ in each occurrence independently is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —C(O)—, —O—, —S—, —C(O)OC(O)— or a bond.
  • R′ 2 is C1-C6 alkyl, —OH, —NH 2 , —SH, aryl, ester, or
  • R′ 2 is —OH, and the values and preferred values for the remainder of the variables are as described immediately above.
  • Z′ is —C(O)O—. In certain other embodiments Z′ is —OC(O)—. In certain other embodiments Z′ is —C(O)NH—. In certain other embodiments Z′ is —NHC(O)—. In certain other embodiments Z′ is —NH—. In certain other embodiments Z′ is —CH ⁇ N—. In certain other embodiments Z′ is —N ⁇ CH—. In certain other embodiments Z′ is —C(O)—. In certain other embodiments Z′ is —O—. In certain other embodiments Z′ is —S—. In certain other embodiments Z′ is —S—S—. In certain other embodiments Z′ is —S ⁇ N—.
  • Z′ is —N ⁇ S—. In certain other embodiments Z′ is —C(S)O—. In certain other embodiments Z′ is —OC(S)—. In certain other embodiments Z′ is —OP(O)(OR 4 )0—. In certain other embodiments Z′ is OP(OR 4 )O—. In certain other embodiments Z′ is —C(O)OC(O)—. In certain other embodiments Z′ is a bond.
  • both R′ groups adjacent to the —OH group is an optionally substituted bulky alkyl group. In a particular embodiment both R′ groups adjacent to the —OH group are tert-butyl.
  • M′ is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • M′ is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • At least one R′ is
  • n 0.
  • n 1
  • n 0, m is 1 and Z is —C(O)O—.
  • n is 0, m is 1, Z is —C(O)O— and the two R′ groups adjacent to the —OH are t-butyl.
  • 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
  • n 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.
  • n 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.
  • n 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 are —OH.
  • n 0, m is 1, Z is —C(O)O—, the two R′ groups adjacent to the —H are t-butyl, M′ is
  • n 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.
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include a macromonomer represented by Structural Formulas I and I′.
  • R and R 1 -R 6 are independently —H, —OH, or a C1-C10 optionallyu substituted linear or branched alkyl group.
  • n is an integer from 0 to 24.
  • each of R and R 1 -R 8 are independently —H, —OH, or a C1-C10 alkyl group.
  • n is an integer from 0 to 24.
  • R′ is —H, optionally substituted C1-C20 alkyl or optionally substituted aryl group.
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include a macromonomer represented by Structural Formulas III and III′ and an antioxidant polymer represented by Structural Formula IV and IV′.
  • each of R, and R 1 -R 8 are independently —H, —OH, or a C1-C10 alkyl group.
  • n is an integer from 0 to 24.
  • m is an integer equal to 2 or greater.
  • R′ is —H, optionally substituted C 1 -C20 alkyl or optionally substituted aryl group.
  • the variables are as defined above.
  • Repeat units of the antioxidant polymers as described immediately above suitable for use in the compositions and methods of the present invention include substituted benzene molecules.
  • These benzene molecules are typically based on phenol or a phenol derivative, such that they have at least one hydroxyl or ether functional group.
  • the benzene molecules have a hydroxyl group.
  • the hydroxyl group can be a free hydroxyl group and can be protected or have a cleavable group attached to it (e.g., an ester group).
  • Such cleavable groups can be released under certain conditions (e.g., changes in pH), with a desired shelf life or with a time-controlled release (e.g., measured by the half-life), which allows one to control where and/or when an antioxidant polymer can exert its antioxidant effect.
  • the repeat units can also include analogous thiophenol and aniline derivatives, e.g., where the phenol —OH can be replaced by —SH, —NH—, and the like.
  • Substituted benzene repeat units of an antioxidant polymer as described immediately above suitable for use in the compositions and methods of the present invention are also typically substituted with a bulky alkyl group or an n-alkoxycarbonyl group.
  • the benzene monomers are substituted with a bulky alkyl group. More preferably, the bulky alkyl group is located ortho or meta to a hydroxyl group on the benzene ring, typically ortho.
  • a “bulky alkyl group” is defined herein as an alkyl group that is branched alpha— or beta- to the benzene ring. Preferably, the alkyl group is branched alpha to the benzene ring.
  • the alkyl group is branched twice alpha to the benzene ring, such as in a tert-butyl group.
  • Other examples of bulky alkyl groups include isopropyl, 2-butyl, 3-pentyl, 1,1-dimethylpropyl, 1-ethyl-1-methylpropyl and 1,1-diethylpropyl.
  • the bulky alkyl groups are preferably unsubstituted, but they can be substituted with a functional group that does not interfere with the antioxidant activity of the molecule or the polymer.
  • Straight chained alkoxylcarbonyl groups include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl and n-pentoxycarbonyl.
  • n-propoxycarbonyl is a preferred group.
  • n-alkoxycarbonyl groups are optionally substituted with a functional group that does not interfere with the antioxidant activity of the molecule or the polymer.
  • Antioxidant polymers as described immediately above suitable for use in the compositions and methods of the present invention have two or more repeat units, preferably greater than about five repeat units.
  • the molecular weight of the polymers disclosed herein can be generally selected to be appropriate for the desired application. Typically, the molecular weight can be greater than about 500 atomic mass units (amu) and less than about 2,000,000 amu, greater than about 1000 amu and less than about 100,000, greater than about 2,000 amu and less than about 10,000, or greater than about 2,000 amu and less than about 5,000 amu.
  • Antioxidant polymers as described immediately above suitable for use in the compositions and methods 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.
  • 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.
  • Antioxidant polymers as described immediately above suitable for use in the compositions and methods 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 can be insoluble in a particular medium or substrate, it can be preferably well-mixed with that medium or substrate.
  • Antioxidant polymers as described immediately above suitable for use in the compositions and methods of the present invention can be branched or linear, but are preferably linear. Branched antioxidant polymers can only be formed from benzene molecules having three or fewer substituents (e.g., three or more hydrogen atoms).
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include macromolecule antioxidants represented by Structural Formula J or J′:
  • R and R 1 -R 6 are independently —H, —OH, or a C1-C10 optionally substituted linear or branched alkyl group.
  • n is an integer from 0 to 24.
  • Each R a is independently an optionally substituted alkyl.
  • Each R b is independently an optionally substituted alkyl.
  • Each R c is independently an optionally substituted alkyl or an optionally substituted alkoxycarbonyl.
  • R x is —H or an optionally substituted alkyl.
  • R y is —H or an optionally substituted alkyl.
  • Each R′ is independently —H or an optionally substituted alkyl.
  • R′′ is —H, an optionally substituted alkyl, an optionally substituted aryl or an optionally substituted aralkyl.
  • n is an integer from 1 to 10.
  • m is an integer from 1 to 10.
  • s is an integer from 0 to 5.
  • t is an integer from 0 to 4.
  • u is an integer from 1 to 4.
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include macromolecular antioxidants represented by structural formula J 1 :
  • Each R a is independently an optionally substituted alkyl.
  • Each R b is independently an optionally substituted alkyl.
  • Each R c is independently an optionally substituted alkyl or an optionally substituted alkoxycarbonyl.
  • R x is —H or an optionally substituted alkyl.
  • R y is —H or an optionally substituted alkyl.
  • Each R′ is independently —H or an optionally substituted alkyl.
  • R′′ is —H, an optionally substituted alkyl, an optionally substituted aryl or an optionally substituted aralkyl.
  • n is an integer from 1 to 10.
  • m is an integer from 1 to 10.
  • s is an integer from 0 to 5.
  • t is an integer from 0 to 4.
  • u is an integer from 1 to 4.
