MXPA00003919A - Organic materials stabilized by compounds containing both amine and hindered phenol functionalities - Google Patents

Abstract

The present invention relates to compounds containing dual substitutions of an aromatic amine and hindered phenol functionality useful as stabilizers for organic materials. These compounds are of general formula (I) wherein f is formula (II). R1 and R2 are independently selected from the group consisting of hydrogen, substituted or unsubstituted aryl, and substituted or unsubstituted alkyl of 1 to 20 carbon atoms;R3 is alkylene of 1 to 10 carbon atoms;m is 0 or 1;n is an integer of 1 to 10;q is an integer of 0 to 8;z is 1 or 2, provided that, when q is 0, z must be 1;X represents the links of a chain q links in length, said links being selected from the group consisting of carbon, nitrogen, oxygen, sulfur, silicon, and mixtures thereof;and Y is an aromatic group or f, provided that Y can be f only when q is 0 and m is 1.

Description

ORGANIC MATERIALS STABILIZED THROUGH COMPOUNDS CONTAINING BOTH AMI NA AND FENOL OBSTRUCTIO N BACKGROUND OF THE I NVENTION FIELD OF THE I NVENTION This invention relates to the protection of organic materials, such as rubber, plastic, lubricating oils, petroleum fuels, waxes, and organic liquids, against oxidation by the use of stabilizing compounds containing both amine and amine functions. obstructed phenol.

DESCRI PTION OF THE RELATIVE TECHNIQUE It is well known that organic materials such as rubber, plastic, lubricating oils, petroleum fuels, waxes, and organic liquids need protection against oxidation. Currently, many of these organic materials are exposed to higher operating temperatures and mechanical stresses. New stabilizers have been sought that can protect organic materials against premature oxidation and degradation under these advanced operating conditions. Obstructed phenols have been used as stabilizers in organic materials such as food products, rubber, plastics, oils, etc., for more than 50 years. For example, U.S. Patent No. 3,644,482 discloses clogged phenol stabilizers based on 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate esters. In addition, aromatic amines have also been used as stabilizers of organic materials, especially for use in plastic, rubber and oils. For example, U.S. Patent No. 3,505,225 discloses aromatic amine antioxidants based on diphenylamines substituted with α-methylstyryl-. In addition, U.S. Patent Nos. 4,797.51 1 and 4,837,259 describe the synergistic mixtures of antioxidants of clogged phenols and amines as stabilizers for polypropylene and polyethylene. Aralkyl-substituted diarylamines, such as 4,4'-bis (a, -dimethylbenzyl) diphenylamine (NAUGARD 445, Uniroyal Chemical), and their use as antioxidants for a variety of polymeric materials are known from US Patent Nos. 3,452,056 and 3,505,225. The sterically clogged phenols constitute another well-known class of antioxidant materials. Antioxidant compositions containing mixtures of an amine component and a sterically clogged phenol component, with and without other ingredients, are also known. Thus, U.S. Patent No. 3,304,283 describes an antioxidant composition for mono-olefinic polymers, such as polypropylene, which contains at least one aromatic phenolic thioether, diaryl thioether, aliphatic disulfide, aromatic disulfide, aromatic mercaptan, aliphatic mercaptan, and / or aliphatic thiuramdisulfide in combination with at least one biphenol and / or aromatic amine. U.S. Patent No. 3,432,578 describes the stabilization of conjugated dienes polymers against the adverse effects of ultraviolet radiation using a mixture of a diaryl hydroxyamine, 2,6-di-t-butyl-4-methyl phenol, 1, 3 , 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, dilaurylthiopropionate, and lignin sulfonate. U.S. Patents Nos. 3,567,664 and 3,637,865 both describe the stabilization of polyether polyurethane-based polyols against burning using a mixture of 2,6-di-t-butyl-4-methyl phenol and a p, p-diakyl diphenylamine. . Similarly, U.S. Patent No. 4,007,230 discloses the stabilization of polyether polyurethane-based polyols against burning using a composition consisting of certain clogged phenols such as 2,4-di-methyl-6-octyl phenol. and NAUGARD 445, previously alluded to. US Patent No. 3,644,482 describes esters derived from (4-hydroxy-5-alkylphenyl) -alkane acids, optionally substituted in the 2- or 3- position of the phenyl ring by a second alkyl group, and alkane polyols which they are stabilizers of organic material normally subject to deterioration by oxidation. They are prepared by conventional esterification techniques. Typical moieties are ethylene glycol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and pentaerythroline tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) propionate]. U.S. Patent No. 3,655,559 describes stabilizers for synthetic lubricants based on alkylated diphenylamines and, optionally, any one of numerous other types of antioxidants, among them sterically clogged phenols.

