Efficient, low-energy, low-waste alkylation and arylation method for producing safe and environmentally friendly disubstituted diphenylamine antioxidants.

Abstract

Disclosed are liquid dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions comprising a high concentration of dialkylated diphenylamine, low concentrations of monosubstituted and trisubstituted diphenylamines, and less than 0.1% by mass of unsubstituted diphenylamine. The novel compositions may be prepared by controlled alkylation of diphenylamine with at least one first olefin, subsequent removal of the first olefin by distillation, and alkylation with at least one second olefin, which can effectively reduce the amount of unsubstituted diphenylamine to less than 0.1% by mass and the amount of low molecular weight monosubstituted and disubstituted diphenylamines to not more than 7% by mass. The liquid dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions of this disclosure are considered safe and environmentally friendly, and their manufacturing methods have high reactor efficiency, low energy consumption, and generate little waste.

Description

[Technical Field]

[0001] Certain alkylated and arylated diphenylamines are well known as antioxidants for various fuels and lubricants, including mineral and synthetic oils. Alkyled diphenylamines (ADPA) and arylated diphenylamines may be primarily used in transport and industrial lubricant applications in high-temperature or other more demanding operating environments. For example, ADPA antioxidants may be used to inhibit oxidation and maintain performance in engine oils, industrial oils, gear oils, hydraulic fluids, turbine oils, and greases.

[0002] Numerous methods exist for producing liquid alkylated diphenylamine and / or alkylated arylated diphenylamine compositions containing a substantial amount of disubstituted diphenylamine. For example, U.S. Patents 6,315,925, 6,355,839, and 2,003,115 describe a method for preparing such compositions by using a one-step reaction with a composite mixture of olefin isomers, such as nonene (propylene trimer), as the alkylating agent. Monoalkyldiphenylamine and dialkyldiphenylamine components obtained from isomer mixtures of propylene oligomers or butene oligomers remain stable in liquid form at ambient temperature. U.S. Patents 2,530,769 and 4,824,601 disclose a method for preparing mixed derivatives of diphenylamine (DPA) by alkylating DPA with a mixture of two olefins in a one-step reaction. U.S. Patents 2,943,112 and 6,204,412 disclose a method for preparing mixed derivatives of diphenylamine by sequentially alkylating diphenylamine with two olefins in a two-step reaction method. These methods can produce only liquid alkylated DPA compositions containing less than 80% by mass of dialkylated DPA, more than 0.1% by mass of residual unsubstituted DPA, more frequently more than 0.25% by mass of residual unsubstituted DPA, and more than 10% by mass of monosubstituted DPA, based on the total mass of substituted and unsubstituted DPA in the composition.

[0003] U.S. Patents 4,798,684 and 9,890,346 disclose the preparation of a liquid disubstituted DPA containing more than 80% by mass of dialkyldiphenylamine by using two olefins in a two-step alkylation method. Due to catalyst selection and / or reaction conditions, the resulting composition contains undesirable amounts of monoalkylated DPA and unsubstituted DPA. These harmful components either remain in the final product composition after separation or require distillation at high vacuum and high temperature to remove them. Specifically, the method disclosed in U.S. Patent 4,798,684 applies temperatures above 180°C in the two olefin alkylation steps, resulting in the formation of undesirable amounts of monobutyl DPA and dibutyl DPA in the final product, e.g., more than 10% by mass, possibly up to 20% by mass, and more than 1% by mass of unsubstituted DPA. In addition, this method consumes a large amount of energy and produces an inactivated solid acidic clay catalyst that may not be recyclable. The method disclosed in U.S. Patent 9,890,346 produces aqueous waste from a metal halide catalyst. This catalyst cannot be recovered. Furthermore, this method generates a large amount of organic waste because it uses an excess amount of olefin to inhibit dealkylation and distillation in quantities exceeding 17% by mass of the product. The distillate contains diphenylamine, monoalkyldiphenylamine, and low molecular weight dialkyldiphenylamine. In addition, this method consumes a large amount of energy and has low reactor utilization efficiency.

[0004] For many years, amine antioxidants were considered high-performance chemicals safe for humans and the environment. However, commercially available amine antioxidants based on diphenylamine and the monoalkylated and unsubstituted DPA components in their compositions have been subject to increased environmental and safety scrutiny. The first reports of reproductive / developmental toxicity emerged from the findings of the 2014 OECD 422 study on Irganox® L57, Naugalube® 750, and similar commercially available products. Subsequently, in 2021, diphenylamine was classified as potentially carcinogenic (2B). Since then, increased research into toxicity and environmental fate has revealed evidence that two widely used commercially available diphenylamine-based antioxidants may cause reproductive toxicity in humans after skin or oral exposure, and that diffusion may lead to a potential risk of chronic aquatic toxicity to aquatic organisms. These two commercially available alkylated diphenylamine products contain residual diphenylamine in a concentration range of over 0.1% by mass to 2% by mass, as well as monoalkyldiphenylamine in 15% to 50% by mass, dialkyldiphenylamine in 50% to 80% by mass, and trialkyldiphenylamine in less than 15% by mass. These are associated with trade names such as Irganox® L57, Irganox® L67, Naugalube® 750, Naugalube® 438L, Lubrizol® 5161, Songnox® L670, Songnox® L570, Rianox® 5057, Rianox® 5067, and Yablub® DND.

[0005] In the recently published Harmonized Classification and Labelling (CLH) proposal by ANSES (French Agency for Food, Environment, and Occupational Health and Safety), models of LogKow, water solubility, and toxicokinetic parameters for the major components of these two antioxidant families were documented. The data, originally derived from a 2016 OECD report, shows that monoalkyl DPA (butyl, octyl, and nonyl) and dibutyldiphenylamine components have lower molecular weights, e.g., less than 300 daltons, LogKow values ​​less than 8, and higher water solubility compared to dioctyldiphenylamine and dinonyldiphenylamine components. Consequently, these oral bioavailability and toxicokinetic parameters, measured by AUC 0-inf* (area under the curve from 0 to infinity), are considerably higher compared to dialkyldiphenylamine components with molecular weights greater than 300 daltons. The modeling results and findings disclosed in WO 2023 / 209038 A1 suggest that monosubstituted diphenylamines and disubstituted diphenylamines with low molecular weights of less than approximately 300 daltons, regardless of molecular weight, are considerably more likely to cause harm to humans and the environment compared to disubstituted diphenylamines. This trend is also reflected in the results of reproductive toxicity screening tests (OECD 421) conducted on Irganox® L57 and Irganox® L67, highlighting the correlation between the presence of monosubstituted diphenylamines and disubstituted diphenylamines with molecular weights of less than approximately 300 daltons in diphenylamine-based antioxidant compositions and their bioavailability.

[0006] While the two commercially available liquid alkylated diphenylamines mentioned above are classified as hazardous substances due to their reproductive toxicity, commercially available alkylated and arylated diphenylamine products such as Naugalube® 438, Vanlube® 81, Naugalube® AMS, and Dusantox® 86 are not classified as hazardous substances. These products contain less than 0.1% by mass of unsubstituted diphenylamine, less than 6% by mass of monosubstituted diphenylamine, usually less than 1% by mass (frequently less than 0.2% by mass) of disubstituted diphenylamine with a molecular weight of less than 300 daltons, and more frequently more than 85% by mass of disubstituted diphenylamine with a molecular weight of more than 300 daltons. However, these products are in a solid state at room temperature (25°C). Compared to liquid additives, solid additives are generally less preferred. Solid additives frequently require additional processing, such as heating to temperatures above their melting point and / or safety precautions during use (mixing into lubricant formulations), which can make them inconvenient and inefficient in terms of storage and handling compared to liquid additives at room temperature. [Overview of the project] [Problems that the invention aims to solve]

[0007] Based on current regulations and product safety standards guidance, safe and environmentally friendly dialkylated diphenylamines and / or alkylated arylated disubstituted diphenylamines should contain unsubstituted diphenylamines, monosubstituted diphenylamines, and disubstituted diphenylamines with a molecular weight of less than 300 daltons in unproblematic amounts. An unproblematic amount of unsubstituted diphenylamine is less than 0.1% by mass, e.g., less than 0.02% by mass, based on the total mass of unsubstituted and substituted diphenylamines. An unproblematic amount of monosubstituted diphenylamines and disubstituted diphenylamines with a molecular weight of less than 300 daltons is less than 7% by mass, e.g., less than 5% by mass, or less than 3% by mass, based on the total mass of unsubstituted and substituted diphenylamines. In addition, it is advantageous for safe and environmentally friendly alkylated and arylated diphenylamines to be liquid at ambient temperature (25°C) for convenience and safety in handling the substances. Safe and environmentally friendly alkylated and arylated diphenylamines are commercially available, such as Naugalube® 438, Vanlube® 81, Naugalube® AMS, and Dusantox® 86. However, these products are solid at 25°C. As a result, there is an unmet need in the industry for the production of dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions in liquid form using a low-energy and environmentally friendly method that balances effective antioxidant properties with reduced toxicity to humans and the environment. [Means for solving the problem]

[0008] In this specification, the compositions and manufacturing methods of the present disclosure satisfy these needs and overcome the aforementioned limitations in the art. In particular, the present disclosure relates to an efficient, energy-efficient, and low-waste method for producing dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions that meet specific technical performance objectives set by industrial standards and have lower toxicity to humans and the environment compared to commercially available liquid alkylated DPA products (e.g., Irganox® L57, Irganox® L67, Naugalube® 438L, or Naugalube® 750). [Modes for carrying out the invention]

