阅读说明：本技术 氧化芳香胺和作为抗氧化剂的用途 (Oxidized aromatic amines and use as antioxidants ) 是由 A·达万 A·赛义德 J·彭宁顿 于 2020-04-28 设计创作，主要内容包括：描述了化合物、组合物和方法,其包括用作抗氧化剂的氧化芳香胺,例如基于氨基苯酚、苯基-对苯二胺和二氨基苯的化合物。氧化芳香胺包括具有连接到一个或两个含碳基团的氮的仲胺和/或叔胺基团,该含碳基团具有与氮相隔一个或多个碳原子的羟基和/或醚基。(Compounds, compositions, and methods are described that include oxidized aromatic amines, such as those based on aminophenols, phenyl-p-phenylenediamines, and diaminobenzenes, that are useful as antioxidants. Aromatic amine oxides include secondary and/or tertiary amine groups having a nitrogen attached to one or two carbon-containing groups having a hydroxyl and/or ether group separated from the nitrogen by one or more carbon atoms.)

1. 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, said compound of formula I being:

wherein-R¹、-R²、-R³、-R⁴and-R⁵Independently selected from-H, -OH, alkyl, aryl, alkylaryl and arylalkyl and-NR⁸R⁹Wherein R is⁸And R⁹Independently selected from-H, alkyl, aryl, alkylaryl and arylalkyl, and R as described herein⁶/R⁷or-R¹、-R²、-R³、-R⁴and-R⁵Any two adjacent groups in (a) form one or more ring structures;

wherein R is⁶And R⁷One or both of (i) a carbon-containing group comprising one or more hydroxyl groups separated from the N atom by one or more carbon atoms; if R is⁶Or R⁷(ii) is not (i), it is selected from-H, alkyl, aryl, alkylaryl, and arylalkyl;

wherein the compound of formula I inhibits oxidation of the organic compound in the composition.

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

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 gasoline or a gasoline blend.

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

6. The method of any one of claims 2 to 5, wherein the organic compound comprising an ethylenically unsaturated group is an alkene or alkene.

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

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

9. The method of claim 8, wherein the compound of formula I is present in the composition in an amount in the range of 50ppm 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. The method of any one of the preceding claims, wherein-R¹、-R²、-R³、-R⁴and-R⁵is-OH, and preferably-R³is-OH.

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

14. The method of any one of the preceding claims, wherein R⁶And R⁷Having the formula: - (CR)¹⁰ ₂)_q(CHOH)(CH₂)_zR¹¹，R¹⁰Independently selected from-H and alkyl, wherein q and z are independently (-) (covalent bond), or an integer in the range of 1 to 12, preferably (-), 1 or 2, and R¹¹Selected from the group consisting of C1-C24 linear, branched or cyclic alkyl, aryl, alkyl-aryl and aryl-alkyl.

15. The method of claim 14, wherein R¹⁰is-H; q is 1; z is (-); r¹¹Selected from the group consisting of C1-C18 linear, branched or cyclic alkyl, aryl, alkyl-aryl and aryl-alkyl.

16. The method of any one of the preceding claims, wherein 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, a salt thereof, and a salt thereof, 4-bis [ (2-hydroxyundecyl) amino ] phenol, 4-bis [ (2-hydroxydodecyl) amino ] phenol, 4-bis [ (2-hydroxy) tridecyl) 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-hydroxyalkenyl) amino ] phenol, 4-bis [ (2-hydroxynonadecyl) amino ] phenol, 4-bis [ (2-hydroxyeicosyl) amino ] phenol, and mixtures thereof, 4-bis [ (2-hydroxyeicosanyl) amino ] phenol, 4-bis [ (2-hydroxydocosyl) amino ] phenol and 4-bis [ (2-hydroxytricosyl) amino ] phenol.

17. The method of any one of claims 1-13, wherein R⁶And R⁷One or both of the following formulas: - (CR)¹⁰ ₂)_q(CHOH)(R¹²O)_zR¹¹，R¹⁰Independently selected from-H and alkyl, wherein q is (-) (covalent bond) or an integer in the range of 1 to 12, preferably (-), 1 or 2, R¹¹Is selected from the group consisting of C1-C24 linear, branched or cyclic alkyl, aryl, alkyl-aryl and aryl-alkyl groups, andR¹²independently selected from- (CH)₂)_w-, wherein w is 1,2 or 3 and z is an integer ranging from 1 to 5.

18. The method of claim 17, wherein R¹⁰is-H; q is 1; z is 1; w is 1 or 2, and R¹¹Are C1-C18 linear, branched or cyclic alkyl, aryl, alkyl-aryl and aryl-alkyl groups.

19. The method of claim 1-13, 17, or 18, wherein the compound is selected from the group consisting of: 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, methyl ethyl propyl ester, ethyl, 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 Phenol, 4-bis [ (3-heptadecyloxy-2-hydroxy-propyl) amino ] phenol, 4-bis [ (3-octadecyloxy-2-hydroxy-propyl) amino ] phenol, 4-bis [ (3-alkenyloxy-2-hydroxy-propyl) amino ] phenol, 4-bis [ (3-nonadecyloxy-2-hydroxy-propyl) amino ] phenol, 4-bis [ (3-eicosoxy-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-eicosatrioxy-2-hydroxy-propyl) amino ] phenol -propyl) amino ] phenol.

20. The method of any one of the preceding claims, which isin-R¹、-R²、-R³、-R⁴and-R⁵Is NR⁸R⁹。

21. The method of claim 20, wherein the compound is selected from the group consisting of: 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-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-tridecyloxy-2-hydroxy-propylamino ] benzene, 1, 4-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-alkenyloxy-2-hydroxy-propylamino ] benzene, 1, 4-bis [ 3-nonadecyloxy ] benzene-2-hydroxy-propylamino ] benzene, 1, 4-bis [ 3-eicosoxy-2-hydroxy-propylamino ] benzene, 1, 4-bis [ 3-heneicosoxy-2-hydroxy-propylamino ] benzene, 1, 4-bis [ 3-docosanoxy-2-hydroxy-propylamino ] benzene, and 1, 4-bis [ 3-tricosanoxy-2-hydroxy-propylamino ] benzene.

22. A process for the preparation of a compound of formula I as claimed in claim 1, comprising: reacting a compound having (a) a primary amine and a hydroxyl group; (b) two primary amine groups; (c) reacting the primary and secondary amine groups or (d) the aryl-containing reactant of the primary and tertiary amine groups 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.

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

24. The method of claim 22 or 23, wherein the carbon-and oxygen-containing reactants comprise ethylene oxide-and oxetane-containing reactants.

25. The method of claim 24, wherein the carbon-and oxygen-containing reactant is an ethylene oxide-containing reactant of formula II:

wherein R is¹³Is- (CH)₂) -or- (CH)₂CH₂) -, wherein R¹⁴Is- (CH)₂)_w-, where w is an integer ranging from 1 to 3, t is an integer ranging from 1 to 100, and where R¹⁵Is R¹⁰Optionally substituted with one or more hydroxyl groups, as described herein.

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):

wherein-R¹、-R²、-R³、-R⁴and-R⁵Independently selected from-H, -OH, alkyl, aryl, alkylaryl and arylalkyl and-NR⁸R⁹Wherein R is⁸And R⁹Independently selected from-H, alkyl, aryl, alkylaryl and arylalkyl, and R as described herein⁶/R⁷or-R¹、-R²、-R³、-R⁴and-R⁵Any two adjacent groups in (a) form one or more ring structures;

wherein R is⁶And R⁷One or both of (i) a carbon-containing group comprising one or more hydroxyl groups separated from the N atom by one or more carbon atoms; if R is⁶Or R⁷(ii) is not (i), it is selected from the group consisting of-H, alkyl, aryl, alkylaryl, and arylalkyl.

28. The compound of claim 27, wherein R⁶And R⁷One or both of the following formulas:

-(CR¹⁰ ₂)_q(CHOH)(CH₂)_zR¹¹(ii) a Or

-(CR¹⁰ ₂)_q(CHOH)(R¹²O)_zR¹¹；

Wherein R is¹⁰、R¹¹Q and z have the meanings given herein.