  • variables in J′ are as described as follows:
  • Each R a is independently an optionally substituted alkyl. In one embodiment, each R a is independently a C1-C20 alkyl. In another embodiment, each R a is independently a C1-C10 alkyl. In another embodiment, each R a is independently selected from the group consisting of:
  • Each R b is independently an optionally substituted alkyl.
  • Each R c is independently an optionally substituted alkyl or an optionally substituted alkoxycarbonyl. In one embodiment, each R c is independently a C1-C10 alkyl.
  • R x is —H or an optionally substituted alkyl.
  • R y is —H or an optionally substituted alkyl. In one embodiment, R x and R y are —H.
  • Each R′ is independently —H or an optionally substituted alkyl. In one embodiment, one R′ is —H. In another embodiment, both R′ are —H.
  • R′′ is —H, an optionally substituted alkyl, an optionally substituted aryl or an optionally substituted aralkyl. In one embodiment, R′′ is —H, a C1-C20 alkyl or an optionally substituted aralkyl. In another embodiment, R′′ is —H, a C1-C10 alkyl or a substituted benzyl group. In yet another embodiment, R′′ is —H. In yet another embodiment, R′′ is: In yet another embodiment R′′ is selected from the group consisting of:
  • R′′ is:
  • n is an integer from 1 to 10. In one embodiment, n is an integer from 1 to 6. In another embodiment, n is 1. In yet another embodiment, n is 2. In yet another embodiment, n is 3. In yet another embodiment, n is 4.
  • n is an integer from 1 to 10. In one embodiment, m is 1 or 2. In another embodiment, m is 1.
  • s is an integer from 0 to 5. In one embodiment, s is 0 or 1. In another embodiment, s is 0.
  • t is an integer from 0 to 4. In one embodiment, t is 0.
  • u is an integer from 1 to 4. In one embodiment, u is 1 or 2.
  • antioxidants represented by J′ when n is 1, the either ring C is not: s is not 0, or R′′ is not —H.
  • Each R a is independently a C 1 -C20 alkyl.
  • Each R c is independently a C 1 -C10 alkyl.
  • R′′ is —H, a C1-C20 alkyl or an optionally substituted aralkyl, and the remainder of the variables are as described above for structural formula (I).
  • n 1 or 2.
  • s is 0 or 1.
  • u is 1 or 2, and the remainder of the variables are as described in the immediately preceding paragraph or for J 1 .
  • both R′ are —H and m is 1 and the compounds are represented by structural formula J 3 : and the remainder of the variables are as described in the immediately preceding paragraph or for structural formula J 1 or J 2 .
  • Each R a is independently a C1-C10 alkyl.
  • R′′ is —H, a C1-C10 alkyl or a substituted benzyl group.
  • n is an integer from 1 to 6, and the remainder of the variables are as described in the immediately preceding paragraph or for structural formula J 1 or J 2 .
  • n 1, s is 0 and R′′ is —H and the compounds are represented by structural formula J 4 : with the proviso that ring C is not: and the remainder of the variables are as described above for structural formula J 1 , J 2 , or J 3 .
  • n is 1 and the compounds are represented by structural formula J 5 : and the remainder of the variables are as described above for structural formula J 1 , J 2 , or J 3 .
  • R′′ is —H and the compounds are represented by structural formula J 7 : and the remainder of the variables are as described above for structural formula J 1 , J 2 or J 3 .
  • R′′ is —H and n is 1 and the compounds are represented by structural formula J 8 : and the remainder of the variables are as described above for structural formula J 1 , J 2 or J 3 .
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include alkylated antioxidant macromolecules having formula K: wherein, independently for each occurrence,
  • n and m are integers from 0 to 6, inclusive;
  • Z is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —C(O)—, —O—, —S—, —C(O)OC(O)—, or a bond;
  • R is H, C 1-6 alkyl, —OH, —NH 2 , —SH, aryl, aralkyl, or wherein at least one R adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like);
  • R 1 is H, C 1-6 alkyl, aryl, alkylaryl, —OH, —NH 2 , —SH, or C1-C6 alkyl ester wherein at least one R 1 adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like); and
  • R 2 is H, C 1-6 alkyl, aryl, aralkyl, —OH, —NH 2 , or —SH wherein at least one R 1 adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like);
  • X is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —C(O)—, —O—, —S—, —C(O)OC(O)—, or a bond;
  • M is H, aryl, C-1 to C-20 linear or branched alkyl chain with or without any functional group anywhere in the chain, or
  • R 2 is H, C 1-6 alkyl, —OH, —NH 2 , —SH, aryl, ester, or wherein at least one R 2 is —OH and n, Z, and each R1 are independently as described above.
  • 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 —C(O)—.
  • Z is —O—.
  • Z is —C(O)OC(O)—.
  • Z is a bond.
  • both R groups adjacent to —OH are bulky alkyl groups (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like). In another embodiment, both R groups are tert-butyl.
  • n 0.
  • m 1
  • n is 0, m is 1, and Z is —C(O)O—.
  • n is 0, m is 1, Z is —C(O)O—, and the two R groups adjacent to the OH are tert-butyl.
  • 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
  • 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.
  • 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.
  • 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 groups are —OH.
  • the antioxidant suitable for use in the compounds and methods of the present invention are compounds represented Structural Formula K 1 :
  • Z is —C(O)NR′—, —NR′C(O)—, —NR′—, —CR′ ⁇ N—, —C(O)—, —C(O)O—, —OC(O)—, —O—, —S—, —C(O)OC(O)— or a bond.
  • Each R′ is independently —H or optionally substituted alkyl.
  • Each R is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH 2 , —SH, or
  • Each R 1 is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH 2 or —SH.
  • Each R 2 is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH 2 or —SH.
  • X is —C(O)O—, —OC(O)—, —C(O)NR′—, —NR′C(O)—, —NR—, —CH ⁇ N—, —C(O)—, —O—, —S—, —NR′— or —C(O)OC(O)—.
  • M is an alkyl or Each n and m are independently integers from 0 to 6. Each s, q and u are independently integers from 0 to 4. In certain embodiments M is not when X is —C(O)O— or —OC(O)—.
  • Z is —C(O)NR′—, —NR′C(O)—, —NR′—, —CR′ ⁇ N—, —C(O)—, —C(O)O—, —OC(O)—, —O—, —S—, —C(O)OC (O)— or a bond.
  • Z is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —O— or —C(O)—.
  • Z is —C(O)NH— or —NHC(O)—.
  • Z is not —C(O)O—, —OC(O)—, —O— or —NH—.
  • the present invention relates to a compound of Structural Formula 1 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 —C(O)—.
  • Z is —O—.
  • Z is —C(O)OC(O)—.
  • Z is a bond.
  • R′ is independently —H or optionally substituted alkyl. In certain other embodiments R′ is —H or an alkyl group. In certain other embodiments R′ is —H or a C1-C10 alkyl group. In certain other embodiments R′ is —H.
  • Each R is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH 2 , —SH, or In certain other embodiments, each R is independently an optionally substituted alkyl or optionally substituted alkoxycarbonyl. In certain other embodiment each R is independently an alkyl or alkoxycarbonyl. In certain other embodiments each R is independently a C1-C6 alkyl or a C1-C6 alkoxycarbonyl. In certain other embodiments each R is independently tert-butyl or propoxycarbonyl. In certain other embodiments each R is independently an alkyl group.
  • each R is independently a bulky alkyl group. Suitable examples of bulky alkyl groups include butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like. In certain embodiments each R is tert-butyl. In certain embodiments at least one R adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
  • both R groups adjacent to —OH are bulky alkyl groups (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like). In another embodiment, both R groups are tert-butyl. In another embodiment, both R groups are tert-butyl adjacent to the OH group.