[0009] According to one aspect of the present invention, an efficient, energy-efficient, and low-waste-risk method is provided for producing dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions. This method provides (i) A reaction mixture comprising a first olefin containing a mixture of alkene isomers selected from unsubstituted diphenylamine, propylene oligomer and butene oligomer, and an acidic catalyst, such as an acidic clay catalyst, is reacted to produce a disubstituted diphenylamine of formula I. [ka] Monosubstituted diphenylamine of formula IV, [ka] and a step of forming an intermediate reaction mixture containing a mixture of isomers of residual unsubstituted diphenylamine (R1 is derived from a mixture of alkene isomers), (ii) a step of distilling more than 90%, for example more than 95%, of any unreacted portion of the mixture of alkene isomers, and (iii) The following formula: [ka] (Here, R'1 and R'2 are independently H or linear or branched C)1~12 an alkyl (e.g., C 4~12 alkyl), and R'3 is H or a straight-chain or branched C 1~4 alkyl) adding at least one second olefin selected from the olefins of to the intermediate reaction mixture and reacting the intermediate reaction mixture in the presence of an acidic alkylation catalyst to produce a dialkylated diphenylamine and / or an alkylated arylated disubstituted diphenylamine composition which may include where the proportion of the reaction mixture alkylated by the mixture of the first olefins in step (i) and the extent of the residual unsubstituted diphenylamine alkylated by the second olefin in step (iii) are controlled such that the resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition contains: (1) A mixture of dialkylated diphenylamines of various ratios of at least 90% by mass of formulas I, II, and III based on the total mass of the unsubstituted diphenylamine and substituted diphenylamine in the composition:

Chemical formula

Chemical formula

[0010] The resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition may contain at least 95% by mass of a mixture of disubstituted diphenylamines of formulas I, II, and III, based on the total mass of unsubstituted diphenylamines and disubstituted diphenylamines in the composition. At least 70% by mass, preferably at least 80% by mass of the mixture of dialkylated diphenylamines may contain para,para'-disubstituted diphenylamines. The resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition may contain less than 0.02% by mass of unsubstituted diphenylamine, based on the total mass of unsubstituted diphenylamines and substituted diphenylamines in the composition.

[0011] The resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition may contain a mixture of monosubstituted diphenylamine and disubstituted diphenylamine with a molecular weight of less than 300 daltons, based on the total mass of unsubstituted and substituted diphenylamine in the composition, in an amount of less than 5% by mass.

[0012] The resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition may contain a mixture of less than 3% by mass of trisubstituted diphenylamine, based on the total mass of unsubstituted and substituted diphenylamine in the composition.

[0013] At least one second olefin may be selected from diisobutylene, styrene, α-methylstyrene, α-alkylstyrene, 2-methylbutene-1, 2-methylbutene-2, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, or commercial-grade diisobutylene.

[0014] In step (i), the reaction mixture may react at a temperature range of about 120°C to about 170°C, more frequently about 135°C to about 165°C, and more frequently about 145°C to about 160°C. In step (iii), the reaction mixture may react at a temperature range of about 80°C to about 150°C, more frequently about 100°C to about 140°C, or 115°C to about 135°C.

[0015] Another aspect of the present invention provides a lubricating oil composition. The lubricating oil composition may comprise (A) a lubricating oil and (B) a dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition disclosed herein in an amount effective to provide antioxidant activity. The amount of dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition present in the lubricating oil composition may be about 0.1% by mass to about 10% by mass, based on the total mass of the lubricating oil composition.

[0016] An additional aspect of the present invention provides a method for producing safe and environmentally friendly dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions. The method involves reacting a reaction mixture comprising a dialkylated diphenylamine, a monoalkylated diphenylamine and less than 25% by mass of unsubstituted diphenylamine, an acidic alkylation catalyst, preferably an acidic clay catalyst, and at least one olefin selected from the following formulas: [ka] (Here, R'1 and R'2 are independently H or linear or branched C) 1~12 Alkyl (e.g., C 4~12 It is an alkyl group, and R'3 is H or a linear or branched C. 1~4 (It is alkyl.) The process includes a step of producing a dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition, The resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions are (1) A mixture of dialkylated diphenylamines of formulas I, II, and III in various proportions, at least 90% by mass, based on the total mass of unsubstituted and substituted diphenylamines in the composition. [ka] (R1 is derived from a mixture of alkene isomers of propylene oligomers and / or butene oligomers, and R2 is derived from at least one olefin selected from the following formulas.) [ka] (2) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, less than 0.1% by mass of unsubstituted diphenylamine, (3) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, less than 7% by mass, (a) Monosubstituted diphenylamines of formulas IV and V [ka] (R1 is derived from a mixture of alkene isomers of propylene oligomers and / or butene oligomers, and R2 is derived from at least one olefin), and (b) Disubstituted diphenylamines with a molecular weight of less than 300 daltons A mixture of, and (4) A mixture of trisubstituted diphenylamines in a total mass of less than 5% by mass, based on the total mass of unsubstituted diphenylamines and substituted diphenylamines in the composition. Includes, Here, the composition is liquid at ambient temperature, for example, about 20°C to about 25°C.

[0017] The resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition may contain at least 95% by mass of a mixture of disubstituted diphenylamines, based on the total mass of unsubstituted diphenylamines and disubstituted diphenylamines in the composition.

[0018] Furthermore, a mixture of dialkylated diphenylamines in an amount of at least 70% by mass, preferably at least 80% by mass, may also contain para,para'-disubstituted diphenylamines.

[0019] The resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition may contain less than 0.02% by mass of unsubstituted diphenylamine, based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition.

[0020] The resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition may contain a mixture of monosubstituted diphenylamine and disubstituted diphenylamine with a molecular weight of less than 300 daltons, based on the total mass of unsubstituted and substituted diphenylamine in the composition, in an amount of less than 5% by mass.

[0021] The resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition may contain a mixture of less than 3% by mass of trisubstituted diphenylamine, based on the total mass of unsubstituted and substituted diphenylamine in the composition.

[0022] The reaction mixture may react at a temperature range of approximately 80°C to 150°C, more frequently 100°C to 140°C, and more frequently 115°C to 135°C.

[0023] In addition, at least one olefin may be selected from diisobutylene, styrene, α-methylstyrene, α-alkylstyrene, 2-methylbutene-1, 2-methylbutene-2, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, or commercial-grade diisobutylene.

[0024] According to another aspect of the present invention, the use of a dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition, prepared by the method described herein, in an amount effective in providing antioxidant activity and reducing and / or preventing the toxicity of the lubricating oil composition is provided.

[0025] Throughout this specification, unless otherwise stated, "a" or "an" means one or more than one.

[0026] For the purposes of this disclosure, “disubstituted DPA” refers to dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions. Dialkylation, diarylation, and / or alkylated arylated disubstituted (e.g., disubstituted DPA of formula II below) are also called disubstituted, and trialkylation and / or triarylation are also called trisubstituted. Furthermore, monoalkylation and / or monoarylation are also called monosubstituted. Unless otherwise specified, “substituted diphenylamine” and “substituted DPA” refer to both a single molecular species and a mixture of chemically similar components. For example, “disubstituted diphenylamine” is synonymous with “disubstituted diphenylamines.”

[0027] In one embodiment, this disclosure, Based on the total mass of substituted and unsubstituted DPA compounds in the liquid disubstituted DPA composition, approximately 90% to approximately 100% by mass, frequently approximately 93% to approximately 100% by mass, of one or more dialkylated DPAs or alkylaryl disubstituted DPAs of formulas I, II, and III. [ka] (Here, the disubstituted diphenylamine mainly consists of, for example, more than 70% by mass, frequently more than 80% by mass, para,para'-disubstituted diphenylamine (R1 is derived from a first olefin comprising a mixture of alkene isomers of propylene oligomers and / or butene oligomers, and R2 is derived from at least one second olefin comprising one olefin or a mixture of olefins having any of the following four structures), [Chemical formula] (Here, R'1 and R'2 are each independently H or a linear or branched C 1~12 alkyl (e.g., C 4~12 alkyl), and R'3 is H or a linear or branched C 1~4 alkyl).), less than 0.1% by mass, frequently less than 0.02% by mass or less, of unsubstituted DPA, less than 7% by mass, frequently less than 5% by mass or less, of monoalkylated monoarylated DPA of Formulas IV and V, and disubstituted DPA having a molecular weight less than about 300 daltons [[ID=十九]][Chemical formula] (where R1 is derived from a mixture of alkene isomers of propylene oligomers and / or butene oligomers, and R2 is derived from at least one second olefin), and less than 5% by mass, frequently less than 3% by mass, of trisubstituted DPA and tetrasubstituted DPA (trialkylated DPA and tetraalkylated DPA), (where the substituents of the trisubstituted DPA and tetrasubstituted DPA are selected from derivatives of propylene oligomers or butene oligomers and one olefin or a mixture of olefins having any one of the following four structures) [Chemical formula] It should be noted that there may be some inaccuracies in the chemical formula representation in the original text. It is recommended to double-check with the original technical content for more accurate understanding. Also, the "

化

[0028] The disubstituted DPA compositions of the present invention are liquid at ambient temperature, soluble or miscible with many lubricants and polymers, and provide excellent antioxidant activity and deposit-inhibiting effects as measured by TEOST testing. For the purposes of this disclosure, “ambient temperature” means a temperature in the range of about 20°C to about 25°C. In this specification, the term “liquid” as used with respect to the disubstituted DPA compositions of this disclosure means a liquid physical form that remains liquid after being stored at ambient temperature for at least 30 days.