29. A composition comprising a compound of formula I as claimed in any one of claims 27 or 28, said composition being configured for use as an antioxidant.

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

Technical Field

The invention relates to compositions for oxidizing aromatic amines and their use as antioxidants

Background

Antioxidants find utility in a variety of compositions and industries. For example, antioxidants are used to inhibit chemical oxidation of compositions obtained from the oil and gas industry. Antioxidants also play an important role as food preservatives, and are generally added to various food compositions in order to maintain the properties of the food.

Hydrocarbon-containing compositions may benefit from the use of antioxidants. In fats and oils, antioxidants can inhibit oxidation reactions that would otherwise adversely affect the chemical properties of such fats and oils. In food products, oxidation of edible fats can produce unpleasant odors and tastes, which in turn can lead to spoilage of the food. Oxygen and sunlight can cause oxidation of hydrocarbons, and thus, exposure to oxygen and sunlight can cause oxidation.

Antioxidants are also added to fuels (e.g., gasoline and gasoline/ethanol blends) and lubricants to prevent oxidation of hydrocarbons therein.

Plastics, rubber and adhesive compositions may also benefit from the addition of antioxidants to prevent oxidative damage to the polymer which would otherwise cause the composition to lose flexibility and strength. Oxidative damage to polymer compositions often results in cracking of the surface of the material upon exposure to oxygen and/or ultraviolet radiation.

Some conventional antioxidants require higher concentrations to provide antioxidant activity, are less than ideal for controlling the peroxide formed during oxidation, and also perform poorly in preventing color degradation of fuels. Accordingly, what is needed is a gasoline or gasoline and ethanol blend composition with improved oxidation stability that reduces or eliminates precipitation and gum formation in the fuel and, in turn, reduces or eliminates corrosion or plugging of the internal combustion engine.

Disclosure of Invention

The present disclosure relates to oxidizing aromatic amine compounds, such as aminophenol, n-phenyl-p-phenylenediamine, and diaminobenzene-based compounds, and compositions and methods that include or utilize these compounds to prevent oxidation of organic compounds (i.e., as antioxidants).

The present invention provides compounds of formula I useful in the methods of the present disclosure, which compounds of formula I are:

wherein-R¹、-R²、-R³、-R⁴and-R⁵Independently selected from-H, -OH, alkyl, aryl, alkylaryl and arylalkyl and-NR⁸R⁹Wherein R is⁸And R⁹Independently selected from-H, alkyl, aryl, alkylaryl and arylalkyl, and R as described herein⁶/R⁷or-R¹、-R²、-R³、-R⁴and-R⁵In (1)Any two adjacent groups form one or more ring structures. R⁶And R⁷One or both of (i) a carbon-containing group comprising one or more hydroxyl groups separated from the N atom by one or more carbon atoms; if R is⁶Or R⁷(ii) is not (i), it is selected from the group consisting of-H, alkyl, aryl, alkylaryl, and arylalkyl.

In an embodiment, -R¹、-R²、-R³、-R⁴and-R⁵is-OH, and preferably-R³is-OH. In some embodiments, those-R that are not-OH¹、-R²、-R³、-R⁴and-R⁵is-H and includes the aminophenols of the present disclosure.

Other compounds of formula I include those wherein-R¹、-R²、-R³、-R⁴and-R⁵is-NR⁸R⁹Is not-NR, and is not-NR⁸R⁹Those of-R¹、-R²、-R³、-R⁴and-R⁵is-H and includes the diaminobenzene compounds of the present disclosure.

In some embodiments, R⁶And R⁷One or both of the following formulas: - (CR)¹⁰ ₂)_q(CHOH)(CH₂)_zR¹¹，R¹⁰Independently selected from-H and alkyl, wherein q and z are independently (-) (covalent bond), or an integer in the range of 1 to 12, preferably (-), 1 or 2, and R¹¹Selected 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.

In other embodiments, R⁶And R⁷One or both of the following formulas: - (CR)¹⁰ ₂)_q(CHOH)(R¹²O)_zR¹¹，R¹⁰Independently selected from-H and alkyl, wherein q is (-) (covalent bond) or an integer in the range of 1 to 12, preferably (-), 1 or 2, and R¹¹Is selected from C1-C24 straight, branched or cyclic alkyl, aryl, alkyl-aryl and aryl-alkyl, and R¹²Independently selected from- (CH)₂)_w-, where w is 1,2 or 3. Exemplary compounds include 4-bis [ (alkoxy-hydroxy-alkyl) amino]Phenol and 1, 4-bis [ alkoxy-hydroxy-alkylamino- ]]Benzene.

In an embodiment, the present invention provides a method for inhibiting oxidation of an organic compound, the method comprising: the compound of formula I is added to a composition comprising an organic compound, wherein the compound of formula I inhibits oxidation of the organic compound in the composition. The antioxidant compound may be a compound present in a fuel composition, a lubricant composition, a rubber composition, a plastic composition, or an adhesive composition.

The invention also provides a process for the preparation of a compound of formula I. In this process, there are (a) a primary amine and a hydroxyl group; (b) two primary amine groups; (c) reacting the primary and secondary amine groups or (d) the aryl-containing reactant of the primary and tertiary amine groups with a carbon-containing 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.

Exemplary reactants include those aryl reactants which are 4-aminophenol, 1, 4-diaminobenzene (p-phenylenediamine), and dimethyl-4-phenylenediamine, as well as ethylene oxide-and oxetane-containing reactants, such as those according to formula II:

wherein R is¹³Is- (CH)₂) -or- (CH)₂CH₂) -, wherein R¹⁴Is- (CH)₂)_w-, where w is an integer ranging from 1 to 3, t is an integer ranging from 1 to 100, and where R¹⁵Is R¹⁰Optionally substituted with one or more hydroxyl groups, as described herein.

The oxidized aromatic amine compounds described herein exhibit significantly better antioxidant properties than other known antioxidants and prevent oxidative thermal degradation of organic materials. These antioxidants generally have relatively high antioxidant properties as well as improved thermal stability and performance in a variety of materials including, but not limited to, petroleum-based products (lubricants, gasoline, aviation fuel, and engine oil), plastics, elastomers, cosmetics, cooking oils, and food products.

In turn, oxidizing aromatic amines as antioxidants can inhibit fouling in compositions containing organic compounds. The antioxidant can, in turn, hinder 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.

In addition, the methods of making the oxidized aromatic amine compounds described herein can improve the synthesis and quality of compositions comprising these antioxidants. For example, the disclosed processes can be efficiently and economically performed in the melt phase, thus eliminating or minimizing the use of foreign materials, such as catalysts and solvents. In addition, the method of preparing the oxidized aromatic amine compound can generally reduce or eliminate purification steps of the final product as compared to existing synthetic methods. This in turn can lead to superior performance/cost ratios for the product and reduced waste.

Drawings

Fig. 1 is a graph of the duration (hours) until the pressure inflection point is reached as determined by the oxidation resistance test of various oxidized aromatic amines with heavy coker naphtha according to the present disclosure.

Fig. 2 is a graph of the duration (hours) until the pressure inflection point is reached as determined by the oxidation resistance test of various oxidized aromatic amines with heavy coker naphtha according to the present disclosure.

Fig. 3 is a graph of the duration (hours) until the pressure inflection point is reached as determined by the antioxidant testing of various oxidized aromatic amines with DCU-1 coker naphtha according to the present disclosure.

Fig. 4 is a graph of pressure as a function of time determined from oxidation resistance tests of various oxidized aromatic amines with coker naphtha according to the present disclosure.

Detailed Description

Although the present disclosure provides reference to preferred embodiments, workers 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 does not limit the scope of the claims appended hereto. Furthermore, any examples set forth in this specification are not intended to be limiting and merely set forth some of the many possible implementations for the appended claims.

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 practice of the invention through routine experimentation.

