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CN112694927A - Anti-rust oil composition and preparation method thereof - Google Patents

Anti-rust oil composition and preparation method thereof Download PDF

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Publication number
CN112694927A
CN112694927A CN201911009014.9A CN201911009014A CN112694927A CN 112694927 A CN112694927 A CN 112694927A CN 201911009014 A CN201911009014 A CN 201911009014A CN 112694927 A CN112694927 A CN 112694927A
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CN112694927B (en
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胡海豹
陈晓伟
史军
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
    • C10M137/14—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
    • C07F9/655309—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Lubricants (AREA)

Abstract

本发明提出了一种防锈油组合物及其制备方法。本发明的防锈油组合物，包括以下组分：A)硫代膦酸酯化合物，占组合物总质量的0.1％～10％；B)抗氧剂，占组合物总质量的0.1％～10％；C)防锈剂，占组合物总质量的1％～15％；D)任选的抗泡剂，占组合物总质量的0～200ppm；E)主要量的润滑基础油；其中所述硫代膦酸酯化合物的结构如通式(I)所示：

Figure DDA0002243627250000011
其中各基团的定义见说明书。本发明的防锈油组合物具有优异的防锈性能、降解性能和极压抗磨性能，承载能力高，配伍性好。The present invention provides a rust preventive oil composition and a preparation method thereof. The rust preventive oil composition of the present invention comprises the following components: A) thiophosphonate compound, accounting for 0.1% to 10% of the total mass of the composition; B) antioxidant, accounting for 0.1% to 0.1% of the total mass of the composition 10%; C) rust inhibitor, accounting for 1% to 15% of the total mass of the composition; D) optional anti-foaming agent, accounting for 0 to 200 ppm of the total mass of the composition; E) the main amount of lubricating base oil; wherein The structure of the thiophosphonate compound is shown in the general formula (I):
Figure DDA0002243627250000011
The definition of each group is shown in the specification. The anti-rust oil composition of the invention has excellent anti-rust performance, degradation performance, extreme pressure and anti-wear performance, high bearing capacity and good compatibility.

Description

Anti-rust oil composition and preparation method thereof
Technical Field
The invention relates to an anti-rust oil composition, in particular to an anti-rust oil composition with excellent extreme pressure wear resistance.
Background
The anti-rust oil is a special lubricant and is generally applied to special working occasions. Because the service environment is harsh, the extreme pressure antiwear performance of the lubricant is often required to be special. For this reason, it is generally necessary to select an extreme pressure antiwear agent having excellent properties.
The extreme pressure antiwear agents widely used in the field of lubricating oil at present include tricresyl phosphate (T306), ammonium thiophosphate (T307), thiophosphate (IRGALUBE 353), ammonium phosphate (IRGALUBE 349), and the like, but their antiwear and antifriction properties need to be further improved. For example, CN 1396169a discloses a thiophosphate ester type extreme pressure antiwear agent, which can effectively improve the anti-wear and anti-wear properties of a lubricant using liquid paraffin as base oil. CN 106317109A discloses a thiophosphate extreme pressure antiwear agent, which is used as a hydraulic oil or lubricating oil additive and shows better antirust performance, thermal stability, filterability and hydrolytic stability, but the antiwear and antifriction performance of the thiophosphate extreme pressure antiwear agent is not outstanding. CN 101724492A discloses a zinc thiophosphate type extreme pressure antiwear agent, which is an organic metal salt and does not conform to the development trend of non-ashing of lubricating oil additives.
Disclosure of Invention
The invention provides an anti-rust oil composition and a preparation method thereof.
The anti-rust oil composition comprises the following components:
A) a thiophosphonate compound, which constitutes from 0.1% to 10% (preferably from 1% to 5%) of the total mass of the composition;
B) antioxidant accounting for 0.1-10% (preferably 0.5-5%) of the total mass of the composition;
C) the antirust agent accounts for 1-15% (preferably 2-10%) of the total mass of the composition;
D) an optional antifoaming agent in an amount of 0 to 200ppm (preferably 1 to 50ppm) based on the total weight of the composition;
E) a major amount of a lubricating base oil;
wherein the structure of the thiophosphonate compound is shown as the general formula (I):
Figure BDA0002243627240000021
in the general formula (I), the radical R0Selected from H, C6～C20Aryl radical, C1-300Straight or branched alkyl (preferably phenyl, C)1～C14Alkyl phenyl, C1～C20Straight or branched chain alkyl); each radical R1、R2、R3、R4、R5Are the same or different from each other and are each independently selected from H, C1～C20A linear or branched alkyl group and a group of the formula (II), each group R1、R2、R3、R4、R5At least one group of (a) is a group represented by the formula (II);
Figure BDA0002243627240000022
in the general formula (II), the group R1' is selected from a single bond, C1-20Straight or branched alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radicals R in n repeating units2' the same or different from each other, each independently selected from the group consisting of 2-, 3-or 4-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2-, 3-or 4-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units3' the same or different from each other, each independently selected from a single bond, C having a valence of 2 or 31-20Straight or branched chain alkyl (preferably each independently selected from single bond, 2-valent or 3-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units4' the same or different from each other, each independently selected from a single bond, C having a valence of 2 or 31-20Straight or branched chain alkyl (preferably each independently selected from single bond, 2-valent or 3-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units5' the same or different from each other, each independently selected from the group consisting of 2-, 3-or 4-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2-, 3-or 4-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units6' same or different from each other, each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from single bond, C)1-4Linear or branched alkylene); radical R7' selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); n is an integer of 1 to 10 (preferably an integer of 1 to 3); m in the n repeating units are the same or different from each other and are each independently selected from integers of 0 to 10 (preferably integers of 0 to 5); m' in the n repeating units are the same or different from each other and are each independently selected from integers of 0 to 10 (preferably integers of 0 to 5); in each repeating unit of formula (II), when m is greater than 0, m S atoms are bound to the radical R2'、R5' bonding; when m 'is greater than 0, m' S atoms and the radical R3'、R4' bonding; in each repeating unit of formula (II), when the radical R3When 'is a single bond, m' S atoms and the group R2' bonding when the group R4When 'is a single bond, m' S atoms and the group R5' bonding.
