Liquid alkylated phenyl-alpha-naphthylamine with reduced aquatic toxicity

Abstract

The present invention relates to a method for producing a liquid additive containing an amine of formula (1), comprising the steps of: alkylating phenyl-alpha-naphthylamine with an olefin selected from linear or branched C8-C12 alkenes to obtain a first raw material product containing the amine of formula (1); removing unreacted olefin from the first raw material product by distillation to obtain a second raw material product; and removing unreacted phenyl-alpha-naphthylamine from the second raw material product by distillation to obtain a liquid additive. The present invention also relates to a liquid additive containing the amine of formula (1) and phenyl-alpha-naphthylamine, wherein the liquid additive contains at least 95% by weight of the amine of formula (1), and the concentration of phenyl-alpha-naphthylamine in the liquid additive is less than 0.2% by weight, preferably less than 0.1% by weight. The present invention further relates to the use of liquid additives in lubricants and the like.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a liquid additive containing an amine of formula (1), wherein phenyl-alpha-naphthylamine is provided as a linear or branched C8-C 12 The present invention relates to a method comprising the steps of: alkylating an alkene with an olefin selected from the alkene to obtain a first starting material product containing an amine of formula (1); removing unreacted olefin from the first starting material product by distillation to obtain a second starting material product; and removing unreacted phenyl-alpha-naphthylamine from the second starting material product by distillation to obtain a liquid additive. The present invention also relates to a liquid additive containing an amine of formula (1) and phenyl-alpha-naphthylamine, wherein the liquid additive contains at least 95% by weight of the amine of formula (1), and the concentration of phenyl-alpha-naphthylamine in the liquid additive is less than 0.2% by weight, preferably less than 0.1% by weight. The present invention further relates to the use of liquid additives in lubricants and the like. [Background technology]

[0002] Alkylated phenyl-alpha-naphthylamines (also known as alkylated PANA) are important additives in lubricants, for example, for stabilization against oxidation. While most alkylated PANAs are solid additives, liquid alkylated PANAs are also known and are of commercial interest.

[0003] Lubricants are necessary in aquatic environments, such as on ships or in the vicinity of machinery in lakes and rivers. As a preventative measure, low aquatic toxicity of lubricants and their additives is desirable and is often required by law. [Overview of the project] [Problems that the invention aims to solve]

[0004] The objective of this invention was to find a liquid alkylated PANA with reduced aquatic toxicity. [Means for solving the problem]

[0005] This object is achieved by a method for producing a liquid additive containing an amine of formula (1) [Chemical formula] (wherein R1 is a linear or branched C8 - C 12 alkyl) comprising the steps of: a) alkylating phenyl - alpha - naphthylamine with an olefin selected from linear or branched C8 - C 12 alkenes to obtain a first raw material product containing the amine of formula (1); b) distilling off unreacted olefin from the first raw material product to obtain a second raw material product; c) distilling off unreacted phenyl - alpha - naphthylamine from the second raw material product to obtain the liquid additive The invention is solved by a method comprising the above steps.

DETAILED DESCRIPTION OF THE INVENTION

[0006] The residue R 1 is a linear or branched C8 - C 12 alkyl, for example linear or branched C8, C9, C 10 , C 11 or C 12 alkyl. Mixtures of linear and branched C8 - C 12 alkyl are also possible.

[0007] Preferably, R 1 is a linear or branched C9 alkyl such as n - nonyl, 1 - methyloctyl, 1,1,3 - trimethylhexyl, 1,1,5 - trimethylhexyl, 1,1,3,4 - tetramethylpentyl, 1,1,2,2 - tetramethylpentyl or 1,1,2,4 - tetramethylpentyl. Mixtures of linear and branched C9 alkyl are also possible.

[0008] The term "alkyl" generally means, with respect to R1, a saturated hydrocarbon group consisting only of hydrogen atoms and carbon atoms.

[0009] The residue R1 It may be in the ortho, meta or para position of the phenyl group in formula (1), and the para position is preferred.

[0010] The liquid additive may contain at least 70, 80, 90, 93, 95, 96, 97, 98, 99, 99.5 or 99.8% by weight of the amine of formula (1). Preferably, the liquid additive contains at least 95% by weight of the amine of formula (1).

[0011] Typically, a hydrogen atom is not necessarily shown in the chemical formula. Therefore, the amine of formula (1) may also be represented by the following corresponding formula.

Chemical formula

[0012] The liquid additive may contain phenyl-alpha-naphthylamine, and the concentration of phenyl-alpha-naphthylamine in the liquid additive may be less than 0.2% by weight, preferably less than 0.1% by weight. The concentration of phenyl-alpha-naphthylamine in the liquid additive may be less than 0.2% by weight, less than 0.17% by weight, less than 0.15% by weight, less than 0.12% by weight, less than 0.10% by weight or less than 0.09% by weight. The concentration of phenyl-alpha-naphthylamine in the liquid additive may be 0.00001 - 0.2% by weight, 0.00001 - 0.17% by weight, 0.00001 - 0.15% by weight, 0.00001 - 0.12% by weight, 0.0001 - 0.10% by weight or 0.001 - 0.09% by weight. The concentration of phenyl-alpha-naphthylamine in the liquid additive can be determined by gas chromatography.

[0013] Phenyl-alpha-naphthylamine may be represented by the following formula (2).

Chemical formula

[0014] Typically, hydrogen atoms are not always represented in chemical formulas. Therefore, phenyl-alpha-naphthylamine can also be represented by one of the following two formulas that include a hydrogen atom. [ka]

[0015] The concentration of olefin in the liquid additive may be less than 1% by weight, less than 0.5% by weight, less than 0.3% by weight, less than 0.2% by weight, less than 0.1% by weight, or less than 0.05% by weight. The concentration of olefin in the liquid additive may be determined by gas chromatography.

[0016] Liquid additives typically do not contain organic solvents. The concentration of organic solvents in liquid additives may be less than 5% by weight, less than 3% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.3% by weight, less than 0.2% by weight, less than 0.1% by weight, or less than 0.05% by weight.

[0017] Liquid additives typically do not contain water. The concentration of water in a liquid additive may be less than 5% by weight, less than 3% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.3% by weight, less than 0.2% by weight, less than 0.1% by weight, or less than 0.05% by weight.