The compositions and methods of the present disclosure include or use compounds having nitrogen-and oxygen-containing aromatic chemicals (aromatic amine oxides). The oxidized aromatic amine comprises at least an unsaturated 6-carbon ring structure having at least one nitrogen atom of a secondary or tertiary amine group bonded to an aromatic ring carbon, wherein the nitrogen atom of the secondary or tertiary amine group is attached to a first carbon-containing group (and optionally a second carbon-containing group) that comprises one or more hydroxyl 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) comprises 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 oxidized aromatic amine also includes at least one hydroxyl group or a second amine group (which may be the same or different from the secondary or tertiary amine groups described above) bonded to another aromatic ring carbon. Atoms on the aromatic ring that are not bonded to a secondary or tertiary amine group and a hydroxyl or secondary amine group can be bonded to a hydrogen atom, a hydrocarbon group including aryl and/or alkyl groups, or can form a ring structure (e.g., form a fused ring structure with the aromatic ring).

In some embodiments, the oxidized aromatic amine has an unsaturated 6-carbon ring structure and has one or more hydroxyl groups bonded to a ring atom in addition to a secondary or tertiary amine group. The unsaturated 6 carbon ring structure can be an aromatic 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 a hydroxyl group bonded to a ring atom of an unsaturated 6-carbon ring include those based on phenol, catechol, resorcinol, hydroquinone, hydroxy-hydroquinone, or resorcinol. Exemplary compounds also include those based on hydroxyl-containing fused aromatic chemicals, such as naphthol, hydroxy-anthracene, or indanol.

In some embodiments, the oxidized aromatic amine has an unsaturated 6-carbon cyclic structure having one or more amine groups bonded to a ring atom in addition to a secondary or tertiary amine group comprising at least a first carbon-containing group. The unsaturated 6 carbon ring structure can be an aromatic 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 an amine group bonded to a ring atom of an unsaturated 6 carbon ring include those based on aniline, phenylenediamine, and benzenetriamine. Exemplary compounds also include those based on hydroxyl-containing fused aromatic chemicals, such as naphthylamine, diaminonaphthalene, aminoanthracene, indanamine, and indene diamine.

In embodiments, the first and/or second carbon-containing groups of the secondary or tertiary amine groups comprise: a number of carbon atoms in a range from 1 to about 24, 2 to about 23, or 2 to about 22; a number of hydrogen atoms in a range from 3 to about 40, 4 to about 38, or 5 to about 35; 1. the number of oxygen atoms of 2,3 or 4; or any combination thereof. In a preferred embodiment, the carbon-containing group of the secondary or tertiary amine group comprises only carbon, oxygen and hydrogen.

In some embodiments, the present disclosure provides a "bis" compound, wherein the compound includes a tertiary amine group and the first carbon-containing group and the second carbon-containing group 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 group]In phenol, the first and second carbon-containing groups are the same and are- (CH)₂CHOHCH₂)O(CH₂)₃CH₃。

Other "bis" compounds include those based on diamines, such as phenylenediamine, wherein the compound includes a first secondary amine group bonded to a ring carbon and a second secondary amine group bonded to a ring carbonWherein the first and second amine groups are further bonded to a carbon-containing group comprising a hydroxyl group, an ether group, or both, wherein the carbon-containing groups are the same. For example, in the diaminobenzene compound 1, 4-bis [ 3-hexyloxy-2-hydroxy-propylamino]In benzene, the first and second carbon-containing groups are the same and are- (CH)₂CHOHCH₂)O(CH₂)₅CH₃。

The compounds of the present disclosure are described with reference to formula I below:

in formula I, -R¹、-R²、-R³、-R⁴and-R⁵Independently selected from-H, -OH, alkyl, aryl, alkylaryl and arylalkyl and-NR⁸R⁹。R⁸And R⁹Independently selected from-H, alkyl, aryl, alkylaryl and arylalkyl, and R as described herein⁶/R⁷or-R¹、-R²、-R³、-R⁴and-R⁵Any two adjacent groups in (a) form one or more ring structures. R⁶And R⁷One or both of which are (i) a carbon-containing group comprising one or more hydroxyl and/or ether groups separated from the N atom by one or more carbon atoms, provided that R⁶Or R⁷(ii) is not (i), then it is selected from the group consisting of-H, alkyl, aryl, alkylaryl, and arylalkyl.

May be-R¹、-R²、-R³、-R⁴、-R⁵、-R⁸and-R⁹Exemplary alkyl groups of one or more of (a) may be alkyl groups having a number of carbon atoms in the range of 1 to 18, 1 to 12, 1 to 8, 1 to 6, or 1 to 3, and are selected from linear, branched, and cyclic alkyl groups. Exemplary alkyl species include, but are not limited to:

methyl, methyl,

Ethyl group, ethyl group,

Propyl, isopropyl,

Butyl, isobutyl, sec-butyl, tert-butyl,

Pentyl, cyclopentyl, isopentyl, neopentyl, or neopentyl,

Hexyl, cyclohexyl, 1-, 2-and 3-methylbutyl, 1-, 1, 2-or 2, 2-dimethylpropyl, 1-ethylpropyl, 1-, 2-, 3-or 4-methylpentyl, 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, methylcyclopentyl;

heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 3-ethylpentyl, 2, 3-trimethylbutyl, 2-dimethylpentyl, 2, 3-dimethylpentyl, 2, 4-dimethylpentyl, 3-dimethylpentyl, 3, 4-dimethylpentyl, 4-dimethylpentyl, cycloheptyl, 1-methylcyclohexyl and 2-methylcyclohexyl;

octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 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, 3-trimethylpentyl, 2, 4-trimethylpentyl, 2,3, 3-trimethylpentyl, 2,3, 4-trimethylpentyl and 2,2,3, 3-tetramethylbutyl;

nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyloxy.

May be-R¹、-R²、-R³、-R⁴、-R⁵、-R⁸and-R⁹Exemplary alkylaryl groups for one or more of (a) can be alkylaryl groups having a number of carbon atoms in the range of from 7 to 18 or 7 to 12, such as benzyl, phenethyl, phenylpropyl, phenylisopropyl, phenylbutyl, pentaisobutyl, phenylbutylene, phenyltert-butene, phenylpentene, hexene, and the like.

May be-R¹、-R²、-R³、-R⁴、-R⁵、-R⁸and-R⁹Exemplary arylalkyl groups of one or more of (a) can be a compound having a number of carbon atoms in the range of from 7 to 18 or from 7 to 12Arylalkyl groups such as methyl-phenyl, ethyl-phenyl, propyl-phenyl, butyl-phenyl, pentyl-phenyl, hexyl-phenyl, heptyl-phenyl and octyl-phenyl.

In embodiments, at R⁶And R⁷One or more hydroxyl and/or ether groups are separated from the N atom by two or more carbon atoms, preferably by two carbon atoms.

In embodiments, R⁶And R⁷One or both of which include one or more oxygen atoms in the form of one or more hydroxyl groups. In some embodiments, R⁶And R⁷One or both of the following formulas: - (CR)¹⁰ ₂)_q(CHOH)(CH₂)_zR¹¹Wherein R is¹⁰Independently selected from-H and alkyl, wherein q and z are independently (-) (covalent bond), or an integer in the range of 1 to 12, and R¹¹Selected from the group consisting of C1-C24 linear, branched or cyclic alkyl, aryl, alkyl-aryl and aryl-alkyl. Preferably, q and z are independently (-), 1 or 2. Even more preferably, R¹⁰is-H; q is 1; z is (-); r¹¹Selected from the group consisting of C1-C18 linear, branched or cyclic alkyl, aryl, alkyl-aryl and aryl-alkyl. Exemplary alkyl, alkyl-aryl, and aryl-alkyl groups are described herein. Formula (CR)¹⁰ ₂)_q(CHOH)(CH₂)_zR¹¹Exemplary classes of (a) include the following groups:

in embodiments, R⁶And R⁷One or both of which contain 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. In some embodiments, R⁶And R⁷One or both of the following formulas: - (CR)¹⁰ ₂)_q(CHOH)(R¹²O)_zR¹¹Wherein R is¹⁰Independently selected from-H and alkyl, wherein q is (-) (covalent bond) or an integer in the range of 1 to 12, andR¹¹selected from the group consisting of C1-C24 linear, branched or cyclic alkyl, aryl, alkyl-aryl and aryl-alkyl groups, and R¹²Independently selected from- (CH)₂)_w-, wherein w is 1,2 or 3, and wherein z is an integer in the range of 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. In a preferred aspect, R¹⁰is-H; q is 1; z is 1; w is 1 or 2, and R¹¹Are C1-C18 linear, branched or cyclic alkyl, aryl, alkyl-aryl and aryl-alkyl groups. Exemplary alkyl, alkyl-aryl, and aryl-alkyl groups are described herein.

