Classifications

• • 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.
• 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 poly olefins 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 polyolefms, 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 polyolef ⁇ ns 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(l,l-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(l,l-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 No.s: 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, US Patent Application No.s: 11/184,724, 11/184,716, 11/040,193, 10/761,933, 10/408,679 and 10/761,933, 11/292,813, 11/293,050, 11/293,049, 11/293,844, 11/360,020, 11/389,564 Attorney Docket No.: 3805.1007-001; Patent Application, filed October 27, 2006, Title: Macromolecular Antioxidants And Polymeric Macromolecular Antioxidants, by Ashok L.
• Cholli et al. Attorney Docket No.: 3805.1008-001; Patent Application, filed October 27, 2006, Title: Macromolecular Antioxidants Based On Sterically Hindered Phenols and Phosphites, by Ashok L. Cholli, et al.
• stabilizers such as acid scavengers or organic phosphorus stabilizers and/or iii) co- stabilizers used in polyolefins and other polymeric materials.
• 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-bxAy ⁇ 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 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; and p is an integer equal to or greater than 0.
• 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-buty ⁇ 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):
• Ri, 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 Ri, 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).
• R is -H or a substituted or unsubstituted alkyl, acyl or aryl group
• Ring A is substituted with at least one tert-butyl group, l-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; and 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.
• substituted benzene repeat units having a l-ethenyl-2-carboxylic acid group or an ester thereof the 1 -carbon (i.e., the carbon distal from the carboxylic acid moiety) 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-buty ⁇ 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 -Cj 6 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-c ⁇ -BHA), poly(TBHQ-c ⁇ -sesamol), poly(BHA-c ⁇ -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 Cl-ClO alkyl group, an aryl group, or a ben2yl group.
• R is a tertiary alkyl group, or in preferred embodiments, a tertiary butyl group.
• X is -O-, -NH- or -S-.
• Each Rio is independently an optionally substituted Cl-ClO 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 Rio 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. More preferably, the alkyl group is branched twice alpha to the benzene ring, such as in a group.
• 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):
• Ring A is substituted with at least one tot-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 ter/-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; and p is an integer equal to or greater than O.
• 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): - -
• 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-h ⁇ tyl 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 Cl-ClO alkyl group, an aryl group, a benzyl group, or an acyl group
• n is an integer equal to or greater than 2
• p is an integer equal to or greater than 0.
• R is a C 1 - 10 branched or linear alkyl group.
• 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 O, 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.
• variable Z is H.
• Each variable R is independently -H, -OH, a Cl-ClO alkyl group, or a bond when that position is involved in the polymer chain wherein at least one -OH is adjacent to a Cl-ClO alkyl group, e.g., a tertiary butyl group.
• Each Rio is independently an optionally substituted Cl-ClO 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 Rio 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.
• Ri 2 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.
• of the 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. More preferably, the alkyl group is branched twice alpha to the benzene ring, such as in a tert-buty ⁇ group.
• 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;
• Ri 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 unsubstitut ⁇ d alkoxycarbonyl group, or a bond when part of the polymer chain, provided that:
• At least one OfR 4 , R 5 , R 7 and R 8 is a tert-butyl group or a substituted or unsubstituted alkoxycarbonyl group, and at least two OfR 4 , R5, R 7 and R 8 are -H; or (2) at least one OfR 4 , R 5 , R 7 and R 8 is a tert-butyl group or a substituted or unsubstituted alkoxycarbonyl group, at least one OfR 4 , R 5 , R 7 and R 8 is a hydroxyl, alkoxy, alkoxycarbonyl or aryloxycarbonyl group, and at least one OfR 4 , R5, R 7 and R 8 is -H.
• each X is independently -0-, -NH- or -S-.
• Each Rio is independently an optionally substituted Cl-ClO 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 Ri 0 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-l-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.
• 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).
• Ri is -H or an alkyl group, or -(CH 2 ) k -O-X-Z. Typically, Ri 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 O to 12.
• Each k is independently an integer from O to 12.
• m is an integer from O to 6.
• n is O or 1.
• p is an integer from O 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 polyvinyl alcohol) and copolymers thereof (e.g., poly(ethylene-c ⁇ -vinyl alcohol)).
• the hydroxyl groups of polyvinyl 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:
• a is an integer from 0 to 12;
• R is -OH, -COOH, -NH 2 , -SH or a halogen; and R 10 , Rn and R 12 are each independently -H, -OH, -NH 2 or -SH, provided that at least one OfR 1 O, Rn and R 12 is -OH, -NH 2 or -SH.
