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WO2021078137A1 - 一种含磷化合物及其制备方法、用途 - Google Patents

一种含磷化合物及其制备方法、用途 Download PDF

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Publication number
WO2021078137A1
WO2021078137A1 PCT/CN2020/122396 CN2020122396W WO2021078137A1 WO 2021078137 A1 WO2021078137 A1 WO 2021078137A1 CN 2020122396 W CN2020122396 W CN 2020122396W WO 2021078137 A1 WO2021078137 A1 WO 2021078137A1
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Prior art keywords
group
linear
substituted
branched
branched alkyl
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PCT/CN2020/122396
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English (en)
French (fr)
Inventor
庄敏阳
郑会
刘欣阳
刘伟
何懿峰
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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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Application filed by Sinopec Research Institute of Petroleum Processing , China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to US17/755,076 priority Critical patent/US12358934B2/en
Priority to JP2022523476A priority patent/JP7653426B2/ja
Priority to EP20879404.0A priority patent/EP4050015A4/en
Publication of WO2021078137A1 publication Critical patent/WO2021078137A1/zh
Anticipated expiration legal-status Critical
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    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/094—Esters of phosphoric acids with arylalkanols
    • 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
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions

Definitions

  • the invention relates to a phosphorus-containing compound, in particular to a phosphorus-containing compound capable of promoting biodegradation of lubricating oil, and a preparation method and application thereof.
  • Lubricating oil is a necessary working medium in the normal operation of mechanical equipment and material manufacturing and processing. With the rapid development of the industry, the demand for lubricating oil is also increasing. In the process of storage, transportation and use of lubricating oil, leakage, overflow, improper discharge and environmental pollution are inevitable. Although the acute toxicity of lubricating oil to organisms is very small, the lubricating oil entering the environment will seriously pollute the land, rivers and lakes due to its poor biodegradability. At the same time, the accumulation in the environment will also affect the ecological balance. Therefore, a biodegradation promotion is urgently needed. To improve the biodegradation rate of lubricating oil.
  • biodegradable vegetable oils and synthetic ester oils are used to prepare lubricants, as reported in CN 102408939B Biodegradable lubricating oil composition and its preparation method, the biodegradable industrial gear oil composition reported in CN 105132104A; on the other hand, the development of biodegradation accelerators for lubricating oil, as reported in the patent CN 103642557B, the chemical formula is C 20 H 37 NO 3 amide biodegradation accelerator for lubricating oil, but there are few reports on the biodegradation accelerator for lubricating oil.
  • the inventors of the present invention have conducted in-depth studies and found that the phosphorus-containing compound having a specific structure as the present invention can achieve a good effect of promoting the biodegradation of lubricating oil.
  • the phosphorus-containing compound of the present invention has excellent oxidation resistance, and can inhibit the oxidation of the lubricating oil when it is blended with lubricating oil.
  • the present invention provides the following technical solutions.
  • the present invention provides a phosphorus-containing compound represented by the following formula (I),
  • n is an integer between 0-50 (preferably an integer between 0-20, more preferably an integer between 0-10, and still more preferably 0, 1, 2, 3 or 4);
  • n+1 R groups are the same or different from each other, and are each independently selected from C 1 to C 30 alkylene groups (preferably C 1 to C 10 alkylene groups, more preferably C 1 to C 6 alkylene groups, and even more preferably C 1 to C 4 alkylene);
  • R b group is H or C 1 to C 30 hydrocarbon group (preferably H or C 1 to C 10 hydrocarbon group, more preferably H or C 1 to C 6 straight or branched chain Alkyl group, more preferably H or C 1 -C 4 straight or branched chain alkyl);
  • Each R 0 group is the same or different from each other, and is independently selected from H, C 1 ⁇ C 30 hydrocarbon group and (Preferably each independently selected from H, C 1 ⁇ C 10 linear or branched alkyl groups and More preferably, each independently selected from H, C 1 to C 4 linear or branched alkyl groups and Preferably at least one of R 0 in formula (I) is
  • x R 1 groups are the same or different from each other, and are each independently selected from H, C 1 ⁇ C 30 hydrocarbon group (preferably selected from H, C 1 to C 10 linear or branched alkyl, more preferably selected from H, C 1 to C 6 linear or branched alkyl, further preferably selected from H, C 1 to C 4 linear or branched alkyl), each Ar group is the same or different from each other, and each is independently selected from C 3 to C 30 ring groups (preferably selected from C 6 to C 15 aromatic ring groups Group, more preferably selected from a benzene ring, a naphthalene ring and an anthracene ring), the R 2
  • Each A group is the same or different from each other, and each is independently selected from OH, optional Substituted C 1 ⁇ C 30 hydrocarbon group (preferably optionally by Substituted C 1 ⁇ C 10 linear or branched alkyl, more preferably optionally by The substituted C 1 ⁇ C 6 linear or branched alkyl group is further preferably optionally Substituted C 1 ⁇ C 4 linear or branched alkyl), optionally Substituted C 1 ⁇ C 30 alkoxy (preferably optionally by Substituted C 1 ⁇ C 10 linear or branched alkoxy, more preferably optionally by The substituted C 1 ⁇ C 6 linear or branched alkoxy group is further preferably optionally substituted by Substituted C 1 ⁇ C 4 linear or branched alkoxy) and H, at least one A group in formula (I) is selected from Be Substituted C 1 ⁇ C 30 hydrocarbon group (preferably by The substituted C 1 ⁇ C 10 linear or branched al