Formula (CR)¹⁰ ₂)_q(CHOH)(R¹²O)_zR¹¹Exemplary classes of (a) include the following groups:

preferred compounds of formula I include those wherein-R¹、-R²、-R³、-R⁴and-R⁵Those in which one or more of them is-OH, and those-R which are not-OH¹、-R²、-R³、-R⁴and-R⁵is-H. For example, some preferred compounds of the present disclosure have the following formula Ia, wherein R⁶And R⁷Have the meaning as described herein.

Exemplary compounds of formula Ia include, wherein R⁶And R⁷Each having the formula: - (CR)¹⁰ ₂)_q(CHOH)(CH₂)_zR¹¹4-bis [ (2-hydroxyethyl) amino group]Phenol, 4-bis [ (2-hydroxypropyl) amino group]Phenol, 4-bis [ (2-hydroxybutyl) amino group]Phenol, 4-bis [ (2-hydroxypentyl) amino group]Phenol, 4-bis [ (2-hydroxyhexyl) amino group]Phenol, 4-bis [ (2-hydroxy-2-phenyl) amino group]Phenol, 4-bis [ (2-hydroxy-2-phenylethyl) amino group]Phenol, 4-bis [ (2-hydroxyheptanes)Radical) amino]Phenol, 4-bis [ (2-hydroxyoctyl) amino group]Phenol, 4-bis [ (2-hydroxynonyl) amino group]Phenol, 4-bis [ (2-hydroxydecyl) amino group]Phenol, 4-bis [ (2-hydroxyundecyl) amino]Phenol, 4-bis [ (2-hydroxydodecyl) amino group]Phenol, 4-bis [ (2-hydroxy) tridecyl) amino]Phenol, 4-bis [ (2-hydroxytetradecyl) amino]Phenol, 4-bis [ (2-hydroxypentadecyl) amino group]Phenol, 4-bis [ (2-hydroxyhexadecyl) amino group]Phenol, 4-bis [ (2-hydroxyheptadecyl) amino group]Phenol, 4-bis [ (2-hydroxyoctadecyl) amino group]Phenol, 4-bis [ (2-hydroxyalkenyl) amino group]Phenol, 4-bis [ (2-hydroxynonadecyl) amino group]Phenol, 4-bis [ (2-hydroxyeicosyl) amino group]Phenol, 4-bis [ (2-hydroxyheneicosyl) amino group]Phenol, 4-bis [ (2-hydroxydocosyl) amino group]Phenol and 4-bis [ (2-hydroxyeicosatriyl) amino]Phenol.

Other exemplary compounds of formula Ia, wherein R⁶And R⁷Each having the formula: - (CR)¹⁰ ₂)_q(CHOH)(R¹²O)_zR¹¹Including but not limited to: 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 group]Phenol, 4-bis [ (3-hexyloxy-2-hydroxy) -propyl) amino]Phenol, 4-bis [ (3-heptyloxy-2-hydroxy-propyl) amino group]Phenol, 4-bis [ (3-octyloxy-2-hydroxy-propyl) amino]Phenol, 4-bis [ (3-nonyloxy-2-hydroxy-propyl) amino group]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 group]Phenol, 4-bis [ (3-tridecyloxy-2-hydroxy-propyl) amino group]Phenol, 4-bis [ (3-tetradecyloxy-2) -hydroxy-propyl) amino]Phenol, 4-bis [ (3-pentadecyloxy-2-hydroxy-propyl) amino group]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, 4-bis [ (3-alkenyloxy-2-hydroxy-propyl) amino]Phenol, 4-bis [ (3-nonadecyloxy-2-hydroxy)-propyl) amino]Phenol, 4-bis [ (3-eicosoxy-2-hydroxy-propyl) amino]Phenol, 4-bis [ (3-heneicosyl-2-hydroxy-propyl) amino]Phenol, 4-bis [ (3-docosanyloxy-2-hydroxy-propyl) amino]Phenol and 4-bis [ (3-eicosatrioxy-2-hydroxy-propyl) amino]Phenol.

Other preferred compounds of formula I include those wherein-R¹、-R²、-R³、-R⁴and-R⁵is-NR⁸R⁹Wherein R is⁸And R⁹Independently selected from-H, alkyl, aryl, alkylaryl and arylalkyl and R as described herein⁶/R⁷And is not-NR⁸R⁹Those of-R¹、-R²、-R³、-R⁴and-R⁵is-H. For example, some preferred compounds of the present disclosure have the following sub-formula Ib, wherein R⁶、R⁷And R⁹Or the sub-formula Ic, wherein R⁶And R⁷Have the meaning as described herein.

Exemplary Compounds of sub-formula Ic, wherein R⁶And R⁷Each having the formula: - (CR)¹⁰ ₂)_q(CHOH)(R¹²O)_zR¹¹Including but not limited to:

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-hexyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, 1-bis [ 3-octyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene Phenylaminobenzene, 1-bis [ 3-nonyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, 1-bis [ 3-undecyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, 1-bis [ 3-dodecyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, 1-bis [ 3-tridecyloxy-2-hydroxypropylamino ] -4-phenylaminobenzene, 1-bis [ 3-tetradecyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, 1-bis [ 3-pentadecyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, and mixtures thereof, 1-bis [ 3-hexadecyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, 1-bis [ 3-heptadecyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, 1-bis [ 3-octadecyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, 1-bis [ 3-alkenyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, 1-bis [ 3-nonadecyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, 1-bis [ 3-eicosyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, and mixtures thereof, 1-bis [ 3-heneicosyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene, 1-bis [ 3-docosanyloxy-2-hydroxy-propylamino ] -4-phenylaminobenzene and 1-bis [ 3-tricosanoxy-2-hydroxy-propylamino ] -4-phenylaminobenzene.

Other preferred compounds of formula I include those wherein-R¹、-R²、-R³、-R⁴and-R⁵is-NR⁶R⁷And is not-NR⁶R⁷Those of-R¹、-R²、-R³、-R⁴and-R⁵is-H. For example, some preferred compounds of the present disclosure have the following sub-formulae Id and Ie, wherein R is⁶And/or R⁷Have the meaning as described herein.

Exemplary compounds of formula Ie, wherein R⁷Having the formula: - (CR)¹⁰ ₂)_q(CHOH)(R¹²O)_zR¹¹Including but not limited to: 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-hydroxy-propylamino]Benzene, 1, 4-bis [ 3-nonane ]Oxy-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-tridecyloxy-2-hydroxy-propylamino]Benzene, 1, 4-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 group]Benzene, 1, 4-bis [ 3-octadecyloxy-2-hydroxy-propylamino group]Benzene, 1, 4-bis [ 3-alkenyloxy-2-hydroxy-propylamino]Benzene, 1, 4-bis [ 3-nonadecyloxy]2-hydroxy-2-phenylamino-benzene]Benzene, 1, 4-bis [ 3-eicosoxy-2-hydroxy-propylamino]Benzene, 1, 4-bis [ 3-heneicosanoxy-2-hydroxy-propylamino]Benzene, 1, 4-bis [ 3-docosanyloxy-2-hydroxy-propylamino]Benzene and 1, 4-bis [ 3-tricosanoxy-2-hydroxy-propylamino]Benzene.