According to the invention, in the general formula (I), preferably the radicals R1、R3、R5Are the same or different from each other and are each independently selected from hydrogen and C1-4A linear or branched alkyl group; each radical R2、R4Are the same or different from each other and are each independently selected from hydrogen and C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group represented by the general formula (II), wherein at least one group is selected from the group represented by the general formula (II). Further preferably, in at least one group represented by the general formula (II), at least one of m and m' is greater than 0.
According to the invention, in the general formula (I), it is further preferred that each radical R1、R3、R5Are the same or different from each other and are each independently selected from hydrogen and C1-4A linear or branched alkyl group; each radical R2、R4One group is selected from the group represented by the general formula (II) and the other groupThe radicals are selected from hydrogen. Further preferably, in at least one group represented by the general formula (II), at least one of m and m' is greater than 0.
According to the invention, the thiophosphonate compound may be selected from the following specific compounds or mixtures thereof in any proportion.
Figure BDA0002243627240000031
Figure BDA0002243627240000041
According to the present invention, the method for producing a thiophosphonate compound includes a step of subjecting a phenol compound represented by the general formula (X) to a sulfurization reaction, a phosphonothioylation reaction;
Figure BDA0002243627240000042
in the general formula (X), each group R1”、R2”、R3”、R4”、R5"equal to or different from each other, each independently selected from hydrogen, C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y);
Figure BDA0002243627240000043
wherein the radical R1"' is selected from a single bond, C1-20Straight or branched alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radical R in m repeating units2"'s, which may be the same or different from each other, are each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from single bond, C)1-4Linear or branched alkyleneRadical); radical R3"' is selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radical R in m repeating units4"'s, equal to or different from each other, are each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); radical R in m repeating units5"'s, equal to or different from each other, are each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); m is a positive integer (preferably a positive integer between 1 and 10, more preferably a positive integer between 1 and 3).
According to the invention, in the general formula (X), preferably the radicals R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; each radical R2”、R4"equal to or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group and a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y).
According to the invention, in the general formula (X), it is further preferred that each radical R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; each radical R2”、R4One group in "is selected from the group represented by the general formula (Y), and the other group is selected from hydrogen.
According to the present invention, the phenol compound represented by the general formula (X) may be first subjected to a sulfurization reaction and then subjected to a sulfurization reaction to produce a sulfurized product (sulfurized product of the phenol compound represented by the general formula (X)), or the phenol compound represented by the general formula (X) may be first subjected to a sulfurization reaction and then subjected to a sulfurization reaction to produce a sulfurized product (sulfurized product of the phenol compound represented by the general formula (X)).
According to the present invention, the sulfurization reaction includes a step of reacting the phenol compound represented by the general formula (X) or the phosphonothioylation product of the phenol compound represented by the general formula (X) with a sulfurizing agent. Said vulcanizationThe reaction makes the sulfurizing agent and carbon-carbon double bond (olefinic bond) produce electrophilic addition reaction, when the molecule has 1 carbon-carbon double bond, it can produce monosulfuride, and when the molecule has several carbon-carbon double bonds, it can produce monosulfuride and multisulfurized compound. The vulcanizing agent is preferably inorganic vulcanizing agent and/or organic vulcanizing agent, and the inorganic vulcanizing agent can be selected from sulfur and Na2S、K2S、ZnS、H2One or more of S and SCl; the organic vulcanizing agent can be one or more of di-tert-butyl sulfide (DBPS), dimethyl disulfide (DMDS), dimethyl sulfide (DMS), Ethyl Mercaptan (EM), n-butyl mercaptan (NBM) and tert-nonyl polysulfide (TNPS); the vulcanizing agent is more preferably sulfur and Na2S and thiol. In the sulfurization reaction, the molar ratio of the phenol compound represented by the general formula (X) to the sulfurizing agent is 1: 1 to 6, more preferably 1: 2 to 4. The temperature of the vulcanization reaction is 100-240 ℃, preferably 140-190 ℃; generally, the longer the reaction time, the higher the conversion, and the reaction time is generally 0.5 to 10 hours, preferably 3 to 5 hours, in combination of the conversion of the reaction and the economy of the reaction.
According to the invention, the catalyst may or may not be added during the sulfidation reaction, preferably. The catalyst is preferably selected from C1～6The organic amine and inorganic base of (b) may be selected from, for example, one or more of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, tripropylamine, butylamine, pentylamine, hexylamine, ammonia, sodium hydroxide, potassium hydroxide, zinc hydroxide, sodium oxide, potassium oxide, zinc oxide, sodium carbonate, potassium carbonate and zinc carbonate. The mass of the catalyst is 0.01 to 10%, preferably 0.1 to 5% of the mass of the phenol compound represented by the general formula (X).
According to the present invention, after the completion of the sulfurization reaction, the reaction product may be subjected to a purification treatment by one or more methods selected from water washing, distillation, filtration, drying and recrystallization, without particular limitation; when the organic amine and/or inorganic base catalyst is added in the vulcanization reaction, the purification treatment method comprises one or more of acid washing, water washing, distillation, filtration, drying and recrystallization.