U.S. Patent No. 3,979,180 describes the stabilization of low density polyethylene and ethylene vinyl acetate copolymers with mineral fillers employing a combination of a sterically clogged phenol and / or a substituted diphenylamine of the structure Ar-N H -Ar 'where Ar and Ar' are each substituted phenyl, naphthol, phenyl and naphthol including alkyl substituents of 1 to 20 carbon atoms, and halogen, an organic metal thiophosphorus compound and a trace amount of a metal salt of Transition. US Patent No. 4,341,677 describes oil-in-water emulsions of antioxidants useful for treating fibrous reinforcements, such as glass fibers, to increase the protection of such polymeric materials reinforced with fibers such as polyolefins, polyurethanes, polyamides, polyesters, polycarbonates, polyacetals, polystyrene and styrene copolymers against chemical degradation. The emulsions are based on clogged phenols, such as octadecyl-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) (I RGANOX 1076, Ciba Geigy) and / or diarylamines such as NAUGAR D 445 The Patent of E. U. , No. 4,420,579 describes antioxidant compositions for polyolefins based on nickel thiobis (alkylphenolate) coordination complexes with hydroxy-substituted ligands in combination with co-additives, such as diarylamines and / or clogged phenols. U.S. Patent No. 4,440,671 discloses mixtures of hydrocarbon-substituted diphenylamines, for example, a liquid styrene-alkylated diphenylamine (WINGSTAY 29, Goodyear Tire and Rubber Company) and high molecular weight polyethylene glycols as water tree retardant compositions for polyethylenes. The compositions may optionally contain antioxidants, such as sterically hindered phenols and amines, polymerized 2,2,4-tetramethylhydroquinoline, 4,4'-thio-bis- (6-t-butyl-3-methylphenol), thiodiethylenebis- ( 3, 5-d it-butyl-4-h id roxih id rocina mato), sthetearyl-hyiodipro-pionate, and the like. U.S. Patent No. 5,047,530 discloses tris (N-alky1-p-phenylenediamino) -1,5,5-triazine compounds useful as antiozonants for higher unsaturated polymers. The compounds can be prepared by reacting N-alkylphenylenediamine with a cyanuric halide. U.S. Patent No. 5,120,844 discloses tris-substituted 1,3-triazine compounds having at least one (N-alkyl-p-phenylenediamino) group on the triazine ring. Preferred compositions are those substituted in tris with the alky p-phenylenediamino group. Preferred compounds can be prepared by reacting N-alkylphenylenediamine with a cyanuric halide. Japanese Patent Publication No. 1984-98148 teaches the inhibition of decolorization of crosslinked polyolefins using 4,4'-bis- (2,2'-dimethylbenzyl) diphenylamine with optional antioxidants which are liquid at room temperature such as: , 4'-thio-bis- (7-t-butyl-3-methylphenol); dilauryl dithiopropionate; 2,2-thio [diethyl bis-3- (3,5-diethyl-t-butyl-4-hydroxyphenyl) propionate). These polyolefins necessarily contain crosslinking agents such as the well-known organic peroxides.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to compounds having both aromatic amine and clogged phenol functions, compositions containing such compounds, and their use as stabilizers for organic materials. More particularly, the present invention relates to a compound of the general formula: where f is: R i and R 2 are independently selected from the group consisting of hydrogen, substituted or unsubstituted aryl, and substituted or unsubstituted alkyl of 1 to 20 carbon atoms; R3 is alkylene of 1 to 10 carbon atoms; m is 0 or 1; n is an integer from 1 to 10; q is an integer from 0 to 8; z is 1 or 2, provided that, when q is 0, z must be 1; X represents the links of a chain of q links in length, said links selected from the group consisting of carbon, nitrogen, oxygen, sulfur, silicon and mixtures thereof; and Y is an aromatic group or f, provided that Y can be f only when q is 0 and m is 1. In another aspect, the present invention relates to a stabilizer for organic materials comprising a compound of the general formula: where f is: Ri and 2 are independently selected from the group consisting of hydrogen, substituted or unsubstituted aryl, and substituted or unsubstituted alkyl of 1 to 20 carbon atoms; R3 is alkylene of 1 to 10 carbon atoms; m is 0 or 1; n is an integer from 1 to 10; q is an integer from 0 to 8; z is 1 or 2, provided that, when q is 0, z must be 1; X represents the links of a chain of q links in length, said links being selected from the group consisting of carbon, nitrogen, oxygen, sulfur, silicon and mixtures thereof; and And it is an aromatic group or f, provided that Y can be f only when q is 0 and m is 1. In still another aspect, the present invention relates to a method for stabilizing organic materials comprising adding to said materials at least one stabilizer comprising a compound of the general formula: where f is: Ri and R2 are independently selected from the group consisting of hydrogen, substituted or unsubstituted aryl, and substituted or unsubstituted alkyl of 1 to 20 carbon atoms; R3 is alkylene of 1 to 10 carbon atoms; m is 0 or 1; n is an integer from 1 to 10; q is an integer from 0 to 8; z is 1 or 2, provided that, when q is 0, z must be 1; X represents the links of a chain of q links in length, said links being selected from the group consisting of carbon, nitrogen, oxygen, sulfur, silicon and mixtures thereof; and And it is an aromatic group or f, provided that Y can be f only when q is 0 and m is 1.