• one OfR 1 Q, Rn and R 12 is -OH and the remaining two are optionally -H. More preferably, Rn is -OH and Rio 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.
• about 1% to 100%, such as 10% to 50% or 50% to 100%, of the repeat units of a polymer include pendant functional groups.
• AIl or a fraction of the pendant reactive groups of a derivatizable polymer can be derivatized with an antioxidant.
• about 100% of the pendant reactive groups can be derivatized.
• 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 l-propenyl-3-carboxylic acid substituent or an ester thereof.
• a preferred bulky alkyl group is a fert-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 , Rg, 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 l-propenyl-3-carboxylic acid group or an ester thereof.
• at least one OfR 4 , R 5 , Re, 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 5 -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:
• 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).
• 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-t ⁇ rt-butyl-4-hydroxyphenyl group, particularly when X is -C(O)-.
• m is preferably 2 and n and p are each O.
• a second preferred antioxidant is a 3,4,5-trihydroxyphenyl group, particularly when X is -C(O)-.
• antioxidants are mono and di-terf-butylated-4-hydroxyphenyl groups, 4-acetoxy-3-te/t-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 O.
• n is also typically O.
• Z is typically ascorbic acid.
• X is typically a covalent bond.
• Z is a 3,4,5-trihydroxyphenyl group or a 4-acetoxy-3-te7t-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-te/t-butyl-4-hydroxyphenyl group or a 3,5-di- -f ⁇ ?'t-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-fe ⁇ t-butyl-4-hydroxyphenyl group.
• Other examples include of phenolic antioxidants include 4-acetoxy-3 -tert-buty lphenyl, 3 -tert-butyl-4-hydroxyphenyl,
• a polymer 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-,
• Z' is -C(O)O-.
• 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'i 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 Ri adjacent to the -OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-b ⁇ tyl, 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
• the 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)-, -0-, -S-, -C(O)OC(O)- or a bond.
• R' 2 is C1-C6 alkyl, -OH, -NH 2 , -SH, aryl, ester, or
• 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.
• At least one R' is
• n 0.
• n 1
• n 0, m is 1 and Z is -C(O)O-.
• n O
• m 1
• Z is -C(O)O- and the two R' groups adjacent to the -OH are t-butyl.
• n O
• m 1
• Z is -C(O)O-
• the two R' groups adjacent to the -OH are t-butyl and M' is
• n O
• m 1
• Z is -C(O)O-
• the two R' groups adjacent to the -OH are t-butyl
• M' is
• n O
• m 1
• Z is -C(O)O-
• the two R' groups adjacent to the -OH are t-butyl
• M' is
• n O
• m 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 is 0, m is 1, Z is -C(O)O-, the two R' groups adjacent to the -OH are t-butyl, M' is
• n O
• m 1
• Z is -C(O)O-
• the two R' groups adjacent to the -OH are t-butyl
• M' is
• 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 Ri -R O are independently -H, -OH, or a Cl-ClO optionallyu substituted linear or branched alkyl group, n is an integer from 0 to 24.
• n 0,1,2,3
• each of R and R r Rs are independently -H, -OH, or a Cl-ClO alkyl group, n is an integer from 0 to 24.
• R s 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 HI' and an antioxidant polymer represented by Structural Formula IV and IV.
• each of R, and R]-Rg are independently -H, -OH, or a Cl- ClO alkyl group, n is an integer from 0 to 24. m is an integer equal to 2 or greater. R' is -H, optionally substituted C1-C20 alkyl or optionally substituted aryl group. In in and IV 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-bx ⁇ ty ⁇ 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 Ri-R 6 are independently -H, -OH, or a Cl-ClO 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 Rb is independently an optionally substituted alkyl.
• Each R 0 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.
• s is not 0, or R" is not -H.
• 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 0 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.
• s is not 0, or R" is not -H.
• 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 Cl-ClO 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 0 is independently an optionally substituted alkyl or an optionally substituted alkoxycarbonyl. In one embodiment, each R 0 is independently a Cl-ClO 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 5 a Cl-ClO alkyl or a substituted benzyl group. In yet another embodiment, R' ' is -H. In yet another embodiment, R" is:
• 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. m 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. In certain embodiments for 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 3 is independently a C1-C20 alkyl.
• Each R 0 is independently a Cl- ClO 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).
• J 2 In another embodiment in J 2 : m is 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 .