[0018] Liquid additives are typically liquid at 21°C. Liquid additives may have a melting point below 10°C, preferably below 0°C.

[0019] The liquid additive may have reduced aquatic toxicity. The reduced aquatic toxicity can be determined by comparing the liquid additive with a comparative amine of formula (1) containing 5% by weight of phenyl-alpha-naphthylamine.

[0020] Aquatic toxicity can be short-term aquatic toxicity to fish (e.g., rainbow trout (Oncorhynchus mykiss) or bluegill (Lepomis macrochirus)), long-term aquatic toxicity to fish (e.g., rainbow trout (Oncorhynchus mykiss) or bluegill (Lepomis macrochirus)), short-term aquatic toxicity to aquatic invertebrates (e.g., Daphnia magna), or long-term aquatic toxicity to aquatic invertebrates (e.g., Daphnia magna).

[0021] In one form, aquatic toxicity is the short-term aquatic toxicity to fish and can be determined as the LC50(96h) value in freshwater, as a semi-static test using rainbow trout (Oncorhynchus mykiss). In another form, aquatic toxicity is the short-term aquatic toxicity to fish and can be determined as the LC50(96h) value in freshwater, as a semi-static test using bluegill (Lepomis macrochirus).

[0022] In another form, aquatic toxicity is the long-term aquatic toxicity to aquatic invertebrates and can be determined as a NOEC(21d) value based on reproduction in freshwater, as a semistatic test using Daphnia magna.

[0023] In another preferred form, aquatic toxicity is long-term aquatic toxicity to aquatic invertebrates and can be determined as a LOEC(21d) value based on reproduction in freshwater by Daphnia magna, in accordance with OECD Guideline 202.

[0024] In another form, aquatic toxicity is the toxicity of freshwater aquatic plants of the genus Lemna (duckweed), which can be determined according to OECD Guideline 221.

[0025] Olefins are linear or branched C8-C 12 Alkenes, for example, straight-chain or branched C8, C9, C 10 , C 11or C 12 Selected from alkenes. Linear and branched C8~C 12 Alkene mixtures are also possible. Preferably, the olefins are branched C8, C9, C 10 , C 11 or C 12 Alkenes and other branching C8~C 12 Selected from alkenes. Linear or branched C8~C 12 Olefins selected from alkenes include at least 90, 95, 98, or 99% linear and branched C8-C 12 It may contain alkenes, which can be determined by gas chromatography.

[0026] Preferably, the olefin is a linear or branched (preferably branched) C9 alkene such as n-1-nonene, n-2-nonene, 1,3-dimethyl-2-heptene, or 4,6-dimethyl-1-heptene. Mixtures of linear and branched C9 alkyls are also possible. The olefin selected from linear or branched C9 alkenes may have a linear and branched alkene content of at least 90, 95, 98, or 99%, which can be determined by gas chromatography.

[0027] In another preferred form, the olefin is a C9 alkene available by oligomerization of propylene, such as propylene trimer, trimelpropene, isononene, or C9-rich C 8~10 This is a branched alkene, a C9 alkene commercially available as CAS 97593-01-6 or CAS 68526-55-6. Olefins, which are C9 alkenes obtainable by oligomerization of propylene, may have a C9 alkene content of at least 80, 84, 86, 88, or 90%, which can be determined by gas chromatography.

[0028] Olefins typically contain at least 90, 95, 98, or 99% monounsaturated compounds, which can be determined by gas chromatography.

[0029] Step a) Alkylation The alkylation of phenyl-alpha-naphthylamine with an olefin is typically catalyzed by an acid catalyst. Suitable acid catalysts include proton donors (so-called Brønsted acids), electron acceptor compounds (so-called Lewis acids), cation exchange resins, aluminosilicates, or naturally derived or modified layered silicates.

[0030] Suitable proton donors include salt-forming inorganic or organic acids, such as mineral acids, such as hydrochloric acid, sulfuric acid, or phosphoric acid; carboxylic acids, such as acetic acid or sulfonic acid, such as methanesulfonic acid, benzenesulfonic acid, or p-toluenesulfonic acid.

[0031] Suitable electron acceptor compounds are tin tetrachloride, zinc chloride, aluminum chloride, or boron trifluoride etherate.

[0032] Suitable cation exchange resins include styrene-divinylbenzene copolymers containing sulfoacid groups as ion exchange functional groups, such as the known products Amberlite® and Amberlyst®, e.g., AMBERLITE 200 or Dowex® 50; perfluorinated ion exchange resins, such as DuPont's Nafion® H; or other superacid ion exchange resins.

[0033] Suitable aluminosilicates include amorphous aluminum silicates containing about 10-30% aluminum oxide and about 70-90% silicon dioxide, such as Ketjen (Akzo)'s aluminum silicate HA-HPV (registered trademark), or crystalline aluminum silicates, such as zeolites used as inorganic cation exchangers, such as so-called molecular sieves, or as so-called decomposition catalysts in petrochemicals, such as faujasite, such as Zeolite X, such as 13X (union carbide) or SZ-9 (Grace), Zeolite Y, such as LZ-82 (Union Carbide), Ultrastable Y Zeolite, such as Octacat (Grace), mordenite, such as Zeolon 900H (registered trademark) (Norton), or Zeolite Beta, such as H-BEA (Sudchemie) or Zeolite ZSM-12 (registered trademark) (Mobil Oil).

[0034] Suitable naturally derived layered silicates include montmorillonite, also known as acidic soil or clay, which is activated with mineral acids such as sulfuric acid and / or hydrochloric acid and has a water content of preferably less than 10%, preferably less than 5%, such as so-called Fuller-type soil or clay, such as types commercially available under the name Fulcat® (Rockwood Additives), such as Fulcat 22B, 220, 230 and 240 types (sulfuric acid activated clay), Fulmont® (Rockwood Additives), such as XMP-4, XMP-3 types or Sudchemie K5, K10, K20 and K30 types (hydrochloric acid activated), KS and KSF types (sulfuric acid activated), or KSFO type (hydrochloric acid and sulfuric acid activated) acidic clays, and bentonite-based clays, such as Filtrol® or Retrol® type products, such as F-13 and F-20 (Engelhard Corp.).

[0035] Preferably, the acid catalyst is Fulcat® 22B, which is an acid-activated montmorillonite.