One aromatic compound of the present disclosure that may be used to synthesize the antioxidant compounds of the present disclosure includes aminophenol and diaminobenzene compounds as described herein, which may be prepared using a method according to the present disclosure. In some modes of practice, as a general case, an aryl-containing reactant having (a) a primary amine and a hydroxyl group (e.g., 4-aminophenol), (b) two primary amine groups (e.g., 1, 4-diaminobenzene (p-phenylenediamine)), (c) a primary and secondary amine group (e.g., phenylenediamine), or (d) a primary and tertiary amine group (e.g., dimethyl-4-phenylenediamine) is reacted with a carbon-and oxygen-containing reactant capable of reacting with a primary (and optionally secondary) amine group to provide a product, such as described herein. The carbon-and oxygen-containing reactants may provide one or two groups R when reacting with amine groups⁶And/or R⁷It may have the formula: - (CR)¹⁰ ₂)_q(CHOH)(CH₂)_zR¹¹Or (CR)¹⁰ ₂)_q(CHOH)(R¹²O)_zR¹¹。

In some modes of practice, the reactants include an oxirane or oxetane group as the amine-reactive group. The ethylene oxide-and oxetane-containing reactants can include the desired carbon chemistry and can also include additional oxygen atoms, for example in the form of ether groups. Exemplary ethylene oxide-containing reactants are glycidyl ethers, such as alkyl glycidyl ethers.

In some modes of practice, the ethylene oxide-containing reactant has the formula II:

wherein R is¹³Is- (CH)₂) Or- (CH)₂CH₂) -, wherein R¹⁴Is (CH)₂)_w-, where w is an integer in the range from 1 to 3, t is an integer in the range 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, and where R is¹⁵Is R as described herein¹⁰Optionally substituted with one or more hydroxyl groups.

Nitrogen-and oxygen-containing aromatic Compounds useful as antioxidants are also described in commonly assigned U.S. provisional patent application entitled "Hydroxyminoketone Compounds and Methods for modifying Monomer Polymerization," having the title number: n11244USP1(ECO0169/P1) and filed concurrently herewith.

In a preparative mode, an aminophenol or diaminobenzene compound as described herein may be reacted with a carbon-and oxygen-containing reactant (e.g., a glycidyl ether) in a desired molar ratio. The ratio may be an equimolar ratio or one in which the carbon-and oxygen-containing reactants are greater than the aminophenol or diaminobenzene compound. In an exemplary mode of practice, the carbon-containing and oxygen-containing reactants are reacted in an amount of about two moles more than the aminophenol or diaminobenzene compound.

In some modes of practice, the aromatic-containing reactant and the carbon-and oxygen-containing reactant (e.g., an ethylene oxide-or oxetane-containing reactant) are reacted at a temperature where one or both reactants are in the liquid phase. In some modes of practice, the oxirane/oxetane containing reactant is in the liquid phase at the desired reaction temperature and it solvates the aryl containing reactant. In this regard, the melting point of the aromatic-containing reactant can be higher than the melting point of the carbon-containing and oxygen-containing reactants. In embodiments where the reactants are melted and/or solvated at the desired reaction temperature, any other components (e.g., organic solvents typically used in reaction schemes) may be optional and are not required. Thus, organic solvents may be excluded from the reaction process. In addition, components such as catalysts may also be optional and are therefore not necessary. In certain modes of practice, the synthetic methods do not include the use of (a) an organic solvent, (b) a catalyst, or both (a) and (b).

Exemplary reaction temperatures may range from about room temperature (-25 ℃) to about 250 ℃, about 40 ℃ to about 200 ℃, or about 50 ℃ to about 175 ℃.

Alternatively, the aromatic group-containing reactants and the carbon-and oxygen-containing reactants can be reacted under reflux in an organic solvent (e.g., alcohols such as methanol, butyl carbitol, and butyl glycol) at elevated temperatures (e.g., >100 ℃).

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

The form of the composition and the state of the components therein may also be affected by the inclusion of one or more optional components, such as a solvent, or solvent mixture, or other excipient compounds other than the aromatic amine oxide. The form of the composition and the state of the components therein may also be affected by temperature, and the composition properties may optionally be described at a particular temperature (e.g., such as at a storage temperature of 5 ℃ or below, at room temperature (25 ℃), or at a temperature for a desired application).

As noted above, the aromatic amine oxide may include other components, such as solvents, surfactants, dispersants, and the like. Optional components, if present in the composition, may be described with respect to the weight of the oxidized aromatic amine. The optional components may be present in amounts greater than, about equal to, or less than the weight of the oxidized aromatic amine.

As used herein, the term "optional" or "optionally" means that the subsequently described object (e.g., compound) or event (e.g., processing step) or environment can, but need not, occur, and that the description includes instances where the object, event or environment occurs and instances where it does not.

The compositions of the present disclosure can include those enumerated compounds, and optionally can include other components of the compositions, but in very small amounts (e.g., described in terms of a composition that "consists essentially of" the enumerated components). For example, such compositions may include one or more other components, but at a level of no 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. Compositions consisting essentially of a solid component that is an aromatic amine oxide (e.g., dissolved in a solvent) 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, no other measurable amount of the components is present in addition to the recited components. In some embodiments, the aromatic amine oxide may optionally be present in an amount of less than 1% (wt), less than 0.5% (wt), less than 0.1% (wt), or less than 0.01% (wt) of the total composition.

As used herein, the terms "substantially" and "consisting essentially of" that modify, e.g., the type or amount of an ingredient in a composition, a property, an amount, a method, a location, a value, or a range in describing an embodiment of the present disclosure, mean that the change in the overall composition, property, amount, method, location, value, or range thereof is not affected in a manner that would negate the effect of the intended composition, property, amount, method, location, value, or range. Examples of desired properties include, by way of non-limiting example only, dispersibility, stability, rate, solubility, and the like; the desired values include the weight of the added components, the concentration of the added components, and the like. Effects on modified methods include those caused by variations in the type or amount of materials used in the process, variations in machine settings, effects of environmental conditions on the process, etc. (wherein the manner or degree of effect does not negate one or more of the desired properties or results), and similar approximation considerations. Where modified by the term "substantially" or "consisting essentially of, the appended claims include equivalents to these types and amounts of material.

As used herein, the term "about" used in describing modifications such as amounts, concentrations, volumes, process temperatures, process times, yields, flow rates, pressures, and the like of ingredients in compositions, and ranges thereof, employed in embodiments of the present disclosure, refers to procedures that may be performed, for example, by typical measurement and handling procedures used to prepare compounds, compositions, concentrates, or use formulations; through inadvertent errors in these procedures; variations in numerical quantities occur through differences in the manufacture, source, or purity of the starting materials or ingredients used to carry out the process, and similar close considerations. The term "about" also encompasses amounts that differ from a particular starting concentration or mixture due to aging of the formulation, as well as amounts that differ from a particular starting concentration or mixture due to mixing or processing the formulation. Where modified by the term "about," the claims appended hereto include equivalents to these amounts. Further, when "about" is employed to describe any range of values, e.g., "about 1 to 5," the list means "1 to 5" and "about 1 to about 5" and "about 1 to 5," unless the context clearly limits.

The amount of the oxidized aromatic amine and any other (optional) components in the composition can be described in various ways, such as in terms of weight percent (% wt.) or molar amount of the oxidized aromatic amine in the composition. When other components are used with the aromatic amine oxide, such compounds may also be described in terms of weight ratios in the composition or relative amounts to each other.

The aromatic amine oxide may be present in the composition with a solvent or combination of solvents. The solvent or solvent combination may be selected such that the aromatic amine oxide is soluble in the solvent or solvent combination. Miscible solvents may be selected if the nitrogen-or oxygen-containing aromatic amine is a liquid at ambient conditions.

Useful solvents include any solvent in which the aromatic amine oxide is soluble or can be stably suspended. In some embodiments, the solvent or solvent combination may be selected from water-soluble or water-miscible solvents, such as ethylene glycol-based solvents, and hydrophobic or hydrocarbon solvents, such as aromatic solvents, paraffinic solvents, or mixtures of both.

Exemplary glycol solvents include, but are not limited to, C₁-C₈Glycols such as ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol, ethers of such glycols such as diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, liquid polyethylene glycols, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and low molecular weight polypropylene glycols and the like, and combinations thereof. Commercial solvents such as Butyl Carbitol and Butyl CELLOSOLVE are available and can be obtained from DOW^TMMainly comprising Butyl CARBITOL^TMIt consists essentially of ethylene glycol monobutyl ether.

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

In some embodiments, the solvent is selected from the group consisting of ethylene glycol and aromatic naphtha and combinations thereof.

