Oxygenated aromatic amines and use as antioxidants

Abstract

To provide compositions and uses of oxygenated aromatic amines as antioxidants.SOLUTION: There are described compounds, compositions, and methods that include oxygenated aromatic amines, such as an aminophenol-, phenyl-p-phenylenediamine-, and diaminobenzene-based compound useful as antioxidants. The oxygenated aromatic amines include secondary and / or tertiary amine groups having nitrogen bonded to one or two carbon-containing groups, wherein the carbon-containing groups have hydroxyl groups and / or ether groups separated from the nitrogen by one or more carbon atoms.SELECTED DRAWING: Figure 4

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application Serial No. 62 / 840,133, filed April 29, 2019, the disclosure of which is incorporated herein by reference in its entirety.

[0002] The present invention is directed to compositions and uses of oxygenated aromatic amines as antioxidants. [Background technology]

[0003] Antioxidants are used in various types of compositions and industries. For example, antioxidants are used to inhibit chemical oxidation of compositions obtained in the oil and gas industry. Antioxidants also play an important role as food preservatives and are often added to various food compositions to maintain the properties of the food.

[0004] Hydrocarbon-containing compositions can benefit from the use of antioxidants. In fats and oils, antioxidants can inhibit oxidation reactions that may otherwise have undesirable effects on the chemical properties of such fats and oils. In food products, oxidation of edible fats and oils can cause unpleasant odors and tastes and lead to food spoilage. Oxidation can be caused by exposure to oxygen and sunlight, which leads to oxidation of hydrocarbons.

[0005] Antioxidants are also added to fuels, such as gasoline and gasoline / ethanol blends, as well as lubricants, to prevent the oxidation of the hydrocarbons therein. Gasoline fuels can easily oxidize when exposed to conditions such as heat, oxygen, and ultraviolet light. The oxidation products can cause gums or deposits in the fuel, thereby causing problems such as clogging and corrosion in internal combustion engines. Antioxidants can prevent the polymerization of compounds in gasoline that would otherwise lead to residues that could damage internal combustion engines.

[0006] Plastic, rubber, and adhesive compositions can also benefit from the addition of antioxidants to prevent oxidative damage to the polymer that would otherwise result in loss of flexibility and strength of the composition. Oxidative damage to polymer compositions often results in cracks in the material surface exposed to oxygen and / or UV radiation. Summary of the Invention [Problem to be solved by the invention]

[0007] Some conventional antioxidants must be used in high concentrations to provide antioxidant activity, have poor control over peroxides formed during oxidation, and are ineffective in preventing fuel color deterioration.Therefore, there is a need for a gasoline or gasoline and ethanol blend composition with improved oxidation stability that reduces or eliminates sedimentation and gum formation in the fuel and simultaneously reduces or eliminates corrosion or clogging in internal combustion engines. [Means for solving the problem]

[0008] The present disclosure is directed to oxygenated aromatic amine compounds, such as aminophenols, n-phenyl-p-phenylenediamines, and diaminobenzene-based compounds, as well as compositions and methods that contain or utilize the compounds to prevent oxidation of organic compounds (i.e., as antioxidants).

[0009] The present invention provides a compound of formula I for use in the methods of the disclosure, the compound of formula I being: [ka] In the formula, -R 1 , -R 2 , -R 3 , -R 4 , and -R 5 is -H, -OH, alkyl, aryl, alkylaryl, and arylalkyl, and -NR 8 R 9 are independently selected from R8 and R9 is -H, alkyl, aryl, alkylaryl, and arylalkyl, as well as R as described herein. 6 / R 7 or -R 1 , -R 2 , -R 3 , -R 4 , and -R 5 Any two adjacent groups of R 6 and one or both of R7 are (i) a carbon-containing group containing one or more hydroxyl groups separated from the N atom by one or more carbon atoms, R 6 or R 7 When is not (i), it is selected from --H, alkyl, aryl, alkylaryl, and arylalkyl.

[0010] In an embodiment, -R 1 , -R 2 , -R 3 , -R 4 , and -R 5 At least one of is -OH, preferably -R 3 is -OH. In some embodiments, those -R 1 , -R 2 , -R 3 , -R 4 , and -R 5 is -H, including the aminophenols of the present disclosure.

[0011] Other compounds of formula I include -R 1 , -R 2 , -R 3 , -R 4 , and -R 5 One or more of -NR 8 R 9 and -NR 8 R 9 Not -R 1 , -R 2 , -R 3 , -R 4 , and -R 5is -H, which includes the diaminobenzene compounds of the present disclosure.

[0012] In some embodiments, R 6 and R 7 Either or both of the -(CR 10 2 ) q (CHOH)(CH 2 ) z R 11 is of the formula R 10 is independently selected from -H and alkyl; q and z are independently (-) (a covalent bond) or an integer ranging from 1 to 12, preferably (-), 1, or 2; R 11 is selected from the group consisting of C1-C24 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl. Exemplary compounds include 4-bis[(hydroxyalkyl)amino]phenol and 1,4-bis[hydroxy-alkylamino]benzene.

[0013] In other embodiments, R 6 and R 7 Either or both of the -(CR 10 2 ) q (CHOH)(R 12 O) z R 11 is of the formula R 10 is independently selected from -H and alkyl, q is (-) (a covalent bond) or an integer ranging from 1 to 12, preferably (-), 1, or 2, and R 11 is selected from the group consisting of C1 to C24 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl; R 12 is -(CH 2 ) w -, and w is 1, 2, or 3. Exemplary compounds include 4-bis[(alkoxy-hydroxy-alkyl)amino]phenol and 1,4-bis[alkoxy-hydroxy-alkylamino]benzene.

[0014] In an embodiment, the present invention provides a method for inhibiting oxidation of an organic compound, the method comprising adding a compound of formula I to a composition comprising an organic compound, wherein the compound of formula I inhibits oxidation of the organic compound in the composition. The compound to be protected from oxidation can be present in a fuel composition, a lubricant composition, a rubber composition, a plastic composition, or an adhesive composition.

[0015] The invention also provides a method for preparing a compound of formula I. In this method, an aryl group-containing reactant having either (a) a primary amine and a hydroxyl group, (b) two primary amine groups, (c) a primary and a secondary amine group, or (d) a primary and a tertiary amine group is reacted with a carbon- and oxygen-containing reactant capable of reacting with the primary amine group and / or optionally the secondary amine group to provide a compound of formula I as described herein.

[0016] Exemplary reactants include those aryl group reactants which are 4-aminophenol, 1,4-diaminobenzene (p-phenylenediamine), and dimethyl-4-phenylenediamine, as well as oxirane and oxytane containing reactants such as those according to formula II: [ka] In the formula, R 13 is -(CH 2 )- or -(CH 2 CH 2 )- and R 14 is -(CH 2 ) w -, w is an integer ranging from 1 to 3, t is an integer ranging from 1 to 100, and R 15 is optionally substituted with one or more hydroxyl groups, as described herein; 10 It is.

[0017] The oxygenated aromatic amine compounds described herein exhibit significantly superior antioxidant performance over other known antioxidants, protecting organic materials from oxidative and thermal degradation. These antioxidants generally have relatively high antioxidant properties along with improved thermal stability and performance in a wide range of materials, including, but not limited to, petroleum-based products (lubricants, gasoline, aviation fuel, and engine oils), plastics, elastomers, cosmetics, cooking oils, and foodstuffs.

[0018] In turn, the oxygenated aromatic amines acting as antioxidants can inhibit the fouling of compositions containing organic compounds. Thus, the antioxidants can prevent the formation of polymers, prepolymers, oligomers, and / or other materials that would otherwise become insoluble in the stream and / or precipitate from the stream and deposit on articles in contact with the treated composition.

[0019] Furthermore, the methods for preparing oxygenated aromatic amine compounds described herein allow for improved synthesis and quality of compositions containing these antioxidants. For example, the disclosed processes can be efficiently and economically carried out in the melt phase, thus eliminating or minimizing the use of extraneous materials such as catalysts and solvents. Furthermore, the methods for preparing oxygenated aromatic amine compounds can generally reduce or eliminate purification steps of the final product compared to existing syntheses. This can lead to superior product performance / cost ratios and reduced waste. [Brief description of the drawings]

[0020] [Figure 1] 1 is a graph of the time (hours) to reach the pressure breakpoint determined from antioxidant testing with heavy coker naphtha for various oxygenated aromatic amines of the present disclosure.

[0021] [Diagram 2]1 is a graph of the time (hours) to reach the pressure breakpoint determined from antioxidant testing with heavy coker naphtha for various oxygenated aromatic amines of the present disclosure.

[0022] [Diagram 3] 1 is a graph of the time (hours) to reach pressure breakpoint determined from antioxidant testing with DCU-1 coker naphtha for various oxygenated aromatic amines of the present disclosure.

