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Timestamp: 2015-04-18 03:56:04
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Patent US20100305361 - Macromolecular antioxidants based on sterically hindered phenols and phosphites - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsSterically hindered phenol and phosphite based compounds represented by structural formula II: and their use as antioxidants in a wide range of materials including, but not limited to, food, plastics, elastomers, composites and petroleum based products is disclosed herein....http://www.google.com/patents/US20100305361?utm_source=gb-gplus-sharePatent US20100305361 - Macromolecular antioxidants based on sterically hindered phenols and phosphitesAdvanced Patent SearchPublication numberUS20100305361 A1Publication typeApplicationApplication numberUS 12/789,843Publication dateDec 2, 2010Filing dateMay 28, 2010Priority dateDec 3, 2004Also published asCA2589883A1, EP1828104A1, US7902317, US7956153, US8008423, US8242230, US8252884, US8481670, US8598382, US8691933, US8846847, US20060128931, US20100305251, US20110282098, US20120071596, US20130041171, US20130072586, US20140011901, US20140014880, WO2006060800A1Publication number12789843, 789843, US 2010/0305361 A1, US 2010/305361 A1, US 20100305361 A1, US 20100305361A1, US 2010305361 A1, US 2010305361A1, US-A1-20100305361, US-A1-2010305361, US2010/0305361A1, US2010/305361A1, US20100305361 A1, US20100305361A1, US2010305361 A1, US2010305361A1InventorsAshok L. Cholli, Rajesh KumarOriginal AssigneeCholli Ashok L, Rajesh KumarExport CitationBiBTeX, EndNote, RefManReferenced by (1), Classifications (16), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetMacromolecular antioxidants based on sterically hindered phenols and phosphites
US 20100305361 A1Abstract
75. A compound represented by Structural Formula II:
76. The compound of claim 1, wherein the compound is represented by the following structural formula:
X and Y in each occurrence, independently is a bond, �O�, �NH�, �C(O)NH�, �NHC(O)�, �C(O)O�, �OC(O)� or �CH2�,
FIG. 1, is a comparison of the Oxidative Induction Time (OIT) of one embodiment of the invention, namely, tris[N-(4-hydroxyphenyl),-3-(2,6-di-tert.-butyl,4-hydroxyphenyl)propionamide]phosphate, versus commercially available Irganox�.
In another particular embodiment, for compounds of the present invention represented by structural formulas I-III, R1, R2. 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 �CH2�; and the remainder of the variables are as described above for structural formulas I-III.
wherein at least one R′ adjacent to the �OH group is an optionally substituted bulky alkyl group (e.g., butyl, sec-butyl, test-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
R′, is an optionally substituted C1-C6 alkyl, an optionally substituted aryl, an optionally substituted aralkyl, �OH, �NH2, �SH, or C1-C6 alkyl ester wherein at least one R1 adjacent to the �OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).).
X′ is �C(O)O�, �OC(O)�, �C(O)NH�, �NHC(O)�, �NH�, �C(O)�, �O�, �S�, �C(O)OC(O)� or a bond. In one embodiment X′ is �C(O)O�. In another embodiment X′ is �OC(O)�. In yet another embodiment X′ is �C(O)NH�. In yet another embodiment X′ is �NHC(O)�. In yet another embodiment X′ is �NH�. In yet another embodiment X′ is �CH═N�. In yet another embodiment X′ is �C(O)�. In yet another embodiment X′ is �O�. In yet another embodiment X′ is �S�. In yet another embodiment X′ is �C(O)OC(O)�. In yet another embodiment X′ is a bond.
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 two or more carbocyclic aromatic rings are fused to one another. Examples include 1-naphthyl, 2-naphthyl, 1-anthracyl and 2-anthracyl. Also included within the scope of the term �carbocyclic aromatic ring�, as it is used herein, 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.
The term �heteroaryl�, �heteroaromatic�, �heteroaryl ring�, �heteroaryl group� and �heteroaromatic group�, used alone or as part of a larger moiety as in �heteroaralkyl� 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. Heteroaryl groups have one or more ring heteroatoms. Examples of 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-benzothienyl, 2-benzofuranyl, 3-benzofuranyl, 2-indolyl, 3-indolyl, 2-quinolinyl, 3-quinolinyl, 2-benzothiazole, 2-benzooxazole, 2-benzimidazole, 2-quinolinyl, 3-quinolinyl, 1-isoquinolinyl, 3-quinolinyl, 1-isoindolyl and 3-isoindolyl. Also included within the scope of the term �heteroaryl�, as it is used herein, 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.