The amount of aromatic amine oxide (with one or more optional components) in a solvent or solvent combination can be described in one or more ways, such as by the percent solids (wt) of the components in the composition, or by the molar amount of the solid components in the composition.

By way of example, a stock composition of an aromatic amine oxide can be dissolved in a solvent to a concentration of about at least about 0.00001% (wt), at least about 5% (wt), such as an amount in the range of about 0.00001% (wt) to about 50% (wt).

In some modes of practice, the oxidized aromatic amines of the present disclosure can be used as antioxidants. The oxidized aromatic amine antioxidants of the present disclosure can be used to retard the oxidation of organic materials in the composition. Oxidation is a chemical reaction that can generate free radicals, leading to reactions that can form undesirable products in the composition or alter the properties of the composition with undesirable species.

In some modes of practice, the oxidized aromatic amine acts as an antioxidant, preventing the occurrence of fouling in compositions comprising organic compounds. The term "fouling" refers to the formation of polymers, prepolymers, oligomers, and/or other materials that do not dissolve in and/or precipitate from a stream and deposit on equipment under the conditions in which the equipment is operated. The oxidized aromatic amines may also be referred to as "antifoulants" because they prevent or reduce such formation.

The aromatic amine oxide may be used in conjunction with compositions containing organic materials and "process equipment" (e.g., reactors, reactor beds, piping, valves, distillation columns, trays, condensers, heat exchangers, compressors, fans, impellers, pumps, recyclers, intercoolers, sensors, etc.) that are associated with the process and may foul by oxidation of the organic components therein. The term also includes collections of these components where more than one component is part of a "system".

In some modes of practice, the compositions of the present disclosure having nitrogen-and oxygen-containing aromatic anti-polymerizers and solvents (e.g., ethylene glycol) are used with processes involving distillation columns for separating and purifying organic compounds, such as vinyl monomers. For example, ethylbenzene may be subjected to a catalytic dehydrogenation reaction in a process known in the art, resulting in the formation of styrene. The reaction product comprising styrene also comprises other compounds, such as aromatics (e.g., toluene and benzene), unreacted ethylbenzene, and other materials (e.g., polymers). This mixture of compounds is usually 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 a pure product stream having a higher purity. Optionally, the oxidized aromatic amine antioxidant is used with one or more secondary components, such as stabilizers like Butylated Hydroxytoluene (BHT) and Tertiary Butyl Catechol (TBC). In exemplary practice, these components are used in a distillation column that is used to separate and purify the vinyl monomer.

The aromatic amine oxide-containing composition may be introduced into the stream from the reaction bed to the distillation column or may be added directly to the distillation column. The composition may be added prior to heating the monomer composition or while heating the monomer composition in a distillation column. In embodiments, the aromatic amine oxide has a boiling point higher than that of the desired compound or distillate (e.g., monomer, such as styrene) undergoing the distillation column, and during the distillation, the desired compound is separated from the aromatic amine oxide due to the temperature difference. In embodiments, the boiling point difference between the compound of interest and the oxidized aromatic amine is about 10 ℃ or greater, about 15 ℃ or greater, about 20 ℃ or greater, about 25 ℃ or greater, about 30 ℃ or greater, about 35 ℃ or greater, about 40 ℃ or greater, about 45 ℃ or greater, or about 50 ℃ or greater.

Alternatively, or in addition to adding the aromatic amine oxide during distillation, the composition may optionally or further be added to a distillation effluent stream, such as a purified styrene stream. Optionally, another antioxidant may be added to the distillation effluent stream prior to or with the oxidation of the aromatic amine antioxidant.

The aromatic amine oxide, optionally used in combination with one or more other components, may be used with any "hydrocarbon process stream" that may include unsaturated monomers to stabilize the stream during transport and storage. In certain modes of practice, the aromatic amine oxide may be used in conjunction with "petroleum products," which refers to any hydrocarbon product obtained from a subterranean reservoir, any product derived from such hydrocarbon products, or any mixture thereof. The polymerizable monomer is present in the petroleum product or may be chemically derived from the petroleum product. Non-limiting examples of petroleum products include, but are not limited to, crude oil, distilled crude oil, crude oil fractions, heavy oil or bitumen, hydrogenated oil, refined oil, byproducts of petroleum product processing (such as pyrolysis, hydrotreating, or phase separation), or mixtures of two or more of these. The liquid petroleum product is a petroleum product that is substantially liquid at 20 ℃.

The oxidized aromatic amine may be added to or may be present in a "petroleum process stream," the latter referring to any petroleum product disposed within a petroleum process facility in fluid contact with the interior surface thereof.

Petroleum process streams may include or be capable of forming compounds as by-products that are oxidized to undesirable species. The process stream may be substantially static, e.g., placed in a settler (separator) or storage vessel for a selected contact time, e.g., up to two years of petroleum production. The process stream may be substantially dynamic, such as a liquid petroleum product disposed within a pipe during transport of the product from a first location to a second location. In some embodiments, the process stream includes one or more other components associated with petroleum processing; these components are not particularly limited.

The term "petroleum process equipment" or "petroleum process equipment" refers to a manufactured article having an interior surface comprising a metal, wherein one or more petroleum products are contacted with a metal fluid at any time period and at any temperature as further determined from the context. Petroleum processing equipment includes items for removing petroleum products from a subterranean reservoir, 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.

In embodiments, the composition comprising an aromatic amine oxide is thermally stable and possesses antioxidant activity in a process stream at a temperature of about 20 ℃ to 400 ℃, e.g., about 100 ℃ to 400 ℃, or about 100 ℃ to 350 ℃, or about 100 ℃ to 300 ℃, or about 100 ℃ to 250 ℃, or about 100 ℃ to 200 ℃, or about 100 ℃ to 150 ℃.

In embodiments, the composition comprising the aromatic amine oxide may be introduced into the composition with the organic compound, such as a liquid petroleum process stream, in a batch, continuous, or semi-continuous manner. In some embodiments, the oxidized aromatic amine (and any other optional components) is introduced manually; and in other embodiments their introduction is automated. In embodiments, the amount of aromatic amine oxide introduced in a selected unit of time varies with the variable composition of the associated process stream. This dose variability can be done manually: passing periodic tests of the internal surfaces of the process equipment and then up-or down-regulating the amount of the composition based on the results of the tests; or automatically: by monitoring one or more conditions within the petroleum processing equipment and signaling a need to apply more composition into the process stream.

In some embodiments, the oxidized aromatic amine is added to a petroleum product that is a crude oil, a reduced crude oil, a heavy oil, a bitumen, a coker feed, a hydrotreater influent, a hydrotreater effluent, a flashed crude oil, a light cycle oil, or a diesel or naphtha refinery stream. Thus, antioxidants can be used to treat refinery reactant streams that are prone to oxidation. In embodiments, the aromatic amine oxide is added to a petroleum processing facility, which is typically associated with the collection, processing, transportation, or storage of one or more of crude oil, distilled crude oil, crude oil fractions, heavy oil, bitumen, coker feed, flashed crude oil, light cycle oil, or diesel or naphtha refinery streams, including specifically piping and associated infrastructure for fluidly connecting process facility items together to facilitate the treatment of the process streams disposed therein. Antioxidants can be added to the naphtha product described more specifically herein.

Antioxidants can be used to treat reactive naphtha products having varying levels of reactivity. The reactivity level of the naphtha product will vary as the unsaturation in the product is different. Naphtha products obtained from different refineries may exhibit varying degrees of reactivity, which can be determined using bromine testing.

The equipment treated with the oxidized aromatic amine and any other optional components can reduce or eliminate fouling of the internal surfaces of the equipment. In embodiments, fouling is measured as the relative increase in solids retention in a treated composition compared to the solids retention in an untreated composition over the same period of time. In embodiments, fouling is measured as the relative reduction in weight or volume of deposits resulting from the same contact time period of a treated process stream in an associated process equipment article relative to the selected contact time period of the process equipment with a corresponding untreated process stream. In other words, the reduction in fouling is a relative reduction in the measured weight or volume of solids deposited or precipitated from process equipment in contact with the treated process stream over a selected period of time as compared to the weight or volume of solids deposited or precipitated from the untreated process stream over the same period of time.