[0023] [Figure 4] 1 is a graph of pressure change over time determined from antioxidant testing with coker naphtha for various oxygenated aromatic amines of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] Although the present disclosure provides reference to preferred embodiments, those skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. Reference to various embodiments is not intended to limit the scope of the claims appended hereto. Moreover, any examples described herein are not intended to be limiting, but merely set forth some of the many possible embodiments of the appended claims.

[0025] Additional advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by routine experimentation in the practice of the invention.

[0026] The compositions and methods of the present disclosure include or use compounds with aromatic chemical properties that contain nitrogen and oxygen (oxygenated aromatic amines). Oxygenated aromatic amines include at least an unsaturated six-carbon ring structure with at least one nitrogen atom of a secondary or tertiary amine group bonded to an aromatic ring carbon, the nitrogen atom of the secondary or tertiary amine group being bonded to a first carbon-containing group (and optionally a second carbon-containing group), which structure includes one or more hydroxyl groups and / or ether groups separated from the N atom by one or more carbon atoms. Preferably, the first carbon-containing group (and optionally the second carbon-containing group) includes one or more hydroxyl groups and one or more ether groups separated from the N atom by one or more carbon atoms. Preferably, the hydroxyl and ether groups are separated from the nitrogen by two or three carbon atoms. The oxygenated aromatic amine also includes at least a hydroxyl group, or either a second amine group (which may be the same or different from the aforementioned secondary or tertiary amine group) bonded to another aromatic ring carbon. The secondary or tertiary amine groups, and the atoms on the aromatic ring that are not bound to the hydroxyl or secondary amine groups, can be bound to a hydrogen atom, a hydrocarbon group including an aryl and / or alkyl group, or can form a ring structure (e.g., forming a fused ring structure with an aromatic ring).

[0027] In some embodiments, the oxygenated aromatic amine has an unsaturated 6-carbon ring structure, and in addition to a secondary or tertiary amine group, one or more hydroxyl groups are attached to the ring atom. The unsaturated 6-carbon ring structure can be an aryl ring or can be part of a fused ring structure that includes the unsaturated 6-carbon ring structure. Exemplary compounds of the present disclosure that include hydroxyl groups attached to the ring atom of the unsaturated 6-carbon ring include those based on phenol, pyrocatechol, resorcinol, hydroquinone, hydroxylhydroquinone, or fluororucitol. Exemplary compounds also include those based on hydroxyl-containing fused aromatic chemistry, such as naphthol, hydroxyl anthracene, or indenol.

[0028] In some embodiments, the oxygenated aromatic amine has an unsaturated six-carbon ring structure, with one or more amine groups attached to the ring atom in addition to a secondary or tertiary amine group that contains at least a first carbon-containing group. The unsaturated six-carbon ring structure can be an aryl ring or can be part of a fused ring structure that includes the unsaturated six-carbon ring structure. Exemplary compounds of the present disclosure that include an amine group attached to a ring atom of an unsaturated six-carbon ring include those based on aniline, benzenediamine, and benzenetriamine. Exemplary compounds also include those based on hydroxyl-containing fused aromatic chemistries such as naphthylamine, diaminonaphthalene, aminoanthramine, indenylamine, and indenyldiamine.

[0029] In embodiments, the first and / or second carbon-containing group of the secondary or tertiary amine group comprises a number of carbon atoms ranging from 1 to about 24, 2 to about 23, or 2 to about 22, a number of hydrogen atoms ranging from 3 to about 40, 4 to about 38, or 5 to about 35, a number of oxygen atoms of 1, 2, 3, or 4, or any combination thereof. In preferred embodiments, the carbon-containing group of the secondary or tertiary amine group comprises only carbon, oxygen, and hydrogen.

[0030] In some embodiments, the disclosure provides "bis" compounds, which include a tertiary amine group, and in which the first and second carbon-containing groups bonded to the nitrogen atom of the tertiary amine group are the same. For example, in the aminophenol compound 4-bis[(3-butoxy-2-hydroxy-propyl)amino]phenol, the first and second carbon-containing groups are the same and are -(CH 2 CHOHCH 2 )O(CH 2 ) 3 CH 3 It is.

[0031] Other "bis" compounds include compounds based on diamines, such as phenylenediamine, which contain a first secondary amine group bonded to a ring carbon and a second secondary amine group bonded to a ring carbon, where the first and second amine groups are further bonded to carbon-containing groups that contain a hydroxyl group, an ether group, or both, where the carbon-containing groups are the same. For example, in the diaminobenzene compound 1,4-bis[3-hexyloxy-2-hydroxy-propylamino]benzene, the first and second carbon-containing groups are the same and are -(CH 2 CHOHCH 2 )O(CH 2 ) 5 CH 3 It is.

[0032] The compounds of the present disclosure are described with reference to Formula I. [ka]

[0033] In formula I, -R 1 , -R 2 , -R 3 , -R 4 , and -R 5 is -H, -OH, alkyl, aryl, alkylaryl, and arylalkyl, and -NR 8 R 9 are independently selected from R 8 and R 9 is -H, alkyl, aryl, alkylaryl, and arylalkyl, as well as R as described herein. 6 / R 7 or -R 1 , -R 2 , -R 3 , -R 4 , and -R 5 Any two adjacent groups of R may form one or more ring structures. 6 and R 7is a carbon-containing group containing one or more hydroxyl and / or ether groups separated from the N atom by one or more carbon atoms; 6 or R 7 When is not (i), it is selected from --H, alkyl, aryl, alkylaryl, and arylalkyl.

[0034] -R 1 , -R 2 , -R 3 , -R 4 , -R 5 , -R 8 , and -R 9 Exemplary alkyl groups, which may be one or more of: may have a number of carbon atoms ranging from 1 to 18, 1 to 12, 1 to 8, 1 to 6, or 1 to 3, and may be selected from linear, branched, and cyclic alkyl groups. Exemplary alkyl group types include: Methyl, ethyl, Propyl, isopropyl, Butyl, isobutyl, sec-butyl, tert-butyl, Pentyl, cyclopentyl, isopentyl, neopentyl, hexyl, cyclohexyl, 1-, 2-, and 3-methylbutyl, 1,1-, 1,2-, or 2,2-dimethylpropyl, 1-ethyl-propyl, 1-, 2-, 3-, or 4-methylpentyl, 1,1-, 1,2-, 1,3-, 2,2-, 2,3-, or 3,3-dimethylbutyl, 1- or 2-ethylbutyl, 1-ethyl-1-methylpropyl, and 1,1,2- or 1,2,2-trimethylpropyl; heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3,4-dimethylpentyl, 4,4-dimethylpentyl, cycloheptyl, 1-methylcyclohexyl, and 2-methylcyclohexyl; octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 3,3-dimethylhexyl, 3,4-dimethylhexyl, 3-ethyl-2-methylpentyl, 3-ethyl-3-methylpentyl, 2,2,3-trimethylpentyl, 2,2,4-trimethylpentyl, 2,3,3-trimethylpentyl, 2,3,4-trimethylpentyl, and 2,2,3,3-tetramethylbutyl; Includes, but is not limited to, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyloxy.

[0035] -R 1 , -R 2 , -R 3 , -R 4 , -R 5 , -R 8 , and -R 9 Exemplary alkylaryl groups, of which one or more can be, can be alkylaryl groups having a number of carbon atoms ranging from 7 to 18 or 7 to 12, such as phenmethyl, phenethyl, phenpropyl, phenisopropyl, phenbutyl, phenisobutyl, phen-sec-butylene, phen-tert-butylene, phen-pentylene, and hexylene.

[0036] -R 1 , -R 2 , -R 3 , -R 4 , -R 5 , -R 8 , and -R 9 Exemplary arylalkyl groups, which may be one or more of, may be arylalkyl groups having a number of carbon atoms ranging from 7 to 18 or 7 to 12, such as methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, and octylphenyl.

[0037] In embodiments, R 6 and R 7 In one or both of the formulas, the one or more hydroxyl and / or ether groups are separated from the N atom by more than one carbon atom, preferably by two carbon atoms.