  • Each R 1 is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH 2 or —SH. In certain other embodiments, each R 1 is independently an optionally substituted alkyl or optionally substituted alkoxycarbonyl. In certain other embodiment each R 1 is independently an alkyl or alkoxycarbonyl. In certain other embodiments each R 1 is independently a C1-C6 alkyl or a C1-C6 alkoxycarbonyl. In certain other embodiments each R 1 is independently tert-butyl or propoxycarbonyl. In certain other embodiments each R 1 is independently an alkyl group.
  • each R 1 is independently a bulky alkyl group. Suitable examples of bulky alkyl groups include butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like. In certain embodiments each R 1 is tert-butyl. In certain embodiments at least one R 1 adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
  • both R 1 groups adjacent to —OH are bulky alkyl groups (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like). In another embodiment, both R 1 groups are tert-butyl. In another embodiment, both R 1 groups are tert-butyl adjacent to the OH group.
  • Each R 2 is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH 2 or —SH. In certain other embodiments, each R 2 is independently an optionally substituted alkyl or optionally substituted alkoxycarbonyl. In certain other embodiment each R 2 is independently an alkyl or alkoxycarbonyl. In certain other embodiments, each R 2 is independently an optionally substituted alkyl. In certain other embodiment each R 2 is independently an alkyl. In certain other embodiments each R 2 is independently a C1-C10 alkyl. In certain other embodiments each R 2 is independently a C1-C6 alkyl.
  • each R 2 is independently a bulky alkyl group or a straight chained alkyl group. In certain other embodiments each R 2 is independently methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, 2-propyl or 1,1-dimethylhexyl. In certain embodiments each R 2 is methyl or tert-butyl.
  • X is —C(O)O—, —OC(O)—, —C(O)NR′—, —NR′C(O)—, —NR′—, —CH ⁇ N—, —C(O)—, —O—, —S—, —NR′— or —C(O)OC(O)—.
  • X is —NH—, —S— or —O—.
  • X is —O—.
  • X is a bond.
  • M is an alkyl or In certain embodiment M is alkyl. In certain other embodiments M is a C1-C20 linear or branched chain alkyl. In certain other embodiments M is a C5-C20 linear or branched chain alkyl. In certain other embodiments M is decane.
  • Each n and m are independently integers from 0 to 6. In certain embodiments each n and m are independently integers from 0 to 2.
  • the antioxidant suitable for use in the compositions and methods of the present invention is represented by a compound of Structural Formula K 1 wherein n is 0.
  • the antioxidant suitable for use in the compositions and methods of the present invention is represented by a compound of Structural Formula K 1 wherein m is 1.
  • the antioxidant suitable for use in the compositions and methods of the present invention is represented by a compound of Structural Formula K 1 and the attendant definitions, wherein n is 0 and m is 1.
  • the antioxidant suitable for use in the compositions and methods of the present invention is represented by a compound of Structural Formula K 1 wherein n is 0, m is 1, and Z is —C(O)O—.
  • the antioxidant suitable for use in the compositions and methods of the present invention is represented by a compound of Structural Formula K 1 wherein n is 0, m is 1, Z is —C(O)O—, and the two R groups adjacent to the OH are tert-butyl.
  • Each s, q and u are independently integers from 0 to 4. In certain embodiments, each s and q are independently integers from 0 to 2. In certain embodiments, s is 2.
  • a Structural Formula K 1 the compound is represented by a Structural Formula selected from:
  • the antioxidants which are suitable for use in the compositions and methods of the present invention include alkylated antioxidant macromolecules having formula L. where M is C1 to C20-linear or branched alkyl chains.
  • n and m are integers from 0 to 6, inclusive;
  • Z is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —C(O)—, —O—, —S—, —C(O)OC(O)—, or a bond;
  • R is H, C 1-6 alkyl, —OH, —NH 2 , —SH, aryl, ester, or wherein at least one R adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like);
  • R 1 is H, C 1-6 alkyl, aryl, aralkyl, —OH, —NH 2 , —SH, or C1-C6 alkyl ester wherein at least one R 1 adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like); and
  • R 2 is H, C 1-6 alkyl, aryl, aralkyl, —OH, —NH 2 , —SH, or ester, wherein at least one R 1 adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like);
  • X is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —C(O)—, —O—, —S—, —C(O)OC(O)—, or a bond;
  • M is H, aryl, C-1 to C-20 linear or branched alkyl chain with or without any functional group anywhere in the chain, or
  • the antioxidants which are suitable for use in the compositions and methods of the present invention are sterically hindered phenol and phosphite based compounds, represented by a formula selected from I-III:
  • the antioxidants which are suitable for use in the compositions and methods of the present invention are sterically hindered phenol and phosphate based compounds, represented by a formula selected from O, P and Q.
  • R is:
  • X and Y in each occurrence independently is a bond, —O—, —NH—, —C(O)NH—, —NHC(O)—, —C(O)O—, —OC(O)— or —CH 2 —.
  • X and Y in each occurrence independently is a bond or —CH 2 —.
  • X and Y in each occurrence independently is a bond, —O— or —CH 2 —.
  • X and Y in each occurrence independently is a bond, —NH— or —CH 2 —.
  • X and Y in each occurrence independently is a bond, —C(O)NH— or —CH 2 —.
  • X and Y in each occurrence independently is a bond, —NHC(O)—, or —CH 2 —. In yet another embodiment, X and Y in each occurrence independently is a bond, —C(O)O— or —CH 2 —. In yet another embodiment, X and Y in each occurrence independently is a bond, —OC(O)— or —CH 2 —.
  • n and m in each occurrence independently is 0 or a positive integer. In one embodiment, n and m in each occurrence independently is 0 to 18. In another embodiment, n and m in each occurrence independently is 0 to 12. In yet another embodiment, n and m are in each occurrence independently is 0 to 6.
  • i and j in each occurrence independently is 0, 1, 2, 3 or 4. In one embodiment i and j in each occurrence independently is 0, 1 or 2. In a particular embodiment, i is 0. In another particular embodiment j is 2.
  • R′′ is an optionally substituted alkyl. In one embodiment R′′ is C1-C6 alkyl.
  • R is: and n and m in each occurrence independently is 0 to 12, and the remainder of the variables are as described above for structural formulas O, P and Q.
  • R, n and m are as described immediately above, and R 1 and R 2 in each occurrence, independently is an optionally substituted alkyl; i and j in each occurrence independently is 0, 1 or 2; and the remainder of the variables are as described above for structural formulas O, P and Q.
  • R 1 , R 2 , i and j are as described immediately above, and R is: n and m in each occurrence, independently is 0 to 6; and the remainder of the variables are as described above for structural formulas O, P and Q.
  • R 1 , R 2 , i, j, R, n and m are as described immediately above, and X and Y in each occurrence, independently is a bond or —CH 2 —; and the remainder of the variables are as described above for structural formulas O, P and Q.
  • R 1 , R 2 , i, j, R, n and m are as described immediately above, and X and Y in each occurrence, independently is a bond, —O— or —CH 2 —; and the remainder of the variables are as described above for structural formulas O, P and Q.
  • R 1 , R 2 , i, j, R, n and m are as described immediately above, and X and Y in each occurrence, independently is a bond, —NH— or —CH 2 —; and the remainder of the variables are as described above for structural formulas O, P and Q.
  • R 1 , R 2 , i, j, R, n and m are as described immediately above, and X and Y in each occurrence, independently is a bond, —C(O)NH— or —CH 2 —; and the remainder of the variables are as described above for structural formulas O, P and Q.