[0029] The reactive alkylated DPA composition of this disclosure comprises about 25% by mass or less of unreacted DPA and about 4% by mass or less of trialkylated DPA formed by the reaction of DPA and a selected first olefin in the presence of an acidic clay catalyst.

[0030] In many embodiments, the mass ratio of the first olefin alkylated in the first step to DPA is about 1 to about 7, and often about 2 to about 5.

[0031] As is understood in the art, “propylene trimmer,” “propylene tetramer,” and “propylene pentamer” as used herein are complex mixtures of branched alkene isomers derived from the oligomerization of propylene, respectively. In many embodiments, the first olefin may include a mixture of alkene isomers of propylene oligomer and / or butene oligomer. The propylene trimmer, propylene tetramer, and propylene pentamer are C9-, C9-, respectively. 12 -, and C 15 - Contains a rich array of isomers. As is understood in this field, in the case of propylene trimmers, C9 isomers (e.g., C8 and C) are abundant. 10 In addition to the above, in the case of propylene tetramer, C 12 isomers (e.g., C 11 and C 13 In addition to ) in the case of propylene pentamer, C 15 isomers (e.g., C 14 and C 16 In addition to the above, a certain amount of other carbon chain lengths may be present. Propylene trimmers, propylene tetramers, and propylene pentamers suitable for this disclosure are known and commercially available or can be prepared by known oligomerization methods. Often, at least 60% by mass, at least 70% by mass, at least 80% by mass, or more of the propylene oligomer are C9 isomers (in the case of propylene trimmers), C 12 Isomers (in the case of propylene tetramers), or C 15 This results in isomers (in the case of propylene pentamers). As is understood in the art, "butentrimers" and "butenetetramers" as used herein are complex mixtures of branched alkene isomers derived from the oligomerization of butene, respectively.

[0032] In many embodiments, at least one second olefin is any olefin or mixture of olefins having any of the following structures: [ka] Here, R'1 and R'2 may each be independently H or a linear or branched alkyl group, but the total number of carbon atoms in the second olefin is 5 to 12. In some embodiments, R'1 and R'2 may be the same. In many embodiments, R'1 and R'2 are not the same. In many embodiments, R'3 is H or a linear or branched C 1~4 It is alkyl. The second olefin represented by the above formula is known and may be commercially available and / or prepared by known methods.

[0033] Furthermore, this specification discloses methods for producing the dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions of this disclosure.

[0034] In one embodiment, a method for producing a dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition is: (i) A reaction mixture comprising an unsubstituted DPA, a first olefin comprising a mixture of alkene isomers selected from propylene trimmer, propylene tetramer, propylene pentamer, commercially available nonene, commercially available propylene tetramer, buten trimmer and butene tetramer, and an acidic alkylation catalyst is reacted, and based on the total mass of the reaction mixture excluding the acidic clay, 10 to 30% by mass of unreacted first olefin, less than 25% by mass, more frequently less than 20% by mass of unreacted diphenylamine, and the remainder monosubstituted DPA of formula IV, [ka] Disubstituted DPA of formula I, [ka] and a step of forming an intermediate reaction mixture containing a mixture of isomers of trisubstituted DPA at a high temperature. (ii) A step of distilling the unreacted first olefin from the intermediate reaction mixture to obtain a reactive reaction mixture of less than 10% by mass, and frequently less than 5% by mass. (iii) The step of adding at least one second olefin selected from the following formulas to the intermediate reaction mixture and reacting the intermediate reaction mixture in the presence of an acidic alkylation catalyst to produce a disubstituted DPA composition, [ka] (Here, R'1 and R'2 are independently H or linear or branched C) 1~12 Alkyl (e.g., C 4~12 It is an alkyl group, and R'3 is H or a linear or branched C. 1~4 (It is alkyl.) Here, the proportion of the reaction mixture alkylated by the alkene isomer mixture in step (i) and the degree of residual unsubstituted DPA alkylated by the second olefin in step (ii) control the resulting disubstituted DPA composition as follows: (1) Based on the total mass of unsubstituted DPA and substituted DPA in the composition, the composition comprises at least 90% by mass, for example, at least 93% by mass or at least 95% by mass of a mixture of dialkylated DPAs of formulas I, II and III (wherein at least 70% by mass, for example, at least 80% by mass of the mixture of dialkylated DPAs includes para,para'-disubstituted DPAs), [ka] (2) Based on the total mass of unsubstituted DPA and substituted DPA in the composition, the composition contains less than 0.1% by mass, for example less than 0.02% by mass, or unsubstituted DPA that cannot be detected by chromatography. (3) Based on the total mass of unsubstituted DPA and substituted DPA in the composition, less than 7% by mass, for example less than 5% by mass or less than 3% by mass, (a) Monoalkylated DPA of formulas IV and V [ka] and (b) Disubstituted DPA with a molecular weight of less than 300 daltons It contains a mixture of, (4) The composition contains a mixture of trialkylated DPA in an amount of less than 5% by mass, for example, less than 3% by mass or less than 1% by mass, based on the total mass of unsubstituted DPA and substituted DPA in the composition. Here, the composition is a liquid at ambient temperature.

[0035] As described above, in many embodiments, based on the total mass of unsubstituted DPA and substituted DPA in the composition, 90% by mass, 95% by mass, or more of the resulting disubstituted DPA composition is a mixture of dialkylated DPA.

[0036] Frequently, unsubstituted DPA is present in compositions at a concentration of less than 0.1% by mass, for example less than 0.02% by mass, based on the total mass of unsubstituted and substituted DPA in the composition, or is not detectable by gas chromatography.

[0037] Typically, based on the total mass of unsubstituted and substituted DPA in the composition, less than 5% by mass, for example, less than 3% by mass or less than 1% by mass of the resulting composition is excess alkylated DPA, particularly DPA having three or more alkyl substituents, such as trisubstituted diphenylamine.

[0038] In addition, based on the total mass of unsubstituted and substituted DPA in the composition, less than 7% by mass of the resulting composition, for example, less than 5% by mass or less than 3% by mass, consists of monoalkylated DPA and disubstituted DPA with a molecular weight of less than 300 daltons.

[0039] Manufactured using low-energy and environmentally friendly methods, the resulting liquid disubstituted DPA composition offers both effective antioxidant properties and reduced toxicity to humans and the environment.

[0040] The alkylation reactions in steps (i), (ii), and (iii) above are Friedel-Crafts type reactions catalyzed by an acidic catalyst. The acidic alkylation catalysts used in steps (i) and (iii) do not need to be the same, but are often the same. This disclosure is not limited to a specific type of solid acidic alkylation catalyst, and includes various catalysts for Friedel-Crafts type reactions that are known in the art, as well as mixtures of such catalysts. For example, suitable catalysts include acidic clay, zeolite, and phosphotungstic acid. Preferably, an acidic clay catalyst is used in this method. Acidic clay catalysts have the additional advantage of preferentially promoting the formation of dialkylated DPA and producing a pale colored product. The acidic clay catalyst can be easily removed by decantation or filtration and can be reused many times.

[0041] Examples of suitable acidic clays include bentonite-based acid-activated clays such as F-20X, F-24X, F-25X from EP Engineered Clays and Tonsil® from Clariant, Montmorillonite K-10, K30, APC from Sud-Chemie, Envirocat® EPZ-10, EPZG, or EPIC from Contract Chemicals, and acid-activated phyllosilicates, such as those commercially available under the name Fulcat® from ALTANA's BYK division, e.g., Fulcat®-22B, -22F, and -435.

[0042] In step (i), an unsubstituted DPA is reacted with a reaction mixture comprising a first olefin containing a mixture of alkene isomers selected from propylene trimmer, propylene tetramer and propylene pentamer, commercially available nonene, commercially available propylene tetramer, buten trimmer, and butene tetramer, and an acidic alkylation catalyst to form an intermediate reaction mixture containing a mixture of disubstituted DPA isomers, residual unsubstituted DPA, unreacted first olefin, and an acidic clay catalyst. The alkene isomer mixture in the reaction mixture may be propylene trimmer, propylene tetramer, propylene pentamer, commercially available nonene, commercially available propylene tetramer, buten trimmer, butene tetramer, or any combination thereof, as described herein. In many embodiments, the alkene isomer mixture is selected from propylene trimmer, propylene tetramer, commercially available nonene, and commercially available propylene tetramer. More frequently, the alkene isomer mixture is commercially available nonene and commercially available propylene tetramer. Frequently, mixtures of alkene isomers are commercially available nonene.

[0043] As detailed below, only a portion of the unsubstituted DPA in the reaction mixture of step (i) is alkylated with a propylene trimmer, propylene tetramer and / or propylene pentamer, commercially available nonene, commercially available propylene tetramer, buten trimmer, or butene tetramer. Therefore, a certain amount of residual unsubstituted DPA remains in the intermediate reaction mixture formed by the alkylation in step (i).

[0044] In many embodiments, in step (ii), the unreacted first olefin is distilled from the intermediate reaction mixture. In alternative embodiments, in step (ii), the unreacted first olefin is not distilled from the intermediate reaction mixture. Rather, the first olefin remains in the intermediate reaction mixture.

[0045] In step (iii), at least one second olefin is added to the intermediate reaction mixture, and the intermediate reaction mixture is reacted in the presence of an acidic alkylation catalyst to produce a disubstituted DPA composition. At least one second olefin is selected from the following formulas. [ka] (Here, R'1 and R'2 are independently H or linear or branched C) 1~12 Alkyl (e.g., C 4~12 It is an alkyl group, and R'3 is H or a linear or branched C. 1~4 The olefins represented by the above formula (which are alkyl) are known, commercially available, and / or may be prepared by known methods.