DESCRIPTION OF THE PREFERAL MODALITIES As set forth above, the dual-function stabilizers of the present invention are of the general Formula: where f is: R t and R 2 are independently selected from the group consisting of hydrogen, substituted or unsubstituted aryl, and substituted or unsubstituted alkyl of 1 to 20 carbon atoms; R3 is alkylene of 1 to 10 carbon atoms; m is 0 or 1; n is an integer from 1 to 10; q is an integer from 0 to 8; z is 1 or 2, provided that, when q is 0, z must be 1; X represents the links of a chain of q links in length, said links being selected from the group consisting of carbon, nitrogen, oxygen, sulfur, silicon and mixtures thereof; and And it is an aromatic group or f, provided that Y can be f only when q is 0 and m is 1. Thus Ri and R2 in f of Formula I can be the same or different and can be hydrogen, or an alkyl, functionalized alkyl, or aralkyl group of 1 to 20 carbon atoms. Where Rt and / or R 2 are alkyl, they can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicocyl, or isomers thereof, for example, isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, and the like. Here it is noted that any use of the term "alkyl" in the context of a starting material or the final compounds of this invention is considered to include cycloalkyl structures substituted with cycloalkyl and alkyl as well as, for example, cyclopentyl, cyclohexyl, 4- methylcyclohexyl, and the like. Additionally, where Ri and / or R2 are alkyl, the alkyl group can be mono- or poly-substituted, for example, with functional groups or aryl groups. Such functional groups include, for example, halides, hydroxyl groups, aldehyde groups, carboxyl groups, sulfonyl groups, sulfoxy groups, thiol groups, amino groups, amido groups, and the like, either alone or as a mixture. Aryl substituents include, for example, phenyl, naphthyl, biphenyl, azulenyl, anthracenyl, phenanthrenyl, and the like, the substituents of which may also be substituted to form, for example, tolyl groups, xylyl groups, anilyl groups, and the similar ones. Similarly, where Ri and / or R2 are aryl, they can be, for example, phenyl, naphthyl, biphenyl, azulenyl, anthracenyl, phenanthrenyl, and the like, the substituents of which may also be substituted to form, for example, tolyl groups, xylyl groups, anilinyl groups, and the like. It is preferred that at least one of Ri and R2 is tert-butyl and more preferred than both are tert-butyl. R3 in f in Formula I is an aikylene group of 1 to 10 carbon atoms, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decienan, and their isomers, i.e. be branched or unbranched, for example, isopropylene, isobutylene, 2-ethylhexylene, and the like. It is preferred that R3 is an unbranched alkylene group and more preferably ethylene. In Formula I, (X) q refers to a portion that may or may not be present. That is, if q is 0, X is not present; if q is any of 1 to 8, 1 to 8 X's will be present correspondingly. Those skilled in the art will understand that when X is present, z must necessarily be 2, and X then forms a link or links between the two Y's. As an example, when z and q are both 2, the formula for the compound resulting from the invention will be: F-NH-fO-8-fc Y-X-X-Y- N NHH - F - < n X in Formula I can be carbon, nitrogen, sulfur or silicon. Where q is more than 1, the various X's can be the same or different. Those skilled in the art will understand that the carbon, nitrogen, oxygen, sulfur or silicon referred to represent only those atoms that are the links that bind the two Y's and that such additional atoms or bonds that may be necessary to satisfy the valence requirements of the Chain atoms will be present as well. For example, X could be carbon substituted with an oxygen atom to form a carbonyl group, or, where q is 2 and X is carbon, the structure could be ... Y-CH2-CH2-Y ... Another example could be ... Y-CH = CH-Y ... The additional possibilities will be easily apparent to those of ordinary skill. And, in Formula I, it is an aromatic group, which can be substituted or not replaced. It is preferred that Y is phenyl, naphthyl, biphenyl, azulenyl, anthracenyl, or phenanthrenyl and more preferred that this is phenyl. Where two Y's are present in the compounds of the invention, ie, where z is 2, they may be the same or different, but it is preferred that they be the same. Additionally, when, and only when, z and m are both 1, Y can also be f. In Formula I, n is an integer from 1 to 10. It will be understood that the maximum value for n will depend on the identity of the group chosen as Y. That is, the portion included within the brackets in Formula I may be attached to any and all available carbon atoms in the aromatic group that is Y. Therefore, if Y is phenyl and has no other groups attached to it, Y will have six available carbon atoms, and the maximum value of n would be 6 On the other hand, if Y is biphenyl and has no other groups attached to it, Y will have ten available carbon atoms, and the maximum value of n would be 10. It is preferred that n is an integer from 1 to 6, more preferably from 1 to 3, and most preferably 1. Preferred compounds of the present invention are N- (4'-an ili nof en il) -3- (3", 5" -di-t-butyl-4"-hydroxypheni I) propionamide; n-. {P - [(1 ', 4'-dimethylpentyl) amino] phenyl] -3- (3", 5" -di-t-butyl-4"-hydroxyphenyl) propionamide; N, N'-phenylene-bis [3- (3", 5" -di-t-butyl-4"-hydroxyphenyl) propionamide] The compounds of this invention can be used as partial or complete replacements for antioxidants of clogged phenol and / or amine that are currently in use may also be used in combination with each other or with other additives typically found in organic materials When employed as stabilizers, the compounds of the present invention act as antioxidants and / or antiozonants for, inter alia, plastic materials, rubbers, lubricating oils, and petroleum fuels.