[0038] In embodiments, R 6 and R 7 One or both of R contains one or more oxygen atoms in the form of one or more hydroxyl groups. 6 and R 7 Either or both of the -(CR 10 2 ) q (CHOH)(CH 2 ) z R 11 The formula is R 10 is independently selected from -H and alkyl, q and z are independently (-) (a covalent bond) or an integer ranging from 1 to 12, R 11 is selected from the group consisting of C1 to C24 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl. Preferably, q and z are independently (-), 1, or 2. Even more preferably, R 10 is -H, q is 1, z is (-), and R 11 is selected from C1 to C18 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl groups. Exemplary alkyl, alkyl-aryl, and aryl-alkyl groups are described herein. -(CR 10 2 ) q (CHOH)(CH 2 ) z R 11 Exemplary species of the formula include the following groups: [ka]

[0039] In embodiments, R6 and R 7 One or both of R contains two or more oxygen atoms, at least one in the form of a hydroxyl group and at least one in the form of an ether group. 6 and R 7 Either or both of the -(CR 10 2 ) q (CHOH)(R 12 O) z R 11 is of the formula R 10 is independently selected from -H and alkyl, q is (-) (a covalent bond) or an integer ranging from 1 to 12, and R 11 is selected from C1 to C24 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl groups; R 12 is -(CH 2 ) w -, w is 1, 2, or 3, z is an integer ranging from 1 to 100, 1 to 50, 1 to 25, 1 to 15, 1-10, 1-5, or t is 2, 3, or 4. 10 is -H, q is 1, z is 1, w is 1 or 2, and R 11 is a C1-C18 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl. Exemplary alkyl, alkyl-aryl, and aryl-alkyl groups are described herein.

[0040] (CR 10 2 ) q (CHOH)(R 12 O) z R 11 Exemplary species of the formula include the following groups: [ka]

[0041] Preferred compounds of formula I include -R 1 , -R2 , -R 3 , -R 4 , and -R 5 one or more of -R 1 , -R 2 , -R 3 , -R 4 , and R 5 For example, some preferred compounds of the present disclosure have the following sub-formula Ia, where R 6 and R 7 has the meaning described herein. [ka]

[0042] R 6 and R 7 Both are -(CR 10 2 ) q (CHOH)(CH 2 ) z R 11Exemplary compounds of sub-formula Ia, which are of the formula: , 4-bis[(2-hydroxytridecyl)amino]phenol, 4-bis[(2-hydroxytetradecyl)amino]phenol, 4-bis[(2-hydroxypentadecyl)amino]phenol, 4-bis[(2-hydroxyhexadecyl)amino]phenol, 4-bis[(2-hydroxyheptadecyl)amino]phenol, 4-bis[(2-hydroxyoctadecyl)amino]phenol, 4-bis[(2-hydroxyeleyl)amino]phenol, 4-bis[(2-hydroxynonadecyl)amino]phenol, 4-bis[(2-hydroxyeicosyl)amino]phenol, 4-bis[(2-hydroxyheneicosyl)amino]phenol, 4-bis[(2-hydroxydocosyl)amino]phenol, and 4-bis[(2-hydroxytricosyl)amino]phenol.

[0043] R 6 and R 7 Both are -(CR 10 2 ) q (CHOH)(R 12 O) z R 11Other exemplary compounds of sub-formula Ia are of the formula: 4-bis[(3-methoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-ethoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-propoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-butoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-pentyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-hexyloxy-2-hydroxy-propyl)amino]phenol, amino]phenol, 4-bis[(3-heptyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-octyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-nonyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-decyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-undecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-dodecyloxy-2-hydroxy-propyl)amino]phenol , 4-bis[(3-tridecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-tetradecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-pentadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-hexadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-heptadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-octadecyloxy-2-hydroxy-propyl)amino]phenol phenol, 4-bis[(3-eleyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-nonadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-eicosyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-heneicosyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-docosyloxy-2-hydroxy-propyl)amino]phenol,and 4-bis[(3-tricosyloxy-2-hydroxypropyl)amino]phenol.

[0044] Other preferred compounds of formula I include -R 1 , -R 2 , -R 3 , -R 4 , and -R 5 One or more of -NR 8 R 9 and R 8 and R 9 is -H, alkyl, aryl, alkylaryl, and arylalkyl, as well as R as described herein; 6 / R 7 and -NR 8 R 9 Not -R 1 , -R 2 , -R 3 , -R 4 , and -R 5 For example, some preferred compounds of the present disclosure include those in which R 6 , R 7 , and R 9 or the following sub-formula Ib, 6 and R 7 has the following sub-formula Ic, which has the meaning described herein: [ka] R 6 and R7 are both -(CR 10 2 ) q (CHOH)(R 12 O) z R 11Exemplary compounds of sub-formula Ic include 1-bis[3-methoxy-2-hydroxy-ethylamino]-4-phenylaminobenzene, 1-bis[3-ethoxy-2-hydroxy-propylamino]-4-phenylaminobenzene, 1-bis[3-propoxy-2-hydroxy-propylamino]-4-phenylaminobenzene, 1-bis[3-butoxy-2-hydroxy-propylamino]-4-phenylaminobenzene, 1-bis[3-pentyloxy-2-hydroxy-propylamino]-4-phenylaminobenzene, 1-bis[3-pentyloxy-2-hydroxy-propylamino]-4-phenylaminobenzene, 1-bis[3-pentyloxy-2-hydroxy-propylamino]-4-phenylaminobenzene, 1-bis[3-pentyloxy-2-hydroxy-propylamino]-4-phenylaminobenzene, 1-bis[3-but ...butoxy-2-hydroxy-propylamino]-4-phenylaminobenzene, 1-bis[3-pentyloxy-2-hydroxy-propylamino]-4-phenylaminobenzene, 1-bis[3-butoxy 1-bis[3-hexyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-octyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-nonyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-undecyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-dodecyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-tridecyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-tetradecyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-pentadecyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-hexadecyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-heptadecyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-octadecyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-eleyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-nonadecyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-eicosyloxy-2-hydroxypropylamino]-4-phenylaminobenzene, 1-bis[3-heneicosyloxy-2-hydroxypropylamino]-4-phenylaminobenzene,These include, but are not limited to, 1-bis[3-docosyloxy-2-hydroxy-propylamino]-4-phenylaminobenzene and 1-bis[3-tricosyloxy-2-hydroxy-propylamino]-4-phenylaminobenzene.

[0045] Other preferred compounds of formula I include -R 1 , -R 2 , -R 3 , -R 4 , and -R 5 One or more of -NR 6 R 7 and -NR 6 R 7 Not -R 1 , -R 2 , -R 3 , -R 4 , and R 5 For example, some preferred compounds of the present disclosure have the following sub-formulae Id and Ie, where R 6 and / or R 7 has the meaning described herein. [ka]

[0046] R 7 But -(CR 10 2 ) q (CHOH)(R 12 O) z R 11Exemplary compounds of sub-formula Ie, which are of the formula: 1,4-bis[3-methoxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-ethoxy-2-hydroxy-ethylamino]benzene, 1,4-bis[3-propoxy-2-hydroxy-propylamino]benzene, 4-bis[3-butoxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-pentyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-hexyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-heptyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-octyloxy-2-hydroxypropylamino]benzene, 1,4-bis[3-nonyloxy-2-hydroxypropylamino]benzene, 1,4-bis[3-decyloxy-2-hydroxypropylamino]benzene, 1,4-bis[3-undecyloxy-2-hydroxypropylamino]benzene, 1,4-bis[3-dodecyloxy-2-hydroxypropylamino]benzene, 1,4-bis[3-tri ... 1,4-bis[3-tetradecyloxy-2-hydroxypropylamino]benzene, 1,4-bis[3-pentadecyloxy-2-hydroxypropylamino]benzene, 1,4-bis[3-hexadecyloxy-2-hydroxypropylamino]benzene, 1,4-bis[(3-heptadecyloxy-2-hydroxypropylamino]benzene, 1,4-bis[3-octadecyloxy-2-hydroxypropylamino]benzene, 1,4-bis[3-eleyloxy-2-hydroxypropylamino]benzene , 1,4-bis[3-nonadecyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-eicosyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-heneicosyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-docosyloxy-2-hydroxy-propylamino]benzene, and 1,4-bis[3-tricosyloxy-2-hydroxy-propylamino]benzene.

[0047] Aromatic compounds of the present disclosure that can be used to synthesize antioxidant compounds of the present disclosure include the aminophenol and diaminobenzene compounds described herein and can be prepared using the methods of the present disclosure. In some implementations, and as a general matter, an aryl group-containing reactant having either (a) a primary amine and hydroxyl group, such as 4-aminophenol, (b) two primary amine groups, such as 1,4-diaminobenzene (p-phenylenediamine), (c) a primary and secondary amine group, such as phenylphenylenediamine, or (d) a primary and tertiary amine group, such as dimethyl-4-phenylenediamine, is reacted with a carbon- and oxygen-containing reactant capable of reacting with the primary (and optionally secondary) amine group to provide a product such as those described herein. The carbon- and oxygen-containing reactant, upon reaction with the amine group, forms a product R 6 and / or R 7 These can provide one or both of the groups -(CR 10 2 ) q (CHOH)(CH 2 ) z R 11 , or (CR 10 2 ) q (CHOH)(R 12 O) z R 11 It may be of the formula:

[0048] In some implementations, the reactants include oxirane or oxytane groups as amine reactive groups. The oxirane and oxytane containing reactants can include the desired carbon chemistry and can also include additional oxygen atoms, such as in the form of ether groups. An exemplary oxirane containing reactant is a glycidyl ether, such as an alkyl glycidyl ether.