According to the invention, preferably, the structure of the thiophosphoryl acylating agent is shown as the formula (Z):
Figure BDA0002243627240000061
wherein R is0Selected from H, C6～C20Aryl radical, C1-300Straight or branched alkyl (preferably phenyl, C)1～C14Alkyl phenyl, C1～C20Straight or branched chain alkyl); the group A is selected from F, Cl, Br, I, OH (preferably Cl, Br). Specifically, the thiophosphoryl chloride, thiophosphonyl dichloride and C can be selected as the thiophosphoryl acylating agent1-300One or more of a straight-chain or branched alkyl thiophosphonyl dichloride and a phenyl thiophosphonyl dichloride (preferably a phenyl thiophosphonyl dichloride).
According to the present invention, it is preferred that the reaction conditions of the sulfurized product of the phenol compound represented by the general formula (X) or the phenol compound represented by the general formula (X) with a thiophosphoryl acylating agent are: the mol ratio of the sulfur-phosphorus acylating agent to the phenol compound shown by the general formula (X) is 1: 1 to 10 (preferably 1: 1 to 5); the reaction temperature is 50-150 ℃ (preferably 60-100 ℃); in general, the conversion is higher as the reaction time is longer, and the reaction time is usually 0.5 to 10 hours (preferably 3 to 5 hours). In the thiophosphorylation reaction, a catalyst may be added or not added, and preferably, a catalyst is added. The catalyst is preferably C1～10The organic amine and inorganic ammonium of (b) may be selected from, for example, one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine and ammonia. The amount of the catalyst added is preferably 0.1 to 60%, more preferably 10 to 40% by mass of the phenol compound. In the phosphonothioacylation reaction, a solvent may be added or may not be added, and the solvent is preferably added. The solvent is preferably one or more of toluene, xylene, petroleum ether and cyclohexane, and for example, toluene and/or xylene may be used. The amount of the solvent is 5 mass% of the phenol compound represented by the general formula (X)0% to 500% (preferably 100% to 300%). The catalyst and the solvent may be removed by one or more methods including acid washing, water washing, distillation, filtration, drying and recrystallization, and are not particularly limited.
According to the present invention, after the completion of the reaction of the sulfurized product of the phenol compound represented by the above general formula (X) or the phenol compound represented by the general formula (X) with the thiophosphoryl acylating agent, the reaction product may be subjected to a purification treatment by one or more methods selected from among washing with water, distillation, filtration, drying and recrystallization, without particular limitation.
According to the present invention, the phenol compound represented by the general formula (X) is preferably derived from a natural plant cashew nut. The cashew nut shell contains a large amount of cashew nut shell oil, the main component of the cashew nut shell oil is meta-phenol, generally called cardanol, and the structure of the cashew nut shell oil is as follows:
Figure BDA0002243627240000071
wherein R is C15H(31+x)And x is 0, -2, -4 or-6.
The thiophosphonate compounds of the present invention may be compounds of a single structure or may be mixtures comprising compounds of different structures.
The thiophosphonate compound has outstanding bearing capacity and excellent wear resistance and wear reduction performance, can be used as an extreme pressure anti-wear agent to be applied to lubricating oil and lubricating grease, and has the advantages of simple preparation method, convenient operation, green and easily obtained raw materials, high product yield and high purity.
According to the invention, the antioxidant can be amine antioxidant and/or phenol antioxidant, for example, one or more of N-phenyl-naphthylamine, octyl diphenylamine, butyl diphenylamine, phenothiazine, 2, 6-di-tert-butyl-p-cresol and 2, 6-di-tert-butyl-cresol can be selected, amine antioxidant is preferred, and common trade marks comprise T531, V81, T511 and T501.
According to the invention, the rust inhibitor can be one or more of phosphate amine salt, alkenyl succinate, alkaline barium naphthalene sulfonate and barium petroleum sulfonate, preferably phosphate amine salt and/or alkenyl succinate, and commonly used commercial brands comprise T703, T746, T747 and T701.
According to the invention, the optional anti-foaming agent may be chosen from methylsilicones and/or siloxanes, preferably methylsilicones, commonly used trade designations including T901.
According to the invention, the lubricating base oil is preferably a synthetic lubricating base oil, which may be selected, for example, from ester synthetic base oils and/or polyalphaolefin synthetic oils. The ester synthetic base oil is preferably a polyol ester base oil and/or a diester base oil, and more preferably a polyol ester base oil. The polyol ester base oil may be one or more selected from trimethylolpropane ester and pentaerythritol ester, for example, trimethylolpropane oleate, trimethylolpropane stearate, pentaerythritol oleate and pentaerythritol stearate. The diester can be one or more of dioctyl sebacate, dioctyl adipate, dioctyl methyl adipate, hexanediol dicaprylate and decanediol dicaprylate.
The method for producing the rust preventive oil composition of the present invention comprises a step of mixing the above-mentioned respective components. The mixing temperature is preferably between 40 ℃ and 90 ℃, and the mixing time is preferably between 1 hour and 6 hours.
The anti-rust oil composition disclosed by the invention has excellent anti-rust performance, degradation performance and extreme pressure anti-wear performance, and is high in bearing capacity and good in compatibility.
Detailed Description
Unless otherwise specified, the percentages mentioned below are percentages by mass.
The present invention will be further illustrated by the following examples and comparative examples, but the present invention is not limited thereto.
According to the invention, as said C1-300Straight or branched alkyl, such as C1-20Straight or branched alkyl (preferably C)1-10Straight or branched alkyl, more preferably C1-4Linear or branched alkyl) or polyolefin based. Specific examples of the polyolefin group include those having a number average molecular weight Mn of 300-0 polyolefin group. In this case, the number average molecular weight Mn of the polyolefin group is preferably 500-2000, more preferably 500-1500. According to the present invention, the polyolefin group is (substantially) saturated (exhibits a long-chain alkyl structure), but depending on the kind of polyolefin as a starting material or the method of producing the polyolefin, the polyolefin group may also contain a small amount of an olefinic double bond in the molecular chain (such as one remaining or introduced during the production of the polyolefin), but this does not affect the achievement of the effect of the present invention, and the present invention is not intended to clarify the amount, and the present invention still classifies such polyolefin group as an "alkyl group".