The plastic materials may be a thermoplastic polyolefin, such as polyethylene or polypropylene; polystyrenes; polyvinylhalides; or other thermoplastic resins, including engineering thermoplastics. Engineered thermoplastics include resins such as polyamides, polyesters, polyacetals, polyphenylene oxides, polyphenylene sulphides, copolymers or terpolymers of aliphatic polyketones, poly (ether sulfones), polycarbonates, liquid crystalline polymers, poly (ether ether ketones), and poly (arylates). The rubbers include highly unsaturated polymers such as natural or synthetic elastomers, for example, cis-polyisoprene, polybutadiene, poly (styrene-butadiene), polychloroprene, polyacrylonitrile, and the like, as well as elastomers having lower unsaturation such as EPDM, EPPR, and butyl or halogenated butyl rubbers. Lubricating oils may include lubricating oils, transmission oils, engine oils, and greases. Petroleum fuels and organic liquids can be gasoline, diesel fuel, or jet fuel.

Plastic Materials The stabilization of polyethylene resins, both intertwined and non-interlaced, is extremely important in particular applications. In particular, long-term service is important in wire and cable sheathing where the cabling must maintain its stability for very long periods of time, such as 20 to 30 years or more, in both indoor and outdoor applications. The ability to stabilize polymers such as linear low density polyethylene against long-term degradation is an important step forward in technology. The thermoplastic polyolefins which can be stabilized against degradation using the compounds of the present invention include homopolymers derived from mono- and di-ethylenically unsaturated hydrocarbon monomers of C3 and more such as polypropylene, polyisobutylene, polymethylbutene-1, polymethylpentene-1, polybutene-1, polystyrene, polyisobutylene, and the like; copolymers derived from two or more monomers such as ethylenepropylene copolymers having at least a majority of propylene, copolymers of propylene-butene-1, copolymers of propylene-isobutylene, and blends of a majority of polypropylene with a minority of polyethylene, polypropylene and polybutene-1, and polypropylene and polyisobutylene. Homopolymers, copolymers and their foregoing polyolefin blends can be combined with minor amounts by weight, ie, less than about 50 weight percent and preferably less than about 20 weight percent, of one or more compatible or compatibilized polymers other than those mentioned, for example, polyvinyl halides, chlorinated polyolefins, polyesters, polyamides, polyacrylates, and the like. The amount of the stabilizers of the present invention incorporated into the preceding polyolefins will be, at a minimum, that required to impart a significant level of stability against degradation by oxidation. In general, such amounts may vary from about 0.01 to about 5.0, and preferably from about 0.1 to about 0.5, weight percent of polyolefin homopolymer, copolymer, or polyolefin blend. Although amounts of the stabilizer in excess of about 5 weight percent can be used, such amounts can have a detrimental effect on the physical and mechanical properties of the polyolefin substrate, in which case they should be avoided ordinarily. The processes used to incorporate the stabilizers to the polyolefin are not critical and, in general, follow any of the known processes for incorporating additives into polyolefin resins. For example, these materials can be introduced into the polyolefin and homogeneously distributed throughout the polymer by grinding, extrusion mixing, or some other mechanical work procedure. The stabilizer can be added to the polyolefin by means of a pre-concentrate or in a carrier system, for example, in a suitable solvent or co-solvent. Following common practice, other additives can be introduced to the polyolefin before, during and / or after the addition of the stabilizer. Such additives include other stabilizers, colorants, reinforcements, fillers, antistatic agents, lubricants, plasticizers, and the like, present in their customary amounts.

Hules The compounds of the invention can be advantageously used as antiozonants to protect highly unsaturated polymers such as natural or synthetic elastomers. Representative of the highly unsaturated polymers that can be employed in the practice of this invention are diene elastomers. Such elastomers will typically have an iodide number of between about 100 and about 250, although highly unsaturated rubbers having a higher or a lower iodide number (eg, 50-100) may also be employed. Illustrative of the diene elastomers that can be used are polymers based on conjugated dienes such as 1,3-butadiene; 2-methyl-1,3-butadiene; 1, 3-pentadiene; 2,3-dimethyl-1,3-butadiene; and the like, as well as copolymers of such dienes conjugated with monomers such as styrene, alpha-methylstyrene, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, and the like. Highly unsaturated oils include natural rubber, cis-polyisoprene, polybutadiene, poly (styrene-butadiene), polychloroprene, and poly (acrylonitrile-butadiene). In addition, mixtures of two or more highly unsaturated rubbers with elastomers having lower unsaturation such as EPDM, EPR, butyl or halogenated butyl rubber are also within the scope of the invention. The novel compounds of the invention can be used in combination with other antiozonants and with waxes that are commonly used to protect against static attack. The other antiozonants that may be used include any of the class of commonly recognized para-phenylenediamine materials: N-phenyl-N '- (1,3-dimethylbutyl) -p-phenylenediamine; N-phenyl-N '-isopropyl I-p-phenylenediamine; N-phenyl-N '- (1 -methylheptyl) -p-phenylenediamine; N-f-enyl-1-cyclohexyl-p-phenylenediamine; mixed diaryl-p-phenylenediamines; N, N'-diphenyl-p-phenylenediamine; N, N'-d'-beta-naphthyl-p-phenylenediamine; N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine; N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine; N, N'-b1s (1-methylpentyl) -p-phenylenediamine; N-phenyl-N'-alkyl-p-phenylenediamine; 6-ethoxy-1,2-dihydro-2,2,4-trimethyquinoline; nickel dibutyl dithiocarbamate; and the similar ones. The highly unsaturated polymers to be protected can be formulated in a conventional manner with the many usual ingredients for making compounds, for example, plasticizing and softening oils, fillers, reinforcing pigments, and carbon blacks. The novel compounds of the invention can be added to a polymer saturated at a level of 0.1 to about 10 parts by weight per hundred parts by weight of hydrocarbon rubber (hereinafter PHR). For these purposes, it is assumed that the polymer is a natural or synthetic rubber. A more preferred level of addition is about one to about six parts PH R. The most preferred level is from about two to about four parts PH R. When the compounds of the invention are used in combination with other antiozonants such as the class of p-phenylenediamine materials, can be added in a mixture that totalizes the ranges specified above. The compounds of the invention can be mixed with other antiozonants in ratios ranging from 1: 3 to 3: 1. More preferred is a range of proportions from 2: 3 to 3: 2.