[0049] In some embodiments, the oxirane-containing reactant is of formula II: [ka] In the formula, R 13 is -(CH 2 )- or -(CH 2 CH 2 )- and R 14 is -(CH 2 ) w -, w is an integer ranging from 1 to 3, t is an integer ranging from 1 to 100, 1 to 50, 1 to 25, 1 to 15, 1 to 10, 1 to 5, or t is 2, 3, or 4; R 15 is, as described herein, R optionally substituted with one or more hydroxyl groups; 10 It is.

[0050] Nitrogen- and oxygen-containing aromatic compounds that can be used as antioxidants are also described in commonly assigned U.S. provisional patent application entitled "Polyhydroxyaminophenol Compounds and Methods for Preventing Monomer Polymerization," having docket number N11244USP1 (ECO0169 / P1) and filed concurrently with this application.

[0051] In the preparation mode, the aminophenol or diaminobenzene compound described herein can be reacted with a carbon- and oxygen-containing reactant, such as a glycidyl ether, in a desired molar ratio. This ratio can be an equimolar ratio, or a molar ratio in which the carbon- and oxygen-containing reactant is greater than the aminophenol or diaminobenzene compound. In an exemplary implementation mode, the carbon- and oxygen-containing reactant is reacted in about 2 molar excess relative to the aminophenol or diaminobenzene compound.

[0052] In some implementations, the aryl group-containing reactant and the carbon- and oxygen-containing reactant (e.g., oxirane or oxytane-containing reactant) are reacted at a temperature where one or both reactants are in the liquid phase. In some implementations, the oxirane / oxytane-containing reactant is in the liquid phase at the desired reaction temperature, which solvates the aryl group-containing reactant. In this regard, the aryl group-containing reactant can have a higher melting point than the carbon- and oxygen-containing reactant. In embodiments where the reactants are melted and / or solvated at the desired reaction temperature, any other components, such as organic solvents, typically used in the reaction scheme can be optional and not required. Thus, organic solvents can be omitted from the reaction method. Additionally, components such as catalysts can also be optional and therefore not required. In some implementations, the synthesis method does not include the use of (a) an organic solvent, (b) a catalyst, or both (a) and (b).

[0053] Exemplary reaction temperatures can range from about room temperature (about 25°C) to about 250°C, from about 40°C to about 200°C, or from about 50°C to about 175°C.

[0054] Alternatively, aryl-group-containing and carbon- and oxygen-containing reactants can be reacted in organic solvents such as alcohols, such as methanol, butyl carbitol, and butyl glycol, at elevated temperatures (eg, >100° C.) under reflux.

[0055] The composition comprising the oxygenated aromatic amine and any one or more optional components may be in any desired form, such as liquid form, dry form, or as a suspension or dispersion. The oxygenated aromatic amine may be in any desired physical state in the composition, such as dissolved, partially dissolved, suspended, or dry mixture. The oxygenated aromatic amine may optionally be in particulate form in the composition. If the oxygenated aromatic amine is in particulate form, the particles may optionally be described in terms of particle size (e.g., particle size range) and / or shape. The form of the composition and the state of the components therein may be selected by the selection of the oxygenated aromatic amine, with an understanding of its physical properties.

[0056] The form of the composition and the state of the ingredients therein can also be affected by the inclusion of one or more optional ingredients, such as a solvent, or solvent mixture, or other excipient compounds different from the oxygenated aromatic amine. The form of the composition and the state of the ingredients therein can also be affected by temperature, and the properties of the composition can optionally be described as being contextual at a particular temperature (e.g., at a storage temperature such as below 5°C, at room temperature (25°C), or at a temperature used for the desired application).

[0057] As stated, the oxygenated aromatic amine-containing composition may include other ingredients such as solvents, surfactants, dispersants, etc. When optional ingredients are present in the composition, they may be described in terms of weight relative to the oxygenated aromatic amine. The optional ingredients may be present in greater, about the same amount, or less by weight than the oxygenated aromatic amine.

[0058] As used herein, the term "optionally" or "optionally" means that the subsequently described thing (e.g., compound), event (e.g., processing step), or circumstance may occur, but need not occur, and that the description includes cases where the thing, event, or circumstance occurs as well as cases where it does not occur.

[0059] The compositions of the present disclosure may include those recited compounds, and may optionally include other components in the composition, but in very small amounts (e.g., described with respect to a composition "consisting essentially" of the recited components). For example, such compositions may include one or more other components, but not in an amount greater than about 1% (wt), greater than about 0.5% (wt), greater than about 0.1% (wt), or greater than about 0.01% (wt) of the total composition. A composition consisting essentially of a solid component (e.g., dissolved in a solvent) that is an oxygenated aromatic amine may optionally include one or more other (e.g., solid) components, but in an amount less than about 1% (wt) of the total composition weight. In a composition "consisting" of the recited components, there are no other measurable amounts of components other than the recited components. In some embodiments, the oxygenated aromatic amine may optionally be present in an amount less than 1% (wt), less than 0.5% (wt), less than 0.1% (wt), or less than 0.01% (wt) of the total composition.

[0060] As used herein, the terms "substantially" and "consist essentially of" modifying the type or amount, property, measurable amount, manner, location, value, or range of a component in a composition, for example, when describing an embodiment of the present disclosure, refer to variations that do not affect the generally recited composition, property, amount, manner, location, value, or range in a manner that invalidates the intended composition, property, amount, manner, location, value, or range. Examples of intended properties include, by way of non-limiting examples only, dispersibility, stability, speed, solubility, and the like, and intended values ​​include weight of added component, concentration of added component, and the like. Effects on the modified method include effects caused by variations in the type or amount of materials used in the process, variations in machine settings, effects of ambient conditions on the process, and the like, where the manner or degree of the effect does not invalidate one or more intended properties or results, and similar approximation considerations. When modified by the terms "substantially" or "consist essentially of," the claims appended hereto include equivalents of these types and amounts of materials.

[0061] As used herein, the term "about" to modify amounts, concentrations, volumes, process temperatures, process times, yields, flow rates, pressures, and similar values ​​and ranges of components in compositions, for example, used in describing embodiments of the present disclosure, refers to variations in numerical quantities that may occur, for example, due to typical measuring and handling procedures used to make compounds, compositions, concentrates, or use formulations; due to accidental errors in these procedures; due to differences in manufacture, source, or purity of starting materials or components used to carry out the methods, and due to similar approximation considerations. The term "about" also encompasses amounts that differ due to degradation of formulations having a particular initial concentration or mixture, and amounts that differ due to mixing or processing formulations having a particular initial concentration or mixture. When modified by the term "about", the appended claims include equivalents of these amounts. Furthermore, when "about" is used to describe any range of values, unless otherwise limited by the context, for example, the statement "about 1 to 5" means "1 to 5" and "about 1 to about 5" and "1 to about 5" and "about 1 to 5".

[0062] The amounts of the oxygenated aromatic amine and any other (optional) components in the composition can be described in a variety of ways, such as the weight percent (wt%) or molar amount of the oxygenated aromatic amine in the composition. When other components are used together with the oxygenated aromatic amine, such compounds can also be described in terms of their weight ratio in the composition or in terms of their relative amounts relative to each other.

[0063] The oxygenated aromatic amine can be present in a composition that includes a solvent or a combination of solvents. The solvent or combination of solvents can be selected such that the oxygenated aromatic amine is soluble in the solvent or combination of solvents. If the nitrogen- and oxygen-containing aromatic polymerization inhibitor is a liquid at ambient conditions, a miscible solvent can be selected.

[0064] Useful solvents include any solvent in which the oxygenated aromatic amine is soluble or can be stably suspended in. In some embodiments, the solvent or combination of solvents can be selected from water-soluble or water-miscible solvents, such as glycol-based solvents, as well as hydrophobic or hydrocarbon solvents, such as aromatic solvents, paraffinic solvents, or a mixture of both.

[0065] Exemplary glycol solvents are C 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 13 1 -C 8 Examples of suitable solvents include, but are not limited to, glycol, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycols, ethers of such glycols such as dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and low molecular weight polypropylene glycols, and combinations thereof. Commercially available solvents such as Butyl Carbitol and Butyl CELLOSOLVE™, which primarily comprise Butyl CARBITOL™, which primarily consists of ethylene glycol monobutyl ether, can be used and are available from DOW.

[0066] Other exemplary hydrophobic or hydrocarbon solvents include heavy aromatic naphtha, toluene, ethylbenzene, the isomeric hexanes, benzene, xylenes, such as ortho-xylene, para-xylene, or meta-xylene, and mixtures of two or more thereof.

[0067] In some embodiments, the solvent is selected from glycols and aromatic naphtha, and combinations thereof.