• Each R a is independently a Cl-ClO alkyl.
• R" is -H, a C 1 -C 10 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 and the compounds are represented by structural formula J 5 :
• R" is -H and the compounds are represented by structural formula J 7 :
• R" is -H and n is 1 and the compounds are represented by structural formula J 8 :
• antioxidants which are suitable for use in the compositions and methods of the present invention include alkylated antioxidant macromolecules having formula K:
• n and m are integers from 0 to 6, inclusive;
• R is H, Ci -6 alkyl, -OH, -NH 2 , -SH, aryl, aralkyl, or
• R adjacent to the -OH group is a bulky alkyl group (e.g., butyl, .sec-butyl, tert-butyl, 2-propyI, 1,1-dimethylhexyl, and the like);
• R is H, C 1-6 alkyl, aryl, alkylaryl, -OH, -NH 2 , -SH, or C1-C6 alkyl ester wherein at least one Ri adjacent to the -OH group is a bulky alkyl group (e.g., butyl, jec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like); and
• R 2 is H, C] -6 alkyl, aryl, aralkyl, -OH, -NH 2 , or -SH wherein at least one Ri adjacent to the -OH group is a bulky alkyl group (e.g., butyl, r ⁇ c-butyl, tert-butyl, 2- propyl, 1,1-dimethylhexyl, and the like);
• M is H, aryl, C-I to C-20 linear or branched alkyl chain with or without any functional group anywhere in the chain, or
• R 2 is H, Ci -6 alkyl, -OH, -NH 2 , -SH, aryl, ester, or
• R 2 is -OH and n, Z, and each Rl are independently as described above.
• both R groups adjacent to -OH are bulky alkyl groups (e.g., butyl, jec-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 and m is 1. In another embodiment, for compounds of formula K, n is 0, m is 1, and Z is
• n is 0, m is 1, Z is -C(O)O-, and the two R groups adjacent to the OH are te ⁇ t-butyl.
• n is 0, m is 1, Z is
• n O
• m 1
• Z is -C(O)O-
• the two R groups adjacent to the OH are t-butyl
• M is
• n is 0, m is I 5 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 O
• m 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 :
• 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,
• 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.
• M is an alkyl or ,
• n and m are independently integers from O to 6.
• s, q and u are independently integers from O to 4.
• M is not
• 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 -C(O)-.
• Z is -0-.
• 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 Cl-ClO 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,
• 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 or propoxycarbonyl. In certain other embodiments each R is independently an alkyl group. In certain embodiments 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.
• each R is tert-butyl.
• 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 Ri 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 Ri is independently an optionally substituted alkyl or optionally substituted alkoxycarbonyl. In certain other embodiment each Ri is independently an alkyl or alkoxycarbonyl. In certain other embodiments each Ri is independently a C1-C6 alkyl or a C1-C6 alkoxycarbonyl. In certain other embodiments each Ri is independently tert-butyl or propoxycarbonyl. In certain other embodiments each Ri is independently an alkyl group. In certain embodiments each Ri 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.
• each R] is tert- bntyl,
• at least one Ri 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 Ri groups adjacent to -OH are bulky alkyl groups (e.g., butyl, sec-butyl, tert-b ⁇ tyl, 2-propyl, 1,1-dimethylhexyl, and the like). In another embodiment, both Ri groups are tert-butyl. In another embodiment, both R) 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.
• 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 Cl-ClO alkyl. In certain other embodiments each R 2 is independently a C1-C6 alkyl. In certain other embodiments 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 -NH-, -S- or -0-.
• X is -0-.
• X is a bond.
• M is an alkyl or .
• 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.
• M is not X is -C(O)O- or -OC(O)-.
• 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.
• M is Cl to C20- linear or branched alkyl chains.
• n and m are integers from 0 to 6, inclusive;
• R is H, Ci -6 alkyl, -OH, -NH 2 , -SH, aryl, ester, or
• R adjacent to the -OH group is a bulky alkyl group (e.g., butyl, ⁇ ec-butyl, tert-bntyl, 2-propyl, 1,1-dimethylhexyl, and the like);
• Ri is H, Ci -6 alkyl, aryl, aralkyl, -OH, -NH 2 , -SH, or C1-C6 alkyl ester wherein at least one Ri 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, Ci -6 alkyl, aryl, aralkyl, -OH, -NH 2 , -SH, or ester, wherein at least one Ri 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);
• M is H, aryl, C-I to C-20 linear or branched alkyl chain with or without any
• 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:
• Ri and R 2 in each occurrence independently is an optionally substituted alkyl, optionally substituted aryl or optionally substituted aralkyl. In one embodiment, each Ri and R 2 are independently an optionally substituted alkyl. In another embodiment, each Ri and R 2 are independently a linear or branched C1-C6 alkyl.