These proportions mean that they indicate that the percentages are 40:60 to 60:40 where in all cases the compounds of the present invention are the first number of each proportion. It should be noted that in certain applications and with certain other antiozonants, the PHR ranges of antiozonant listed above may be varied in order to obtain optimum protection. Reasonable experimentation can be undertaken in order to optimize the proportions and overall levels of the mixture when the compounds of the invention are mixed with other antioxidants and antiozonants that are known in the art. The compounds of the invention can be used for good utilization with antioxidants and antiozonants of the prior art in mixtures to improve particular properties. Although the compounds of the invention have been described above as antiozonants when used in rubber formulations, it is clear that the materials can also function as antioxidants for rubber, thus providing protection against degradation by oxidation as well as protection against ozone. It is noted that when used as an antioxidant, the levels are typically much lower per one hundred parts of rubber hydrocarbon than when anti-ozonation protection is required. The compounds of the invention can be advantageously used in a tire as a component of any or all of the thermosetting rubber-containing portions of the tire. These include drawing portions, side faces, and carcass of a truck, passenger, or off-highway vehicle tire that also contains many different layers of reinforcement therein. These components typically contain more than one thermophilic rubber polymer in a mixture that must be protected from ozone degradation as well as oxidation attack. The methods for incorporating these compounds to the rim are conventional and well known. These compounds improve the safety of burning the existence of rubber in which they are incorporated compared to conventional p-phenylenediamines. The unsaturated polymers can optionally be protected against both oxidation and ozone degradations by mixing the compounds of the invention with conventional antioxidants. Many kinds of phenols, amines, etc. , they work as antioxidants. The Index of Commercial Antioxidants and Antiozonants, 3rd Edition, published by The Goodyear Tire and Rubber Company lists materials commonly seen as materials that have antioxidant properties, and is incorporated herein by reference. Representative classes of such antioxidant materials are sterically clogged phenols, alkyl substituted diphenylamines, aryl substituted diphenylamines, aralkyl substituted diphenylamines, naphthylamines, reaction products of a diarylamine with a ketone, mono-phenols, bisphenols, polyphenols, hydroquinone derivatives. , and polymerized quinolines. The antioxidant system may contain one or more of these materials. The optimal levels of addition (PH R) for antioxidants can be easily determined through routine experimentation and can vary widely depending on the end use.

EXAMPLES General Synthesis of Stabilizers N- (4'-annylinophenyl) -3- (3", 5" -di-t-butyl-4"-hydroxyphenyl) propionamide Example 1 N- (4'-anilinophenyl) -3- (3", 5" -di-t-butyl-4"-hydroxyphenyl) propionamide (hereinafter Stabilizer A) was synthesized by charging a round bottom flask with four necks, of one liter, with propionate of 3- (3,5-di-t-butyl-4-hydroxyphenyl) (Reagent 1) and usually a slight excess (of 5 to 10 percent) of 4-aminodiphenylamine ( Reagent 2) Reagent 1 can be prepared as the reaction product by Michael addition of 2,6-di-t-butylphenol with methyl acrylate Reagent 2 is commercially available from Aldrich Chemical Company and Uniroyal Chemical Company. The ratio of Reagent 1 to Reagent 2 can vary from 1.5 to 0.67 A preferred ratio of Reagent 1 to Reagent 2 is 1.2 to 0.84, and the most preferred ratio of Reagent 1 to Reagent 2 is 1.0 to 0.91. reaction vessel itself was equipped with a shovel agitator, nitrogen sprayer accommodated below the surface, a thermocouple, and a gas outlet tube that leads to a cold trap. The reaction vessel was heated between 180 and 250 ° C and preferably between 200 and 230 ° C, and most preferably at 230 ° C. The reaction was monitored by High Performance Liquid Chromatography (HPLC) until the yield was maximized of the product - usually from 2 to 16 hours, and more preferably from 4 to 8 hours. At the end of the reaction, the sprayer was removed, the reaction was cooled to 120 ° C and a mixture of organic solvents, usually a mixture of a saturated aliphatic solvent and an unsaturated aromatic solvent such as octane and toluene, was added over 1 hour. The crystallization of the product in either octane and toluene was completed, but the purity or crystallization yield was usually affected. The crystallization solution was maintained at 1 15 ° C and cooled slowly until the crystallization was complete, usually between 25 and 90 ° C. The product was filtered, washed with octane, and dried. This process gives a light gray product with between 65 percent and 85 percent yield. The purified product was melted between 139 and 144 ° C, although the raw or less purified product melts between 1 10 and 140 ° C. NMR 1 H (CDCl 3, 300 MHz): 1.44 (s, 18H), 2.63. (t, J = 7.8Hz, 2H), 2.99 (t, J = 7.8Hz, 2 H), 5.12 (s, 1 H), 5.69 (s, broad, 1 H), 6.91 -7.35 (m, 1 1 H). NMR 13C (CDCl 3, 75 MHz): 170.7, 152.3, 143.6, 139.5, 136.2, 131.6, 131.2, 129.4, 121.5, 120.6, 1 19.0, 1 17.1, 40.1, 34.4, 31.9, 30.4 . I R (cm-1): 3620, 3430, 3272, 2955, 1649. Elemental Analysis. Calculated: C 78.34 percent, H 8.16 percent, N 6.30 percent, OR 7.20 percent. Found: C 78.53 percent, H 8.34 percent, N 6.27 percent, OR 6.49 percent.