The oxidized aromatic amines can also inhibit fouling of process equipment that is detrimental in the primary fractionation process, light ends fractionation, non-aromatic halovinyl fractionation and stabilization, process gas compression, dilution steam systems, caustic towers, quench water separators (pyrolysis gasoline), butadiene extraction, propane dehydrogenation, diesel and gasoline fuel stabilization, olefin metathesis, styrene purification, hydroxy hydrocarbon purification, and stabilization of compositions during transportation and storage.

The aromatic amine oxide may be added at any given point and at one or more locations in the process. For example, the anti-polymerizer composition may be added in an interstage cooler or compressor or directly upstream of an intercooler or compressor. Aromatic amine oxides may be added to the process equipment continuously or intermittently as needed to prevent or reduce fouling.

The aromatic amine oxide can be introduced into the desired system by any suitable method. For example, it may be added neat or in the form of a dilute solution. In some embodiments, the aromatic amine oxide-containing composition may be applied as a solution, emulsion, or dispersion that is sprayed, dropped, poured, or injected into the desired opening in the system or onto process equipment or process condensate. In some embodiments, the composition may be added with wash oil or tempered water.

After introducing the composition into the process equipment, it was observed that the treated process equipment deposited less on the equipment than process equipment without the addition of the composition. The reduction or prevention of fouling may be assessed by any known method or test. In some embodiments, fouling may be reduced or prevented by measuring the time required for the samples with and without the antifoulant composition to gel.

In other embodiments, the oxidized aromatic amine antioxidants of the present disclosure are added to a fuel or lubricant. Antioxidants can inhibit oxidation of organic components in the fuel or lubricant, thereby preventing the formation of undesirable components that can degrade, malfunction, or otherwise damage the performance of the device (e.g., engine) in which the fuel or lubricant is used. In certain modes of practice, oxidized aromatic amine antioxidants may be used in conveyor lubricants to facilitate movement of conveyor belts made of stainless steel or plastic.

The oxidized aromatic amine antioxidants of the present disclosure can be added to low temperature oils, jet fuels, and gasoline, including specifically aviation gasoline, turbine oils, transformer oils, hydraulic oils, waxes, and industrial greases.

The antioxidants of the present disclosure can improve gasoline-based fuels that are stored for extended periods of time that would otherwise deteriorate due to polymerization and oxidation reactions in the gasoline composition. The degradation process of gasoline-based fuels can be complicated by the presence of various hydrocarbons in the composition. For example, the antioxidants of the present disclosure can prevent gum formation and color darkening when gasoline compositions darken when stored for extended periods.

Compounds having unsaturation, such as olefins and dienes, are susceptible to oxidation and polymerization in the presence of oxygen. These unsaturated compounds may be present in the fuel composition due to secondary refining operations and the mixing of hydrocarbon streams from thermal processes. Other non-organic contaminants in the hydrocarbon composition (e.g., copper) can promote the formation of peroxides in the composition and can lead to polymerization reactions. Copper contamination may result from contact of the hydrocarbon composition with equipment used to transport, store, or refine the hydrocarbon material. Copper is also used to refine chemicals used in refining and vehicle fuel systems.

The oxidized aromatic amine antioxidant may be used in gasoline fuels containing cracked components from various secondary processing operations such as Fluid Catalytic Cracking (FCC), VB and coking. The antioxidants of the present disclosure can improve fuel properties by preventing oxidation, preventing deposit formation, and increasing corrosion inhibition and water absorption.

The oxidized aromatic amine antioxidant may be added to a gasoline composition, for example, a gasoline composition derived from petroleum and comprising primarily hydrocarbons. A typical use is gasoline as a fuel for internal combustion engines.

Gasoline hydrocarbons typically have five to twelve carbon atoms and typically have a higher octane number. Octane ratings of about 85% or greater, about 86% or greater, about 87% or greater, about 88% or greater, about 89% or greater, about 90% or greater, about 91% or greater, about 92% or greater, or about 93% or greater are common commercial preparations. The octane rating of gasoline is typically measured relative to a mixture of isooctane (i.e., 2, 4-trimethylpentane) and n-heptane by running a fuel sample under controlled conditions with a specific test engine at a variable compression ratio. For example, the octane rating of 93-octane gasoline is typically the same as a mixture of 93% (v/v) isooctane and 7% (v/v) n-heptane. A typical gasoline may include a mixture of paraffins, naphthenes, aromatics, and olefins.

The oxidized aromatic amine antioxidant may be added to a gasoline blend, such as a blend of gasoline and ethanol. In the ethanol mixture, ethanol may be present in the gasoline ethanol mixture in any desired amount in the range of 0.1% (vol) to 99% (vol). More specific ethanol-gasoline blends may contain 1-5% (vol.) ethanol, 5-10% (vol.) ethanol, 10-15% (vol.) ethanol, 15-20% (vol.) ethanol, 20-25% (vol.) ethanol, 25-30% (vol.) ethanol, 30-40% (vol.) ethanol, 40-50% (vol.) ethanol, 50-60% (vol.) ethanol, 60-70% (vol.) ethanol, 70-80% (vol.) ethanol, 80-90% (vol.) ethanol, or 90-99% (vol.) ethanol, with the remainder being gasoline.

The antioxidants of the present disclosure may be used with pyrolysis gasoline (Pygas) or pyrolysis gasoline products. Pyrolysis gasoline is a naphtha-based product having a high octane blend and includes olefins, paraffins, and aromatics. In the production of ethylene and propylene, pyrolysis gasoline may be produced as a by-product of pyrolysis of high temperature naphtha. The antioxidant may be used with pure pyrolysis gasoline or the antioxidant may be added to a pyrolysis gasoline blend, for example a blend comprising other hydrocarbon agents or ethanol. The antioxidants of the present disclosure can be added to a distilled pyrolysis gasoline product, such as by distillation using a BTX process that separates pyrolysis gasoline to separate it into its components, including benzene.

The antioxidants of the present disclosure can be incorporated into the gasoline product at any suitable location. For example, for addition to pyrolysis gasoline, it is typically processed through a hydrotreater prior to mixing with other gasoline to form mogas, and an antioxidant can be introduced into the gasoline upstream or downstream of the hydrotreater, for example, prior to mixing the pyrolysis gasoline with the other gasoline.

Antioxidants can be used in the gasoline product at desired concentrations. Exemplary amounts of the oxidized aromatic amine antioxidant in the gasoline product range from about 1ppm to about 5000ppm, from about 2.5ppm to about 2500ppm, from about 5ppm to about 1500ppm, from about 7.5ppm to about 1250ppm, from about 10ppm to about 1000ppm, from about 50ppm to about 1000ppm, from about 100ppm to about 1000ppm, from about 250ppm to about 1000ppm, from about 50ppm to about 750ppm, from about 100ppm to about 500ppm, or from about 250ppm to about 500 ppm.

The oxidized aromatic amine antioxidant may be used as the sole antioxidant in treating a composition having an organic compound, or may be used as an antioxidant in a treating composition with one or more other antioxidants. For example, the aromatic amine oxide antioxidant may be the primary antioxidant in the treatment composition, e.g., in an amount greater than 50% (wt), about 60% (wt) or more, about 70% (wt) or more, about 80% (wt) or more, about 90% (wt) or more, about 95% (wt) or more, about 99% (wt) or more in the treatment composition.

The oxidized aromatic amine antioxidant or mixture of antioxidants can be used in pure form or in a solvent such as an aromatic solvent.

By adding the antioxidant of the present disclosure, a gasoline product with enhanced oxidation stability can be provided, thereby achieving less gum formation.

The test to determine antioxidant efficacy is an induction period test according to ASTM D-525/IP:40, in which a measured quantity of fuel (50mL) is oxidized under specified conditions in a container containing gasoline and an antioxidant. The test was run at the desired feed rate (depending on reactivity) at the desired temperature (e.g., in the range of 95 to 150 ℃) and with oxygen at a pressure of about 100 psi. The pressure is read or continuously recorded at regular time intervals until a break is reached. The time required for the sample to reach this point was observed and reported as the induction period.