[0036] Modified layered silicates, also known as columnar clays, are derived from the above-mentioned naturally occurring layered silicates containing oxides of, for example, zirconium, iron, zinc, nickel, chromium, cobalt, magnesium, or rare earth elements between silicate layers. Suitable modified layered silicates are products manufactured by Contract Chemicals, Envirocat® EPZ-10, EPZG, or EPIC.

[0037] The acid catalyst may be added, for example, in an amount of 1 to 50% by weight, preferably 5 to 25% by weight, and very preferably 5 to 20% by weight, relative to the weight of the amine reactant used, or, if a so-called Brønsted acid or Lewis acid is used, in an amount of 0.002 to 10 mol%, preferably 0.1 to 5.0 mol%, relative to the weight of the amine.

[0038] In the alkylation step, the molar ratio of phenyl-alpha-naphthylamine to olefin can be in the range of 1:0.8 to 1:20, 1:1 to 1:15, 1:2 to 1:10, 1:3 to 1:10, 1:4 to 1:10, or 1:5 to 1:10.

[0039] The alkylation of phenyl-alpha-naphthylamine can be carried out with or without a solvent, preferably without one. If a solvent is used, it must be inert under the given reaction conditions and have a sufficiently high boiling point. Suitable solvents are optionally halogenated hydrocarbons, polar aprotic solvents, liquid amides, and alcohols. Examples of solvents include petroleum ether fractions, preferably those with high boiling points, toluene, mesitylene, dichlorobenzene, tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide (DMA), hexamethyltriamide (HMPTA), glyme and diglyme, dimethyl sulfoxide (DMSO), tetramethylurea (TMU), and higher alcohols, such as butanol or ethylene glycol.

[0040] The alkylation of phenyl-alpha-naphthylamine can be carried out at reaction temperatures of at least 100°C, 120°C, or 140°C and up to 250°C, 210°C, or 180°C.

[0041] Alkylation can be carried out by introducing the starting material and acid clay as catalysts into a suitable reaction vessel and heating to a specified temperature. In another process variation, the olefin may be added to the reaction mixture afterward. The olefin feeding time is typically 0.5 to 24 hours. After feeding the olefin to phenyl-alpha-naphthylamine, the reaction mixture can be held at the reaction temperature for 30 minutes to 24 hours, for example, at least 2, 4, 6, 8, 10, 12, 14, 16, or 18 hours. Alkylation is preferably carried out without the addition of an organic solvent.

[0042] The progression of alkylation can be tracked, for example, by gas chromatography. Typically, the amount of phenyl-alpha-naphthylamine is less than 20%, 15%, 10%, or 5%, based on the total amount of phenyl-alpha-naphthylamine and alkylated phenyl-alpha-naphthylamine.

[0043] Alkylation is preferably carried out under ambient pressure. High-pressure alkylation is possible, for example, in an autoclave under absolute pressures of 1 to 10 bar.

[0044] Acid catalysts can exist in a dissolved form or as a solid. Acid catalysts used in alkylation can be removed from the reaction mixture by filtration, centrifugation, decantation, extraction, precipitation, neutralization, evaporation, or distillation. Solid acid catalysts used in alkylation can be removed from the reaction mixture by filtration, centrifugation, or decantation. Dissolved acid catalysts used in alkylation can be removed from the reaction mixture by extraction, precipitation, neutralization, evaporation, or distillation. Acid catalysts are typically reusable. After removal of solid acid catalysts, they can be washed with olefins, for example, before recycling them in the alkylation process.

[0045] At the end of step a), alkylation step a) yields a first starting material product containing the amine of formula (1) and typically unreacted olefins and unreacted phenyl-alpha-naphthylamine. The amounts of unreacted olefins and unreacted phenyl-alpha-naphthylamine in the first starting material product usually depend on the reaction conditions in step a). The amount of unreacted olefins in the first starting material product may be at least 5% by weight, 10% by weight, 20% by weight, 30% by weight, 50% by weight, or 70% by weight. The amount of unreacted phenyl-alpha-naphthylamine in the first starting material product may be at least 0.3% by weight, 0.5% by weight, 0.7% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, or 10% by weight.

[0046] Step b) Distillation of olefins Step b) involves removing unreacted olefins from the first raw material product by distillation to obtain the second raw material product. Unreacted olefins typically arise from olefins in molar excess compared to the phenyl-alpha-naphthylamine used in alkylation step a).

[0047] Distillation conditions are typically adapted to the boiling point of the olefin. Typically, olefin distillation is achieved at high temperatures and / or in a vacuum. For example, in step b), the first raw material product may be heated in a sump to a temperature of at least 50°C, 80°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C in a vacuum of 1000 millibars, 800 millibars, 700 millibars, 600 millibars, 500 millibars, 400 millibars, 300 millibars, 200 millibars, or less than 100 millibars.

[0048] Preferably, in step b), the first raw material product can be heated to 80-280°C under a vacuum of 1000-20 millibars or to 100-180°C under a vacuum of 600-100 millibars.

[0049] The distillation in step b) may be carried out with a reflux ratio in the range of 10:1 to 1:2, preferably 5:1 to 1:1.5, and particularly 3:1 to 1:1.1. The reflux ratio is usually calculated as the portion recycled up to the top of the distillation column: the portion collected in the distillate receiver.

[0050] The second raw material product obtained in step b) typically contains up to 10% by weight, 5% by weight, 4% by weight, 3% by weight, 2% by weight, 1% by weight, or 0.5% by weight of olefin. The amount of olefin can be determined by gas chromatography.

[0051] If distillation in step b) is performed in batches, it may take 30 minutes to 24 hours, 1 hour to 18 hours, or 2 hours to 12 hours. Distillation can also be performed as a continuous process, a semi-batch process, or a combination of both (for example, if two distiller setups are used).

[0052] The distillation in step b) may be carried out in a conventional distillation apparatus, such as a distillation vessel, a distillation apparatus with a packed column, a tray column, or a column with a bed of packed elements. The structural material may be stainless steel, glass, glass lining, or fluoropolymer.

[0053] Unreacted olefins removed by distillation can be recycled, for example, in the alkylation of step a). Unreacted olefins can be recovered in situ in a tank, for example, and then added to the alkylation. Unreacted olefins can also be fed directly and added continuously to the alkylation.

[0054] A method for producing a liquid additive optionally further comprises step d) recycling the unreacted olefin removed by distillation from step b) in the alkylation of step a). The unreacted olefin may be recovered in a tank before being recycled in the alkylation of step a).