EXAMPLE 2 Reagent 2 in Excess The synthesis of Stabilizer A described in Example 1 is carried out using 11.68 g of Reagent 1 (0.04 moi) and 8.1 g of Reagent 2 (0.044 mole), ie, an excess amount was used of Reagent 2. A product of the type described in Example 1 was obtained.

EXAMPLE 3 Reagent 1 in Excess The synthesis of Stabilizer A described in Example 1 is carried out using 17.52 g of Reagent 1 (0.06 mol) and 7.36 g of Reagent 2 (0.04 mol), that is, an excess amount of Reagent 1 was used. A product of the type described in Example 1 was obtained.

Example 4 N-. { p - [(1 ', 4'-dimethylpentyl) amino] phenyl} -3- (3", 5" -di-t-butyl-4"-hydroxyphenyl) propionamide N-. {Pt (1 ', 4'-dimethylpentyl) amino] phenyl.} -3- (3", 5"-di-t-butyl-4" -hydroxy phenyl) propionamide (Stabilizer B). A quantity of 73 g (0.25 mol) of Reagent 1, and 61.8 g was placed in a 500 ml four-necked round bottom flask equipped with a thermocouple, a mechanical stirrer, a condenser and a Stark-Dean trap with condenser. (0.3 mol) of N- (1,4-dimethylpentyl) -p-phenylenediamine. (N- (1,4-dimethylpentyl) -p-phenylene diamine can be made by the condensation of p-nitroaniline with methyl isoamyl ketone, followed by hydrogenation). Under a blanket of nitrogen, the mixture was heated at 230 ° C for six hours.

The reaction was monitored by HPLC to observe the disappearance of the starting materials and the formation of the title compound.

After cooling to 100 ° C, 200 g of toluene was added. The toluene solution was extracted with dilute hydrochloric acid, followed by washing with a solution of sodium carbonate and water. The solvent was removed by stripping with vacuum. The resulting product (16 g) was an oil. The HPLC analysis of relative area (@ 280 nm detection) of this product was 87 percent.

Example 5 N, N'-phenylene-bis [3- (3", 5" -di-t-butyl-4"-hydroxyphenyl) propionamide] N, N'-phenylene-bis [3- (3", 5" -di-t-butyl-4"-hydroxyphenyl) propionamide] (Stabilizer C). A mixture of Reagent 1 (73.3 g, 0.26 mol) and p-phenylenediamine (10.8 g, 0. 1 mol) was placed in a three-necked round bottom flask, equipped with a Stark-Dean receiver, a thermocouple and an inlet. for gas. The reaction mixture was heated 9 hours at 230 ° C under N2, with stirring. The resulting product mixture was recrystallized from acetonitrile. Matter ,! purified, N, N'-phenylene-bis [3- (3", 5" -di-t-butyl-4"-hydroxyphenyl) propionamide], has a melting point in the range of 238-245 ° C.

Oxidation Induction Times Circular discs of 0.25 mm films were cut from the material to be tested and placed on aluminum trays for use in a Perkin-Elmer DSC-2C differential type scanning calorimeter. The DSC calorimeter test chamber is purged with nitrogen during conditioning at a Socratic temperature of 200 ° C followed by an immediate change to oxygen at a flow rate of 20 cc's per minute to induce thermal degradation by oxidation. The Oxidation Induction Time (OIT) is the time in minutes between reaching a Socratic temperature of 200 ° C when the oxygen environment is introduced and the time in which the DSC detects the start of oxidation.

Example 6 Stabilizer for Plastics The antioxidant properties of the novel product in a fully formulated plastic were determined in the Oxidation Induction Time (OIT) test under ASTM D3895 conditions at 200 ° C. The plastic formulation contained 0.2 percent Stabilizer A dual-function antioxidant, 2.5 percent of a carbon black, and 97.3 percent of linear low density polyethylene (LLDPE). The ILO results of several antioxidants of the state of the art are included in Table 1. In the ILO test, a longer ILO value indicates better stability of the formulation against oxidation. The results in Table 1 are the average of at least three tests.

