JP-2026514424-A - Efficient, low-energy, and low-waste alkylation and arylation methods for producing safe and environmentally friendly disubstituted diphenylamine antioxidants.

JP2026514424AJP 2026514424 AJP2026514424 AJP 2026514424AJP-2026514424-A

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.

Inventors

フイユアン・チェン
トラヴィス・ベナンティ
デイヴィッド・スピラ
アラン・ノリス
ロバート・ジー・ローランド
シリル・ミグダル

Assignees

ランクセス・コーポレーション

Dates

Publication Date: 20260511
Application Date: 20240327
Priority Date: 20230331

Claims (20)

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. Monosubstituted diphenylamine of formula IV, 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: (Here, R'1 and R'2 are independently H or linear or branched C1-12 alkyl (e.g., C4-12 alkyl), and R'3 is H or linear or branched C1-4 alkyl.) The process includes 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. 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: ( R1 is derived from the mixture of the first olefins, and R2 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 ( R1 is derived from the mixture of the first olefins, and R2 is derived from at least one of the second olefins), and (b) a mixture of disubstituted diphenylamines having a molecular weight of less than 300 daltons, and (4) a mixture of trisubstituted diphenylamines in an amount of less than 5% by mass, based on the total mass of unsubstituted and substituted diphenylamines in the composition. Herein, the composition is liquid at ambient temperature, in this method.
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 diphenylamines and disubstituted diphenylamines in the composition.
The method according to claim 1, wherein the mixture of dialkylated diphenylamines comprises at least 70% by mass, preferably at least 80% by mass, of a para,para'-disubstituted diphenylamine.
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.
The method according to claim 1, wherein the resulting dialkylated diphenylamine and/or alkylated arylated disubstituted diphenylamine composition contains less than 5% by mass of a mixture of monosubstituted diphenylamine and disubstituted diphenylamine with a molecular weight of less than 300 daltons, based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition.
The method according to claim 1, 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.
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.
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.
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 about 135°C to about 165°C, and more frequently about 145°C to about 160°C.
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, frequently about 100°C to about 140°C, and frequently 115°C to about 135°C.
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: (Here, R'1 and R'2 are independently H or linear or branched C1-12 alkyl (e.g., C4-12 alkyl), and R'3 is H or linear or branched C1-4 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, ( 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.) (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 ( R1 is derived from the mixture of the first olefins, and R2 is derived from at least one olefin), and (b) a mixture of disubstituted diphenylamines having a molecular weight of less than 300 daltons, and (4) a mixture of trisubstituted diphenylamines in an amount of less than 5% by mass, based on the total mass of unsubstituted and substituted diphenylamines in the composition. Includes, The method wherein the composition is liquid at ambient temperature.
The method according to claim 11, wherein the resulting dialkylated diphenylamine and/or alkylated arylated disubstituted diphenylamine composition contains 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.
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.
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.
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 300 daltons, based on the total mass of unsubstituted diphenylamine and substituted diphenylamine in the composition, in an amount of less than 5% by mass.
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.
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.
The method according to any one of claims 11 to 17, wherein the acidic alkylation catalyst is an acidic clay catalyst.
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, frequently about 100°C to about 140°C, and frequently 115°C to about 135°C.
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.

Description

Certain alkylated and arylated diphenylamines are well-known 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 lubrication 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. 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 (a 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. 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. U.S. Patents 4,798,684 and 9,890,346 disclose a method for preparing 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, e.g., more than 10% by mass, possibly up to 20% by mass, of monobutyl DPA and dibutyl DPA, and more than 1% by mass of unsubstituted DPA in the final product. 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. 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. In the recently published Harmonized Classification and Labelling (CLH) proposal by ANSES (French Agency for