[0046] Frequently, at least one second olefin is commercially available diisobutylene, styrene, α-methylstyrene, α-alkylstyrene, 2-methylbutene-1, 2-methylbutene-2, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, or any combination thereof, for example, from Lyondell Basell, Maruzen, or Idemitsu, and is about 95% by mass or more of 2,4,4-trimethylpentene isomers. In many embodiments, the second olefin is diisobutylene. For example, frequently, at least 50% by mass of the second olefin, for example, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or more is diisobutylene.

[0047] In some embodiments, the mixture of alkene isomers is a propylene trimer and / or propylene tetramer, and at least one second olefin is diisobutylene.

[0048] In some embodiments, the mixture of alkene isomers is a propylene trimmer and / or propylene tetramer, and at least one second olefin is α-methylstyrene.

[0049] Excess propylene oligomers or butene oligomers present in the intermediate reaction mixture resulting from the first alkylation reaction are frequently removed from the intermediate reaction mixture (e.g., by stripping or distillation, frequently under vacuum) before adding at least one second olefin, and the recovered material may be recycled for reuse in this method. Alternatively, if at least one second olefin is more reactive than a mixture of alkene isomers selected from propylene trimmers, propylene tetramers, propylene pentamers, buten trimmers, and butene tetramers, this method may be carried out without removing excess propylene oligomers from the intermediate reaction mixture before adding the second olefin. Preferably, excess propylene oligomers or butene oligomers present in the intermediate reaction mixture resulting from the first alkylation reaction are removed by distillation, which frequently requires vacuum, for the advantages of a faster reaction, higher reactor efficiency / load, and convenient separation and subsequent recycling of excess portions of both the recovered first and second olefins.

[0050] An additional acidic catalyst may be added to the intermediate reaction mixture to catalyze the alkylation in step (iii). The acidic catalyst from step (i) may be removed from the intermediate reaction mixture (e.g., by filtration) before adding at least one second olefin, but is not required. If the catalyst from step (i) is removed from the intermediate reaction mixture before adding the second olefin, an additional acidic catalyst is added to the intermediate reaction mixture to catalyze the alkylation in step (iii). The acidic catalyst may be recycled for reuse in this method.

[0051] In step (iii), at least one second olefin selected from the olefins of the above formula reacts efficiently and selectively with the residual unsubstituted DPA in the intermediate reaction mixture to form dialkylated DPA, and based on the total mass of unsubstituted DPA and substituted DPA, the amount of unsubstituted DPA decreases to less than 0.1% by mass, frequently less than 0.02% by mass, and the amount of monoalkylated DPA and disubstituted DPA with a molecular weight of less than 300 daltons decreases to less than 7% by mass, frequently less than 5% by mass, frequently less than 3% by mass.

[0052] Importantly, the proportion of unsubstituted DPA in the reaction mixture alkylated by the alkene isomer mixture in step (i), and the degree of residual unsubstituted DPA alkylated by at least one second olefin in step (iii), control the resulting disubstituted DPA composition as follows: (1) Based on the total mass of unsubstituted diphenylamines and substituted diphenylamines in the composition, the composition contains at least 90% by mass, for example, at least 93% by mass or at least 95% by mass of a mixture of dialkylated diphenylamines of formulas I, II, and III, [ka] (R1 is derived from a mixture of alkene isomers, and R2 is derived from at least one secondary olefin.) (2) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, the composition contains less than 0.1% by mass, for example less than 0.02% by mass, or unsubstituted diphenylamine that cannot be detected by chromatography. (3) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, less than 7% by mass, for example less than 5% by mass or less than 3% by mass, (a) Monoalkylated diphenylamines of formulas IV and V [ka] (Here, R1 is derived from a mixture of first olefins, and R2 is derived from at least one second olefin.) and (b) Disubstituted DPA with a molecular weight of less than 300 daltons It contains a mixture of, (4) The composition contains a mixture of trialkylated diphenylamines in an amount of less than 5% by mass, for example, less than 3% by mass or less than 1% by mass, based on the total mass of unsubstituted diphenylamines and substituted diphenylamines in the composition. Here, the composition is a liquid at ambient temperature.

[0053] In particular, in step (i), the proportion of unsubstituted DPA in the reaction mixture alkylated by a first olefin containing a mixture of alkene isomers of propylene oligomers and / or butene oligomers is controlled to ensure that the final disubstituted DPA composition is liquid at ambient temperature and to suppress the formation of excess alkylated DPA components, especially trialkylated DPA. In this regard, in order to ensure that the final disubstituted DPA composition formed after subsequent alkylation with at least one second olefin in step (iii) is liquid at ambient temperature, a sufficiently large proportion of unsubstituted DPA in the reaction mixture in step (i) is alkylated by the mixture of first olefins. The proportion of unsubstituted DPA alkylated by the propylene oligomer or butene oligomer in step (i) is not high enough that the final product formed after subsequent alkylation with the second olefin in step (iii) has more than 5% by mass of excess alkylated DPA components, especially trialkylated DPA, based on the total mass of unsubstituted diphenylamine and substituted diphenylamine, and to form dialkylated DPA in the reaction intermediate composition.

[0054] In step (iii), residual unsubstituted DPA in the intermediate reaction mixture is alkylated with at least one second olefin, and the concentration of unsubstituted DPA in the resulting disubstituted DPA composition is less than 0.1% by mass, for example less than 0.02% by mass, based on the total mass of substituted and unsubstituted DPA in the final composition, or is undetectable by gas chromatography.

[0055] Frequently, at least 60%, at least 70%, at least 80%, or at least 90% of the unsubstituted DPA in the reaction mixture is alkylated with a mixture of first olefins selected from propylene trimmers, propylene tetramers, propylene pentamers, commercially available nonene, commercially available propylene tetramers, buten trimmers, and butene tetramers. In certain embodiments, the mixture of first olefins is a propylene trimmer, and the proportion of unsubstituted DPA in the reaction mixture alkylated by the propylene trimmer is at least 80% or at least 90%. In certain embodiments, the mixture of first olefins is commercially available nonene, and the proportion of unsubstituted DPA in the reaction mixture alkylated by the commercially available nonene is at least 70%, for example, at least 80% or at least 90%. The precise lower limit of the proportion of unsubstituted DPA that needs to be alkylated with a propylene oligomer or butene oligomer to ensure a liquid final product varies depending on the identity of the specific mixture of the first olefin and the specific second olefin, as well as the reaction conditions such as the type of catalyst and reaction temperature.

[0056] Generally, the reaction conditions, such as temperature, pressure, and the concentrations of the reactants, are the same as those used in other Friedel-Crafts reactions known in the art. Examples of suitable reaction conditions are, but are not limited to, those listed below.

[0057] Frequently, the molar ratio of a mixture of a first olefin selected from propylene trimers, propylene tetramers, and propylene pentamers to the unsubstituted DPA alkylated in step (i) is in the range of approximately 2.5:1 to approximately 3.5:1, and frequently in the range of approximately 2.8:1 to approximately 3.2:1. Frequently, the mass ratio of the acidic alkylation catalyst to the unsubstituted DPA alkylated in step (i) is in the range of approximately 0.2:1 to approximately 1:1, and frequently in the range of approximately 0.4:1 to approximately 0.8:1.

[0058] The preferred reaction temperature for the alkylation reaction of the unsubstituted DPA and the mixture of the first olefin in step (i) is frequently in the range of about 120°C to about 170°C, frequently about 135°C to about 165°C, and more frequently about 145°C to about 160°C. Within the preferred temperature range, the acidic clay exhibits optimized reactivity for the alkylation reaction with the first olefin and deactivates at a slower rate compared to the deactivation rate at temperatures above 170°C. Furthermore, in acidic clay catalysts with slower deactivation rates, the catalyst may be recycled.

[0059] This method is not limited to any specific technique for preparing the reaction reaction. The reaction components may be added in a single dose or in multiple additions, and may be added to the reaction mixture by weighing at a constant rate, a variable rate, or by another addition method.

[0060] The reaction of unsubstituted DPA with a mixture of a first olefin selected from propylene trimmers, propylene tetramers, propylene pentamers, commercially available nonene, commercially available propylene tetramers, buten trimmers, and butene tetramers allows the reaction to proceed until a target proportion of unsubstituted DPA is alkylated, as described above.

[0061] In reaction step (ii), more than 90% by mass, for example more than 95% by mass, of unreacted first olefin is removed from the intermediate reaction mixture by vacuum distillation. Unsubstituted and disubstituted DPA are not removed during the distillation process. Distillation may be carried out under vacuum at an absolute pressure of 5 Torr to 100 Torr, and more frequently, 10 Torr to 30 Torr.

[0062] In the alkylation reaction of step (iii), the molar ratio of at least one second olefin in the intermediate reaction mixture to residual unsubstituted DPA and monosubstituted diphenylamine is frequently in the range of about 2:1 to about 7:1, and more frequently in the range of about 3:1 to about 5:1. The method is not limited to any particular technique for adding at least one second olefin to the intermediate reaction mixture. The second olefin may be added in a single dose or in multiple doses, and may be added to the reaction mixture by weighing at a constant rate, a variable rate, or by another method of addition.

[0063] Frequently, the mass ratio of the acidic alkylation catalyst to the residual unsubstituted DPA in the intermediate reaction mixture is in the range of approximately 0.4:1 to approximately 1:1, and frequently, it is in the range of approximately 0.6:1 to approximately 0.8:1.