  • R 1 , R 2 , i,j, R, n and m are as described immediately above, and X and Y in each occurrence, independently is a bond, —NHC(O)—, or —CH 2 —; and the remainder of the variables are as described above for structural formulas O, P and Q.
  • R 1 , R 2 , i, j, R, n and m are as described immediately above, and X and Y in each occurrence, independently is a bond, —C(O)O— or —CH 2 —; and the remainder of the variables are as described above for structural formulas O, P and Q.
  • R 1 , R 2 , i, j, R, n and m are as described immediately above, and X and Y in each occurrence, independently is a bond, —OC(O)— or —CH 2 —; and the remainder of the variables are as described above for structural formulas O, P and Q.
  • n and m in each occurrence independently is 0 or a positive integer. In one embodiment, n and m in each occurrence, independently is 0 to 18. In another embodiment, n and m in each occurrence, independently is 0 to 12. In yet another embodiment, n and m in each occurrence, independently is 0 to 6.
  • i and j in each occurrence independently is 0, 1, 2, 3 or 4. In one embodiment, i and j in each occurrence, independently is 0, 1 or 2. In a particular embodiment, i is 0. In another particular embodiment, j is 2.
  • Z′ is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —C(O)—, —O—, —S—, —C(O)OC(O)— or a bond.
  • Z′ is —C(O)O—.
  • Z′ is —OC(O)—.
  • Z′ is —C(O)NH—.
  • Z′ is —NHC(O)—.
  • Z′ is —NH—.
  • Z′ is —CH ⁇ N—.
  • Z′ is —C(O)—. In yet another embodiment, Z′ is —O—. In yet another embodiment, Z′ is —S—. In yet another embodiment, Z′ is —C(O)OC(O)—. In yet another embodiment, Z′ is a bond.
  • R′ is an optionally substituted C1-C6 alkyl, —OH, —NH 2 , —SH, an optionally substituted aryl, an ester or
  • R′ adjacent to the —OH group is an optionally substituted bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
  • bulky alkyl group e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like.
  • R′ 1 is an optionally substituted C1-C6 alkyl, an optionally substituted aryl, an optionally substituted aralkyl, —OH, —NH 2 , —SH, or C1-C6 alkyl ester wherein at least one R 1 adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like). ).
  • R′ 2 is an optionally substituted C1-C6 alkyl, an optionally substituted aryl, an optionally substituted aralkyl, —OH, —NH 2 , —SH, or ester.
  • X′ is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —C(O)—, —O—, —S—, —C(O)OC(O)— or a bond.
  • X′ is —C(O)O—.
  • X′ is —OC(O)—.
  • X′ is —C(O)NH—.
  • X′ is —NHC(O)—.
  • X′ is —NH—.
  • X′ is —CH ⁇ N—.
  • X′ is —C(O)—. In yet another embodiment X′ is —O—. In yet another embodiment X′ is —S—. In yet another embodiment X′ is —C(O)OC(O)—. In yet another embodiment X′ is a bond.
  • M′ is H, an optionally substituted aryl, an optionally substituted C1-C20 linear or branched alkyl chain with or without any functional group anywhere in the chain, or
  • o is 0 or a positive integer. Preferably o is 0 to 18. More preferably o is 0 to 12. Even more preferably o is 0 to 6.
  • R′ 2 is C1-C6 alkyl, —OH, —NH 2 , —SH, aryl, ester, aralkyl or
  • R′ 2 is —OH, and the values and preferred values for the remainder of the variables for R are as described immediately above.
  • the present invention relates to a compound of formula O, P and Q, wherein M is
  • p is 0, 1, 2, 3 or 4; and the values and preferred values for the remainder of the variables are as described above for formulas O, P and Q.
  • a in each occurrence independently is a bond, —O—, —NH—, —S—, —C(O)—, —C(O)NH—, —NHC(O)—, —C(O)O—, —OC(O)—, —CH ⁇ N— or —N ⁇ CH—.
  • a in each occurrence independently is —C(O)NH— or —NHC(O)—.
  • B is a C1-C6 alkyl.
  • C in each occurrence independently is —H, an optionally substituted alkyl group or
  • C is:
  • R 1 and R 2 in each occurrence independently is an optionally substituted alkyl, optionally substituted aryl or optionally substituted aralkyl. In one embodiment, each R 1 and R 2 in each occurrence, independently is an optionally substituted alkyl. In another embodiment, each R 1 and R 2 in each occurrence, independently is a C1-C6 alkyl.
  • i and j in each occurrence independently is 0, 1, 2, 3 or 4. In one embodiment i and j in each occurrence, independently is 0, 1 or 2. In a particular embodiment, i is 0. In another particular embodiment, j is 2.
  • k is a positive integer from 1 to 20. In one embodiment, k is a positive integer from 1 to 12. In another embodiment, k is a positive integer from 1 to 6.
  • 1 is 0 or a positive integer from 1 to 20. In one embodiment, 1 is 0 or a positive integer from 1 to 12. In another embodiment, 1 is 0 or a positive integer from 1 to 6.
  • n and m in each occurrence independently is 0 or a positive integer. In one embodiment, n and m in each occurrence independently is 0 to 18. In another embodiment, n and m in each occurrence independently is 0 to 12. In yet another embodiment, n and m are in each occurrence independently is 0 to 6.
  • s is a positive integer from 1 to 6.
  • q is a positive integer from 1 to 3.
  • Z in each occurrence independently is a bond, an optionally substituted alkylene group, —S—, —O— or —NH—.
  • Z is a single bond.
  • i and j in each occurrence independently is 0, 1, 2, 3 or 4. In one embodiment i and j in each occurrence, independently is 0, 1 or 2. In a particular embodiment, i is 0. In another particular embodiment, j is 2.
  • k is a positive integer from 1 to 20. In one embodiment, k is a positive integer from 1 to 12. In another embodiment, k is a positive integer from 1 to 6.
  • 1 is 0 or a positive integer from 1 to 20, and when D is —(CH 2 ) 1 NHC(O)(CH 2 ) h —, —(CH 2 ) 1 OC(O)(CH 2 ) h —, —(CH 2 ) 1 S—(CH 2 ) h —, or —(CH 2 ) 1 O(CH 2 ) h —, 1 is not 0.
  • 1 is 0 or a positive integer from 1 to 12.
  • l is 0 or a positive integer from 1 to 6.
  • h is 0 or a positive integer from 1 to 20, When Z is not a bond and D is —(CH 2 ) 1 C(O)O(CH 2 ) h —, —(CH 2 ) 1 C(O)NH(CH 2 ) h —, —(CH 2 ) 1 C(O)O(CH 2 ) h —, —(CH 2 ) 1 NH(CH 2 ) h —, —(CH 2 ) 1 S—(CH 2 ) h —, or —(CH 2 ) 1 O(CH 2 ) h —, h is not 0.
  • h is 0 or a positive integer from 1 to 12. In another embodiment, h is 0 or a positive integer from 1 to 6. In another embodiment, h is 0.
  • the present invention is directed to macromolecular antioxidants represented by a structural formula selected from Structural Formulas 1-6, wherein R is:
  • D a for each occurrence, is independently —C(O)NR d —, —NR d C(O)—, —NR d —, —CR d ⁇ N—, —C(O)—, —C(O)O—, —OC(O)—, —O—, —S—, —C(O)OC(O)— or a bond.
  • D a is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —O— or —C(O)—.
  • D a is —NH—, —C(O)NH— or —NHC(O)—.
  • D a is not —C(O)O—, —OC(O)—, —O— or —NH—.
  • the present invention relates to a compound of Structural Formula I and the attendant definitions, wherein D a is —OC(O)—.