• 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 -.
• X and Y in each occurrence independently is a bond, -NHC(O)-, or -CH 2 -.
• n and m in each occurrence independently is O or a positive integer. In one embodiment, n and m in each occurrence independently is O to 18. In another embodiment, n and m in each occurrence independently is O to 12. In yet another embodiment, n and m are in each occurrence independently is O to 6.
• i and j in each occurrence independently is O, 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:
• 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 Ri 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.
• Ri, 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
• Ri, 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
• Ri, 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.
• Ri, 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.
• Ri, 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 O or a positive integer. In one embodiment, n and m in each occurrence, independently is O to 18. In another embodiment, n and m in each occurrence, independently is O to 12. In yet another embodiment, n and m in each occurrence, independently is O 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-.
• Z' is -OC(O)-.
• Z' is -C(O)NH-.
• Z' is -NHC(O)- .
• Z' is -NH-.
• 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'i 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 Ri 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-.
• X' is -OC(O)-.
• X' is -C(O)NH-.
• X' is -NHC(O)- .
• X' is -NH-.
• X' is -C(O)- . In yet another embodiment X' is -0-. 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 O or a positive integer.
• Preferably o is O to 18. More preferably o is O to 12. Even more preferably o is O to 6.
• P and Q R is:
• R' 2 is C1-C6 alkyl, -OH, -NH 2 , -SH, aryl, ester, aralkyl or
• the present invention relates to a compound of formula O, P and Q, wherein M is
• R is:
• 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:
• Ri and R 2 in each occurrence independently is an optionally substituted alkyl, optionally substituted aryl or optionally substituted aralkyl.
• each R 1 and R 2 in each occurrence independently is an optionally substituted alkyl.
• each Rj and R 2 in each occurrence independently is a C1-C6 alkyl.
• Z in each occurrence independently is a bond, an optionally substituted alkylene group, -S-, -O- or -NH-.
• i and j in each occurrence independently is O, 1, 2, 3 or 4.
• i and j in each occurrence independently is O, 1 or 2.
• i is O.
• j is 2.
• k is a positive integer from 1 to 20.
• k is a positive integer from 1 to 12.
• 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. In certain embodiments:
• 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, Ic 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 ) I NHC(O)(CH 2 ) H -, -(CH 2 ),OC(O)(CH 2 ) h -, -(CH 2 ),S-(CH 2 ) h -, or -(CH 2 ), O(CH 2 ) h -, 1 is not 0.
• 1 is 0 or a positive integer from 1 to 12.
• 1 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 -
• h is not 0.
• h is 0 or a positive integer from 1 to 12.
• h is 0 or a positive integer from 1 to 6.
• h is 0.
• R is:
• A is -NHC(O)- or -C(O)O- and
• B is a bond or a C1-C24 alkylene, and i and j are 0, 1, 2, 3 or 4.
• the present invention is directed to macromolecular antioxidants represented by a structural formula selected from Structural Formulas 1- 6, wherein R is: wherein:
• 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 -C(O)-.
• D a is -0-.
• D a is -C(O)OC(O)-.
• D a is a bond.
• Each P H I is independently -H or optionally substituted alkyl.
• R d is -H or an alkyl group.
• Rd is -H or a Cl-ClO alkyl group.
• R d is -H.
• R 0 and R 0 ' are independently H or an optionally substituted alkyl. In one embodiment, R 0 and R 0 ' are H. In another embodiment, one OfR 0 and R 0 ' is H and the other is an optionally substituted alkyl. More specifically, the alkyl is a Cl-ClO alkyl. Even more specifically, the alkyl is a Cl O 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 Ci-C 6 alkyl or a Ci-C 6 alkoxycarbonyl.
• each R a is independently tert-butyl or propoxycarbonyl.
• each R a is independently an alkyl group.
• each R a is independently a bullcy alkyl group. Suitable examples of bulky alkyl groups include butyl, sec-butyl, tert-bntyl, 2-propyl, 1,1-dimethylhexyl, and the like. In certain embodiments each R a is fer/-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-bvttyl 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.
• V is -C(O)O-.
• Z' is -OC(O)-.
• Z' is -C(O)NH-.
• Z' is -NHC(O)- .