In the present specification, the term "single bond" is sometimes used in the definition of a group. By "single bond", it is meant that the group is absent. For example, assume the formula-CH2-A-CH3Wherein the group a is defined as being selected from the group consisting of a single bond and a methyl group. In this respect, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly simplified to-CH2-CH3。
In the context of the present specification, the expression "number + valence + group" or the like refers to a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring, a combination thereof, or the like) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure. For example, "3-valent straight or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight or branched alkane (i.e., the base chain to which the straight or branched alkyl corresponds), and "2-valent straight or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom). For example, the 2-valent propyl group may be-CH2-CH2-CH2－*、
Figure BDA0002243627240000091
The 3-valent propyl group may be
Figure BDA0002243627240000092
The 4-valent propyl group may be
Figure BDA0002243627240000093
Wherein represents a binding end in the group that may be bonded to other groups.
According to the invention, in each recurring unit of formula (II), when m is greater than 0, m S atoms are bound to the radical R2'、R5' bonding; when m 'is greater than 0, m' S atoms and the radical R3'、R4' bonding; in each repeating unit of formula (II), when the radical R3When 'is a single bond, m' S atoms and the group R2' bonding when the group R4When 'is a single bond, m' S atoms and the group R5' bonding.
According to the invention, in each recurring unit of formula (II), when m is 0, there is no S atom with the radical R2'、R5' bonding; when m' is 0, there is no S atom with the group R3'、R4' bonding; in each repeating unit of formula (II), when the radical R3'if not singly bound, m' S atoms with radicals R3' bonding when the group R4'if not singly bound, m' S atoms with radicals R4' bonding.
According to the invention, in each recurring unit of formula (II), the radical (S)m、(S)m’、R2'、R3'、R4'、R5' bond formation rules are met.
According to the invention, m S atoms are bound to the radical R2'、R5' bonding means that the terminal S atom of the m S atoms (or only one S atom present) is bonded to the group R2'、R5' bonded (when m is 1, there is only one S atom, when this S atom is bonded to the group R2'、R5A' bond); m' S atoms and radicals R3'、R4'bonding means that the terminal S atom of the m' S atoms (or only one S atom present) is bonded to the group R3'、R4'bonded (when m' is 1, there is only one S atom, when this S atom is bonded to the radical R3'、R4A 'bond').
According to the invention, in each recurring unit of formula (II), in the radical R2'、R3'、R4'、R5' when bonded to each other, may be via the group R2'、R3'、R4'、R5Either binding end of' forms a covalent bond. In each repeating unit of formula (II), in the group (S)mOr (S)m' and R2'、R3'、R4'、R5' when bonded to each other, may be bonded to the group R2'、R3'、R4'、R5Either binding end of' forms a covalent bond.
According to the invention, in each recurring unit of the formula (II), when the radical R is3'、R4' non-single bond, m ' is greater than 0, m ' S atoms and the group R3'、R4' bonding, R3'、R4' Each is independently selected from the group consisting of 3 valent C1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl); when the group R3'、R4'non-single bond, m' is 0, there is no S atom and no group R3'、R4' bonding, R3'、R4' Each is independently selected from 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3'、R4' non-single bond, when m is greater than 0, R2'、R5' Each is independently selected from the group consisting of 3 valent C1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl); when the group R3'、R4' non-single bond, when m is 0, R2'、R5' Each is independently selected from 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3' is a single bond, R4When 'a non-single bond and m' are greater than 0,m' S atoms and radicals R2'、R4' bonding, R4' selected from the group consisting of 3-valent C1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl); when the group R3' is a single bond, R4'non-single bond, m' is 0, there is no S atom and no group R2'、R4' bonding, R4' selected from the group consisting of 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3' is a single bond, R4' non-single bond, when m is greater than 0, R2' selected from the group consisting of C having a valence of 41-20Straight or branched alkyl (preferably selected from C having a valence of 4)1-4Straight or branched alkyl), R5' selected from the group consisting of 3-valent C1-20Straight or branched alkyl (preferably selected from 3-valent C)1-4Straight or branched chain alkyl); when the group R3' is a single bond, R4' non-single bond, when m is 0, R2' selected from the group consisting of 3-valent C1-20Straight or branched alkyl (preferably selected from 3-valent C)1-4Straight or branched alkyl), R5' selected from the group consisting of 2-valent C1-20Straight or branched alkyl (preferably selected from 2-valent C)1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3' non-Single bond, R4' is a