  • D a is —C(O)O—.
  • D a is —C(O)NH—.
  • D a is —NHC(O)—.
  • D a is —NH—.
  • D a is —CH ⁇ N—.
  • D a is —C(O)—.
  • D a is —O—.
  • D a is —C(O)OC(O)—.
  • D a is a bond.
  • Each R d is independently —H or optionally substituted alkyl. In certain other embodiments R d is —H or an alkyl group. In certain other embodiments R d is —H or a C1-C10 alkyl group. In certain other embodiments R d is —H.
  • R c and R c ′ are independently H or an optionally substituted alkyl. In one embodiment, R c and R c ′ are H. In another embodiment, one of R c and R c ′ is H and the other is an optionally substituted alkyl. More specifically, the alkyl is a C 1 -C 10 alkyl. Even more specifically, the alkyl is a C10 alkyl.
  • R a for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH 2 , or —SH.
  • each R a is independently an optionally substituted alkyl or optionally substituted alkoxycarbonyl.
  • each R a is independently an alkyl or alkoxycarbonyl.
  • each R a is independently a C 1 -C 6 alkyl or a C 1 -C 6 alkoxycarbonyl.
  • each R a is independently tert-butyl or propoxycarbonyl.
  • each R a is independently an alkyl group. In certain embodiments each R a is independently a bulky alkyl group. Suitable examples of bulky alkyl groups include butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like. In certain embodiments each R a is tert-butyl. In certain embodiments at least one R a adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
  • both R a groups adjacent to —OH are bulky alkyl groups (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
  • both R a groups are tert-butyl.
  • both R a groups are tert-butyl adjacent to the OH group.
  • R b for each occurrence, is independently H or optionally substituted alkyl. In certain embodiment, R b is H.
  • n′ and m′ are independently integers from 0 to 18. In another embodiment, n′ and m′ in each occurrence, independently is 0 to 12. In yet another embodiment, n′ and m′ in each occurrence, independently is 0 to 6. In certain embodiments each n′ and m′ are independently integers from 0 to 2. In a specific embodiment, n′ is 0. In another specific embodiment, m is an integer from 0 to 2. In another specific embodiment, n′ is 0 and m′ is 2.
  • Each p′ is independently an integer from 0 to 4. In certain embodiments, each p′ is independently an integer from 0 to 2. In certain embodiments, p′ is 2.
  • R is:
  • n and m in each occurrence independently is 0 or a positive integer. In one embodiment, n and m in each occurrence, independently is 0 to 18. In another embodiment, n and m in each occurrence, independently is 0 to 12. In yet another embodiment, n and m in each occurrence, independently is 0 to 6.
  • i and j in each occurrence independently is 0, 1, 2, 3 or 4. In one embodiment, i and j in each occurrence, independently is 0, 1 or 2. In a particular embodiment, i is 0. In another particular embodiment, j is 2.
  • Z′ is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —C(O)—, —O—, —S—, —C(O)OC(O)— or a bond.
  • Z′ is —C(O)O—.
  • Z′ is —OC(O)—.
  • Z′ is —C(O)NH—.
  • Z′ is —NHC(O)—.
  • Z′ is —NH—.
  • Z′ is —CH ⁇ N—.
  • Z′ is —C(O)—. In yet another embodiment, Z′ is —O—. In yet another embodiment, Z′ is —S—. In yet another embodiment, Z′ is —C(O)OC(O)—. In yet another embodiment, Z′ is a bond.
  • R′ is an optionally substituted C1-C6 alkyl, —OH, —NH 2 , —SH, an optionally substituted aryl, an ester or
  • R′ adjacent to the —OH group is an optionally substituted bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
  • bulky alkyl group e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like.
  • R′ 1 is an optionally substituted C1-C6 alkyl, an optionally substituted aryl, an optionally substituted aralkyl, —OH, —NH 2 , —SH, or C1-C6 alkyl ester wherein at least one R 1 adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
  • a bulky alkyl group e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like.
  • R′ 2 is an optionally substituted C1-C6 alkyl, an optionally substituted aryl, an optionally substituted aralkyl, —OH, —NH 2 , —SH, or ester.
  • X′ is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —C(O)—, —O—, —S—, —C(O)OC(O)— or a bond.
  • X′ is —C(O)O—.
  • X′ is —OC(O)—.
  • X′ is —C(O)NH—.
  • X′ is —NHC(O)—.
  • X′ is —NH—.
  • X′ is —CH ⁇ N—.
  • X′ is —C(O)—. In yet another embodiment X′ is —O—. In yet another embodiment X′ is —S—. In yet another embodiment X′ is —C(O)OC(O)—. In yet another embodiment X′ is a bond.
  • M′ is H, an optionally substituted aryl, an optionally substituted C1-C20 linear or branched alkyl chain with or without any functional group anywhere in the chain, or
  • o is 0 or a positive integer. Preferably o is 0 to 18. More preferably o is 0 to 12. Even more preferably o is 0 to 6.
  • R is:
  • n and m in each occurrence independently is 0 or a positive integer. In one embodiment, n and m in each occurrence, independently is 0 to 18. In another embodiment, n and m in each occurrence, independently is 0 to 12. In yet another embodiment, n and m in each occurrence, independently is 0 to 6.
  • i and j in each occurrence independently is 0, 1, 2, 3 or 4. In one embodiment, i and j in each occurrence, independently is 0, 1 or 2. In a particular embodiment, i is 0. In another particular embodiment, j is 2.
  • Z′ in each occurrence independently is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —C(O)—, —O—, —S—, —C(O)OC(O)— or a bond.
  • Z′ is —C(O)O—.
  • Z′ is —OC(O)—.
  • Z′ is —C(O)NH—.
  • Z′ is —NHC(O)—.
  • Z′ is —NH—.
  • Z′ is —CH ⁇ N—.
  • Z′ is —C(O)—. In yet another embodiment, Z′ is —O—. In yet another embodiment, Z′ is —S—. In yet another embodiment, Z′ is —C(O)OC(O)—. In yet another embodiment, Z′ is a bond.
  • R′ in each occurrence independently is C1-C6 alkyl, —OH, —NH 2 , —SH, an optionally substituted aryl, an ester or
  • R′ adjacent to the —OH group is an optionally substituted bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
  • bulky alkyl group e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like.
  • R′ 1 in each occurrence independently is C1-C6 alkyl, an optionally substituted aryl, an optionally substituted aralkyl, —OH, —NH 2 , —SH, or C1-C6 alkyl ester wherein at least one R 1 adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like). ).
  • R′ 2 in each occurrence independently is C1-C6 alkyl, an optionally substituted aryl, an optionally substituted aralkyl, —OH, —NH 2 , —SH, or ester.
  • X′ in each occurrence independently is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH ⁇ N—, —C(O)—, —O—, —S—, —C(O)OC(O)— or a bond.
  • X′ is —C(O)O—.
  • X′ is —OC(O)—.
  • X′ is —C(O)NH—.
  • X′ is —NHC(O)—.
  • X′ is —NH—.
  • X′ is —CH ⁇ N—.
  • X′ is —C(O)—. In yet another embodiment X′ is —O—. In yet another embodiment X′ is —S—. In yet another embodiment X′ is —C(O)OC(O)—. In yet another embodiment X′ is a bond.
  • M′ is H, an optionally substituted aryl, C1-C20 linear or branched alkyl chain with or without any functional group anywhere in the chain, or
  • o is 0 or a positive integer. Preferably o is 0 to 18. More preferably o is 0 to 12. Even more preferably o is 0 to 6.