[0064] The preferred reaction temperatures for the alkylation reaction of residual unsubstituted DPA with at least one second olefin in step (iii) are frequently in the range of about 80°C to about 150°C, frequently in the range of about 80°C to about 140°C, frequently in the range of about 100°C to about 140°C, and frequently in the range of 115°C to about 135°C. The preferred temperature range allows the reaction mixture to have a low concentration of unsubstituted diphenylamine when the reaction reaches equilibrium. For example, the temperature range of about 80°C to about 135°C promotes the alkylation of diphenylamine with the second olefin, producing a low concentration of unsubstituted diphenylamine. Furthermore, within the preferred temperature range, the acidic clay can optimize the reactivity to the alkylation reaction with the second olefin, but does not catalyze the decomposition of the second olefin to form smaller olefins. That is, at temperatures above 160°C, the acidic clay catalyzes the decomposition of the second olefin, which decomposes into lower molecular weight molecules that are more reactive to alkylation compared to the second olefin. For example, when diisobutylene or other vinylidene olefins are used as the second olefin, they decompose at a much slower rate compared to the decomposition rate that occurs at temperatures above 160°C. At temperatures above 160°C, acidic clay catalyzes the decomposition of diisobutylene to isobutylene. Compared to diisobutylene, isobutylene has a lower molecular weight and is more reactive to alkylation. This results in the formation of monosubstituted diphenylamines and disubstituted diphenylamines with a molecular weight of less than 300 daltons.

[0065] The reaction between the residual unsubstituted DPA in the intermediate reaction mixture and the second olefin is allowed to proceed until the concentration of unsubstituted DPA in the product is less than 0.1% by mass, for example less than 0.02% by mass, based on the total mass of substituted and unsubstituted DPA in the product composition, or until it becomes undetectable by gas chromatography. In addition, the reaction between the monosubstituted DPA in the intermediate reaction mixture and the second olefin is allowed to proceed until the concentration of monosubstituted DPA in the product is less than 5% by mass, for example less than 3% by mass, based on the total mass of substituted and unsubstituted DPA in the product composition.

[0066] The alkylation reactions of this disclosure are not limited to a specific type of reaction vessel and may be carried out in an open reaction vessel, for example under reflux conditions, or in a closed reaction vessel under pressure, frequently at a pressure of less than 60 psig, for example, less than 40 psig or less than 20 psig. The reactions may be carried out in the presence of an added organic solvent, but are frequently carried out in the absence of the added solvent.

[0067] As described above, the ratio of unsubstituted DPA alkylated by a propylene oligomer to the ratio of residual unsubstituted DPA alkylated by at least one second olefin may be adjusted to optimize the properties and performance of the composition (particularly deposit and oxidation control). For example, in a given reaction system of a specific propylene oligomer (first olefin), a catalyst, and a second olefin, the ratio may be optimized to obtain a desired liquid composition while maintaining or maximizing a high dialkylated DPA content in the resulting disubstituted DPA composition, in order to optimize deposit and oxidation control.

[0068] The acidic alkylation catalyst can be removed from the disubstituted DPA composition by filtration or other known separation methods. Unreacted olefins (and olefin by-products) may be removed from the disubstituted DPA composition by known techniques, e.g., stripping or distillation, frequently under vacuum. The temperature for distilling the olefins is usually below 165°C, which is obtained by steam heating. Unreacted first and second olefins may be recycled for reuse in this method.

[0069] The disubstituted DPA compositions of this disclosure are useful as antioxidants in lubricants and polymers, etc. In particular, the disubstituted DPA compositions provide excellent antioxidant activity in lubricants, as well as excellent sediment and sludge control effects, especially in motors, engines, turbines, chains, gears, hydraulics, compressors, and other lubricating oils and lubricating fluids, as well as applications in industrial, marine, aerospace, automotive and grease applications, industrial greases and automotive greases.

[0070] In an alternative manufacturing method, a method for producing a dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition comprises reacting a reaction mixture containing a dialkylated diphenylamine, a monoalkylated diphenylamine, and an unsubstituted diphenylamine in an amount less than 25% by mass, for example less than 20% by mass, less than 15% by mass, or less than 10% by mass, an acidic clay catalyst, and at least one olefin selected from the following formulas. [ka] (Here, R'1 and R'2 are independently H or linear or branched C) 1~12 Alkyl (e.g., C 4~12 It is an alkyl group, and R'3 is H or a linear or branched C. 1~4 The olefin represented by the above formula (which is alkyl) is known, commercially available, and / or may be prepared by known methods. The aforementioned reaction mixture is a liquid mixture derived from the reaction of an unsubstituted or substituted diphenylamine with a mixture of alkene isomers of a propylene oligomer and / or a butene oligomer.

[0071] The resulting product is (1) Based on the total mass of unsubstituted diphenylamines and substituted diphenylamines in the composition, the composition comprises a mixture of dialkylated diphenylamines of formulas I, II, and III in an amount of at least 90% by mass, for example, at least 93% by mass, or at least 95% by mass. [ka] (R1 is derived from a mixture of alkene isomers of propylene oligomers and / or butene oligomers, and R2 is derived from at least one secondary olefin.) (2) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, the composition contains less than 0.1% by mass, for example less than 0.02% by mass, or unsubstituted diphenylamine that cannot be detected by chromatography. (3) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, less than 7% by mass, for example less than 5% by mass or less than 3% by mass, (a) Monosubstituted diphenylamines of formulas IV and V [ka] (R1 is derived from a mixture of alkene isomers of propylene oligomers and / or butene oligomers, and R2 is derived from at least one secondary olefin.) and (b) Disubstituted DPA with a molecular weight of less than 300 daltons It contains a mixture of, (4) The composition contains a mixture of trialkylated diphenylamines in an amount of less than 5% by mass, for example, less than 3% by mass or less than 1% by mass, based on the total mass of unsubstituted diphenylamines and substituted diphenylamines in the composition. Here, the composition is liquid at ambient temperature.

[0072] In many embodiments, alternative methods for producing alkylated DPA compositions or arylated DPA compositions are used, and based on the total mass of unsubstituted DPA and substituted DPA in the composition, 93% by mass, 95% by mass, or more of the resulting disubstituted DPA composition is a mixture of dialkylated DPA. Frequently, unsubstituted DPA is present in the resulting composition in less than 0.1% by mass, e.g., less than 0.02% by mass, based on the total mass of unsubstituted DPA and substituted DPA in the composition. Typically, based on the total mass of unsubstituted DPA and substituted DPA in the composition, less than 5% by mass, e.g., less than 3% by mass or less than 1% by mass of the resulting composition is excess alkylated DPA, particularly trisubstituted DPA. In addition, based on the total mass of unsubstituted DPA and substituted DPA in the composition, less than 7% by mass, e.g., less than 5% by mass or less than 3% by mass of the resulting composition is disubstituted DPA with a molecular weight of less than 300 daltons, and is a mixture of monosubstituted diphenylamine and disubstituted DPA with a molecular weight of less than 300 daltons.

[0073] The alkylation reaction of the above alternative method is a Friedel-Crafts reaction catalyzed by an acidic catalyst. This disclosure is not limited to a specific type of solid acidic alkylation catalyst, and includes various catalysts for Friedel-Crafts reactions that are known in the art, as well as mixtures of such catalysts. For example, suitable catalysts include acidic clay, zeolite, and phosphotungstic acid. Preferably, an acidic clay catalyst is used in this method. The acidic clay catalyst is expected to have the additional advantage of preferentially promoting the formation of dialkylated DPA and producing a pale colored product. The acidic clay catalyst can be easily removed by decantation or filtration and reused many times.

[0074] Examples of suitable acidic clays include bentonite-based acid-activated clays such as F-20X, F-24X, F-25X from EP Engineered Clays and Tonsil® from Clariant, Montmorillonite K-10, K30, APC from Sud-Chemie, Envirocat® EPZ-10, EPZG, or EPIC from Contract Chemicals, and acid-activated phyllosilicates, such as those commercially available under the name Fulcat® from ALTANA's BYK division, e.g., Fulcat®-22B, -22F, and -435.

[0075] In the alternative method, the reaction mixture comprises a dialkylated diphenylamine, a monoalkylated diphenylamine, and less than 25% by mass of a nonalkylated diphenylamine, an acidic clay catalyst, and at least one olefin selected from the following formulas. [ka] (Here, R'1 and R'2 are independently H or linear or branched C) 1~12 Alkyl (e.g., C4~) 12 It is an alkyl group, and R'3 is H or a linear or branched C. 1~4 (It is alkyl.)

[0076] Frequently, the olefin used in the alternative method is the second olefin described above. For example, the olefin used in the alternative method is commercially available diisobutylene, styrene, α-methylstyrene, α-alkylstyrene, 2-methylbutene-1, 2-methylbutene-2, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2 ​​or any combination thereof, or commercial-grade diisobutylene having more than 95% by mass of 2,4,4-trimethylpentene isomers. In many embodiments, the olefin is diisobutylene. For example, frequently, at least 50% by mass, for example 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more or more of the olefin is diisobutylene. In some embodiments, the olefin is α-methylstyrene.