[0055] Step c) Distillation of phenyl-alpha-naphthylamine Step c) involves removing unreacted phenyl-alpha-naphthylamine from the second raw material product by distillation to obtain a liquid additive.

[0056] Typically, the distillation of phenyl-alpha-naphthylamine is achieved at high temperatures and / or in a vacuum. For example, in step c), the second raw material product may be heated in a sample to a temperature of at least 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 210°C, 220°C, 230°C, 240°C, or 250°C in a vacuum of 400 millibars, 300 millibars, 200 millibars, or less than 10 millibars. In a preferred embodiment, in step c), the second raw material product may be heated in a sample to at least 100°C in a vacuum of less than 400 millibars. In another preferred embodiment, in step c), the second raw material product may be heated in a sump under a vacuum of less than 200 millibars to at least 150°C. In another preferred embodiment, in step c), the second raw material product may be heated in a sump under a vacuum of less than 100 millibars to at least 200°C.

[0057] Preferably, in step c), the second raw material product can be heated to 100-300°C under a vacuum of 400-1 millibar, or to 180-300°C under a vacuum of less than 200 millibar, or to 210-280°C under a vacuum of less than 150 millibar.

[0058] In another preferred embodiment of step c), the second raw material product may be heated to 120-270°C under a vacuum of 400-1 millibar, or to 150-300°C under a vacuum of 200-5 millibar, or to 210-280°C under a vacuum of 150-5 millibar.

[0059] The distillation in step c) may be carried out with a reflux ratio in the range of 1:1 to 1:20, preferably 1:3 to 1:10, and particularly 1:4 to 1:8. The reflux ratio is usually calculated as the portion recycled up to the top of the distillation column: the portion collected in the distillate receiver.

[0060] When distillation is performed in batches, it can take 30 minutes to 24 hours, 1 hour to 18 hours, or 2 hours to 12 hours. Distillation can also be performed as a continuous or semi-batch process.

[0061] The distillation in step c) may be carried out in a distillation column having at least 3, 4, 5, or 10 theoretical separation steps.

[0062] The distillation in steps b) and c) may be carried out in the same still or in two different stills.

[0063] The distillation in step c) may be carried out in a conventional distillation apparatus, such as a distillation vessel, a distillation apparatus having a packed column, a tray column, or a column having a bed of packed elements.

[0064] The phenyl-alpha-naphthylamine removed by distillation in step c) can be recycled in the alkylation in step a).

[0065] The liquid additive obtained from step c) can be cooled to, for example, below 100°C and then filled into, for example, a drum.

[0066] The liquid additive obtained from step c) can be used in the lubricant without further purification.

[0067] Methods for producing liquid additives typically do not involve crystallization steps such as crystallization of phenyl-alpha-naphthylamine, crystallization of olefins, crystallization of the amine of formula (1), or crystallization of reaction by-products.

[0068] A method for producing liquid additives includes steps a), b), and c), which are usually carried out in alphabetical order.

[0069] Use as a lubricant The present invention also relates to the use of liquid additives in lubricants, for example, as lubricant additives.

[0070] A method for lubricating a moving surface may include steps a), b), and c) for obtaining a liquid additive, a step of blending the liquid additive with a base oil to obtain a compound lubricant, and a step of bringing the moving surface into contact with the compound lubricant.

[0071] Lubricants are compositions that can reduce friction between surfaces (preferably metal surfaces), such as the surfaces of mechanical devices. Mechanical devices can be mechanisms consisting of devices that operate on mechanical principles. Suitable mechanical devices include bearings, gears, joints, and guide devices. Mechanical devices can be operated at temperatures ranging from -40°C to 180°C. Lubricants are usually specially formulated for virtually all types of machinery and manufacturing processes. The type and concentration of base oils and / or lubricating additives used in these lubricants may be selected based on the requirements of the machine or process being lubricated, the quality demanded by the machine's manufacturer and user, and government regulations. Typically, each lubricant has a set of specific performance requirements. In addition to proper lubrication of the machine or process, these requirements include maintaining the quality of the lubricant itself and the impact of the lubricant's use and disposal on energy consumption, environmental quality, and user health.

[0072] Typical lubricants include automotive lubricants (e.g., gasoline engine oil, diesel engine oil, gas engine oil, gas turbine oil, automatic transmission fluid, gear oil) and industrial lubricants (e.g., industrial gear oil, lubricating oil for pneumatic tools, high-temperature oil, gas compressor oil, pressure fluid, metalworking fluid).

[0073] Examples of lubricants include accelerator lubricants, medium and heavy-duty oils, industrial engine oils, marine engine oils, automotive engine oils, crankshaft oils, compressor oils, refrigeration oils, hydrocarbon compressor oils, ultra-low temperature lubricants, high temperature lubricants, cable lubricants, textile machine oils, refrigeration oils, aerospace lubricants, aircraft turbine oils, transmission oils, gas turbine oils, spindle oils, spin oils, traction fluids, transmission oils, plastic transmission oils, passenger car transmission oils, and truck transmission oils. These include industrial transmission oils, industrial gear oils, insulating oils, instrument oils, brake fluids, transmission fluids, buffer oils, heat distribution fluids, transformer oils, greases, chain oils, minimum-volume lubricants for metalworking, oils for hot and cold working, water-based metalworking fluids, neat-oil metalworking fluids, semi-synthetic metalworking fluids, synthetic metalworking fluids, excavators for geotechnical investigations, pressure fluids, biodegradable lubricants or lubricating greases or waxes, chainsaw oils, release agents, molding fluids, lubricants for guns, pistols and rifles or watches, and food-grade approved lubricants.

[0074] Lubricants are typically lubricating fluids, lubricating oils, or lubricating greases.

[0075] The lubricant may contain at least 0.1% by weight, preferably at least 0.5% by weight, and particularly at least 1% by weight of a liquid additive.

[0076] In another embodiment, the lubricant may contain 0.1 to 20% by weight, preferably 0.5 to 15% by weight, and especially at least 1 to 10% by weight of a liquid additive.

[0077] The lubricant comprises a liquid additive and a base oil. The emulsifier package may contain at least 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, or 80% by weight of the base oil. The lubricant may contain up to 99.9% by weight, 98% by weight, 95% by weight, 90% by weight, 80% by weight, 70% by weight, or 50% by weight of the base oil.