single bond, m ' is greater than 0, m ' S atoms and the group R3'、R5' bonding, R3' selected from the group consisting of 3-valent C1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl); when the group R3' non-Single bond, R4When 'is a single bond and m' is 0, there is no S atom or group R3'、R5' bonding, R3' selected from the group consisting of 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3' non-Single bond, R4' is a single bond, when m is greater than 0, R2' selected from the group consisting of 3-valent C1-20Straight or branched alkyl (preferably selected from 3-valent C)1-4Straight or branched alkyl), R5' selected from the group consisting of C having a valence of 41-20Straight or branched alkyl (preferably selected from C having a valence of 4)1-4Straight or branched chain alkyl); when the group R3' non-Single bond, R4' is a single bond, and when m is 0, R2' selected from the group consisting of 2-valent C1-20Straight or branched alkyl (preferably selected from 2-valent C)1-4Straight or branched alkyl), R5' selected from the group consisting of 3-valent C1-20Straight or branched alkyl (preferably selected from 3-valent C)1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3'、R4' are all single bonds, m ' is greater than 0, m ' S atoms and the radical R2'、R5' bonding, when m is greater than 0, R2'、R5' Each is independently selected from the group consisting of C having a valence of 41-20Straight or branched chain alkyl (preferably each independently selected from C having a valence of 41-4Straight or branched chain alkyl), when m is 0, R2'、R5' Each is independently selected from the group consisting of 3 valent C1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3'、R4When 'are all single bonds, m' is 0, and m is greater than 0, R2'、R5' Each is independently selected from the group consisting of 3 valent C1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl); when the group R3'、R4When 'are all single bonds, m' is 0, and m is 0, R2'、R5' Each is independently selected from 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the present invention, in each repeating unit of formula (II), for example, a structure may be formed including: -CH2-CH2-CH2-CH2-CH2-*、
Figure BDA0002243627240000111
Figure BDA0002243627240000112
The main raw materials used are as follows:
cashew nut shell oil, Shanghai Bingsheng chemical science and technology Co., Ltd, Industrial products
Sulfur powder, national chemical reagent group, Inc., analytical purity
Triethylamine, chemical reagent of national drug group, analytical purity
Phenylthiophosphonodichloride, national pharmaceutical group chemical reagents Ltd, analytical purity
Trimethylphenol phosphate, TCP, Nengmadzu chemical Co., Ltd, Industrial products
Octyl diphenylamine, V81, Beijing rifampicin commercial Co., Ltd, Industrial products
N-phenyl-naphthylamine, T531, Tianjin Ningchemist Co., Ltd, Industrial products
Alkenyl succinate, T703, N.C. Hi-Tech Co., Ltd, Beijing Huarui, Industrial products
Basic barium naphthalenesulfonate, T747, N.C. Hi Tech Co., Ltd, Beijing Huarui New City
Methyl Silicone oil, T901, Beijing Huarui New City science and technology Co., Ltd, Industrial products
Polyol ester base oil, Hi-Tech Co Ltd of Beijing Huarui New City, Industrial products
Example 1 preparation of sulfurized cardanol
62g of cardanol (about 0.2mol) and 12.8g of sulfur powder (0.4mol) were placed in a 250ml three-neck reaction flask, and stirring and heating were started. The reaction temperature was maintained at 190 ℃ and the reaction was continued for 3 hours. And after the reaction is finished, cooling, and filtering to obtain dark brown red viscous liquid, namely the vulcanized cardanol, wherein the product conversion rate is 89.3%.
Example 2 preparation of Cardanol disulfide Phenylthiophosphonate
25g of the sulfurized cardanol obtained in example 1, 8g of triethylamine and 50g of toluene were placed in a reaction flask, and heated and stirred, 5g of phenylthiophosphonyl dichloride was added thereto, and the reaction temperature was maintained at 90 ℃ for 4 hours. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Washing the reaction product with distilled water to neutrality, distilling the organic phase at 100Pa and 150 deg.c under reduced pressure for 1 hr to eliminate water and solvent to obtain brown yellow transparent liquid with reaction conversion rate of 95.1%.
Examples 3 to 6 of Rust preventive oil composition and comparative example 1
The formulation compositions of examples 3 to 6 and comparative example 1 of the rust preventive oil composition are shown in Table 1. The components are added into a mixing container according to the proportion, heated and stirred for 4 hours at the temperature of 80 ℃, and the rust preventive oil composition is prepared respectively.
TABLE 1
Figure BDA0002243627240000121
The examples and comparative examples of the rust preventive oil composition were subjected to the examination of frictional properties, the examination of indexes such as flash point, acid value before and after oxidation, wet box, pour point, evaporation loss, etc., and the test results are shown in Table 2.
TABLE 2
Figure BDA0002243627240000131

Claims (15)