[0077] The olefin selected from the olefins represented by the above formula reacts efficiently and selectively with a reaction mixture containing dialkylated diphenylamine, monoalkylated diphenylamine, and less than 25% by mass of unsubstituted diphenylamine. Based on the total mass of unsubstituted DPA and substituted DPA, the amount of unsubstituted DPA decreases to less than 0.1% by mass, frequently less than 0.02% by mass, and the amount of monosubstituted DPA and disubstituted diphenylamine with a molecular weight of less than 300 daltons decreases to less than 5% by mass, frequently less than 3% by mass. The resulting disubstituted DPA composition is (1) Based on the total mass of unsubstituted diphenylamines and substituted diphenylamines in the composition, the composition contains at least 90% by mass, for example, at least 93% by mass or at least 95% by mass of a mixture of dialkylated diphenylamines of formulas I, II, and III, [ka] (R1 is derived from a mixture of alkene isomers of propylene oligomer and butene oligomer, and R2 is derived from at least one olefin.) (2) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, the composition contains 0.1% by mass, for example, 0.02% by mass, or unsubstituted diphenylamine that cannot be detected by chromatography. (3) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, less than 7% by mass, for example less than 5% by mass or less than 3% by mass, (a) Monosubstituted diphenylamines of formulas IV and V [ka] (R1 is derived from a mixture of alkene isomers of propylene oligomers and / or butene oligomers, and R2 is derived from at least one olefin.) and (b) Disubstituted DPA with a molecular weight of less than 300 daltons It contains a mixture of, (4) The composition contains a mixture of trisubstituted diphenylamines in an amount of less than 5% by mass, for example, less than 3% by mass or less than 1% by mass, based on the total mass of unsubstituted DPA and substituted DPA in the composition. Here, the composition is a liquid at ambient temperature.

[0078] Generally, the reaction conditions, such as temperature, pressure, and the concentrations of the reactants, are the same as those used in other Friedel-Crafts reactions known in the art. Examples of suitable reaction conditions are, but are not limited to, those listed below.

[0079] This method is not limited to any specific technique for preparing the reaction reaction. The reaction components may be added in a single dose or in multiple additions, and may be added to the reaction mixture by weighing at a constant rate, a variable rate, or by another addition method.

[0080] The alternative methods are not limited to specific techniques for adding at least one olefin to the reaction mixture. The olefin may be added in a single dose or in multiple additions, at a constant rate or variable rate, or by metering and adding it to the reaction mixture by another method.

[0081] According to the alternative method, the preferred reaction temperatures for the alternative alkylation reaction with at least one olefin are frequently in the range of about 80°C to about 150°C, frequently about 100°C to about 140°C, and frequently 115°C to about 135°C.

[0082] The reaction between the reaction mixture and the olefin can proceed until the concentration of unsubstituted DPA in the product is less than 0.1% by mass, for example less than 0.02% by mass, or until it is no longer detectable by gas chromatography, based on the total mass of substituted and unsubstituted DPA in the resulting composition.

[0083] The alkylation reactions of this disclosure are not limited to a specific type of reaction vessel and may be carried out in an open reaction vessel, for example under reflux conditions, or in a closed reaction vessel under pressure, frequently at a pressure of less than 60 psig, for example, less than 40 psig or less than 20 psig. The reactions may be carried out in the presence of an added organic solvent, but are frequently carried out in the absence of the added solvent.

[0084] In many embodiments of the alternative method, the acidic alkylation catalyst can be removed from the disubstituted DPA composition by filtration or other known separation methods. Unreacted olefins (and olefin by-products) may be removed from the disubstituted DPA composition by known techniques, such as stripping or distillation, frequently under vacuum. Unreacted olefins may be recycled for reuse in this method.

[0085] The disubstituted DPA compositions of this disclosure are useful as antioxidants in lubricants and polymers, etc. In particular, the disubstituted DPA compositions provide excellent antioxidant activity in lubricants, as well as excellent deposit and sludge suppression effects, especially in motors, engines, turbines, chains, gears, hydraulics, compressors, and other lubricating oils and lubricating fluids, as well as applications in industrial, marine, aerospace, automotive and grease industries, as well as applications in industrial greases and automotive greases.

[0086] In many embodiments, the lubricating oil composition comprises (A) a lubricating oil and (B) a disubstituted DPA composition of the present disclosure in an amount effective to provide antioxidant activity. The lubricating oil may be any natural, synthetic, or mixture thereof lubricating oil with a lubricating viscosity suitable for the intended application, and a wide range of lubricating oils are known in the art. In many embodiments, the lubricating oil is the main component, i.e., present in greater than 50% by mass, for example, 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, or 98% or more by mass, based on the mass of the lubricating oil composition.

[0087] In many embodiments, the amount of the disubstituted DPA composition of the Disclosure present in the lubricating oil composition is about 0.1% to about 10% by mass, frequently about 0.2% to about 5% by mass, about 0.2% to about 3% by mass, or about 0.5% to 2% by mass, based on the total mass of the lubricating oil composition.

[0088] The lubricating oil composition may contain any number of other additives commonly used in such compositions, such as dispersants, detergents, corrosion inhibitors / rust inhibitors, other antioxidants, anti-wear agents, defoamers, friction modifiers, seal swelling agents, emulsifiers, viscosity index improvers, pour point depressants, and others. The types and uses of these additives are publicly known and are described, for example, in U.S. Patent Application Publication No. 2019 / 01277656, which is incorporated herein by reference for disclosure of such additional additives useful in forming lubricating oil compositions.

[0089] Generally, lubricating oil compositions typically contain additives in a total concentration range of about 0.2% to about 30% by mass, for example, about 0.2% to about 20% by mass, about 0.2% to about 15% by mass, about 0.5% to about 10% by mass, or about 0.5% to about 5% by mass. [Examples]

[0090] Analysis Procedure Gas chromatography: The chemical composition of the product and the reaction mixture collected from the reactor during the reaction was analyzed by capillary column gas chromatography. The mass percentages of the unsubstituted DPA and disubstituted DPA components shown in the table below are based on the total mass of unsubstituted and substituted DPA in each composition. [Table 1]

[0091] Performance testing: The oxidation resistance of the oil was measured at 180°C using ASTM D6186 differential scanning calorimetry (PDSC). The oxidation induction time was reported in minutes. Deposit formation was measured using ASTM D7097 thermal oxidation simulation test (TEOST).

[0092] Comparative Example 1 Comparative Example 1 simulated the procedure of Experimental Example 6 of U.S. Patent No. 9,890,346. 50 grams (0.30 mol, 50 ml) of DPA and 5 grams (0.037 mol, 2 ml, Aldrich) of AlCl3 powder were charged into a dry, clean 300 ml Parr reactor. The reactor was sealed and pressurized to 50 psig with nitrogen, and degassed three times. The reactor was then heated to approximately 184°C over approximately 1 hour. 75.5 grams (1.51 mol, 98 ml) of propylene tetramer (first olefin) was added to the reactor over more than 4 hours using an FMI precision pump, and the reaction was held at 185±1°C for 2.5 hours. The mixture was cooled to 140°C, and 51 grams (0.45 mol, 71 ml) of diisobutylene as the second olefin was added in three portions over more than 4 hours. The reaction mixture was stirred and held at 140±1°C for a further 3 hours. The reaction mixture was treated with a standard water washing procedure to remove the catalyst. 142 grams of a yellowish-brown crude product were obtained.

[0093] The crude reaction product was stripped at a pressure of 10 to 15 torr over a distillation head temperature range of 120°C to 190°C. 29 grams of a colorless distillate were obtained. After removing most of the olefins, 113 grams of a brownish viscous liquid were obtained as the final product. The product mixture was distilled further at a pressure of 1.7 torr to 2.2 torr over a distillation head temperature range of 200°C to 258°C until the composition of 92.5 grams of the mixture in the pot contained less than 5% by mass of monosubstituted diphenylamine. 17.3 grams of a yellowish-brown distillate were obtained. The composition of the obtained samples was analyzed individually by gas chromatography. The mass and composition of the crude reaction mixture, the final product in the pot, and the distillate are shown in Table 1 below. [Table 2]

[0094] The results indicate that disubstituted DPA was obtained with 95% analytical accuracy by distilling more than 17% by mass of the substance (e.g., distillates of DPA and specific substituted DPAs) from the crude product after the olefin had already been stripped, at a temperature exceeding 200°C and under high vacuum (less than 1 Torr). The distillates shown in Table 1 contained unsubstituted diphenylamine, monosubstituted diphenylamine, and relatively low molecular weight disubstituted diphenylamine. The distillation technique of Comparative Example 1 is expensive and has the disadvantages of high energy consumption, high carbon emissions, and high material loss.

[0095] Comparative Example 2 Comparative Example 2 simulated the procedure of Experimental Example 4 disclosed in U.S. Patent No. 9,890,346. Three 100 ml three-neck flasks (A, B, and C) were placed on a parallel workstation equipped with synchronized overhead stirring and heating. At room temperature, 22 g of Naugalube® 438 L (NL 438 L), 32.2 g of anhydrous AlCl, and 14.8 g (2.9 equivalents) of nonene were added to reactor A. At room temperature, 23 g of NL 438 L and 32.3 g of anhydrous AlCl were added to reactor B. At room temperature, 31 g of NL 438 L and 3 g of Fitrol® 20X, pre-dried after removing approximately 9% by mass of water, were added to reactor C. Reactors A, B, and C were heated to 130°C with stirring. The reactors were maintained at 130 ± 5°C for 30 minutes. A certain amount of sample was taken from the reactor and treated by extracting the organic mixture to CH2Cl2 using an appropriate amount of CH2Cl2 and H2O. Subsequently, gas chromatography was performed for compositional analysis.