[0068] The amount of oxygenated aromatic amine in a solvent or combination of solvents (including one or more optional components) can be described in one or more ways, such as by the percent solids (by weight) of the component in the composition, or the molar amount of the solid component in the composition.

[0069] As an example, a stock composition of oxygenated aromatic amines can be dissolved in a solvent to a concentration of at least about 0.00001% (by weight), at least about 5% (by weight), such as an amount ranging from about 0.00001% (by weight) to about 50% (by weight).

[0070] In some implementations, the oxygenated aromatic amines of the present disclosure can be used as antioxidants.The oxygenated aromatic amine antioxidants of the present disclosure can be used to retard the oxidation of organic materials in compositions.Oxidation is a chemical reaction that can generate free radicals, thereby causing reactions that can form undesirable products in compositions or change the properties of compositions in undesirable materials.

[0071] In some implementations, the oxygenated aromatic amine acts as an antioxidant to prevent fouling of compositions containing organic compounds. The term "fouling" refers to the formation of polymers, prepolymers, oligomers, and / or other materials that become insoluble in the stream and / or precipitate from the stream and deposit on the equipment under the conditions under which the equipment is operated. The oxygenated aromatic amine can then be called an "antifoulant" since it prevents or reduces such formation.

[0072] The oxygenated aromatic amine antioxidants may be used in combination with compositions containing organic compounds and "process equipment" associated with the process, such as reactors, reactor beds, pipes, valves, distillation columns, trays, condensers, heat exchangers, compressors, fans, impellers, pumps, recirculators, intercoolers, sensors, etc. that may be subject to fouling due to oxidation of the organic components therein. The term also includes sets of these components where multiple components are part of a "system."

[0073] In some implementations, the disclosed compositions comprising aromatic polymerization inhibitors containing nitrogen and oxygen and solvents (e.g., glycols) are used in processes involving distillation columns used to separate and purify organic compounds such as vinyl monomers. For example, in processes known in the art, ethylbenzene can be subjected to catalytic dehydrogenation reactions resulting in the formation of styrene. The reaction products containing styrene also include other materials such as aromatic compounds such as toluene and benzene, unreacted ethylbenzene, and polymers. This mixture of compounds is typically fractionated using one or more distillation columns. Typically, heat is used to help separate the components in the distillation column. After distillation, the fractionated components can be separated into pure product streams of higher purity. Optionally, the oxygenated aromatic amine antioxidant is used with one or more secondary components such as stabilizers such as butylated hydroxytoluene (BHT) and tert-butylcatechol (TBC). In an exemplary embodiment of the implementation, these components are used in the distillation columns used to separate and purify vinyl monomers.

[0074] The oxygenated aromatic amine-containing composition can be introduced into the stream leading from the reaction bed to the distillation column or added directly to the distillation column. The composition can be added before heating the monomer composition or while heating the monomer composition in the distillation column. In an embodiment, the oxygenated aromatic amine has a boiling point higher than that of the desired compound or distillate (e.g., monomers such as styrene) that is fed to the distillation column, and during the distillation process, the desired compound is separated from the oxygenated aromatic amine compound due to the temperature difference. In an embodiment, the boiling point difference between the desired compound and the oxygenated aromatic amine is about 10°C or more, about 15°C or more, about 20°C or more, about 25°C or more, about 30°C or more, about 35°C or more, about 40°C or more, about 45°C or more, or about 50°C or more.

[0075] Alternatively, or in addition to adding the oxygenated aromatic amine during the distillation process, the composition can optionally, or additionally, be added to a distillation effluent stream, such as a refined styrene stream. Optionally, another antioxidant can be added to the distillation effluent stream before or together with the oxygenated aromatic amine antioxidant.

[0076] The oxygenated aromatic amines, optionally used in combination with one or more other components, can be used with any "hydrocarbon process stream" that may contain unsaturated monomers to stabilize the stream during transportation and storage. In some implementations, the oxygenated aromatic amines can be used in combination with "petroleum products," which refers to any hydrocarbon product obtained from an underground reservoir, any product derived therefrom, or any mixture thereof. The polymerizable monomers can be contained in or chemically derived from a petroleum product. Non-limiting examples of petroleum products include, but are not limited to, crude oil, reduced crude oil, crude distillates, heavy oil, or by-products of petroleum product processing, such as bitumen, hydrotreated oil, refined oil, pyrolysis, hydrotreating, or phase separation, or mixtures of two or more thereof. A liquid petroleum product is a petroleum product that is substantially liquid at 20°C.

[0077] The oxygenated aromatic amines may be added to or present in a "petroleum process stream," which refers to any petroleum product located within and in fluid contact with the interior surfaces of petroleum process equipment.

[0078] Petroleum process streams may contain or be capable of forming compounds that are oxidized to undesirable materials as by-products. Process streams may be substantially static, such as petroleum products placed in a settler (separator) or storage vessel for a selected contact period, such as up to two years. Process streams may be substantially dynamic, such as liquid petroleum products placed in a pipe during transportation of the product from a first location to a second location. In some embodiments, the process stream includes one or more additional components associated with petroleum processing, such components are not particularly limited.

[0079] "Petroleum processing equipment" or "petroleum processing unit" refers to a man-made object having an inner surface that includes metal and that further comprises one or more petroleum products, for any period of time and at any temperature, as determined by context. Petroleum processing equipment includes items for removing petroleum products from underground reservoirs, for transporting one or more petroleum products from a first location to a second location, or for separating, refining, treating, separating, distilling, reacting, metering, heating, cooling, or containing one or more petroleum products.

[0080] In embodiments, compositions including oxygenated aromatic amines are thermally stable and have antioxidant activity during stream processing at temperatures between about 20° C. and about 400° C., e.g., between about 100° C. and 400° C., or between about 100° C. and 350° C., or between about 100° C. and 300° C., or between about 100° C. and 250° C., or between about 100° C. and 200° C., or between about 100° C. and 150° C.

[0081] In embodiments, the composition comprising the oxygenated aromatic amine can be introduced into a composition comprising an organic compound, such as a liquid petroleum process stream, in a batch, continuous, or semi-continuous manner. In some embodiments, the oxygenated aromatic amine (and any other optional components) are introduced manually, while in other embodiments, their introduction is automated. In embodiments, the amount of oxygenated aromatic amine introduced over a selected unit of time varies with the variable composition of the associated process stream. Such variability in feed can be implemented manually by periodically testing the internal surfaces of the process equipment, after adjusting the amount of composition up or down based on test results, or automatically, after monitoring one or more conditions inside the petroleum process equipment and signaling the need to apply more composition to the process stream.

[0082] In some embodiments, the oxygenated aromatic amine antioxidant is added to a petroleum product that is crude oil, reduced crude oil, heavy oil, bitumen, coker charge, hydrotreater influent, hydrotreater effluent, flash crude oil, light cycle oil, or diesel or naphtha refinery stream. Thus, the antioxidant can be used to treat refinery reactant streams that are susceptible to oxidation. In embodiments, the oxygenated aromatic amine is added to petroleum process equipment traditionally associated with the gathering, processing, transporting, or storing of one or more of crude oil, reduced crude oil, crude distillate, heavy oil, bitumen, coker charge, flash crude oil, light cycle oil, or diesel or naphtha refinery stream, including pipes and related infrastructure used to fluidly connect process equipment items together to facilitate the processing of process streams located therein. The antioxidant can be added to naphtha products as more specifically described herein.

[0083] The antioxidants can be used to treat reactive naphtha products having various levels of reactivity. The level of reactivity in naphtha products may vary due to different levels of unsaturation in the products. Naphtha products obtained from different refineries may exhibit different levels of reactivity, and such reactivity can be determined using the bromine test.

[0084] Equipment treated with oxygenated aromatic amines and any other optional components can reduce or eliminate fouling on the interior surfaces of the equipment. In an embodiment, fouling is measured as a relative increase in the retention of solids in the treated composition compared to the retention of solids in the untreated composition over the same period. In an embodiment, fouling is measured as a relative reduction in the weight or volume of sediment resulting from a selected contact period of the treated process stream in the relevant process equipment item compared to the same contact period of the process equipment with the corresponding untreated process stream. In other words, the reduction in fouling is the relative reduction in the measured weight or volume of solids deposited or precipitated from the process equipment contacted with the treated process stream over a selected period of time when compared to the weight or volume of solids deposited or precipitated from the untreated process stream over the same period of time.

[0085] The oxygenated aromatic amines can also inhibit undesirable fouling of process equipment in primary fractionation processes, light ends fractionation, non-aromatic vinyl halide fractionation and stabilization, process gas compression, dilution steam systems, caustic towers, quench towers, quench water separators (cracked gasoline), butadiene extraction, propane dehydrogenation, diesel and gasoline fuel stabilization, olefin metathesis, styrene refining, hydroxyhydrocarbon refining, stabilization of compositions during transportation and storage.