[0078] The base oil may be selected from the group consisting of mineral oil (oils of Group I, II, or III), polyalphaolefin (oils of Group IV), polymerized and copolymerized olefins, alkylnaphthalenes, alkylene oxide polymers, silicone oils, phosphate esters, and carboxylic acid esters (oils of Group V). Preferably, the base oil is selected from base oils of Group I, Group II, Group III, or mixtures thereof, according to the API definition. The definition of base oil is the same as that given in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System," Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. The said publication classifies base oils as follows:

[0079] a) Group I base oils contain less than 90% saturated matter (ASTM D2007) and / or more than 0.03% sulfur (ASTM D2622), and have a viscosity index of 80 or more and less than 120 (ASTM D2270).

[0080] b) Group II base oils contain 90% or more saturated material and 0.03% or less sulfur, and have a viscosity index of 80 or more and less than 120.

[0081] c) Group III base oils contain 90% or more saturated material and 0.03% or less sulfur, and have a viscosity index of 120 or higher.

[0082] d) The base oils of Group IV contain polyalphaolefins. Polyalphaolefins (PAOs) include known PAO materials that typically contain relatively low molecular weight hydrogenated polymers or oligomers of alphaolefins, including C2-C32 alphaolefins, but are not limited to these. C8-about C16 alphaolefins such as 1-octene, 1-decene, and 1-dodecene are preferred. Preferred polyalphaolefins are poly-1-octene, poly-1-decene, and poly-1-dodecene.

[0083] e) Base oils in Group V include base oils not listed in Groups I to IV. Examples of base oils in Group V include alkylnaphthalenes, alkylene oxide polymers, silicone oils, and phosphate esters.

[0084] Examples of synthetic base oils include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and copolymerized olefins (e.g., polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene)), alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene), polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenols), and alkylated diphenyl ethers and alkylated diphenyl sulfides, as well as their derivatives, analogs, and congeners.

[0085] Alkylene oxide polymers and interpolymers, and their derivatives, in which terminal hydroxyl groups are modified by esterification, etherification, etc., constitute another class of known synthetic base oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether with a molecular weight of 1000 or diphenyl ether of polyethylene glycol with a molecular weight of 1000 to 1500) and their mono- and polycarboxylic acid esters, such as acetate esters of tetraethylene glycol, mixed C3-C8 fatty acid esters, and C13 oxoacid diesters.

[0086] Silicone oils such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysilicone oils and silicate oils constitute another useful class of synthetic base oils, including tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-ethylhexyl) disiloxane, poly(methyl)siloxane, and poly(methylphenyl)siloxane. Other synthetic base oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl esters of decylphosphonic acid) and high molecular weight tetrahydrofuran.

[0087] Lubricants typically further contain lubricant additives. Suitable lubricant additives may be selected from viscosity index improvers, polymer thickeners, antioxidants, corrosion inhibitors, cleaning agents, dispersants, defoamers, dyes, anti-wear additives, extreme pressure additives (EP additives), anti-wear additives (AW additives), friction modifiers, metal deactivators, and pour point depressants.

[0088] Viscosity index improvers include high molecular weight polymers that increase the relative viscosity of oil at high temperatures compared to its relative viscosity at low temperatures. Examples of viscosity index improvers include polyacrylates, polymethacrylates, alkyl methacrylates, vinylpyrrolidone / methacrylate copolymers, polyvinylpyrrolidone, polybutene, olefin copolymers, such as ethylene-propylene copolymers or styrene-butadiene copolymers, or polyalkenes, such as PIBs, styrene / acrylate copolymers and polyethers, and combinations thereof. The most common viscosity index improvers are methacrylate polymers and copolymers, acrylate polymers, olefin polymers and copolymers, and styrene-butadiene copolymers. Other examples of viscosity index improvers include polymethacrylates, polyisobutylene, alpha-olefin polymers, alpha-olefin copolymers (e.g., ethylene-propylene copolymers), polyalkylstyrenes, phenol condensates, naphthalene condensates, and styrene-butadiene copolymers. Of these, polymethacrylates having a number average molecular weight of 10,000 to 300,000 and alpha-olefin polymers or alpha-olefin copolymers having a number average molecular weight of 1,000 to 30,000, particularly ethylene-alpha-olefin copolymers having a number average molecular weight of 1,000 to 10,000, are preferred. Viscosity index improvers can be added and used, either alone or in mixtures, in amounts conveniently ranging from ≥0.05% to ≤20.0% by weight relative to the weight of the base stock.

[0089] Suitable (polymer) thickeners include, but are not limited to, polyisobutene (PIB), oligomer copolymer (OCP), polymethacrylate (PMA), styrene-butadiene copolymer, or high-viscosity esters (compound esters).

[0090] Examples of antioxidants include phenolic antioxidants such as hindered phenolic antioxidants, or non-phenolic antioxidants.

[0091] Useful phenolic antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols, which contain sterically hindered hydroxyl groups, and these include derivatives of dihydroxyaryl compounds in which the hydroxyl groups are in the ortho or para positions relative to each other. Typical phenolic antioxidants include hindered phenols substituted with alkyl groups having six or more carbon atoms and alkylene derivatives of these hindered phenols. Examples of this type of phenolic material are 2-t-butyl-4-heptylphenol, 2-t-butyl-4-octylphenol, 2-t-butyl-4-dodecylphenol, 2,6-di-t-butyl-4-heptylphenol, 2,6-di-t-butyl-4-dodecylphenol, 2-methyl-6-t-butyl-4-heptylphenol, and 2-methyl-6-t-butyl-4-dodecylphenol. Other useful hindered monophenol antioxidants include, for example, hindered 2,6-di-alkylphenol propionate derivatives. Bisphenol antioxidants can also be used in combination with the present invention. Examples of ortho-linked phenols include 2,2'-bis(4-heptyl-6-t-butyl-phenol), 2,2'-bis(4-octyl-6-t-butyl-phenol), and 2,2'-bis(4-dodecyl-6-t-butyl-phenol). Examples of para-linked bisphenols include 4,4'-bis(2,6-di-t-butyl-phenol) and 4,4'-methylene-bis(2,6-di-t-butylphenol).