• Z' is -NH-.
• Z' is -C(O)- . In yet another embodiment, Z' is -0-. 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, r ⁇ c-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
• an optionally substituted bulky alkyl group e.g., butyl, r ⁇ c-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like.
• R'i 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 Ri adjacent to the -OH group is a bulky alkyl group (e.g., butyl, ,yec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
• a bulky alkyl group e.g., butyl, ,yec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like.
• R 5 2 is an optionally substituted C1-C6 alkyl, an optionally substituted aryl, an optionally substituted aralkyl, -OH, -NH 2 , -SH, or ester.
• 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-,
• R' in each occurrence independently is C1-C6 alkyl, -OH, -NH 2 , -SH, an optionally substituted aryl, an ester or wherein at least one 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).
• 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).
• R'i 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 Ri adjacent to the -OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-buty ⁇ , 2-propyl, 1,1-dimethylhexyl, and the like). ).
• R' 2 in each occurrence independently is C1-C6 alkyl, an optionally substituted aryl, a'n 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)-, -0-, -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 -NHC(O)- .
• X' is -C(O)- . In yet another embodiment X' is -0-. 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 O or a positive integer.
• Preferably o is O to 18. More preferably o is O to 12. Even more preferably o is O to 6.
• R is:
• R' 2 is C1-C6 alkyl, -OH, -NH 2 , -SH, aryl, aralkyl, ester, or
• 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.
• R.3 and R 4 in each occurrence independently is Cl -C 16 alkyl, -0-(Cl -C 16 alkyl), -NH(aryl), -NH 2 , -OH, or -SH.
• p in each occurrence independently is an integer equal to or greater than 2.
• Specific examples of polymers which are useful in the compositions methods of the present invention include:
• R and R' are independently H or optionally substituted alkyl and at least one ofR and R' is H;
• 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 O to 4; and m and n, for each occurrence, are independently integers from O to 6.
• antioxidants suitable for use in the methods and compositions of the present invention include compounds represented by Structural Formula II:
• 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; and
• m for each occurrence, is independently an integer from 0 to 6.
• 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: a. 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 0,0001% 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
• 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. c.
• 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 monoolefms and diolefms for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-l-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefms, 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
• Polyolefins i.e. the polymers of monoolefms exemplified in the preceding paragraph, for example polyethylene and polypropylene
• 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, Ha and/or Ilia of the Periodic Table.
• the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
• 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 (ion
• 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 for instance, 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
• STABILIZERS ACID SCAVENGERS OR ACID STABILIZERS
• 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.
• ORGANIC PHOSPHORUS STABILIZERS examples of organic phosphorus stabilizers (or phosphorus stabilizers) include phosphates, phosphites and phosphonites which are suitable for use in the methods of the present invention.
• 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(l,ldimethylethyl)dibenzo[d,fj[l,2,3]dioxaphosphepin-6-yl]oxy]-N,N-[bis[2- - - -
• 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'-bi ⁇ henylene- diphosphonite (formula (H)), (2,4,6-tri-tert-butylphenyl) 2-butyl-2-ethyl-l,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.
• CO-STABILIZERS in certain embodiments of the present invention, in addition to antioxidants and stabilizers described above the 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,
• 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.
• 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- hy droxyphenyl)adipate .
• 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(
• 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)
• O-, N- and S-benzyl compounds for example 3,5,3',5'-tetra-tert- butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5- dimethy lbenzylmercaptoacetate, 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-buty 1-4-hydroxybenzy lmercaptoacetate .
• 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-(l,l,3,3-tetramethylbutyl)phenyl]-2,2- bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
• Aromatic hydroxybenzyl compounds for example l,3,5-tris-(3,5- di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, l,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-octy lmercapto-4, 6-bis(3 , 5 -di-tert- butyl-4-hydroxyanilino)-l,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyphenoxy)-l,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1,2,3-triazine, l,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5- tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyan
• Benzylphosphonates for example dimethyl 2,5-di-tert-butyl-4- hydroxybenzylphosphonate, diethyl 3 , 5 -di-tert-buty 1-4-hydroxybenzylphosphonate, dioctadecyl 3, 5 -di-tert-buty 1-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl- 4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3 , 5 -di-tert-buty 1-4-hydroxybenzylphosphonic acid. 1.12.
• 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.
• esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methyIphenyI)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 5 N'- bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, triniethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-
• 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-l-phospha ⁇ j-trioxabicyclop ⁇ 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-l - 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(l ,4- dimethylpentyl)-p-phenylenediamine, N,N'-bis(l-ethyl-3-methylpentyl)-p- phenylenediamine, N,N'-bis(l -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-(l,3- dimethylbutyl)-N'-phenyl-
• 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, l-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(l,2,2,6,6-pentamethyl- 4-piperidyl) sebacate, bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(l,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4- hydroxybenzylmalonate, the condensate of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl- 4-hydroxy
• 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 1-1), in particular the light stabilizer 1-a-l, l-a-2, 1-b-l, 1-c-l, l-c-2, 1- d-1, l-d-2, l-d-3, 1-e-l, 1-f-l, 1-g-l, l-g-2 or 1-k-l 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-I to D-5 therein.
• Sterically hindered amines substituted on the N-atom by a hydroxy-substituted alkoxy group for example compounds such as l-(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 l-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-tetramethyl- piperidine, l-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, bis(l-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(l-(2-
• 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- 42251
• 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.
• Tinuvin ® 400 Ciba Specialty Chemicals Corp., 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2- ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine and 4,6-diphenyl-2-(4- hexyloxy-2-hydroxyphenyl)-s-triazine .
• 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-l,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N 9 N 1 - bis(salicy
• 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. 6. Hydroxylamines,.
• N,N-dihydrocarbylhydroxylamines selected from the group consisting of N,N-dibenzylhydroxylamine, N,N-dimethyl- hydroxylamine, N,N-diethylhydroxylamine, N,N-bis(2-hydroxypropyl)hydroxyl- amine, N,N-bis(3 -hydroxypropyl)hydroxylamine, N,N-bis(2-carboxy ethyl)hydroxyl- amine, N,N-bis(benzylthiomethyl)hydroxylamine, N,N-dioctylhydroxylarnine, N,N- dilaurylhydroxylamine, N,N-didodecylhydroxylamine, N 5 N- ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine s N 5 N- dioctadecylhydroxylamme, N-hexadecyl-N-tetradecylhydroxylamine, N
• 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,
• 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.
• 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. 16.
• Other 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 polyolefms 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 polyolefms to be stabilized.
• the fillers and reinforcing agents are added to the poly olefins in concentrations of about 0.001 % to about 80% by weight, about 0.005% to about 70% by weight, about
• carbon black as filler is added to the polyolefms in concentrations, judiciously, of from about
• glass fibers as reinforcing agents are added to the polyolefms in concentrations, judiciously, of T/US2006/04225!
• 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- C 12, more typically C3-C7 alkyl ester.
• alkyl groups examples include methyl, ethyl, 72-propyl, wo-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 h ⁇ teroaryl 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-
• 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 ⁇ (as in 3,4-dihydro-2H-pyrrolyl), ⁇ (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.
• An "aralkyl group”, as used herein 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-(C 1-C3 alkyl), -
• An optionally substituted alkyl group as defined herein may contain one or more substituents.
• 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 WlH, W2H, W3H, to WnH.
• two types of antioxidant moieties of the present invention can be represented by: WlH and W2H.
• WlH and W2H can have rate constants of kl and k2 respectively.
• the reactions involving these moieties and peroxyl radicals can be represented as:
• ROO. is a peroxyl radical resulting from, for example, initiation steps involving oxidation activity, for example:
• 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: a) The activity of proposed macromolecular antioxidant is dependent on the regeneration of WlH in equation (5) either through inter- or intra-molecular activities involving homo- or hetero-type antioxidant moieties. b) Depending on the rates constants of WlH and W2H it is possible to achieve performance enhancements by many multiples and not just incremental improvements.
• 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.
• Nonpolar Solvents Masada, Hiromitsu; Mikuchi, Fumio; Doi, Yasuo;
• Polyolefin samples have been stabilized with selective additives described in this disclosure using extrusion methods. These stabilized polyolefms 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). While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=37698023

Family Applications (1)

Country Status (3)

Cited By (9)

Families Citing this family (45)

Citations (9)

Family Cites Families (159)

• 2006
  • 2006-10-27 EP EP06827034A patent/EP1966293A1/en not_active Withdrawn
  • 2006-10-27 US US11/589,319 patent/US20070149660A1/en not_active Abandoned
  • 2006-10-27 WO PCT/US2006/042251 patent/WO2007050991A1/en active Application Filing
• 2008
  • 2008-04-15 US US12/082,967 patent/US7705075B2/en not_active Expired - Fee Related

Patent Citations (9)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events