An optionally substituted aryl group as defined herein may contain one or more substitutable ring atoms, such as carbon or nitrogen ring atoms. Examples of suitable substituents on a substitutable ring carbon atom of an aryl group include �OH, C1-C3 alkyl, C1-C3 haloalkyl, �NO2, C1-C3 alkoxy, C1-C3 haloalkoxy, �CN, �NH2, C1-C3 alkylamino, C1-C3 dialkylamino, �C(O)NH2, �C(O)NH(C1-C3 alkyl), �C(O)(C1-C3 alkyl), �NHC(O)H, �NHC(O)(C1-C3 alkyl), �C(O)N(C1-C3 alkyl)2, �NHC(O)O�(C1-C3 alkyl), �C(O)OH, �C(O)O�(C1-C3 alkyl), �NHC(O)NH2, �NHC(O)NH(C1-C3 alkyl), �NHC(O)N(C1-C3 alkyl)2, �SO2NH2�SO2NH(C1-C3alkyl), �SO2N(C1-C3alkyl)2, NHSO2H or NHSO2(C1-C3 alkyl). Preferred substituents on aryl groups are as defined throughout the specification. In certain embodiments optionally substituted aryl groups are unsubstituted
An optionally substituted alkyl group as defined herein may contain one or more substituents. Examples of suitable substituents for an alkyl group include those listed above for a substitutable carbon of an aryl and the following: ═O, ═S, ═NN(R**)2, ═NNHC(O)R**, ═NNHCO2 (alkyl), ═NNHSO2 (alkyl), ═NR**, Spiro cycloalkyl group or fused cycloalkyl group. R** in each occurrence, independently is �H or C1-C6 alkyl. Preferred substituents on alkyl groups are as defined throughout the specification. In certain embodiments optionally substituted alkyl groups are unsubstituted.
Without wishing to be bound by any theory or limited to any mechanism it is believed that 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. As used herein a homo-type antioxidant macromolecule comprises antioxidant moieties which are all same, for example, hindered phenolic, �OH groups. As used herein a hetero-type antioxidant macromolecule comprises at least one different type of moiety, for example, kindred phenolic and aminic groups in the one macromolecule.
a) Consumption of free radicals W1. according to equation (5) can result in a decrease of reactions of W1. with hydroperoxides and hydrocarbons (RH). b) The regeneration of W1H provides extended protection of materials. This is a generous benefit to sacrificial type of antioxidants that are used today. Regeneration of W1H assists in combating the oxidation process The increase in the concentration of antioxidant moieties W1H (according to equation 5) extends the shelf life of materials. In certain embodiments of the present invention, the following items are of significant interest for enhanced antioxidant activity in the design of the macromolecular antioxidants of the present invention:
a) The activity of proposed macromolecular antioxidant is dependent on the regeneration of W1H in equation (5) either through inter- or intra-molecular activities involving home- or hetero-type antioxidant moieties. b) Depending on the rates constants of W1H and W2H it is possible to achieve performance enhancements by many multiples and not just incremental improvements. In certain embodiments of the present invention, more than two types of antioxidant moieties with different rate constants are used in the methods of the present invention.
Docket No.: 3805.1000-000; Provisional Patent Application No. 60/632,893, filed Dec. 3, 2004, Title: Process For The Synthesis Of Polyalkylphenol Antioxidants, by Suizhou Yang, et al; Docket No.: 3805.1001-000; Provisional Patent Application No. 60/633,197, filed Dec. 3, 2004, Title: Synthesis Of Sterically Hindered Phenol Based Macromolecular Antioxidants, by Ashish Dhawan, et al.; Docket No.: 3805.1002-000; Provisional Patent Application No. 60/633,252, filed Dec. 3, 2004, Title: One Pot Process For Making Polymeric Antioxidants, by Vijayendra Kumar, et al.; Docket No.: 3805.1003-000; Provisional Patent Application No. 60/633,196, filed Dec. 3, 2004, Title: Synthesis Of Aniline And Phenol-Based Macromonomers And Corresponding Polymers, by Rajesh Kumar, et al.; Docket No.: 3805.1004-002; patent application Ser. No. 11/184,724, filed Jul. 19, 2005, Title: Anti-Oxidant Macromonomers And Polymers And Methods Of Making And Using The Same, by Ashok L. Cholli; Docket No.: 3805.1004-005; patent application Ser. No. 11/184,716, filed Jul. 19, 2005, Title: Anti-Oxidant Macromonomers And Polymers And Methods Of Making And Using