[0092] Examples of usable non-phenolic antioxidants include aromatic amine antioxidants, which can be used alone or in combination with phenol. Typical examples of non-phenolic antioxidants include alkylated and non-alkylated aromatic amines, for example, formula R 8 R 9 R 10N aromatic monoamine (wherein R is the formula) 8 R is an aliphatic, aromatic, or substituted aromatic group. 9 R is an aromatic or substituted aromatic group, 10 is H, alkyl, aryl or R 11 S(O) x R 12 And R 11 R is an alkylene, alkenylene, or aralkylene group, 12 (where x is a higher alkyl group or alkenyl, aryl, or alkaryl group, and x is 0, 1, or 2). Aliphatic group R 8 It may contain 1 to about 20 carbon atoms, preferably about 6 to 12 carbon atoms. The aliphatic group is a saturated aliphatic group. Preferably, R 8 and R 9 Both are aromatic groups or substituted aromatic groups, and the aromatic group can be a fused ring aromatic group such as naphthyl. Aromatic group R 8 and R 9 It can be bonded together with other groups such as S.

[0093] Typical aromatic amine antioxidants have alkyl substituents with at least about six carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, aliphatic groups contain about 14 or fewer carbon atoms. Common types of amine antioxidants useful in this composition include diphenylamine, phenylnaphthylamine, phenothiazine, imidodibenzyl, and diphenylphenylenediamine. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants may also be used.

[0094] Specific examples of aromatic amine antioxidants useful in the present invention include p,p'-dioctyldiphenylamine, t-octylphenyl-alphanaphthylamine, phenyl-alphanaphthylamine, and p-octylphenyl-alphanaphthylamine. Alkylphenol sulfides and their alkali or alkaline earth metal salts are also useful antioxidants.

[0095] Examples of corrosion inhibitors include various oxygen-containing materials, nitrogen-containing materials, sulfur-containing materials, and phosphorus-containing materials, as well as metal-containing compounds (salts, organometallics, etc.) and non-metal-containing or ashless materials. Examples of corrosion inhibitors include hydrocarbyl-, aryl-, alkyl-, arylalkyl- and alkylaryl type cleaning agents (neutral, overbasic), sulfonates, phenates, salicylates, alcoholates, carboxylates, salixalates, phosphates, phosphates, thiophosphates, amines, amine salts, amine phosphates, amine sulfonates, alkoxylated amines, etheramines, polyetheramines, amides, imides, azoles, diazoles, triazoles, benzotriazoles, benzothiadols, and mercury compounds. Examples of additive types include, but are not limited to, putobenzothiazole, toltriazole (TTZ type), heterocyclic amines, heterocyclic sulfides, thiazoles, thiadiazoles, mercaptothiadiazoles, dimercaptothiadiazoles (DMTD type), imidazoles, benzimidazoles, dithiobenzimidazoles, imidazolines, oxazolines, Mannich reaction products, glycidyl ethers, anhydrides, carbamates, thiocarbamates, dithiocarbamates, polyglycols, or mixtures thereof.

[0096] Detergents include cleaning agents that adhere to dirt particles and prevent them from adhering to the critical surface. Detergents can also adhere to the metal surface itself, keeping it clean and preventing corrosion. Examples of cleaning agents include calcium alkyl salicylates, calcium alkyl phenates, and calcium alkali sulfonates using alternative metal ions such as magnesium, barium, or sodium. Examples of usable cleaning agents and dispersants include metal-based cleaning agents such as neutral and basic alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates, alkenyl succinimides and alkenyl succinimide esters and their borohydrogen, phenate, and Salienius complex cleaning agents, and ashless dispersants modified with sulfur compounds. These agents may be added and used individually or in mixtures, preferably in amounts ranging from ≥0.01% to ≤1.0% by weight relative to the weight of the base stock, and may also be high total base number (TBN), low TBN, or high / low TBN mixtures.

[0097] Dispersants are lubricant additives that help prevent the formation of sludge, varnish, and other deposits on critical surfaces. Dispersants can be succinimide dispersants (e.g., N-substituted long-chain alkenyl succinimides), Mannich dispersants, ester-containing dispersants, condensation products of fatty hydrocarbyl monocarboxylic acid acylating agents with amines or ammonia, alkylaminophenol dispersants, hydrocarbyl-amine dispersants, polyether dispersants, or polyetheramine dispersants. In one embodiment, the succinimide dispersant comprises a polyisobutylene-substituted succinimide, and the polyisobutylene from which the dispersant is derived may have a number average molecular weight of about 400 to about 5000 or about 950 to about 1600. In one embodiment, the dispersant comprises a borooxide dispersant. Typically, the borooxide dispersant comprises a succinimide dispersant containing a polyisobutylene succinimide, and the polyisobutylene from which the dispersant is derived may have a number average molecular weight of about 400 to about 5000. The borooxide dispersant is described in more detail above within the description of the extreme pressure agent.

[0098] The defoaming agent may be selected from silicones, polyacrylates, and the like. The amount of defoaming agent in the lubricant composition described herein may range from ≥0.001% by weight to ≤0.1% by weight based on the total weight of the formulation. As a further example, the defoaming agent may be present in an amount of about 0.004% by weight to about 0.008% by weight.

[0099] Suitable extreme pressure additives are sulfur-containing compounds. In one embodiment, the sulfur-containing compound may be a sulfurized olefin, a polysulfide, or a mixture thereof. Examples of sulfurized olefins include sulfurized olefins derived from propylene, isobutylene, and pentene; polysulfides containing organic sulfides and / or benzyl disulfides; bis-(chlorobenzyl) disulfide; dibutyl tetrasulfide; di-tert-butyl polysulfide; and sulfurized methyl esters of oleic acid; sulfurized alkylphenols; sulfurized dipentene; sulfurized terpenes; sulfurized Diels-Alder adducts; alkylsulfphenyl N'N-dialkyldithiocarbamates, or mixtures thereof. In one embodiment, sulfurized olefins include sulfurized olefins derived from propylene, isobutylene, pentene, or mixtures thereof. In one embodiment, sulfur-containing compounds for extreme pressure additives include dimercaptothiadiazole or its derivatives, or mixtures thereof. Examples of dimercaptothiadiazoles include compounds such as 2,5-dimercapto-1,3,4-thiadiazole or hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole or their oligomers. Oligomers of hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole are typically formed by forming sulfur-sulfur bonds between 2,5-dimercapto-1,3,4-thiadiazole units to form two or more derivatives or oligomers of the thiadiazole units. Suitable 2,5-dimercapto-1,3,4-thiadiazole derivatives include, for example, 2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole or 2-tert-nonyldithio-5-mercapto-1,3,4-thiadiazole. The number of carbon atoms in the hydrocarbyl substituent of hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole is typically 1 to 30, or 2 to 20, or 3 to 16. Examples of extreme pressure additives include compounds containing boron and / or sulfur and / or phosphorus. The extreme pressure additive may be present in the lubricant composition at a concentration of 0% to about 20% by weight, or about 0.05% to about 10.0% by weight, or about 0.1% to about 8% by weight.