Other tests may be used to assess the quality of fuels to be treated with the antioxidants of the present disclosure. Another test measures the presence of existing gums in the fuel composition. For example, ASTM D-381/IP:131,2 takes a quantity of fuel (50mL) and vaporizes it under controlled temperature and airflow conditions. The resulting residue was weighed and reported as gm/m³. This test can be used to understand how much gum is already present in the gasoline sample and can be incorporated into the accelerated aging test.

Another test is an environmental burn-in test. Standard environmental aging tests were performed for three months. For example, in such tests, 400mL samples of gasoline containing antioxidant were stored in triplicate in 500mL borosilicate glass bottles at ambient temperature for three months. After completion of the first, second and third months, one group was tested for current gums according to ASTM D-381, and the results were reported as gm/m³. The color of the fuel is also recorded after each month.

The oxidized aromatic amine antioxidant may be selected with the desired components, tested under selected conditions (e.g., time and temperature), and using a selected gasoline composition.

The ability of the aromatic amine oxide antioxidant to affect the water resistance characteristics of gasoline, or to alter the fuel characteristics to prevent rusting of iron-containing components when the fuel is contacted with water, can be tested.

For example, in fats and oils, antioxidants can delay the onset of oxidation or slow the rate of oxidation reactions. Fats and oils often deteriorate because oxidation of lipids produces compounds that cause different odors and tastes and continues to affect other molecules in the food. These foods deteriorate due to exposure to oxygen and sunlight, which can cause oxidation of the food. Thus, the oxidized aromatic amine antioxidants of the present disclosure can be added to food products to inhibit oxidation of one or more components of the food products.

Exemplary food products may include oxidized aromatic amine antioxidants of the present disclosure, including but not limited to: fermented beverages such as wine and malt-based fermented beverages such as beer and beer-based beverages; foods with high protein and/or fat content, such as dairy products like milk, yogurt, cheese, ice cream, etc.; cream; whipping cream; oil or fat based food preparations, such as vegetable oils, butter products, spreads, margarines, shortening and the like; baked products such as biscuits, muffins, waffles, pancakes, bread, biscuits and pastries; cereals, cereal products; granola; muesli; jam, jelly, orange jam, fruit preserves, fruit juice, concentrated fruit juice, fruit puree; canning vegetables and mashed vegetables; processed meat products such as ground beef, ground chicken, ground pork and sausage; chocolate, candy and chewing gum.

Exemplary concentrations of the oxidized aromatic amine antioxidants of the present disclosure present in the food product range from about 1ppm to about 500ppm, or from about 1ppm to about 50 ppm.

The oxidized aromatic amine antioxidants of the present disclosure may also be added to cosmetic and pharmaceutical formulations.

In other embodiments, the oxidized aromatic amine antioxidants of the present disclosure are added to the polymer composition. The polymer composition may be a polymer composition such as a plastic, rubber or adhesive composition. The antioxidants of the present disclosure can prevent oxidative damage to the polymer components in the composition that would otherwise result in a loss of strength and flexibility of the composition. For example, polymer decomposition via oxidation can result in ozonolysis or cracking.

Polymer compositions that are natural rubber, diene-containing polymers (e.g., polybutadiene), and other unsaturated rubbers may be significantly damaged by ozone cleavage and therefore may benefit from the inclusion of aromatic amine oxide antioxidants. Other easily oxidizable polymers include polypropylene and polyethylene.

The antioxidant of the present disclosure is present in the oxygen-containing aromatic amine polymer composition at an exemplary concentration in the range of about 100ppm to about 5% (wt).

Example 1:

synthesis of 4-aminophenol-Butyl Glycidyl Ether (BGE)

To a 250mL three-necked round bottom flask equipped with a temperature probe, nitrogen inlet, condenser, and magnetic stir bar was added butyl glycidyl ether. Then, 4-aminophenol was added to the well stirred reaction mixture. Table 1 also provides the amount and chemistry of each chemical added. The resulting suspension was heated to 120 ℃ under a nitrogen blanket and stirred for 8 hours or until the reaction was complete. As the reaction was completed, the suspension turned into a homogeneous dark amber product. The resulting product was characterized by NMR and ESI-MS.

TABLE 1

	MW(g/mol)	Purity of	Quantity (g)	n (mole)	Molar ratio of
						4-aminophenols	109.12	98％	20	0.179619	1
BGE	130.18	95％	49.2	0.359041	2.00

Examples 2 to 13

Synthesis of oxyaromatic amines

Using a procedure similar to example 1, various aromatic amine oxides were produced by using different starting amine and epoxide reactants at different molar ratios. 4-aminophenol, phenylenediamine and N-phenyl-phenylenediamine are used as amine reactants, while 2-ethylhexyl glycidyl ether and butyl glycidyl ether are used as epoxide reactants. The molar ratio of amine to epoxide was varied.

TABLE 2

Advantageously, the synthesis method provides an easily customizable way to prepare oxidized aromatic amines having desired oxygen-containing chemicals attached to one or more amine groups of the compound.

As provided in table 2, the examples of aromatic amine oxides, designated as AO-1 to AO-10 and related to examples 2 to 6 and 8 to 10 of AO-1 to AO-8, were tested for antioxidant performance as described herein and as shown in fig. 1 to 4. AO-9 and AO-10 were not tested. Comparative antioxidants (CAO-1-4) comprising Phenylenediamine (PDA), hindered (tertiary) phenol, and PDA/hindered (tertiary) phenol blends are along with the antioxidants of the present disclosure and are also shown in fig. 1-4.

Example 14

Oxidation resistance test/Oxidation stability test-heavy Coke naphtha

To demonstrate the effectiveness of the compounds of the present disclosure in stabilizing a reactive naphtha sample, heavy coker naphthas from different refineries were used. Solutions of various aromatic amine oxides according to examples 2 to 13 were prepared in a heavy aromatic naphtha and tested according to ASTM D525 method. The ASTM D525 method involves measuring the stability of the finished gasoline under accelerated oxidation conditions. According to this method, a naphtha sample is placed in a pressure vessel equipped with a digital manometer along with a candidate aromatic amine oxide. The pressure vessel was closed and oxygen was introduced into the vessel through a Schrader-type valve fitting until an overpressure of about 689.5kPa (100psig) was reached. The vessel is then heated to about 100 ℃ in an oil or dry bath until a pressure drop is found, indicating a loss of antioxidant activity. The time period elapsed before the pressure drop is manifested is referred to as the "turning point", while a longer induction time indicates an enhanced stabilizer efficacy of the candidate treatment. In this example, the aromatic amine oxide antioxidant was used at 500 ppm.

The oxidized aromatic amine compounds of the present disclosure exhibit antioxidant properties that are at least as excellent as and in many cases also superior to other commercially available or art-known antioxidants (see, e.g., CAO-1-4).

The results are shown in FIG. 1.

Example 15

Oxidation resistance test/Oxidation stability test-heavy Coke naphtha

The effectiveness of the compounds of the present disclosure in stabilizing coker naphtha, solutions of various aromatic amine oxides according to examples 2 to 13 were prepared in heavy aromatic naphtha and tested according to ASTM D525 method, as described in example 14. In this example, the oxidized aromatic amine antioxidant was used at 1000 ppm. The results are shown in FIG. 2.

Example 16

Oxidation resistance test/Oxidation stability test-DCU-1 coker naphtha

The effectiveness of the compounds of the present disclosure in stabilizing delayed coking unit (DCU-1) coker naphtha, solutions of various aromatic amine oxides according to examples 2 to 13 were prepared in heavy aromatic naphtha and tested according to ASTM D525 method, as described in example 14. In this example, the aromatic amine oxide antioxidant was used at 250 ppm.

The results are shown in FIG. 3.

Example 17

Oxidation resistance test/Oxidation stability test-heavy Coke naphtha

The effectiveness of the compounds of the present disclosure in stabilizing coker naphtha, solutions of various aromatic amine oxides according to examples 2 to 13 were prepared in heavy aromatic naphtha and tested according to ASTM D525 method, as described in example 14. In this example, the aromatic amine oxide antioxidant was used at 500 ppm.

The results are shown in fig. 4 and illustrate the change in pressure over time.