The Same, by Ashok L. Cholli; Docket No.: 3805.1005-000; Provisional Patent Application No. 60/655,169, filed Feb. 22, 2005, Title: Nitrogen And Hindered Phenol Containing Dual Functional Macromolecules: Synthesis And Their Antioxidant Performances In Organic Materials, by Rajesh Kumar, et al. Docket No.: 3805.1006-000; Provisional Patent Application No. 60/655,169, filed Mar. 25, 2005, Title: Alkylated Macromolecular Antioxidants And Methods Of Making, And Using The Same, by Rajesh Kumar, et al. Docket No.: 3805.1007-000; Provisional Patent Application, filed Oct. 27, 2005, Title: Macromolecular Antioxidants And Polymeric Macromolecular Antioxidants, by Ashok L. Cholli, et al. Docket No.: 0813.2006-003; patent application Ser. No. 11/040,193, filed Jan. 21, 2005, Title: Post-Coupling Synthetic Approach For Polymeric Antioxidants, by Ashok L. Choll, et al.; Docket No.: 0813.2006-002; Patent Application No.: PCT/US2005/001948, filed Jan. 21, 2005, Title: Post-Coupling Synthetic Approach For Polymeric Antioxidants, by Ashok L. Cholli et al.; Docket No.: 0813.2002-008; Patent Application No.: PCT/US2005/001946, filed Jan. 21, 2005, Title: Polymeric Antioxidants, by Ashok L. Choll, et al.; Docket No.: 0813.2002-006; Patent Application No.: PCT/US03/10782, filed Apr. 4, 2003, Title: Polymeric Antioxidants, by Ashok L. Choll, et al.; Docket No.: 0813.2002-004; patent application Ser. No. 10/761,933, filed Jan. 21, 2004, Title: Polymeric Antioxidants, by Ashish Dhawan, et al.; Docket No.: 0813.2002-001; patent application Ser. No. 10/408,679, filed Apr. 4, 2003, Title: Polymeric Antioxidants, by Ashok L. Choll, et al.; In another particular embodiment, the present invention relates to a process for preparing compounds of the present invention. Compounds of the present invention can be prepared by a one pot process, comprising the step of combining a phenol containing compound with a suitable phosphorous containing compound in a suitable solvent under conditions suitable for the reaction of the phenol containing compound with the phosphorous containing compound.
Preparation of tris[N-(4-hydroxyphenyl),-3-(2,6-di-tert.-butyl,4-hydroxyphenyl)propionamide]phosphite, S
A 1 L two-necked round bottom flask equipped with a thermometer, a dropping funnel and a nitrogen inlet was charged with 100 g (0.271 mole) of N-(4-hydroxyphenyl)-3-(2,6-di-tert-butyl, 4-hydroxy phenyl) propionamide, 22 ml (0.271 mole) pyridine in 200 ml of dichloromethane. 7.86 ml (9.033 mmol) of phosphorous trichloride was then added dropwise at a temperature of 0 to 5� C. under nitrogen atmosphere for a period of 30 to 40 minutes. After the addition, the funnel was removed and completion of the reaction was checked by TLC/HPLC. After completion, the dichloromethane was distilled out at 40� C. To the residue was added 100 ml of methanol to get white crystalline precipitate, which was then filtered and washed several times with cold methanol. The product was characterized by spectroscopic techniques. The melting point is in the range of 224-245� C.
Stabilization of polypropylene by tris[N-(4-hydroxyphenyl),-3-(2,6-di-tert.-butyl,4-hydroxyphenyl)propionamide]phosphite S
The results are shown in FIG. 1, which shows that tris[N-(4-hydroxyphenyl),-3-(2,6-di-tert.-butyl,4-hydroxyphenyl)propionamide]phosphite has a significantly higher oxidative induction time than commercially available Irganox�.
Referenced byCiting PatentFiling datePublication dateApplicantTitleWO2014061036A2 *Oct 18, 2013Apr 24, 2014Reliance Industries LimitedTetraoxa diphosphaspiro compounds* Cited by examinerClassifications U.S. Classification564/16International ClassificationC07F9/576Cooperative ClassificationC08K5/20, C08K5/04, C08K5/52, C09K15/322, C08K13/02, C07C231/02, C08G2261/1426, C08G2261/1432, C08G61/00, C08G61/10, C08G2261/1422European ClassificationC08G61/10, C08G61/00, C07C231/02Legal EventsDateCodeEventDescriptionJun 7, 2014FPAYFee paymentYear of fee payment: 4Aug 11, 2010ASAssignmentFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHOLLI, ASHOK L.;KUMAR, RAJESH;SIGNING DATES FROM 20100724 TO 20100727;REEL/FRAME:024824/0239Owner name: POLNOX CORPORATION, MASSACHUSETTSRotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services