[0100] Examples of wear-resistant additives include organic borates, organic phosphites such as didodecyl phosphite, organic sulfur-containing compounds such as sperm whale oil or sulfur terpenes, zinc dialkyldithiophosphates, zinc diaryldithiophosphates, phosphosulfur hydrocarbons, and any combination thereof.

[0101] Examples of friction modifiers include metal-containing compounds or materials, ashless compounds or materials, or mixtures thereof. Metal-containing friction modifiers include metal salts or metal ligand complexes, in which case the metal may include alkali metals, alkaline earth metals, or transition metals. Such metal-containing friction modifiers may also have low ash content properties. Examples of transition metals include Mo, Sb, Sn, Fe, Cu, and Zn. Examples of ligands include alcohols, polyols, glycerols, partially ester glycerols, thiols, carboxylates, carbamates, thiocarbamates, dithiocarbamates, phosphates, thiophosphates, dithiophosphates, amides, imides, amines, thiazoles, thiadiazoles, dithiazoles, diazoles, triazoles, and hydrocarbyl derivatives of other polar molecular functional groups containing effective amounts of O, N, S, or P, either alone or in combination. In particular, Mo-containing compounds, such as Mo-dithiocarbamate, Mo(DTC), Mo-dithiophosphate, Mo(DTP), Mo-amine, Mo(Am), Mo-alcolate, and Mo-alcohol-amide, may be especially effective.

[0102] Examples of ashless friction modifiers include lubricant materials containing an effective amount of polar groups, such as hydroxyl-containing hydrocarbyl base oils, glycerides, partial glycerides, and glyceride derivatives. Examples of polar groups in friction modifiers include hydrocarbyl groups containing an effective amount of O, N, S, or P, either individually or in combination. Other friction modifiers that may be particularly effective include, for example, fatty acid salts (both ash-containing and ashless derivatives), fatty alcohols, fatty amides, fatty esters, hydroxyl-containing carboxylates, and equivalent synthetic long-chain hydrocarbyl acids, alcohols, amides, esters, and hydroxycarboxylates. In some cases, fatty organic acids, fatty amines, and sulfurized fatty acids may be used as suitable friction modifiers. Examples of friction modifiers include fatty acid esters and amides, organic molybdenum compounds, molybdenum dialkylthiocarbamates, and molybdenum dialkyldithiophosphates.

[0103] Suitable metal deactivators include benzotriazoles and their derivatives, such as 4- or 5-alkylbenzotriazoles (e.g., triazoles) and their derivatives, 4,5,6,7-tetrahydrobenzotriazole and 5,5'-methylenebisbenzotriazole, Mannich bases of benzotriazoles or triazoles, such as 1-[bis(2-ethylhexyl)aminomethyl)triazole and 1-[bis(2-ethylhexyl)aminomethyl)benzotriazole, and alkoxyalkylbenzotriazoles, such as 1-(nonyloxymethyl)benzotriazole, 1-(1-butoxyethyl)benzotriazole and 1-(1-cyclohexyloxybutyl)triazole, and combinations thereof. Examples of additional, non-limiting, metal deactivators include 1,2,4-triazoles and their derivatives, such as Mannich bases of 1,2,4-triazoles such as 3-alkyl(or aryl)-1,2,4-triazole and 1-[bis(2-ethylhexyl)aminomethyl-1,2,4-triazole], alkoxyalkyl-1,2,4-triazoles such as 1-(1-butoxyethyl)-1,2,4-triazole and acylated 3,2,4-triazoles, imidazole derivatives, such as 4,4'-methylenebis(2-undecyl-5-methylimidazole) and bis[(N-methyl)imidazole-2-yl]carbinol octyl ether and combinations thereof. Further non-limiting examples of one or more metal deactivators include sulfur-containing heterocyclic compounds, such as 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and its derivatives, and 3,5-bis-[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin-2-one, and combinations thereof. Further non-limiting examples of one or more metal deactivators include amino compounds, such as salicylidenepropylenediamine, salicyaminoguanidine and its salts, and combinations thereof. The amount of one or more metal deactivators in the composition is not particularly limited, but is typically present in amounts of about 0.01 to about 0.1% by weight, about 0.05 to about 0.01% by weight, or about 0.07 to about 0.1% by weight based on the weight of the composition.Alternatively, one or more metal deactivators may be present in amounts less than about 0.1% by weight, less than about 0.7% by weight, or less than about 0.5% by weight, based on the weight of the composition.

[0104] Examples of pour point depressants (PPDs) include polymethacrylates, alkylated naphthalene derivatives, and combinations thereof. Commonly used additives, such as alkyl aromatic polymers and polymethacrylates, are also useful for this purpose. Typically, the treatment rate is in the range of ≥0.001% to ≤1.0% by weight relative to the weight of the base stock.

[0105] Examples of deemulsifiers include trialkyl phosphates and various polymers and copolymers of ethylene glycol, ethylene oxide, and propylene oxide, or mixtures thereof.

[0106] The present invention - Amine of formula (1) [ka] (In the formula, R1 is a straight chain or branched C8~C 12 (It is alkyl) - Phenyl-alpha-naphthylamine and A liquid additive containing, It contains at least 95% by weight of the amine of formula (1), The liquid additive also relates to a liquid additive in which the concentration of phenyl-alpha-naphthylamine is less than 0.2% by weight, preferably less than 0.1% by weight.

[0107] The liquid additive can preferably be obtained by a method for producing the liquid additive, which includes steps a), b), and c) and optionally d).