[0086] The oxygenated aromatic amine can be added at any point in the process, in one or more locations. For example, the polymerization inhibitor composition can be added directly to the interstage cooler or compressor, or upstream of the intercooler or compressor. The oxygenated aromatic amine can be added continuously or intermittently to process equipment as needed to prevent or reduce fouling.

[0087] The oxygenated aromatic amine can be introduced into the desired system by any suitable method. For example, it may be added neat or in a dilute solution. In some embodiments, the composition containing the oxygenated aromatic amine may be applied as a solution, emulsion, or dispersion that is sprayed, dripped, dumped, or injected into the desired opening in the system, or into the process equipment or process condensate. In some embodiments, the composition may be added with a cleaning oil or tempered water.

[0088] After introducing the oxygenated aromatic amine into the process equipment, the treated process equipment may be observed to have less buildup on the equipment than process equipment without the addition of the composition. Reduction or prevention of buildup may be evaluated by any known method or test. In some embodiments, reduction or prevention of buildup may be accessed by measuring the time it takes for samples to gel with and without the antifoulant composition.

[0089] In other embodiments, the oxygenated aromatic amine antioxidants of the present disclosure are added to fuels or lubricants. The antioxidants can inhibit the oxidation of organic components in the fuel or lubricant, thereby preventing the formation of undesirable components that can lead to poor performance, malfunction, or damage to equipment, such as engines, that uses the fuel or lubricant. In some implementations, the oxygenated aromatic amine antioxidants can be used in conveyor lubricants to facilitate the operation of stainless steel or plastic conveyor belts.

[0090] The oxygenated aromatic amine antioxidants of the present disclosure can be added to low temperature oils, jet fuels, and gasolines including aviation gasoline, turbine oils, transformer oils, hydraulic fluids, waxes, and industrial greases in industrial applications.

[0091] The antioxidants of the present disclosure can improve gasoline-based fuels that are stored for long periods of time, which would otherwise deteriorate due to polymerization and oxidation reactions of the gasoline composition. The process of gasoline-based fuel decomposition can be complicated due to the various hydrocarbons present in the composition. For example, the antioxidants of the present disclosure can prevent gum formation and color darkening in the darkening of gasoline compositions when stored for long periods of time.

[0092] Compounds with unsaturation, such as olefins and dienes, are susceptible to oxidation and polymerization in the presence of oxygen. These unsaturated compounds may arise in fuel compositions by blending hydrocarbon streams from secondary refining operations and thermal processes. Other non-organic contaminants in the hydrocarbon composition, such as copper, may promote the formation of peroxides in the composition and cause polymerization reactions. Copper contamination can occur when the hydrocarbon composition comes into contact with equipment used to transport, store, or refine the hydrocarbon material. Copper may also be introduced into refinery chemicals used in refineries and vehicle fuel systems.

[0093] The oxygenated aromatic amine antioxidants can be used in gasoline fuels containing cracked components obtained from various secondary processing operations such as fluid catalytic cracking (FCC), VB, and coker. The antioxidants of the present disclosure can improve fuel properties by preventing oxidation, preventing deposit formation, corrosion inhibition, and increasing water uptake.

[0094] The oxygenated aromatic amine antioxidants can be added to gasoline compositions, such as those derived from petroleum, that contain primarily hydrocarbons. A typical use is in gasoline as a fuel for internal combustion engines.

[0095] Gasoline hydrocarbons typically have 5-12 carbon atoms and typically have higher octane levels. Octane numbers of about 85% or more, about 86% or more, about 87% or more, about 88% or more, about 89% or more, about 90% or more, about 91% or more, about 92% or more, or about 93% or more are common commercial preparations. The octane number of gasoline is typically measured by running a fuel sample through a specific test engine with a variable compression ratio under controlled conditions against a mixture of isooctane (i.e., 2,2,4-trimethylpentane) and n-heptane. For example, 93-octane gasoline typically has the same octane number as a mixture of 93% (v / v) isooctane and 7% (v / v) n-heptane. A typical gasoline may contain a mixture of paraffins, naphthenes, aromatics, and olefins.

[0096] The oxygenated aromatic amine antioxidants can be added to gasoline blends, such as blends of gasoline and ethanol. In ethanol blends, the ethanol can be present in the gasoline-ethanol blend in any desired amount ranging from 0.1% (volume) to 99% (volume). More specific ethanol-gasoline blends can have 1-5% (volume) ethanol, 5-10% (volume) ethanol, 10-15% (volume) ethanol, 15-20% (volume) ethanol, 20-25% (volume) ethanol, 25-30% (volume) ethanol, 30-40% (volume) ethanol, 40-50% (volume) ethanol, 50-60% (volume) ethanol, 60-70% (volume) ethanol, 70-80% (volume) ethanol, 80-90% (volume) ethanol, or 90-99% (volume) ethanol, with the remainder being gasoline.

[0097] The antioxidant of the present disclosure can be used with pyrolysis gasoline (Pygas) or pyrolysis gasoline products. Pyrolysis gasoline is a naphtha-based product with a high octane mixture and contains olefins, paraffins, and aromatics. Pyrolysis gasoline can be produced as a by-product of high temperature naphtha cracking in the process of producing ethylene and propylene. The antioxidant can be used with pure pyrolysis gasoline, or the antioxidant can be added to blends containing other hydrocarbon preparations or pyrolysis gasoline blends such as ethanol. The antioxidant of the present disclosure can be added to distilled pyrolysis gasoline products, such as those distilled using the BTX process to separate pyrolysis gasoline into its components, including benzene.

[0098] The antioxidants of the present disclosure can be introduced into the gasoline product at any suitable location. For example, for addition to pyrolysis gasoline, which is typically treated in a hydrotreater before being blended with other gasoline to form motor gasoline, the mixed antioxidants can be introduced into the gasoline upstream or downstream of the hydrotreater, such as before the pyrolysis gasoline is blended with other gasoline.

[0099] The antioxidants can be used in the gasoline product at any desired concentration. Exemplary amounts of the oxygenated aromatic amine antioxidant in the gasoline product range from about 1 ppm to about 5000 ppm, about 2.5 ppm to about 2500 ppm, about 5 ppm to about 1500 ppm, about 7.5 ppm to about 1250 ppm, about 10 ppm to about 1000 ppm, about 50 ppm to about 1000 ppm, about 100 ppm to about 1000 ppm, about 250 ppm to about 1000 ppm, about 50 ppm to about 750 ppm, about 100 ppm to about 500 ppm, or about 250 ppm to about 500 ppm.

[0100] The oxygenated aromatic amine antioxidant can be used as the sole antioxidant for treating a composition having an organic compound, or can be used as an antioxidant together with one or more other antioxidants in the treatment composition. For example, the oxygenated aromatic amine antioxidant can be the primary antioxidant in the treatment composition, such as greater than 50% (by weight), about 60% (by weight) or more, about 70% (by weight) or more, about 80% (by weight) or more, about 90% (by weight) or more, about 95% (by weight) or more, about 99% (by weight) or more of the antioxidant in the treatment composition.

[0101] The oxygenated aromatic amine antioxidant, or mixture of antioxidants, can be used in neat form or in a solvent, such as an aromatic solvent.

[0102] The addition of the antioxidants of the present disclosure can provide gasoline products with increased oxidative stability and reduce gum formation.

[0103] The test to determine antioxidant efficacy is the induction period test according to ASTM D-525 / IP:40, in which a measured amount of fuel (50 mL) is oxidized under specified conditions in a container containing gasoline and antioxidant. The test begins at the desired temperature, such as in the range of 95-150°C, with the desired feed rate (depending on reactivity), and with oxygen at a pressure of approximately 100 psi. Pressure is read at specified intervals or recorded continuously until a pause is reached. The time required for the sample to reach this point is observed and reported as the induction period.

[0104] Other tests can be used to evaluate the quality of fuels treated with the antioxidants of the present disclosure. Another test measures the presence of gums present in a fuel composition. For example, ASTM D-381 / IP:131,2 takes a volume of fuel (50 mL) and evaporates it under controlled conditions of temperature and air flow. The resulting residue is weighed and the gm / m 3 This test can be run to understand the amount of gum already present in a gasoline sample and can be factored into an accelerated aging test.

[0105] Another test is the ambient aging test. A standard ambient aging test is conducted for a period of three months. For example, in such a test, 400 mL samples of gasoline containing antioxidants are stored in triplicate in 500 mL borosilicate glass bottles at ambient temperature for three months. At the end of one month, two months, and three months, one set is subjected to the actual gum test according to ASTM D-381, and the results are reported in gm / m 3 The fuel color is also recorded upon completion of each month.