[0096] The composition of the Naugalube® 438L starting material used in the three parallel reactions, and the sample composition during the processes in the three reactors A, B, and C, were determined by gas chromatography, and the results are shown in Table 2 below. [Table 3]

[0097] As shown in Table 2, when aluminum chloride (reactor B) was used as a catalyst, dealkylation of substituted DPA occurred in the reaction mixture. However, when acidic clay was used as a catalyst (reactor C), dealkylation was minimal. When aluminum chloride (reactor A) was used as a catalyst and Naugalube® 438L was heated in the presence of nonene, dealkylation of DPA was suppressed, but excess trialkylated DPA was produced by nonylation.

[0098] Furthermore, as shown in Table 2, approximately 5% of Naugalube® 438L was dealkylated during heating to 130°C in the presence of the metal halide catalyst AlCl3 and in the absence of nonene. An increase in the mass percentages of DPA, monononylated DPA, and nonene based on the total mass of the reaction mixture indicated dealkylation. However, in the presence of acidic clay, e.g., Filtrol 20X, and in the absence of nonene, only approximately 0.3% of Naugalube® 438L was dealkylated. In the same comparative experiment, Naugalube® 438L was heated in the presence of AlCl3 and nonene. The reaction showed that Naugalube® 438L continued to react with nonene, increasing the amount of trinonylated diphenylamine from 6.9% by mass to 10.5% by mass. Therefore, unless the amount of the first olefin is properly controlled, an undesirable reaction between DPA and the first olefin in the presence of the second olefin will form excess alkylated DPA. Thus, using commercially available acid-activated clay as a catalyst reduces the generation of olefins and other organic waste, improves reactor efficiency, and enhances both yield and product quality.

[0099] Examples 1-3: General synthesis method [ka]

[0100] Example 1 of the present invention 55.7 grams (0.33 mol, 48 ml) of DPA and 28.8 grams of pre-dried acidic clay Filtrol® 20X (EP Engineered Clays) were charged into a dry, clean 300 ml Parr reactor. The reactor was sealed and pressurized to 50 psig with nitrogen, and degassed three times. The reactor was then heated to approximately 155°C over 40 minutes. Next, 116 grams (0.92 mol, 156 ml) of nonene (first olefin) were charged into the reactor, and the reaction mixture was held at 155°C for 6.5 hours. A distillation column, condenser, and vacuum pump were attached to the Parr reactor. Most of the unreacted nonene (e.g., 56 grams) was removed by distillation under vacuum for 1 hour. After removal of the first olefin, the final vacuum level was approximately 20 torr. Subsequently, the reactor was cooled to 125°C, and 84 grams (0.75 mol, 117 ml) of diisobutylene (secondary olefin) were added to the reactor over 20 minutes. The reaction mixture was held with the diisobutylene at 125°C for 10 hours, after which heating and stirring were stopped to halt the reaction. The crude reaction mixture was filtered using a 300 ml pressure filter at 80°C under a nitrogen atmosphere and a pressure of 50 psig. The colorless, transparent filtrate was stripped under a vacuum of 10 torr at temperatures up to 160°C to remove unreacted olefins. Without further purification, a clear, pale yellowish-brown viscous liquid (113 g) was obtained.

[0101] The composition of the product was determined by gas chromatography, and its chemical formula and structure were determined by high-resolution mass spectrometry. The results are shown in Table 3 below. [Table 4]

[0102] As described above and shown in Table 3, the final product produced by Example 1 had a high dialkyl DPA content (93% by mass), a low trialkyl DPA content (0.3% by mass), and a low unsubstituted DPA content (less than 0.02% by mass), and the resulting product was liquid at ambient temperature.

[0103] A sample of the reaction mixture (prepared according to Example 1) was taken before distillation of nonene, and its composition was determined by gas chromatography. The results are shown in Table 4 below. [Table 5]

[0104] As shown in Table 4, the composition of the reaction mixture after the reaction of the first olefin is 5.6% by mass of unsubstituted DPA, based on the total mass of substituted and unsubstituted DPA. When clay and nonene are removed, this increases further (7.3% by mass), indicating that the composition may undergo additional reactions with the second olefin, resulting in a final product composition containing less than 0.1% by mass of unsubstituted DPA.

[0105] Example 2 of the present invention 50 g (0.30 mol, 43 ml) of DPA and 30 g of pre-dried acidic clay Filtrol® 20X (EP Engineered Clays) were charged into a dry, clean 300 ml Parr reactor. The reactor was sealed and pressurized to 50 psig with nitrogen, and degassed three times. Next, the reactor was heated to approximately 130°C over 50 minutes, and 122 g (0.725 mol, 158 ml) of propylene tetramer was added to the reactor over 5 minutes. The reactor was continued to heat for 20 minutes until the temperature reached 155°C. The reaction was maintained at 155°C for 6 hours. A distillation column, condenser, and vacuum pump were installed. Most of the unreacted propylene tetramer was removed under vacuum at 155°C over approximately 1 hour. The final vacuum level was approximately 20 torr. While stirring and maintaining the reactor temperature at 155°C, 80 g (0.48 mol, 108 ml) of propylene tetramer was added over 20 minutes. After holding the reaction for 165 minutes, the propylene tetramer was repeatedly distilled under vacuum in a temperature range of 155°C to 140°C. After removing most of the propylene tetramer, the reactor was cooled to approximately 125°C, and 80 g (0.714 mol, 111 ml) of diisobutylene was added to the reactor over 35 minutes. After holding the reaction at 125°C for 8 hours, heating and stirring were stopped to halt the reaction. The crude reaction mixture was filtered using a 300 ml pressure filter at 80°C, under a nitrogen atmosphere, and at a pressure of 50 psig. The colorless, transparent filtrate was stripped under a vacuum of 10 torr at temperatures up to 160°C to remove unreacted olefins. A pale yellowish-brown viscous liquid (120 g) was obtained.

[0106] The composition of the product was determined by gas chromatography. Analysis shows that the composition of the final product, based on the total mass of the product, contains 1.4% by mass of diisobutylene dimer, less than 0.02% by mass of unsubstituted DPA, 0.2% by mass of monoalkylated DPA, 96.5% by mass of dialkylated DPA, and 1.7% by mass of trialkylated DPA.

[0107] Example 3 of the present invention In a dry and clean 300 ml Parr reactor, 50.2 g (0.30 mol, 43 ml) of DPA, 25.5 g of pre-dried Filtrol 20X, and 33 g (0.26 mol, 44.6 ml) of nonene (propylene trimmer) were charged. The reactor was sealed and pressurized to 50 psig with nitrogen, and degassed three times. The reactor was then heated to approximately 155°C over approximately 80 minutes, and 94.1 g (0.75 mol, 127.2 ml) of nonene was added to the reactor at a rate of 1.1 grams per minute. The reaction was maintained at 155°C for 7.4 hours. A distillation column, condenser, and vacuum pump were installed, and distillation was performed under vacuum for 1 hour to remove most of the unreacted nonene (47.2 g). The final vacuum level was approximately 20 torr. The reactor was cooled to 130°C, and 27 g (0.22 mol, 30 ml) of α-methylstyrene was added to the reactor over 180 minutes. The reaction with α-methylstyrene was maintained at 120°C for approximately 1 hour, after which heating and stirring were stopped to halt the reaction. The crude reaction mixture was filtered using a 300 ml pressure filter at 80°C, under a nitrogen atmosphere, and at a pressure of 50 psig. The colorless, transparent filtrate was stripped under a vacuum of 10 torr at temperatures up to 180°C to remove unreacted olefins. A pale yellowish-brown viscous liquid (111 g) was obtained.

[0108] The composition of the product was determined by gas chromatography. Analysis shows that the final product composition contains approximately 10% by mass of α-methylstyrene dimers and trimers, dimers of diisobutylene, less than 0.02% by mass of unsubstituted DPA, 0.7% by mass of monoalkylated DPA and monoarylated DPA, 95% by mass of alkylated alkylated disubstituted DPA, and 5.5% by mass of trisubstituted DPA.

[0109] Example 4 of the present invention (alternative manufacturing method) A Dean-Stark trap filled with toluene was attached to a 1-liter plastic kettle reactor. 291 grams of 438 L of Naugalube® (containing approximately 0.5% by mass of unsubstituted diphenylamine and 20% by mass of monononylated diphenylamine), 185 grams of toluene, and 30 grams of Filtrol 20X were added to the plastic kettle. The reactor was heated to 120°C, and then 25 grams of α-methylstyrene were added using a dropping funnel over approximately 1 hour at 120°C. The reaction was then carried out at 120°C for 2 hours. The reaction mixture was filtered to remove the Filtrol 20X catalyst, and stripping was performed at 150°C under a vacuum of 20 torr for 1 hour. 283 grams of a yellowish-brown viscous liquid product were obtained.

[0110] Gas chromatography analysis shows that the final product composition contains 0.3% nonene dimer, 1.42% α-methylstyrene dimer, less than 0.02% DPA, 4.5% monoalkylated DPA, approximately 93% total dialkylated DPA, and approximately 1% total trialkylated DPA.