  • R is:
  • R′ 2 is C1-C6 alkyl, —OH, —NH 2 , —SH, aryl, aralkyl, ester, or
  • R′ 2 is —OH, and the values and preferred values for the remainder of the variables for R are as described immediately above.
  • the present invention relates to a compound of formula 1-6, wherein M is
  • p is 0, 1, 2, 3 or 4; and the values and preferred values for the remainder of the variables are as described above for formulas 1-6.
  • macromolecular antioxidants which are suitable for use in the compositions and methods of the present invention, for example, high molecular weight dimers, and tetramers etc., are shown below.
  • p in each occurrence independently is an integer equal to or greater than 2.
  • polymers which are useful in the compositions methods of the present invention include:
  • antioxidants suitable for use in the methods and compositions of the present invention include compounds represented by Structural Formula I: wherein:
  • R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H;
  • Z is —C(O)NR c —, —NR c C(O)—, —NR c —, —CR c ⁇ N—, —C(O)—, —C(O)O—, —OC(O)—, —O—, —S—, —C(O)OC(O)— or a bond;
  • R c is independently H or optionally substituted alkyl
  • R a for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH 2 , —SH;
  • R b for each occurrence, is independently H or optionally substituted alkyl
  • s for each occurrence, is independently an integer from 0 to 4.
  • n and n are independently integers from 0 to 6.
  • antioxidants suitable for use in the methods and compositions of the present invention include compounds represented by Structural Formula II: wherein:
  • R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H;
  • R a for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH 2 , or —SH;
  • R b for each occurrence, is independently H or optionally substituted alkyl.
  • s for each occurrence, is independently an integer from 0 to 4.
  • n for each occurrence, is independently an integer from 0 to 6.
  • antioxidants suitable for use in the methods and compositions of the present invention include compounds represented by Structural Formula III: wherein R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H.
  • compositions for use in stabilization of polyolefins include but are not limited to:
  • an antioxidant in the concentration range , from about 0.0001% to about 50%, from about 0.0005% to about 20%, from about 0.005% to about 10%, from about 0.05% to about 5% or from about 0.01% to about 1%) with acid scavengers, for example, in amounts of from about 0.0005% to about 50%, from about 0.0001% to about 20%, from about 0.005% to about 10%, from about 0.05% to about 5% or from about 0.01% to about 1% by weight, based on the weight of polyolefin to be stabilized.
  • an antioxidant in the concentration range from about 0.0005% to about 50%, from about 0.0001% to about 20%, from about 0.005% to about 10%, from about 0.05% to about 5% or from about 0.01% to about 1%) along with organic phosphorus stabilizers.
  • the organic phosphorus stabilizers are used for example, in amounts of, from about 0.001% to about 30%, from about 0.005% to about 20%, from about 0.01% to about 5%, from about 0.05% to about 2% or from about 0.1% to about 1%, by weight, based on the weight of the polyolefin to be stabilized.
  • an antioxidant in the concentration range from about 0.0005% to about 50%, from about 0.0001% to about 50%, from about 0.005% to about 10%, from about 0.05% to about 5% or from about 0.01% to about 1%) along with acid scavengers and organic phosphorus stabilizers in concentrations described in a. and b. above.
  • an antioxidant in combination with other known commercially available antioxidants, such as, for example, Irganox® 1010, Irganox® 1330, Irganox® 1076 and Irganox® 1135 or other antioxidants described above or incorporated herein by reference along with the formulations described in a.-c. above.
  • polyolefins and mixtures of polyolefins can be stabilized by contacting the polyolefin or mixture of polyolefins with a composition of the present invention.
  • These polyolefins and mixtures of polyolefins include, but are not limited to substituted polyolefins, polyacrylates, polymethacrylates and copolymers of polyolefins.
  • substituted polyolefins include, but are not limited to substituted polyolefins, polyacrylates, polymethacrylates and copolymers of polyolefins.
  • the following are examples of some types of polyolefins which can be stabilized by the methods of the present invention:
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE) and ultra low density polyethylene (ULDPE).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • LDPE low density poly
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, for example polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
  • These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either p- or s-coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerization medium.
  • the catalysts can be used by themselves in the polymerization or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
  • These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (iono
  • Blends of polymers mentioned under 1. with impact modifiers such as ethylene-propylene-diene monomer copolymers (EPDM), copolymers of ethylene with higher alpha-olefins (such as ethylene-octene copolymers), polybutadiene, polyisoprene, styrene-butadiene copolymers, hydrogenated styrene-butadiene copolymers, styrene-isoprene copolymers, hydrogenated styrene-isoprene copolymers.
  • TPO's thermoplastic polyolefins
  • polyolefins of the present invention are for example polypropylene homo- and copolymers and polyethylene homo- and copolymers.
  • polypropylene high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and polypropylene random and impact (heterophasic) copolymers.
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • heteroophasic polypropylene random and impact copolymers.
  • Acid scvaangers or stabilizers are defined herein as antacids or co-stabilizers which neutralize the acidic catalysts or other components present in the polymers.
  • the acid scavengers which are suitable for use in the methods of the present invention include but are not limited to: zinc oxide, calcium lactate, natural and synthetic hydrotalcites, natural and synthetic hydrocalumites, and alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate and zinc pyrocatecholate. Combinations of acid scavengers may also be employed.
  • the acid scavengers are used for example, in amounts of from about 0.0005% to about 50% by weight, about 0.0001% to about 20% by weight, about 0.005% to about 5% by weight, about 0.01% to about 3% by weight, about 0.05% to about 2% by weight, or about 0.1% to about 1% by weight, based on the weight of polyolefin to be stabilized.
  • examples of organic phosphorus stabilizers include phosphates, phosphites and phosphonites which are suitable for use in the methods of the present invention.
  • Specific examples of phosphorus stabilizers include but are not limited to: triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, ethanamine, 2-[[2,4,8,10-tetrakis(1,1dimethylethyl)dibenzo[d,f][1,2,3]dioxaphosphepin-6-yl]oxy
  • organic phosphites and phosphonites which are suitable for use in the methods of the present invention as organic phosphorus stabilizers: tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (formula (D)), tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene-diphosphonite (formula (H)), (2,4,6-tri-tert-butylphenyl)2-butyl-2-ethyl-1,3-propanediol phosphate (formula (J)), or bis(2,4-di-cumylphenyl)pentaerythritol diphosphite (formula (K)).
  • the organic phosphorus stabilizers are used, for example, in amounts of from about 0.001% to about 50% by weight, about 0.005% to about 20% by weight, about 0.01% to about 5% by weight, 0.05% to about 3% by weight, 0.1% to about 2% by weight or 0.1% to about 1% by weight based on the weight of the polyolefin to be stabilized.
  • compositions of the present invention may comprise further co-stabilizers (e.g., additives) such as, for example, the following:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-tert-butyl-4-octadecylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,2,6-
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.
  • 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (Vitamin E).
  • Hydroxylated thiodiphenyl ethers for example 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis-(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
  • 2,2′-thiobis(6-tert-butyl-4-methylphenol 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis-(3,6-di-sec-amylphenol), 4,4′-bis(2,6
  • Alkylidenebisphenols for example 2,2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)-4-nonylphenol],
  • O—, N— and S-benzyl compounds for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • Aromatic hydroxybenzyl compounds for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(
  • Benzylphosphonates for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.
  • esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
  • esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
  • Aminic antioxidants for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl—N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-
  • hindered amine stabilizers are hindered amines which produce nitroxyl radicals that react with alkyl radicals produced during thermo-oxidation of the polymers.