[0106] The oxygenated aromatic amine antioxidants may be tested with a desired selection of components, under selected conditions such as time and temperature, and using a selected gasoline composition.

[0107] Oxygenated aromatic amine antioxidants can be tested for their ability to affect the water resistance properties of gasoline, or to modify the properties of the fuel to prevent rusting of ferrous parts when the fuel comes into contact with water.

[0108] For example, in fats and oils, antioxidants delay the onset of oxidation or slow down the rate of oxidation reactions.Fats and oils generally spoil because the oxidation of lipids leads to the production of compounds that cause different odors and tastes and continue to affect other molecules in food.These foods spoil due to exposure to oxygen and sunlight, which leads to oxidation of the food.Therefore, the oxygenated aromatic amine antioxidants of the present disclosure can be added to food products to inhibit the oxidation of one or more components of the food products.

[0109] Exemplary food products that can contain the oxygenated aromatic amine antioxidants of the present disclosure include, but are not limited to, fermented beverages such as wine, and malt-based fermented beverages such as beer and beer-like beverages; foods with high protein and / or fat content, such as dairy products like milk, yogurt, cheese, ice cream; half-and-half; whipped cream; oil- or fat-based food preparations such as vegetable oils, butter products, spreads, margarines, shortenings, and the like; baked goods such as biscuits, muffins, waffles, pancakes, bread, cookies, and pastries; cereals, cereal-based products; granola; muesli; jams, jellies, marmalades, fruit preserves, fruit-based juices, fruit juice concentrates, fruit-based purees; canned and pureed vegetables; processed meats such as ground beef, ground chicken, ground pork, and sausages; chocolate, candies, and chewing gum.

[0110] Exemplary concentrations of the oxygenated aromatic amine antioxidants of the present disclosure present in the foodstuff range from about 1 ppm to about 500 ppm, or from about 1 ppm to about 50 ppm.

[0111] The oxygenated aromatic amine antioxidants of the present disclosure can also be added to cosmetics and pharmaceuticals.

[0112] In other embodiments, the oxygenated aromatic amine antioxidant of the present disclosure is added to a polymer composition. The polymer composition may be a plastic, rubber, or adhesive composition, etc. The antioxidant of the present disclosure can prevent oxidative damage of the polymer components in the composition, which would otherwise result in the loss of strength and flexibility of the composition. For example, the degradation of the polymer by oxidation can lead to ozonolysis or cracking.

[0113] Polymer compositions that are natural rubber, diene-containing polymers such as polybutadiene, and other rubbers with unsaturation can be seriously damaged by ozone decomposition and therefore can benefit from the inclusion of an oxygenated aromatic amine antioxidant. Other polymers susceptible to oxidation include polypropylene and polyethylene.

[0114] Exemplary concentrations of the oxygenated aromatic amine antioxidants of the present disclosure present in the polymer composition range from about 100 ppm to about 5% (by weight). EXAMPLES

[0115] Example 1:

[0116] Synthesis of 4-aminophenol-butyl glycidyl ether (BGE)

[0117] Butyl glycidyl ether was added to a 250 mL three-neck round bottom flask equipped with a temperature probe, nitrogen inlet, condenser, and magnetic stirrer. 4-aminophenol was then added to the well-stirred reaction mixture. Table 1 also shows the amount and chemical nature of each chemical added. The resulting suspension was heated to 120° C. under a nitrogen blanket and stirred for 8 hours or until the reaction was complete. Once the reaction had proceeded to completion, the suspension was transformed into a homogenous dark amber product. The resulting product was characterized by NMR and ESI-MS. [ka] [Table 1]

[0118] Examples 2 to 13:

[0119] Synthesis of oxygenated aromatic amines

[0120] A variety of oxygenated aromatic amines were produced using different starting amine and epoxide reactants in various molar ratios using a procedure similar to that of Example 1. 4-aminophenol, phenylenediamine, and N-phenyl-phenylenediamine were used as the amine reactants, and 2-ethylhexyl glycide ether and butyl glycide ether were used as the epoxide reactants. The molar ratio of amine to epoxide was varied. [Table 2]

[0121] Advantageously, the synthetic methodology provides a readily customizable approach for preparing oxygenated aromatic amines having the desired oxygen-containing chemistry attached to one or more amine groups of the compound.

[0122] Examples of oxygenated aromatic amines, as provided in Table 2, are designated AO-1 through AO-10 and correlate with Examples 2-6 and 8-10 for AO-1 through AO-8, and were tested for their antioxidant performance as described herein and shown in Figures 1-4. AO-9 and AO-10 were not tested. Comparative antioxidants (CAO-1 through 4) including phenylenediamine (PDA), hindered (tertiary) phenol, and PDA / hindered (tertiary) phenol blends are also shown in Figures 1-4 along with the antioxidants of the present disclosure.

[0123] Example 14

[0124] Antioxidant performance test / Oxidation stability test-Heavy coker naphtha

[0125] Heavy coker naphtha from various refineries was used to demonstrate the effectiveness of the disclosed compounds for stabilizing reactive naphtha samples. Solutions of various oxygenated aromatic amines from Examples 2-13 were prepared in heavy aromatic naphtha and tested according to the ASTM D525 method. The ASTM D525 method is directed to the measurement of the stability of finished gasoline under pro-oxidant conditions. According to this method, naphtha samples are placed in a pressure vessel equipped with a digital pressure gauge along with a candidate oxygenated aromatic amine. The pressure vessel is closed and oxygen is introduced into the vessel through a Schrader-type valve fitting until an overpressure of about 100 psig is reached. The vessel is then heated to about 100° C. in an oil bath or dry bath until a drop in pressure is observed, indicating a loss of antioxidant activity. The time elapsed until a pressure drop is noted is known as the "break point," and longer induction times indicate greater stabilizing efficacy of the candidate treatment. In this example, the oxygenated aromatic amine antioxidant was used at 500 ppm.

[0126] The oxygenated aromatic amine compounds of the present disclosure have demonstrated antioxidant properties that are at least equivalent to, and in many cases superior to, other commercially available antioxidants or antioxidants known in the art (see, e.g., CAO-1-4).

[0127] The results are shown in Figure 1.

[0128] Example 15

[0129] Antioxidant performance test / Oxidation stability test-Heavy coker naphtha

[0130] Effectiveness of the compounds of the present disclosure for stabilizing coker naphtha, solutions of various oxygenated aromatic amines from Examples 2-13 were prepared in heavy aromatic naphtha and tested according to the ASTM D525 method as described in Example 14. In this example, the oxygenated aromatic amine antioxidants were used at 1000 ppm. The results are shown in Figure 2.

[0131] Example 16

[0132] Antioxidant performance test / Oxidation stability test-DCU-1 Coker naphtha

[0133] Effectiveness of compounds of the present disclosure for stabilizing delayed cook unit (DCU-1) coker naphtha, solutions of various oxygenated aromatic amines according to Examples 2-13 were prepared in heavy aromatic naphtha and tested according to ASTM D525 method as described in Example 14. In this example, the oxygenated aromatic amine antioxidants were used at 250 ppm.

[0134] The results are shown in Figure 3.

[0135] Example 17

[0136] Antioxidant performance test / Oxidation stability test-Heavy coker naphtha

[0137] Effectiveness of the compounds of the present disclosure for stabilizing coker naphtha, solutions of various oxygenated aromatic amines according to Examples 2-13 were prepared in heavy aromatic naphtha and tested according to the ASTM D525 method as described in Example 14. In this example, the oxygenated aromatic amine antioxidants were used at 500 ppm.

[0138] The results are shown in Figure 4, which shows the change in pressure over time.

Claims

1. 1. A method for inhibiting oxidation of an organic compound, the method comprising: The method includes adding a compound of formula I to a composition comprising an organic compound, the compound of formula I being: 【Chemistry 1】 In the formula, -R １ , -R ２ , -R ３ , -R ４ , and -R ５ is selected from -H, -OH, alkyl, aryl, alkylaryl, and arylalkyl, and -NR ８ R ９ and R ８ and R ９ is —H, alkyl, aryl, alkylaryl, and arylalkyl, as well as R as described herein. ６ / R ７ or -R １ , -R ２ , -R ３ , -R ４ , and -R ５ any two adjacent groups form one or more ring structures, R ６ and R ７ is a carbon-containing group that contains one or more hydroxyl groups separated from the N atom by one or more carbon atoms; ６ Or R ７ If is not (I), then it is selected from -H, alkyl, aryl, alkylaryl, and arylalkyl; The method, wherein said compound of formula I inhibits oxidation of said organic compounds in said composition.

2. The method of claim 1 , wherein the organic compound comprises an ethylenically unsaturated group.

3. 3. The method of claim 1 or 2, wherein the organic compound is present in a fuel composition or a lubricant composition.