1.一种防锈油组合物，包括以下组分：1. A rust preventive oil composition, comprising the following components: A)硫代膦酸酯化合物，占组合物总质量的0.1％～10％(优选1％～5％)；A) thiophosphonate compound, accounting for 0.1% to 10% (preferably 1% to 5%) of the total mass of the composition; B)抗氧剂，占组合物总质量的0.1％～10％(优选0.5％～5％)；B) antioxidant, accounting for 0.1% to 10% (preferably 0.5% to 5%) of the total mass of the composition; C)防锈剂，占组合物总质量的1％～15％(优选2％～10％)；C) rust inhibitor, accounting for 1% to 15% (preferably 2% to 10%) of the total mass of the composition; D)任选的抗泡剂，占组合物总质量的0～200ppm(优选1～50ppm)；D) optional anti-foaming agent, accounting for 0-200 ppm (preferably 1-50 ppm) of the total mass of the composition; E)主要量的润滑基础油；E) the main amount of lubricating base oil; 其中所述硫代膦酸酯化合物的结构如通式(I)所示：The structure of the thiophosphonate compound is shown in the general formula (I):
Figure FDA0002243627230000011
Figure FDA0002243627230000011
 在通式(I)中，基团R0选自H、C6～C20芳基、C1-300直链或支链烷基(优选苯基、C1～C14烷基苯基、C1～C20直链或支链烷基)；各基团R1、R2、R3、R4、R5彼此相同或不同，各自独立地选自H、C1～C20直链或支链烷基和式(II)所示的基团，各基团R1、R2、R3、R4、R5中的至少一个基团为式(II)所示的基团；In the general formula (I), the group R 0 is selected from H, C 6 -C 20 aryl, C 1-300 straight or branched chain alkyl (preferably phenyl, C 1 -C 14 alkylphenyl, C 1 -C 20 straight chain or branched chain alkyl); each group R 1 , R 2 , R 3 , R 4 , R 5 is the same or different from each other, each independently selected from H, C 1 -C 20 straight chain Or a branched alkyl group and a group represented by formula (II), at least one of the groups R 1 , R 2 , R 3 , R 4 , and R 5 is a group represented by formula (II);
Figure FDA0002243627230000012
Figure FDA0002243627230000012
 在通式(II)中，基团R1'选自单键、C1-20直链或支链的亚烷基(优选选自单键和C1-4直链或支链的亚烷基)；n个重复单元中的基团R2'彼此相同或不同，各自独立地选自2价、3价或4价的C1-20直链或支链烷基(优选各自独立地选自2价、3价或4价的C1-4直链或支链烷基)；n个重复单元中的基团R3'彼此相同或不同，各自独立地选自单键、2价或3价的C1-20直链或支链烷基(优选各自独立地选自单键、2价或3价的C1-4直链或支链烷基)；n个重复单元中的基团R4'彼此相同或不同，各自独立地选自单键、2价或3价的C1-20直链或支链烷基(优选各自独立地选自单键、2价或3价的C1-4直链或支链烷基)；n个重复单元中的基团R5'彼此相同或不同，各自独立地选自2价、3价或4价的C1-20直链或支链烷基(优选各自独立地选自2价、3价或4价的C1-4直链或支链烷基)；n个重复单元中的基团R6'彼此相同或不同，各自独立地选自单键、C1-20直链或支链亚烷基(优选各自独立地选自单键、C1-4直链或支链亚烷基)；基团R7'选自氢、C1-20直链或支链烷基(优选选自氢、C1-4直链或支链烷基)；n为1～10之间的整数(优选1～3之间的整数)；n个重复单元中的m彼此相同或不同，各自独立地选自0～10之间的整数(优选0～5之间的整数)；n个重复单元中的m’彼此相同或不同，各自独立地选自0～10之间的整数(优选0～5之间的整数)；在式(II)的每个重复单元中，当m大于0时，m个S原子与基团R2'、R5'键合；当m'大于0时，m'个S原子与基团R3'、R4'键合；在式(II)的每个重复单元中，当基团R3'为单键时，m’个S原子与基团R2'键合，当基团R4'为单键时，m’个S原子与基团R5'键合。In the general formula (II), the group R 1 ' is selected from a single bond, a C 1-20 linear or branched alkylene (preferably selected from a single bond and a C 1-4 linear or branched alkylene) group); the groups R 2 ' in the n repeating units are the same or different from each other, each independently selected from divalent, trivalent or tetravalent C 1-20 straight or branched chain alkyl (preferably each independently selected from a divalent, trivalent or tetravalent C 1-4 linear or branched alkyl group); the groups R 3 ' in the n repeating units are the same or different from each other, each independently selected from a single bond, a divalent or Trivalent C 1-20 linear or branched alkyl (preferably each independently selected from single bond, divalent or trivalent C 1-4 linear or branched alkyl); groups in n repeating units The groups R 4 ' are the same or different from each other, each independently selected from a single bond, a divalent or trivalent C 1-20 straight or branched chain alkyl group (preferably each independently selected from a single bond, a divalent or trivalent C 1-20 C 1-4 straight-chain or branched chain alkyl); the groups R 5 ' in the n repeating units are the same or different from each other, each independently selected from divalent, trivalent or tetravalent C 1-20 straight chain or Branched alkyl groups (preferably independently selected from divalent, trivalent or tetravalent C 1-4 straight or branched chain alkyl groups); the groups R 6 ' in the n repeating units are the same or different from each other, each independently selected from single bond, C 1-20 linear or branched alkylene (preferably each independently selected from single bond, C 1-4 linear or branched alkylene); group R 7 ' is selected from Hydrogen, C 1-20 linear or branched alkyl (preferably selected from hydrogen, C 1-4 linear or branched alkyl); n is an integer between 1-10 (preferably an integer between 1-3 ); m in the n repeating units are the same or different from each other, each independently selected from an integer between 0 and 10 (preferably an integer between 0 and 5); m' in the n repeating units are the same or different from each other, Each is independently selected from an integer between 0 and 10 (preferably an integer between 0 and 5); in each repeating unit of formula (II), when m is greater than 0, m S atoms and the group R 2 ', R 5 ' are bonded; when m' is greater than 0, m' S atoms are bonded to groups R 3 ', R 4 '; in each repeating unit of formula (II), when the group R 3 When ' is a single bond, m' S atoms are bonded to the group R 2 ', and when the group R 4 ' is a single bond, m' S atoms are bonded to the group R 5 '. 2.按照权利要求1所述的组合物，其特征在于，在通式(I)中，各基团R1、R3、R5彼此相同或不同，各自独立地选自氢、C1-4直链或支链烷基；各基团R2、R4彼此相同或不同，各自独立地选自氢、C1-300直链或支链烃基(优选C1-30直链或支链烷基或者数均分子量Mn为300-3000的聚烯烃基)、通式(II)所示的基团，其中至少一个基团选自通式(II)所示的基团(优选地，在至少一个通式(II)所示的基团中，m和m'中的至少一个大于0)。