[0108] The liquid additive preferably has reduced aquatic toxicity. [Examples]

[0109] raw materials Amine A: n-phenyl-1-naphthylamine, purity >99.5%. Olefin A: Technical quality trimerized propylene, >90 wt% C9, olefin content >98% (ASTM D1319), density approximately 0.74 at 20°C (ASTM D4052). Fulcat(registered trademark) 22B: Acid-activated montmorillonite clay catalyst.

[0110] Gas chromatography The sample (approximately 2% in toluene) was analyzed by gas chromatography using a DB-5 capillary (15 m long, 0.32 mm in diameter) and an FID detector. The temperature program started at 60°C with a holding time of 2 minutes, then heated to 300°C at 30°C / min, and finally held at 300°C for 7 minutes. Typical holding times were 1 minute 30 seconds for olefin A, 14 minutes for amine A, and 21 minutes for alkylated amine A.

[0111] Example 1 Molten amine A (1.0 mol equivalent) and catalyst Fulcat® 22B (11.7 wt%) based on the weight of amine A) were placed in a 2-liter stainless steel laboratory reactor and heated to 150°C. Olefin A (4.0 mol equivalent) was added to the reactor for several hours. When the alkylation reaction was complete, the reactor was cooled to 100°C, the catalyst was filtered off, and washed with olefin A to obtain the first starting material product.

[0112] The excess amount of unreacted olefin A was removed by distillation from the first starting material product under vacuum to obtain a second starting material product containing 11% amine A (based on the total amount of amine 1 and alkylated amine A). The distilled olefin A was recycled for further alkylation reactions.

[0113] Unreacted amine A was removed by distillation from the second starting material product at 210–250°C under a vacuum of 100–150 millibars. The removed amine A can be recycled for further alkylation reactions.

[0114] The final product contained 0.1% amine A and 99.9% alkylated amine A, as determined by gas chromatography. The final product was a clear red liquid.

[0115] Example 2 Molten amine A (1.0 mol equivalent) and catalyst Fulcat® 22B (13.2 wt%) based on the weight of amine A) were placed in a 2-liter stainless steel laboratory reactor and heated to 150°C. Olefin A (4.0 mol equivalent) was added to the reactor for several hours. When the alkylation reaction was complete, the reactor was cooled to 100°C, the catalyst was filtered off, and washed with olefin A to obtain the first starting material product.

[0116] The excess amount of unreacted olefin A was removed by distillation from the first starting material product under vacuum to obtain a second starting material product containing 6% amine A (based on the total amount of amine 1 and alkylated amine A). The distilled olefin A was recycled for further alkylation reactions.

[0117] Unreacted amine A was removed by distillation from the second starting material product at 210–250°C under a vacuum of 100–150 millibars. The removed amine A can be recycled for further alkylation reactions.

[0118] The final product contained 0.1% amine A and 99.9% alkylated amine A, as determined by gas chromatography. The final product was a clear red liquid.

[0119] Example 3 The aquatic toxicity of samples containing <0.1% amine A and >99.9% alkylated amine A (determined by gas chromatography) was tested according to OECD standards.

[0120] OECD Test 202 “Daphnia sp.Acute Immobilization Test” This test assessed acute toxicity and evaluated the effects of the chemical on Daphnia. No toxic effects were observed, and the EC50 was less than 0.223 μg / l. For comparison, the safety data sheet for commercially available amine A shows a high aquatic toxicity EC50 of 0.32 mg / l according to OECD Test 202.

[0121] OECD Test 221 “Lemna sp.Growth Inhibition Test” This study determined the toxicity of a substance to freshwater aquatic plants of the genus Lemna (duckweed). No toxic effects were observed up to the solubility limit.

Claims

1. Formula (1) 【Chemistry 1】 (In the formula, R １ C is either linear or branched. ８ ~C １２ (It is alkyl.) A method for producing a liquid additive containing an amine, a) Phenyl-alpha-naphthylamine, linear or branched C ８ ~C １２ A step of alkylating the alkene with an olefin selected from the alkene to obtain a first starting material product containing the amine of formula (1), b) A step of removing unreacted olefins from the first raw material product by distillation to obtain a second raw material product, c) A step of removing unreacted phenyl-alpha-naphthylamine from the second raw material product by distillation to obtain the liquid additive. A method that includes this.

2. The method according to claim 1, wherein the liquid additive comprises at least 95% by weight of the amine of formula (1).

3. The method according to claim 1 or 2, wherein the liquid additive comprises the phenyl-alpha-naphthylamine, and the concentration of the phenyl-alpha-naphthylamine in the liquid additive is less than 0.2% by weight, preferably less than 0.1% by weight.

4. The olefin is linear or branched C ９ The method according to any one of claims 1 to 3, selected from alkenes.

5. The method according to any one of claims 1 to 4, wherein in step a), the molar ratio of phenyl-alpha-naphthylamine to the olefin is used in the range of 1:0.8 to 1:20, 1:1 to 1:15, 1:2 to 1:10, 1:3 to 1:10, 1:4 to 1:10, or 1:5 to 1:

10.

6. The method according to any one of claims 1 to 5, wherein in step c), the second raw material product is heated in a sump to at least 100°C under a vacuum of less than 400 millibars.

7. The method according to any one of claims 1 to 6, wherein in step c), the second raw material product is heated in a sump to at least 200°C under a vacuum of less than 100 millibars.

8. d) A step of recycling the unreacted olefin removed by distillation from step b) in the alkylation of step a). The method according to any one of claims 1 to 7, further comprising:

9. The method according to any one of claims 1 to 8, which does not include a crystallization step.

10. The method according to any one of claims 1 to 9, wherein the liquid additive has a melting point of less than 10°C.

11. The method according to any one of claims 1 to 10, wherein the liquid additive has reduced aquatic toxicity.

12. - Formula (1) 【Chemistry 2】 (wherein, R １ is a linear or branched C ８ - C １２ alkyl) The amine and, - Phenyl-alpha-naphthylamine and A liquid additive containing, The amine comprises at least 95% by weight of the amine of formula (1), The liquid additive wherein the concentration of phenyl-alpha-naphthylamine in the liquid additive is less than 0.2% by weight, preferably less than 0.1% by weight.

13. The liquid additive according to claim 12, which can be obtained by the manufacturing method described in any one of claims 1 to 11.

14. The liquid additive according to claim 12 or 13, having reduced aquatic toxicity.

15. Use of the liquid additive according to any one of claims 11 to 13 in a lubricant.

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