Naugard Super Q is a polymerized 2,2,4-trimethyl-1,2-dihydroquinoline having a narrower molecular weight distribution than Naugard Q, infra. Naugard A is a reaction product by condensation of diphenylamine and acetone, commercially available from Uniroyal Chemical. It can be prepared according to the conditions described in the U.S. Patent. , No. 2,562, 802. The commercial product is supplied as a light bronze-green powder or as greenish brown scales and has a melting range of 85 to 95 ° C.

Example 7 Stabilizer for Rubber Evaluation of Stabilizer A in a NR / BR Casing Compound for Truck: The non-aged physical properties for Stabilizer A show a promising similarity to the controls of Naugard Q and Novazone AS. The physical aging results also show a slight superiority in almost all percent retention values for Stabilizer A versus controls.

The samples are formulated in two steps. In the first step, a master batch is prepared and in the second step, the master batch is formulated in compound in addition to form three samples, A, B, and C. See Table 2.

Novazone AS is a mixture of N, N'-diaryl-p-phenylenediamines and is commercially available from Uniroyal Chemical Company. 1 - . 1 - Sample 2 - Resistance to Tension (in kg / cm2) 3 - Percent of Retention (Resistance to Tension) 4 - Lengthening (percent to rupture) 5 - Percent to Tension (Lengthening) The Strength and Stretch Elongation properties were measured in accordance with ASTM # D412. The test specimens were in the form of dumbbells. The tensile strength and elongation properties of the test specimens were measured before aging and also after aging with hot air at 100 ° C for three days. The White Lacquer Immersion Test uses ASTM # D1 148 (09.01) and D925 (09.01), which is incorporated herein by reference. The test formulation is formulated for compound, mixed and cured in flat test sheets for subsequent analysis of discoloration and staining characteristics. Specific tests were conducted in accordance with ASTM-D925-83 Method C. Method C judges the degree of staining tendency of the material by determining the amount of discoloration that occurs from the substrate material through a white lacquer coating that has been placed in the test sample. Once the test specimen is mixed and cured, it is coated with a layer of white lacquer according to the ASTM-D925 procedure. It is then exposed to a solar lamp light source in a suitable test chamber for a specific period of time. The Hunter Lab ™ Colorimeter test instrument is used to objectively determine the change in color of white lacquer during a 24-hour exposure to the UV source. ASTM D2244-79, entitled Color Differences in Opaque Materials, reports a number of characteristics by means of the standard difference letters a, b, and L. The color scale L is the scale from 0 to 100 with value 0 that total black totally and a value of 100 that is pure white. Therefore, the higher the value of L, the whiter the sample. The results of the immersion in white lacquer are shown in Table 5.

L - a finite scale (0-100) that determines the colors black (0) and white (100) a - a relative scale that determines the colors green (negative) and red (positive). b - a relative scale that determines the colors blue (negative) and yellow (positive).

The properties of the immersion in white lacquer without aging of Stabilizer A show that they are equivalent to the controls of Naugard Q and Novazone AS. By subjecting to aging for 24 hours under a UV lamp, the results indicate that the non-staining characteristics of Stabilizer A are very close (slightly lower) to Naugard Q, but higher than Novazone AS. The results of this package of experiments conclude that the antioxidant properties of Stabilizer A are superior to Novazone AS and Naugard Q. In addition, the lacquer immersion test showed that Stabilizer A is almost non-stained, comparable to Naugard Q.

Example 8 Stabilizer for Lubricating Oils Stabilizer A was tested on two different Lubrizol lubricating oils using a Bulk Oxidation Test (BOT). The BOT test involves dissolving the additive (0.6 percent in Diesel engine oil and 0.5 percent in Automatic Transmission Fluid oil {ATF.}.) In the oil. The oil is heated (150 ° C for diesel engine oil and 160 ° C for ATF oil) and oxygen is bubbled (1 L / min) through the oil. The kinematic viscosity (K.V.) is then measured over time until this value reaches 200 percent of its original value. In this test, a longer time corresponds to a better stabilizing additive. The two different oils were Diesel 1 18359 and ATF 1 18160 from Lubrizol. A summary of the conditions and results of the test is given in Table 6. The results of the test show that Stabilizer A increases the resistance against oxidation of both Diesel and ATF oils, compared to the resistance of oils without a stabilizer.

In view of the many changes and modifications that can be made without departing from the underlying principles of the invention, reference should be made to the appended claims for an understanding of the scope of protection within the scope of the invention.

Claims (1)