2. The composition according to claim 1, characterized in that, in the general formula (I), each group R 1 , R 3 , R 5 is the same or different from each other, and is independently selected from hydrogen, C 1- 4 Straight-chain or branched-chain alkyl groups; each group R 2 , R 4 are the same or different from each other, each independently selected from hydrogen, C 1-300 straight-chain or branched chain hydrocarbon groups (preferably C 1-30 straight-chain or branched chain alkyl group or polyolefin group with number average molecular weight Mn of 300-3000), group represented by general formula (II), wherein at least one group is selected from the group represented by general formula (II) (preferably, in In at least one group represented by the general formula (II), at least one of m and m' is greater than 0). 3.按照权利要求1所述的组合物，其特征在于，在通式(I)中，各基团R1、R3、R5彼此相同或不同，各自独立地选自氢、C1-4直链或支链烷基；各基团R2、R4中的一个基团选自通式(II)所示的基团，另一个基团选自氢(优选地，在至少一个通式(II)所示的基团中，m和m'中的至少一个大于0)。3. The composition according to claim 1, wherein, in the general formula (I), each group R 1 , R 3 , R 5 is the same or different from each other, and is independently selected from hydrogen, C 1- 4 Linear or branched alkyl groups; one of the groups R 2 and R 4 is selected from the group represented by the general formula (II), and the other group is selected from hydrogen (preferably, in at least one general In the group represented by the formula (II), at least one of m and m' is greater than 0). 4.按照权利要求1所述的组合物，其特征在于，所述硫代膦酸酯化合物选自以下的化合物或其任意比例的混合物：4. The composition according to claim 1, wherein the thiophosphonate compound is selected from the following compounds or mixtures thereof in any proportion:
Figure FDA0002243627230000031
Figure FDA0002243627230000031
 5.按照权利要求1所述的组合物，其特征在于，所述硫代膦酸酯化合物的制备方法包括使通式(X)所示的酚化合物发生硫化反应、硫磷酰化反应的步骤；5. The composition according to claim 1, wherein the preparation method of the thiophosphonate compound comprises the steps of making the phenolic compound represented by the general formula (X) undergo a sulfidation reaction and a thiophosphorylation reaction ;
Figure FDA0002243627230000041
Figure FDA0002243627230000041
 通式(X)中，各基团R1”、R2”、R3”、R4”、R5”彼此相同或不同，各自独立地选自氢、C1-300直链或支链烃基(优选C1-30直链或支链烷基或者数均分子量Mn为300-3000的聚烯烃基)、通式(Y)所示的基团，其中至少一个基团选自通式(Y)所示的基团；In the general formula (X), each group R 1 ", R 2 ", R 3 ", R 4 ", R 5 " is the same or different from each other, and each is independently selected from hydrogen, C 1-300 straight chain or branched chain Hydrocarbyl group (preferably C 1-30 straight or branched chain alkyl group or polyolefin group with number average molecular weight Mn of 300-3000), group represented by general formula (Y), wherein at least one group is selected from general formula ( Y) the group shown;
Figure FDA0002243627230000042
Figure FDA0002243627230000042
 其中基团R1”'选自单键、C1-20直链或支链的亚烷基(优选选自单键和C1-4直链或支链的亚烷基)；m个重复单元中的基团R2”'彼此相同或不同，各自独立地选自单键、C1-20直链或支链的亚烷基(优选各自独立地选自单键、C1-4直链或支链的亚烷基)；基团R3”'选自氢、C1-20直链或支链烷基(优选选自氢、C1-4直链或支链烷基)；m个重复单元中的基团R4”'彼此相同或不同，各自独立地选自氢、C1-20直链或支链烷基(优选各自独立地选自氢、C1-4直链或支链烷基)；m个重复单元中的基团R5”'彼此相同或不同，各自独立地选自氢、C1-20直链或支链烷基(优选各自独立地选自氢、C1-4直链或支链烷基)；m为正整数(优选1～10之间的正整数，更优选1～3之间的正整数)。wherein the group R 1 "' is selected from a single bond, a C 1-20 linear or branched alkylene group (preferably selected from a single bond and a C 1-4 linear or branched alkylene group); m repeats The groups R 2 "' in the unit are the same or different from each other, and each is independently selected from a single bond, a C 1-20 linear or branched alkylene group (preferably each independently selected from a single bond, a C 1-4 linear chain or branched alkylene); the group R 3 "' is selected from hydrogen, C 1-20 linear or branched alkyl (preferably selected from hydrogen, C 1-4 linear or branched alkyl); The groups R 4 ″' in the m repeating units are the same or different from each other, each independently selected from hydrogen, C 1-20 linear or branched alkyl (preferably each independently selected from hydrogen, C 1-4 linear or branched chain alkyl); the groups R 5 ″' in m repeating units are the same or different from each other, each independently selected from hydrogen, C 1-20 straight or branched chain alkyl (preferably each independently selected from hydrogen , C 1-4 straight or branched chain alkyl); m is a positive integer (preferably a positive integer between 1-10, more preferably a positive integer between 1-3). 6.按照权利要求5所述的组合物，其特征在于，在通式(X)中，各基团R1”、R3”、R5”彼此相同或不同，各自独立地选自氢、C1-4直链或支链烷基；各基团R2”、R4”彼此相同或不同，各自独立地选自氢、C1-20直链或支链烷基和通式(Y)所示的基团，其中至少一个基团选自通式(Y)所示的基团。6. The composition according to claim 5, wherein, in the general formula (X), each group R 1 ", R 3 ", R 5 " is the same or different from each other, and is independently selected from hydrogen, C 1-4 straight chain or branched chain alkyl; each group R 2 ", R 4 " is the same or different from each other, each independently selected from hydrogen, C 1-20 straight chain or branched chain alkyl and the general formula (Y ), wherein at least one group is selected from the group represented by the general formula (Y). 7.按照权利要求6所述的组合物，其特征在于，在通式(X)中，各基团R1”、R3”、R5”彼此相同或不同，各自独立地选自氢、C1-4直链或支链烷基；各基团R2”、R4”中的一个基团选自通式(Y)所示的基团，另一个基团选自氢。