  • Sterically hindered amine stabilizers for example 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succ
  • the sterically hindered amine may also be one of the compounds described in U.S. Pat. No. 5,980,783, the entire contents of which are incorporated herein by reference, that is compounds of component I-a), I-b), I-c), I-d), I-e), I-f), I-g), I-h), I-i), I-j), I-k) or I-l), in particular the light stabilizer 1-a-1, 1-a-2, 1-b-1, 1-c-1, 1-c-2, 1-d-1, 1-d-2, 1-d-3, 1-e-1, 1-f-1, 1-g-1, 1-g-2 or 1-k-1 listed on columns 64-72 of said U.S. Pat. No. 5,980,783.
  • the sterically hindered amine may also be one of the compounds described in U.S. Pat. Nos. 6,046,304 and 6,297,299, the entire contents of each of which are incorporated herein by reference, for example compounds as described in claims 10 or 38 or in Examples 1-12 or D-1 to D-5 therein.
  • Sterically hindered amines substituted on the N-atom by a hydroxy-substituted alkoxy group for example compounds such as 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine, the reaction product of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine with a carbon radical from t-amylalcohol, 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(l-(2-hydroxy-2-methylpropoxy)
  • UV absorbers essentially absorb the harmful UV radiation and dissipate it so that is does not lead to photosensitization i.e., dissipation as heat.
  • Esters of substituted and unsubstituted benzoic acids as for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Oxamides for example 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5 ′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubtituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Tris-aryl-o-hydroxyphenyl-s-triazines for example known commercial tris-aryl-o-hydroxyphenyl-s-triazines and triazines as disclosed in, WO 96/28431, EP 434608, EP 941989, GB 2,317,893, U.S. Pat. Nos.
  • Metal deactivators as used herein are compounds which form stable complexes with metal ions and inhibit their reaction with peroxides, for example, N,N′-diphenyloxamide, N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicylo
  • Peroxide scavengers for example, esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ -dodecylmercapto)propionate.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide pentaerythritol tetrakis( ⁇ -dodecylmer
  • N,N-dihydrocarbylhydroxylamines selected from the group consisting of N,N-dibenzylhydroxylamine, N,N-dimethyl-hydroxylamine, N,N-diethylhydroxylamine, N,N-bis(2-hydroxypropyl)hydroxylamine, N,N-bis(3-hydroxypropyl)hydroxylamine, N,N-bis(2-carboxyethyl)hydroxylamine, N,N-bis(benzylthiomethyl)hydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-didodecylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-tetradecylhydroxylamine, N-hexadecyl-N-tetrade
  • the hydroxylamine may be for example the N,N-di(alkyl)hydroxylamine produced by the direct oxidation of N,N-di(hydrogenated tallow)amine.
  • N,N-di(alkyl)hydroxylamine produced by the direct oxidation of N,N-di(hydrogenated tallow)amine.
  • the hydroxylamine prepared by direct hydrogen peroxide oxidation of bis(hydrogenated tallow alkyl)amines that is N,N-di(hydrogenated tallow)hydroxylamine, CAS# 143925-92-2.
  • N,N-di(hydrogenated tallow)hydroxylamine is prepared as in the working Examples of U.S. Pat. No. 5,013,510 the entire contents of which are incorporated herein by reference.
  • Nitrones for example, N-benzyl- ⁇ -phenyl-nitrone, N-ethyl- ⁇ -methyl-nitrone, N-octyl- ⁇ -heptyl-nitrone, N-lauryl- ⁇ -undecyl-nitrone, N-tetradecyl- ⁇ -tridcyl-nitrone, N-hexadecyl- ⁇ -pentadecyl-nitrone, N-octadecyl- ⁇ -heptadecyl-nitrone, N-hexadecyl- ⁇ -heptadecyl-nitrone, N-ocatadecyl- ⁇ -pentadecyl-nitrone, N-heptadecyl- ⁇ -heptadecyl-nitrone, N-octadecyl- ⁇ -hexadecyl-nitrone, nitrone derived from N,N-di
  • Amine-N-oxides for example GenoxTM EP, a di(C 16 -C 18 )alkyl methyl amine oxide, CAS# 204933-93-7, Crompton Corporation.
  • Polyhydric alcohols for example pentaerythritol and glycerol.
  • Basic co-stabilizers for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides and polyurethanes.
  • Nucleating agents for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate, lithium benzoate, disodium bicycle[2.2.1]heptane 2,3-dicarboxylate; organic phosphates and salts thereof, e.g. sodium 2,2′-methylenebis(4,6-di-tert-butylphenyl)phosphate, and polymeric compounds such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono-
  • Clarifiers for example substituted and unsubstituted bisbenzylidene sorbitols.
  • Fillers and reinforcing agents for example, calcium carbonate, silicates, glass fibers, glass bulbs, asbestos, talc, wollastonite, nanoclays, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • Dispersing Agents are compounds which when added to a colloidal solution disperse the particles uniformly, such as, for example, polyethylene oxide waxes or mineral oil.
  • additives for example, plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flame retardants, antistatic agents, antimicrobials and blowing agents.
  • the co-stabilizers are added, for example, in concentrations of from about 0.0001% to about 50% by weight, about 0.0005% to about 20% by weight, about 0.001% to about 10% by weight, from about 0.01% to about 5% by weight, from about 0.05% to about 1% by weight from about 0.1% to about 1% by weight based on the overall weight of the polyolefin to be stabilized.
  • the fillers and reinforcing agents are added to the polyolefins in concentrations of about 0.001% to about 80% by weight, about 0.005% to about 60% by weight, about 0.01% to about 40% by weight, of about 0.05% to about 20% by weight, of about 0.1% to about 10% by weight, of about 0.5% to about 5% by weight, based on the overall weight of the polyolefins to be stabilized.
  • the fillers and reinforcing agents are added to the polyolefins in concentrations of about 0.001% to about 80% by weight, about 0.005% to about 70% by weight, about 0.01% to about 60% by weight, about 0.1% to about 50% by weight about 0.5% to about 40% by weight about 1% to about 20% by weight based on the overall weight of the polyolefins to be stabilized.
  • metal hydroxides especially aluminum hydroxide or magnesium hydroxide
  • carbon black as filler is added to the polyolefins in concentrations, judiciously, of from about 0.001% to about 30% by weight, 0.005% to about 10% by weight, 0.01% to about 5% by weight, of from about 0.05% to about 3% by weight of from about 0.1% to about 2% by weight of from about 0.1% to about 1% by weight based on the overall weight of the polyolefins to be stabilized.
  • glass fibers as reinforcing agents are added to the polyolefins in concentrations, judiciously, of from of about 0.001% to about 80% by weight, about 0.005% to about 60% by weight, about 0.01% to about 40% by weight, of about 0.05% to about 20% by weight, of about 0.1% to about 10% by weight, based on the overall weight of the polyolefins to be stabilized.
  • alkyl as used herein means a saturated straight-chain, branched or cyclic hydrocarbon. When straight-chained or branched, an alkyl group is typically C1-C8, more typically C1-C6; when cyclic, an alkyl group is typically C3-C12, more typically C3-C7 alkyl ester. Examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl and tert-butyl and 1,1-dimethylhexyl.
  • alkoxy as used herein is represented by —OR**, wherein R** is an alkyl group as defined above.
  • acyl as used herein is represented by —C(O)R**, wherein R** is an alkyl group as defined above.
  • alkyl ester as used herein means a group represented by —C(O)OR**, where R** is an alkyl group as defined above.
  • aromatic group used alone or as part of a larger moiety as in “aralkyl”, includes carbocyclic aromatic rings and heteroaryl rings.
  • aromatic group may be used interchangeably with the terms “aryl”, “aryl ring” “aromatic ring”, “aryl group” and “aromatic group”.