[0111] The disubstituted DPA products of Examples 1 and 2 of the present invention were blended into lubricating oil, and their performance in suppressing oxidation induction activity was tested using differential scanning calorimetry (PDSC) technology. Deposit formation was measured using thermal oxidation simulation (TEOST). The results are shown in Table 5 below. [Table 6]

[0112] TEOST data shows deposits in mg, with low values ​​indicating less deposit formation, while PDSC data shows the time to oxidation in minutes, with high values ​​indicating higher protective performance. The TEOST indicator of deposit formation shows that compositions with a high mass% of dialkylated DPA perform better than compositions with a low mass% of dialkylated DPA. The compositions of Examples 1 and 2 were prepared by the methods of the present invention disclosed herein. Both compositions are stable in liquid and exhibit superior deposition inhibition compared to commercially available liquid alkylated DPA, such as Naugalube® 438L. Furthermore, the oxidation induction time measured by the PDSC test shows that compositions with a high mass% of monoalkylated DPA perform better than compositions with a low mass% of monoalkylated DPA. The compositions of Examples 1 and 2 were prepared by the methods of the present invention disclosed herein. Both compositions are stable liquids and exhibit performance equivalent to commercially available liquid alkylated DPA, such as Naugalube® 438L, despite having a lower content of monoalkylated DPA, a more active antioxidant, by approximately 15% by mass in Example 1 and approximately 18% by mass in Example 2.

[0113] [Table 7]

[0114] Table 6 above shows the modeled LogKow, water solubility, and toxicoconnectic parameters of different components from two families of commercially available substituted diphenylamine antioxidants. Each product was modeled using Perceptra PK Explorer with an oral dose of 5 mg per kg of body weight for a 70 kg human. Generally, components with a molecular weight greater than 300 daltons tend to have lower toxicity levels. They also typically have lower oral bioavailability, reduced AUC, lower water solubility, and higher LogKow values ​​compared to components with higher toxicity levels. For example, monobutyl DPA, dibutyl DPA, and monooctyl DPA have higher oral bioavailability, higher AUC (area under the curve), and lower LogKow values ​​compared to components with a molecular weight greater than 300. Furthermore, as shown in Table 5, monononyl DPA, a monosubstituted DPA, had a molecular weight of less than 300 daltons, while dinonyl DPA, a disubstituted DPA, had a molecular weight greater than 300 daltons.

[0115] While specific embodiments of the present invention, including those described above, have been described, this is not intended to be confined to a limited sense. As will be apparent to those skilled in the art from the above specification, modifications may be made without departing from the principles and scope of the present invention as defined by the appended claims.

Claims

1. An efficient, energy-efficient, and low-waste method for producing safe and environmentally friendly dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions, (i) A reaction mixture comprising a first olefin containing a mixture of alkene isomers selected from unsubstituted diphenylamine, propylene oligomer and butene oligomer, and an acidic clay catalyst is reacted to obtain a disubstituted diphenylamine of formula I. 【Chemistry 1】 Monosubstituted diphenylamine of formula IV, 【Chemistry 2】 and a step of forming an intermediate reaction mixture containing an isomer mixture of residual unsubstituted diphenylamine (R １ (It is derived from a mixture of alkene isomers.) (ii) a step of distilling more than 90%, for example more than 95%, of any unreacted portion of the mixture of alkene isomers, and (iii) The following equation: 【Transformation 3】 (Here, R' １ and R' ２ Each of these is independently H or linear or branched C １～１２ Alkyl (e.g., C ４～１２ It is alkyl, and R' ３ is H or linear or branched C １～４ (It is alkyl.) The process involves adding at least one second olefin, selected from the olefins, to the intermediate reaction mixture, and reacting the intermediate reaction mixture in the presence of an acidic alkylation catalyst to produce the dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition. Includes, Here, the proportion of the reaction mixture alkylated by the first olefin mixture in step (i) and the degree of residual unsubstituted diphenylamine alkylated by the second olefin in step (iii) are controlled such that the resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition includes: (1) A mixture of dialkylated diphenylamines of formulas I, II, and III in various proportions, at least 90% by mass, based on the total mass of unsubstituted and substituted diphenylamines in the composition: 【Chemistry 4】 (R １ is derived from the mixture of the first olefins, and R ２ is derived from at least one of the second olefins) (2) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, less than 0.1% by mass of unsubstituted diphenylamine, (3) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, less than 7% by mass, (a) Monoalkylated diphenylamines of formulas IV and V 【Transformation 5】 (R １ R is derived from the mixture of the first olefins, ２ (derived from at least one of the second olefins), and (b) Disubstituted diphenylamines with a molecular weight of less than 300 daltons A mixture of, and (4) A mixture of less than 5% by mass of trisubstituted diphenylamines based on the total mass of unsubstituted diphenylamines and substituted diphenylamines in the composition, Herein, the composition is liquid at ambient temperature, in this method.

2. The method according to claim 1, wherein the resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition contains at least 95% by mass of a mixture of disubstituted diphenylamines of formulas I, II, and III, based on the total mass of unsubstituted diphenylamine and disubstituted diphenylamine in the composition.

3. The method according to claim 1, wherein the mixture of dialkylated diphenylamines comprises at least 70% by mass, preferably at least 80% by mass, a para,para'-disubstituted diphenylamine.

4. The method according to claim 1, wherein the resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition contains less than 0.02% by mass of unsubstituted diphenylamine, based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition.

5. The method according to claim 1, wherein the resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition contains a mixture of monosubstituted diphenylamine and disubstituted diphenylamine with a molecular weight of less than 300 daltons in an amount of less than 5% by mass, based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition.

6. The method according to claim 1, wherein the resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition comprises a mixture of less than 3% by mass of trisubstituted diphenylamine, based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition.

7. The method according to claim 1, wherein at least one of the second olefins is selected from diisobutylene, styrene, α-methylstyrene, α-alkylstyrene, 2-methylbutene-1, 2-methylbutene-2, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, or commercially available diisobutylene.

8. The method according to any one of claims 1 to 7, wherein the acidic alkylation catalyst in each step (i) and (iii) is an acidic clay catalyst.

9. The method according to any one of claims 1 to 7, wherein the reaction mixture in step (i) reacts at a temperature range of about 120°C to about 170°C, more frequently at about 135°C to about 165°C, and more frequently at about 145°C to about 160°C.

10. The method according to any one of claims 1 to 7, wherein the reaction mixture in step (iii) reacts at a temperature range of about 80°C to about 150°C, more frequently about 100°C to about 140°C, and more frequently 115°C to about 135°C.

11. An efficient, energy-efficient, and low-waste method for producing safe and environmentally friendly dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions, A reaction mixture containing dialkylated diphenylamine, monoalkylated diphenylamine, and less than 25% by mass of unsubstituted diphenylamine, an acidic clay catalyst, and at least one olefin selected from the following formulas is reacted: 【Transformation 6】 (Here, R' １ and R' ２ Each of these is independently H or linear or branched C １~１２ Alkyl (e.g., C ４～１２ It is alkyl, and R' ３ is H or linear or branched C １～４ (It is alkyl.) The process includes a step of producing a dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition, The resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine compositions, (1) A mixture of dialkylated diphenylamines of formulas I, II, and III in various proportions, at least 90% by mass, based on the total mass of unsubstituted diphenylamines and substituted diphenylamines in the composition, 【Transformation 7】 (R １ It is derived from a mixture of alkene isomers of propylene oligomers and / or butene oligomers, R ２ (It originates from at least one olefin.) (2) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, less than 0.1% by mass of unsubstituted diphenylamine, (3) Based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, less than 7% by mass, (a) Monosubstituted diphenylamines of formulas IV and V 【Transformation 8】 (R １ R is derived from the mixture of the first olefins, ２ (It is derived from at least one olefin), and (b) Disubstituted diphenylamines with a molecular weight of less than 300 daltons A mixture of, and (4) A mixture of less than 5% by mass of trisubstituted diphenylamines based on the total mass of unsubstituted diphenylamines and substituted diphenylamines in the composition, Includes, The method wherein the composition is liquid at ambient temperature.

12. The method according to claim 11, wherein the resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition comprises a mixture of at least 95% by mass of disubstituted diphenylamines, based on the total mass of unsubstituted diphenylamines and disubstituted diphenylamines in the composition.

13. The method according to claim 11, wherein the mixture of dialkylated diphenylamines comprises at least 70% by mass, preferably at least 80% by mass, a para,para'-disubstituted diphenylamine.

14. The method according to claim 11, wherein the resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition contains less than 0.02% by mass of unsubstituted diphenylamine, based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition.

15. The method according to claim 11, wherein the resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition contains a mixture of monosubstituted diphenylamine and disubstituted diphenylamine with a molecular weight of less than 5% by mass, based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition.

16. The method according to claim 11, wherein the resulting dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition contains a mixture of less than 3% by mass of trisubstituted diphenylamine, based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition.

17. The method according to claim 11, wherein at least one of the olefins is selected from diisobutylene, styrene, α-methylstyrene, α-alkylstyrene, 2-methylbutene-1, 2-methylbutene-2, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, or commercially available diisobutylene.

18. The method according to any one of claims 11 to 17, wherein the acidic alkylation catalyst is an acidic clay catalyst.

19. The method according to any one of claims 11 to 18, wherein the reaction mixture reacts at a temperature range of about 80°C to about 150°C, more frequently about 100°C to about 140°C, and more frequently 115°C to about 135°C.

20. A lubricating oil composition comprising (A) a lubricating oil and (B) a dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition prepared by the method of claim 1 or 11 in an amount effective to provide antioxidant activity.

21. The lubricating oil composition according to claim 20, wherein the dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition is present in the lubricating oil composition in an amount of about 0.1% by mass to about 10% by mass, based on the total mass of the lubricating oil composition.

22. Use in the lubricating oil composition a dialkylated diphenylamine and / or alkylated arylated disubstituted diphenylamine composition, prepared by the method of claim 1 or 11, in an amount effective to provide antioxidant activity and to reduce and / or prevent the toxicity of the lubricating oil composition.

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