7. The composition according to claim 6, wherein, in the general formula (X), each group R 1 ", R 3 ", R 5 " is the same or different from each other, and is independently selected from hydrogen, C 1-4 straight-chain or branched-chain alkyl; one of the groups R 2 ″ and R 4 ″ is selected from the group represented by the general formula (Y), and the other is selected from hydrogen. 8.按照权利要求5的组合物，其特征在于，先使通式(X)所示的酚化合物发生硫化反应、再使其硫化产物发生硫磷酰化反应；或者先使通式(X)所示的酚化合物发生硫磷酰化反应、再使其硫磷酰化产物(通式(X)所示酚化合物的硫磷酰化产物)发生硫化反应。8. according to the composition of claim 5, it is characterized in that, first make the phenolic compound shown in general formula (X) undergo sulfurization reaction, then make its sulfurization product take place phosphorylation reaction; Or first make general formula (X) The phenolic compound shown is subjected to a phosphorylation reaction, and the phosphorylated product thereof (the phosphorylated product of the phenol compound represented by the general formula (X)) is subjected to a sulfuration reaction. 9.按照权利要求8的组合物，其特征在于，所述硫化反应包括使通式(X)所示的酚化合物或通式(X)所示酚化合物的硫磷酰化产物与硫化剂发生反应的步骤。9. according to the composition of claim 8, it is characterized in that, described vulcanization reaction comprises making the phenolic compound shown in general formula (X) or the thiophosphorylation product of phenolic compound shown in general formula (X) and vulcanizing agent to generate reaction steps. 10.按照权利要求9的组合物，其特征在于，所述硫化剂为无机硫化剂和/或有机硫化剂(所述无机硫化剂可以选用硫磺、Na2S、K2S、ZnS、H2S和SCl中的一种或多种；所述有机硫化剂可以选用二叔丁基硫化物(DBPS)、二甲基二硫化物(DMDS)、二甲基硫化物(DMS)、乙基硫醇(EM)、正丁基硫醇(NBM)和叔壬基多硫化物(TNPS)中的一种或多种)。10. according to the composition of claim 9, it is characterized in that, described vulcanizing agent is inorganic vulcanizing agent and/or organic vulcanizing agent (described inorganic vulcanizing agent can select sulfur, Na 2 S, K 2 S, ZnS, H 2 One or more of S and SCl; the organic vulcanizing agent can be selected from di-tert-butyl sulfide (DBPS), dimethyl disulfide (DMDS), dimethyl sulfide (DMS), ethyl sulfide one or more of alcohol (EM), n-butyl mercaptan (NBM), and tert-nonyl polysulfide (TNPS)). 11.按照权利要求9的组合物，其特征在于，所述通式(X)所示的酚化合物与硫化剂的摩尔比为1：1～6(优选1：2～4)，所述硫化反应的温度为100℃～240℃(优选140℃～190℃)。11. The composition according to claim 9, wherein the molar ratio of the phenolic compound represented by the general formula (X) to the vulcanizing agent is 1:1-6 (preferably 1:2-4), and the vulcanizing agent The temperature of the reaction is 100°C to 240°C (preferably 140°C to 190°C). 12.按照权利要求5的组合物，其特征在于，所述硫磷酰化剂的结构如式(Z)所示：12. The composition according to claim 5, wherein the structure of the phosphorylation agent is as shown in formula (Z):
Figure FDA0002243627230000051
Figure FDA0002243627230000051
 其中的R0选自H、C6～C20芳基、C1-300直链或支链烷基(优选苯基、C1～C14烷基苯基、C1～C20直链或支链烷基)；基团A选自F、Cl、Br、I、OH(优选Cl、Br)。wherein R 0 is selected from H, C 6 -C 20 aryl, C 1-300 linear or branched alkyl (preferably phenyl, C 1 -C 14 alkylphenyl, C 1 -C 20 linear or branched alkyl); the group A is selected from F, Cl, Br, I, OH (preferably Cl, Br). 13.按照权利要求5的组合物，其特征在于，所述通式(X)所示酚化合物的硫化产物或通式(X)所示的酚化合物与硫磷酰化剂发生反应的条件为：所述硫磷酰化剂与通式(X)所示酚化合物之间的摩尔比为1：1～10(优选1：1～5)；反应温度为50℃～150℃(优选60℃～100℃)。13. according to the composition of claim 5, it is characterized in that, the condition that the sulfide product of the phenolic compound shown in the general formula (X) or the phenolic compound shown in the general formula (X) and the thiophosphorylation agent are reacted as : the molar ratio between the phosphorylation agent and the phenolic compound represented by the general formula (X) is 1:1-10 (preferably 1:1-5); the reaction temperature is 50°C-150°C (preferably 60°C) ~100°C). 14.按照权利要求1～13之一所述的组合物，其特征在于，所述抗氧剂为胺类抗氧剂和/或酚类抗氧剂；所述防锈剂为磷酸酯胺盐、烯基丁二酸盐、烯基丁二酸酯、碱性萘磺酸钡和石油磺酸钡中的一种或多种；所述任选的抗泡剂为甲基硅油和/或硅氧烷；所述润滑基础油为合成润滑基础油。14. The composition according to any one of claims 1 to 13, wherein the antioxidant is an amine antioxidant and/or a phenolic antioxidant; the rust inhibitor is a phosphate ester amine salt , one or more of alkenyl succinate, alkenyl succinate, basic barium naphthalene sulfonate and barium petroleum sulfonate; the optional antifoaming agent is methyl silicone oil and/or silicon Oxane; the lubricating base oil is a synthetic lubricating base oil. 15.权利要求1～14之一的防锈油组合物的制备方法，包括将上述各组分混合的步骤。15. The preparation method of the rust preventive oil composition according to any one of claims 1 to 14, comprising the step of mixing the above components.
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JPH0827170A (en) * 1994-07-13 1996-01-30 Ikari Yakuhin Kk Organophosphorus agent and herbicide, germicide and insecticide containing the same agent as active component

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3256189A (en) * 1962-10-18 1966-06-14 Texaco Inc Hydrocarbyl ether reaction products
GB1070314A (en) * 1964-01-31 1967-06-01 Shell Int Research Improvements in or relating to lubricant compositions
US4051201A (en) * 1970-04-06 1977-09-27 Stauffer Chemical Company Thiobisphenol esters of pentavalent phosphorus acids
GB1309225A (en) * 1970-04-28 1973-03-07 Monsanto Co Refining esters of organophosphorus acids
US4208357A (en) * 1974-09-06 1980-06-17 The Lubrizol Corporation Process for preparing phosphorus and sulfur containing amides and thioamides
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