  • Carbocyclic aromatic ring groups have only carbon ring atoms (typically six to fourteen) and include monocyclic aromatic rings such as phenyl and fused polycyclic aromatic ring systems in which a carbocyclic aromatic ring is fused to one or more aromatic rings (carbocyclic aromatic or heteroaromatic). Examples include 1-naphthyl, 2-naphthyl, 1-anthracyl and 2-anthracyl.
  • Carbocyclic aromatic ring is a group in which an aromatic ring is fused to one or more non-aromatic rings (carbocyclic or heterocyclic), such as in an indanyl, phthalimidyl, naphthimidyl, phenanthridinyl, or tetrahydronaphthyl, where the radical or point of attachment is on the aromatic ring.
  • heteroaryl refers to heteroaromatic ring groups having five to fourteen members, including monocyclic heteroaromatic rings and polycyclic aromatic rings in which a monocyclic aromatic ring is fused to one or more other aromatic ring (carbocyclic aromatic or heteroaromatic). Heteroaryl groups have one or more ring heteroatoms.
  • heteroaryl groups include 2-furanyl, 3-furanyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-pyrazolyl, 4-pyrazolyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-triazolyl, 5-triazolyl, tetrazolyl, 2-thienyl, 3-thienyl, carbazolyl, 2-benzothienyl, 3-benzothiazo
  • heteroaryl is a group in which an aromatic ring is fused to one or more non-aromatic rings (carbocyclic or heterocyclic), where the radical or point of attachment is on the aromatic ring.
  • heteroatom means nitrogen, oxygen, or sulfur and includes any oxidized form of nitrogen and sulfur, and the quaternized form of any basic nitrogen.
  • nitrogen includes a substitutable nitrogen of a heteroaryl or non-aromatic heterocyclic group.
  • the nitrogen in a saturated or partially unsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl) or NR′′ (as in N-substituted pyrrolidinyl), wherein R′′ is a suitable substituent for the nitrogen atom in the ring of a non-aromatic nitrogen-containing heterocyclic group, as defined below.
  • aralkyl group is an alkyl groups substituted with an aryl group as defined above.
  • An optionally substituted aryl group as defined herein may contain one or more substitutable ring atoms, such as carbon or nitrogen ring atoms.
  • suitable substituents on a substitutable ring carbon atom of an aryl group include —OH, C1-C3 alkyl, C1-C3 haloalkyl, —NO 2 , C1-C3 alkoxy, C1-C3 haloalkoxy, —CN, —NH 2 , C1-C3 alkylamino, C1-C3 dialkylamino, —C(O)NH 2 , —C(O)NH(C1-C3 alkyl), —C(O)(C1-C3 alkyl), —NHC(O)H, —NHC(O)(C1-C3 alkyl), —C(O)N(C1-C3 alkyl) 2 , —NHC(O)O—C1-C3 alkyl), —C
  • substituents on a substitutable ring nitrogen atom of an aryl group include C1-C3 alkyl, NH 2 , C1-C3 alkylamino, C1-C3 dialkylamino, —C(O)NH 2 , —C(O)NH(C1-C3 alkyl), —C(O)(C1-C3 alkyl), —CO 2 R**, —C(O)C(O)R**, —C(O)CH 3 , —C(O)OH, —C(O)O-(C1-C3 alkyl), —SO 2 NH 2 —SO 2 NH(C1-C3alkyl), —SO 2 N(C1-C3alkyl) 2 , NHSO 2 H, NHSO 2 (C1-C3 alkyl), —C( ⁇ S)NH 2 , —C( ⁇ S)NH(C1-C3 alkyl), —C( ⁇ S)N(
  • An optionally substituted alkyl group as defined herein may contain one or more substituents.
  • suitable substituents for an alkyl group include those listed above for a substitutable carbon of an aryl and the following: ⁇ O, ⁇ S, ⁇ NNHR**, ⁇ NN(R**) 2 , ⁇ NNHC(O)R**, ⁇ NNHCO 2 (alkyl), ⁇ NNHSO 2 (alkyl), ⁇ NR**, spiro cycloalkyl group or fused cycloalkyl group.
  • R** in each occurrence, independently is —H or C1-C6 alkyl.
  • Preferred substituents on alkyl groups are as defined throughout the specification. In certain embodiments optionally substituted alkyl groups are unsubstituted.
  • a “spiro cycloalkyl” group is a cycloalkyl group which shares one ring carbon atom with a carbon atom in an alkylene group or alkyl group, wherein the carbon atom being shared in the alkyl group is not a terminal carbon atom.
  • macromolecular antioxidants and polymeric macromolecular antioxidants of the present invention exploit the differences in activities (ks, equilibrium constant) of, for example, homo- or hetero-type antioxidant moieties.
  • Antioxidant moieties include, for example, hindered phenolic groups, unhindered phenolic groups, aminic groups and thioester groups, etc. of which there can be one or more present in each macromolecular antioxidant molecule.
  • a homo- type antioxidant macromolecule comprises antioxidant moieties which are all same, for example, hindered phenolic, —OH groups.
  • a hetero-type antioxidant macromolecule comprises at least one different type of moiety, for example, hindred phenolic and aminic groups in the one macromolecule.
  • This difference in activities can be the result of, for example, the substitutions on neighboring carbons or the local chemical or physical environment (for example, due to electrochemical or stereochemical factors) which can be due in part to the macromolecular nature of molecules.
  • a series of macromolecular antioxidant moieties of the present invention with different chemical structures can be represented by W1H, W2H, W3H, . . . to WnH.
  • two types of antioxidant moieties of the present invention can be represented by: W1H and W2H.
  • W1H and W2H can have rate constants of k1 and k2 respectively.
  • the reactions involving these moieties and peroxyl radicals can be represented as: where ROO. is a peroxyl radical resulting from, for example, initiation steps involving oxidation activity, for example: RH ⁇ R.+H. (3) R.+O2 ⁇ ROO. (4)
  • This transfer mechanism may take place either in intra— or inter-molecular macromolecules.
  • the transfer mechanism (5) could take place between moieties residing on the same macromolecule (intra-type) or residing on different macromolecules (inter-type).
  • the antioxidant properties described immediately above (equation 5) of the macromolecular antioxidants and polymeric macromolecular antioxidants of the present invention result in advantages including, but not limited to:
  • the following items are of significant interest for enhanced antioxidant activity in the design of the macromolecular antioxidants and polymeric macromolecular antioxidants of the present invention:
  • more than two types of antioxidant moieties with different rate constants are used in the methods of the present invention.
  • the present invention pertains to the use of the disclosed compositions to inhibit oxidation in an oxidizable material such as for example a polyolefin.
  • a method of “inhibiting oxidation” is a method that inhibits the propagation of a free radical-mediated process.
  • Free radicals can be generated by heat, light, ionizing radiation, metal ions and some proteins and enzymes.
  • Inhibiting oxidation also includes inhibiting reactions caused by the presence of oxygen, ozone or another compound capable of generating these gases or reactive equivalents of these gases.
  • oxidizable material is any material which is subject to oxidation by free-radicals or oxidative reaction caused by the presence of oxygen, ozone or another compound capable of generating these gases or reactive equivalents thereof.
  • the oxidizable material is a polyolefin, a mixture of polyolefins a substituted polyolefin, (polyacrylates, polymethacrylates) and copolymers of polyolefins as defined above.
  • Polyolefin samples have been stabilized with selective additives described in this disclosure using extrusion methods. These stabilized polyolefins have been tested for their performance using techniques such as melt flow index, gas fading, oxidative induction time (OIT) ( FIG. 1 ) and yellowness index (YI) ( FIG. 2 ).
  • OIT oxidative induction time
  • YI yellowness index
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