REIVI NDICATIONS 1. A compound of the general formula: where f is: Ri and R2 are independently selected from the group consisting of hydrogen, substituted or unsubstituted aryl, and substituted or unsubstituted alkyl of 1 to 20 carbon atoms; R3 is alkylene of 1 to 10 carbon atoms; m is 0 or 1; n is an integer from 1 to 10; q is an integer from 0 to 8; z is 1 or 2, provided that, when q is 0, z must be 1; X represents the links of a chain of q links in length, said links being selected from the group consisting of carbon, nitrogen, oxygen, sulfur, silicon and mixtures thereof; and Y is an aromatic group or f, provided that Y can be f only when q is 0 and m is 1. 2. The compound of claim 1 wherein Rt and R2 are unsubstituted alkyl of 1 to 20 carbon atoms. 3. The compound of claim 2 wherein Ri and R2 are the same. 4. The compound of claim 3 wherein RI and R2 are terbutyl. 5. The compound of claim 1 wherein R3 is an unbranched alkylene of 1 to 10 carbon atoms. 6. The compound of claim 5 wherein R3 is propylene. The compound of claim 1 wherein Y is aromatic. 8. The compound of claim 7 wherein Y is phenyl. 9. The compound of claim 1 wherein said compound is N- (4'-an i linof in il) -3- (3", 5" -di-t-butyl-4"-h id roxif enyl) propionamide 10. The compound of claim 1 wherein said compound is N- { P - [(1 ', 4'-dimethylpentyl) amino] phenyl] -3- (3", 5" -di-t. -butyl-4"-hydroxy phenyl) propionamide. 11. The compound of claim 1 wherein said compound is N, N'-f eni len-bis [3- (3", 5" -di-t-bu ti l-4"-hydroxy in i I) propionamide 12. A stabilizer for organic materials comprising a compound of the general formula: i *), (I) where f is: R t and R 2 are independently selected from the group consisting of hydrogen, substituted or unsubstituted aryl, and substituted or unsubstituted alkyl of 1 to 20 carbon atoms; R3 is alkylene of 1 to 10 carbon atoms; m is 0 or 1; n is an integer from 1 to 10; q is an integer from 0 to 8; z is 1 or 2, provided that, when q is 0, z must be 1; X represents the links of a chain of q links in length, said links being selected from the group consisting of carbon, nitrogen, oxygen, sulfur, silicon and mixtures thereof; and And it is an aromatic group or f, provided that Y can be f only when q is 0 and m is 1. The stabilizer of claim 12 wherein Ri and R2 are unsubstituted alkyl of 1 to 20 carbon atoms. The stabilizer of claim 13 wherein R y and R 2 are the same. 15. The stabilizer of claim 14 wherein Ri and R2 are tert-butyl. 16. The stabilizer of claim 12 wherein R3 is an unbranched alkylene of 1 to 10 carbon atoms. 17. The stabilizer of claim 16 wherein R3 is propylene. 18. The stabilizer of claim 12 wherein Y is aromatic. 19. The stabilizer of claim 18 wherein Y is phenyl. The stabilizer of claim 12 wherein the compound is N- (4'-anilinophenyl) -3- (3", 5" -di-t-butyl-4"-hydroxyphenyl) propionamide. The stabilizer of claim 12 wherein the compound is N- { p - [(1 \ 4'-dimethyl pentyl) amino] phenyl] -3- (3", 5" -di-t-butyl-4) "-hydroxy phenyl) propionamide. 22. The stabilizer of claim 12 wherein the compound is N, N'-phenylene-bis [3- (3", 5" -di-t-butyl-4"-hydroxypheni I) propionamide.] 23. A method for stabilizing organic materials comprising adding to said materials a stabilizer comprising a compound of the general formula: where f is: Ri and R are independently selected from the group consisting of hydrogen, substituted or unsubstituted aryl, and substituted or unsubstituted alkyl of 1 to 20 carbon atoms; R3 is alkylene of 1 to 10 carbon atoms; m is 0 or 1; n is an integer from 1 to 10; q is an integer from 0 to 8; z is 1 or 2, provided that, when q is 0, z must be 1; X represents the links of a chain of q links in length, said links being selected from the group consisting of carbon, nitrogen, oxygen, sulfur, silicon and mixtures thereof; and And it is an aromatic group or f, provided that Y can be f only when q is 0 and m is 1. 24. The method of claim 23 wherein R T and R2 are unsubstituted alkyl of 1 to 20 carbon atoms. 25. The method of claim 24 wherein Ri and R2 are the same. 26. The method of claim 25 wherein Ri and R2 are terbutyl. 27. The method of claim 23 wherein R3 is an unbranched alkylene of 1 to 10 carbon atoms. 28. The method of claim 27 wherein R3 is propylene. 29. The method of claim 23 wherein Y is aromatic. 30. The method of claim 29 wherein Y is phenyl. 31 The method of claim 23 wherein the compound is N- (4'-anilinofeni l) -3- (3", 5" -di-t-butyl-4"-hydraxyphenyl) propionamide 32. The method of claim 23 wherein the compound is N-. {p - [(1 ', 4'-dimethyl pentyl) amino] phenyl] -3- (3", 5" -di-t-butyl-4" -hydroxy phenyl) propionamide. The method of claim 23 wherein the compound is N, N, -phenylene-bis [3- (3", 5" -di-t-butyl-4"-hydroxyphenyl) propionamide]. The present invention relates to compounds containing double substitutions of an aromatic amine and clogged phenol function useful as stabilizers for organic materials. These compounds are of the general formula (I) wherein f is of formula (II). R t and R 2 are independently selected from the group consisting of hydrogen, substituted or unsubstituted aryl, and substituted or unsubstituted alkyl of 1 to 20 carbon atoms; R3 is alkylene of 1 to 10 carbon atoms; m is 0 or 1; n is an integer from 1 to 10; q is an integer from 0 to 8; z is 1 or 2, provided that, when q is 0, z must be 1; X represents the links of a chain of q links in length, said links being selected from the group consisting of carbon, nitrogen, oxygen, sulfur, silicon and mixtures thereof; and Y is an aromatic group or f, provided that Y can be f only when q is 0 and m is

1.