4. The method of claim 3 , wherein the fuel composition comprises a gasoline or a gasoline blend.

5. 5. The method of claim 4, wherein the gasoline or gasoline blend comprises pyrolysis gasoline, a refined product of pyrolysis gasoline, an alcohol such as ethanol, or a combination thereof.

6. The process according to any one of claims 2 to 5, wherein the organic compound containing an ethylenically unsaturated group is an olefin or an alkene.

7. The method of any one of claims 1 to 6, wherein the compound of formula 1 is present in the composition in an amount ranging from 1 ppm to 5000 ppm.

8. 8. The method of claim 7, wherein the compound of formula 1 is present in the composition in an amount ranging from 10 ppm to 2500 ppm.

9. 9. The method of claim 8, wherein the compound of formula 1 is present in the composition in an amount ranging from 50 ppm to 1500 ppm.

10. The method of claim 1 or 2, wherein the organic compound is present in a rubber composition, a plastic composition, or an adhesive composition.

11. The method of claim 1 or 2, wherein the organic compound is present in a food or beverage composition.

12. -R １ , -R ２ , -R ３ , -R ４ , and R ５ At least one of is -OH, preferably -R ３ The method of any one of claims 1 to 11, wherein is -OH.

13. A method according to any one of the preceding claims, wherein the one or more hydroxyl groups are separated from the N atom by more than one carbon atom, preferably by two carbon atoms.

14. R ６ and R ７ One or both of the following is -(CR １０ ２ ) ｑ (CHOH)(CH ２ ) ｚ R １１ and R １０ is independently selected from -H and alkyl, q and z are independently (-) (a covalent bond) or an integer ranging from 1 to 12, preferably (-), 1, or 2; R １１ The method of any one of claims 1 to 13, wherein is selected from the group consisting of C1 to C24 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl.

15. R １０ is -H, q is 1, z is (-), and R １１ The method of claim 14, wherein is a C1 to C18 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl.

16. The compound is 4-bis[(2-hydroxyethyl)amino]phenol, 4-bis[(2-hydroxypropyl)amino]phenol, 4-bis[(2-hydroxybutyl)amino]phenol, 4-bis[(2-hydroxypentyl)amino]phenol, 4-bis[(2-hydroxyhexyl)amino]phenol, 4-bis[(2-hydroxy-2-phenyl)amino]phenol, 4-bis[(2-hydroxy-2-phenylethyl)amino]phenol, 4-bis[(2-hydroxyheptyl)amino]phenol, 4-bis[(2-hydroxyoctyl)amino]phenol, 4-bis[(2-hydroxynonyl)amino]phenol, 4-bis[(2-hydroxydecyl)amino]phenol, 4-bis[(2-hydroxyundecyl)amino]phenol, 4-bis[(2-hydroxydodecyl)amino]phenol, 4-bis[(2-hydroxytri ...

16. The method of any one of claims 1 to 15, wherein the phenol is 4-bis[(2-hydroxytetradecyl)amino]phenol, 4-bis[(2-hydroxypentadecyl)amino]phenol, 4-bis[(2-hydroxyhexadecyl)amino]phenol, 4-bis[(2-hydroxyheptadecyl)amino]phenol, 4-bis[(2-hydroxyoctadecyl)amino]phenol, 4-bis[(2-hydroxyeleyl)amino]phenol, 4-bis[(2-hydroxynonadecyl)amino]phenol, 4-bis[(2-hydroxyeicosyl)amino]phenol, 4-bis[(2-hydroxyheneicosyl)amino]phenol, 4-bis[(2-hydroxydocosyl)amino]phenol, and 4-bis[(2-hydroxytricosyl)amino]phenol.

17. R ６ and R ７ One or both of the following is -(CR １０ ２ ) ｑ (CHOH)(R １２ O) ｚ R １１ and R １０ is independently selected from -H and alkyl, q is (-) (a covalent bond) or an integer ranging from 1 to 12, preferably (-), 1, or 2; R １１ is selected from the group consisting of C1-C24 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl; R １２ But -(CH ２ ) ｗ -, w is 1, 2, or 3, and z is an integer in the range of 1 to 5.

18. R １０ is -H, q is 1, z is 1, w is 1 or 2, and R １１ The method of claim 17, wherein is a C1 to C18 linear, branched, or cyclic alkyl, aryl, alkyl-aryl, and aryl-alkyl.

19. The compound is 4-bis[(3-methoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-ethoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-propoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-butoxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-pentyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-hexyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-heptyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-octyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-nonyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-decyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-undecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-dodecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-tridecyloxy-2-hydroxy-propyl)amino]phenol phenol, 4-bis[(3-tetradecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-pentadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-hexadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-heptadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-octadecyloxy-2-hydroxy-propyl)amine]phenol, 4-bis[(3-eleyloxy-2-hydroxy-propyl)amino]phenol, no]phenol, 4-bis[(3-nonadecyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-eicosyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-heneicosyloxy-2-hydroxy-propyl)amino]phenol, 4-bis[(3-docosyloxy-2-hydroxy-propyl)amino]phenol, and 4-bis[(3-tricosyloxy-2-hydroxy-propyl)amino]phenol,The method according to claims 1 to 13, 17 or 18.

20. -R １ , -R ２ , -R ３ , -R ４ , and R ５ At least one of the following is NR ８ R ９ The method according to any one of claims 1 to 19, wherein

21. The compound may be 1,4-bis[3-methoxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-ethoxy-2-hydroxy-ethylamino]benzene, 1,4-bis[3-propoxy-2-hydroxy-propylamino]benzene, 4-bis[3-butoxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-pentyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-hexyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-hept ... propylamino]benzene, 1,4-bis[3-octyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-nonyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-decyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-undecyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-dodecyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-tri ... bis[3-tetradecyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-pentadecyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-hexadecyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[(3-heptadecyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-octadecyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-eleyloxy-2-hydroxy-propylamino]benzene, 1, 21. The method of claim 20, wherein the aryloxy group is selected from the group consisting of 4-bis[3-nonadecyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-eicosyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-heneicosyloxy-2-hydroxy-propylamino]benzene, 1,4-bis[3-docosyloxy-2-hydroxy-propylamino]benzene, and 1,4-bis[3-tricosyloxy-2-hydroxy-propylamino]benzene.

22. an aryl group-containing reactant having either (a) a primary amine and a hydroxyl group, (b) two primary amine groups, (c) a primary and a secondary amine group, or (d) a primary and a tertiary amine group; with a carbon and oxygen containing reactant capable of reacting with the primary amine groups, and / or optionally the secondary amine groups; 2. A method for preparing a compound of formula I according to claim 1, comprising providing a compound of formula I as described herein.

23. 23. The method of claim 22, wherein the aryl group-containing reactant is selected from the group consisting of 4-aminophenol, 1,4-diaminobenzene (p-phenylenediamine), and dimethyl-4-phenylenediamine.

24. 24. The method of claim 22 or 23, wherein the carbon- and oxygen-containing reactants comprise oxirane- and oxytane-containing reactants.

25. the carbon- and oxygen-containing reactant is an oxirane-containing reactant of formula II, 【Chemistry 2】 In the formula, R １３ But -(CH ２ )- or -(CH ２ CH ２ )-, and R １４ But -(CH ２ ) ｗ -, w is an integer ranging from 1 to 3, t is an integer ranging from 1 to 100, R １５ is optionally substituted with one or more hydroxyl groups as described herein; １０ 25. The method of claim 24, wherein:

26. 26. The method of any one of claims 22 to 25, which does not include the use of (a) an organic solvent, (b) a catalyst, or both (a) and (b).

27. A compound of formula (I) 【Chemistry 3】 In the formula, -R １ , -R ２ , -R ３ , -R ４ , and -R ５ is selected from -H, -OH, alkyl, aryl, alkylaryl, and arylalkyl, and -NR ８ R ９ and R ８ and R ９ is —H, alkyl, aryl, alkylaryl, and arylalkyl, as well as R as described herein. ６ / R ７ or -R １ , -R ２ , -R ３ , -R ４ , and -R ５ any two adjacent groups form one or more ring structures, R ６ and R ７ is a carbon-containing group that contains one or more hydroxyl groups separated from the N atom by one or more carbon atoms; ６ Or R ７ A compound of formula (I) wherein when is not (i), it is selected from --H, alkyl, aryl, alkylaryl, and arylalkyl.

28. R ６ and R ７ Either or both of - (CR １０ ２ ) ｑ (CHOH)(CH ２ ) ｚ R １１ ,or - (CR １０ ２ ) ｑ (CHOH)(R １２ O) ｚ R １１ is of the formula In the formula, R １０ , R １１ 28. The compound of claim 27, wherein , q, and z have the meanings herein.

29. 29. A composition comprising a compound of formula I according to claim 27 or 28 adapted for use as an antioxidant.

30. 30. The composition of claim 29, comprising a solvent or one or more excipient compounds.

Images