  • the present invention also provides a method for preparing a phosphorus-containing compound, which includes:
  • Step (1) reacting the compound represented by formula (II) and/or its inorganic acid salt with the compound represented by formula (III) to obtain the product of step (1);
  • n is an integer between 0-50 (preferably an integer between 0-20, more preferably an integer between 0-10, and still more preferably 0, 1, 2, 3 or 4);
  • n+1 R groups are the same or different from each other, and are each independently selected from C 1 to C 30 alkylene groups (preferably C 1 to C 10 alkylene groups, more preferably C 1 to C 6 alkylene groups, and even more preferably C 1 to C 4 alkylene);
  • R b group is H or C 1 to C 30 hydrocarbon group (preferably H or C 1 to C 10 hydrocarbon group, more preferably H or C 1 to C 6 straight or branched chain Alkyl group, more preferably H or C 1 -C 4 straight or branched chain alkyl);
  • Each R 0 'group is the same or different from each other, and is each independently selected from H, C 1 ⁇ C 30 hydrocarbon group (preferably each independently selected from H, C 1 ⁇ C 10 linear or branched alkyl group, more preferably Each independently selected from H, C 1 to C 4 linear or branched alkyl), preferably at least one R 0 'is H;
  • Each A'group is the same or different from each other, and each is independently selected from XA"', C 1 to C 30 hydrocarbon groups optionally substituted by XA"' (preferably C 1 to C 10 hydrocarbon groups optionally substituted by XA"' A straight or branched chain alkyl group, more preferably a C 1 to C 6 straight chain or branched alkyl group optionally substituted by XA"', and even more preferably a C 1 to C 4 straight chain optionally substituted by XA"' Or branched chain alkyl), C 1 to C 30 alkoxy optionally substituted by XA"' (preferably C 1 to C 10 linear or branched alkoxy optionally substituted by XA"', more It is preferably a C 1 to C 6 linear or branched alkoxy group optionally substituted by XA"', and more preferably a C 1 to C 4 linear or branched chain alkoxy group optionally substituted by XA"') and H, A"' is
  • X groups are each independently selected from O or S, a is 0 or 1, each R"' is the same or different from each other, and each is independently selected from A"', C 1 ⁇ C 30 hydrocarbon group (Preferably a C 1 to C 10 linear or branched alkyl group, more preferably a C 1 to C 6 linear or branched alkyl group, still more preferably a C 1 to C 4 linear or branched alkyl group), any is selected from straight or branched C 1 ⁇ C 10 alkyl group substituted with a C 7 ⁇ C 15 aryl group (preferably an optionally substituted linear or branched alkyl group of C 1 ⁇ C 10 to C 7 ⁇ C 12 arylalkyl, more preferably optionally substituted straight-chain or branched-chain C 1 ⁇ C 10 alkyl benzyl group) and optionally substituted straight-chain or branched-chain alkyl group of C 1 ⁇ C 10 C 6 ⁇ C 15 aryl group
  • step (2) reacting the product of step (1) with the compound represented by formula (IV) to obtain the product of step (2);
  • x is an integer between 0 and 5 (preferably an integer between 0 and 4, more preferably 0, 1, 2 or 3), and y is an integer between 1 and 5 (preferably an integer between 1 and 4, More preferably 1, 2 or 3), the sum of x+y ⁇ the number of hydrogen atoms that can be substituted on the Ar group;
  • the x R 1 groups are the same or different from each other, and are each independently selected from H, C 1 ⁇ C 30 (Preferably selected from H, C 1 to C 10 linear or branched alkyl, more preferably selected from H, C 1 to C 6 linear or branched alkyl, further preferably selected from H, C 1 ⁇ C 4 linear or branched alkyl),
  • the Ar group is a C 3 to C 30 ring group (preferably a C 6 to C 15 aromatic ring group, more preferably a benzene ring, a naphthalene ring or an anthracene ring)
  • the R 2 group is a single bond or a C 1 to
  • the present invention also provides the use of the phosphorus-containing compound represented by the above formula (I) or the phosphorus-containing compound prepared by the method for preparing the above-mentioned phosphorus-containing compound as a biodegradation agent for lubricating oil.
  • the present invention also provides a lubricating oil composition
  • a lubricating oil composition comprising a lubricating oil base oil, a phosphorus-containing compound selected from the above-mentioned formula (I), a phosphorus-containing compound prepared by the above-mentioned method for preparing a phosphorus-containing compound, and parts thereof Or at least one of the products obtained by all condensation dehydration reactions.
  • the phosphorus-containing compound of the present invention has very excellent biodegradability and anti-oxidation properties, and is particularly suitable for promoting the biodegradation of lubricating oil products.
  • the phosphorus-containing compound of the present invention has excellent oxidation resistance, and can inhibit the oxidation of the lubricating oil when it is blended with lubricating oil.
  • the preparation method of the phosphorus-containing compound of the present invention is simple, efficient and high in yield.
  • the phosphorus-containing compound with excellent biodegradability and anti-oxidation performance of the present invention can be prepared.
  • the term "single bond” is sometimes used in the definition of a group.
  • the so-called “single bond” means that the group does not exist.
  • the structural formula -CH 2 -A-CH 3 where the group A is defined as being selected from single bonds and methyl groups.
  • A is a single bond, it means that the group A does not exist, and the structural formula is correspondingly simplified to -CH 2 -CH 3 .
  • the number of a certain group is 0, which means that part of the group does not exist.
  • the groups connected to both ends of the group are bonded to each other.
  • the number of the group is 0, which means that other groups connected by the group are not substituted by the group.
  • the structural formula -CH 2 -(A) n -CH 3 if n is 0, the structural formula is -CH 2 -CH 3 .
  • the structural formula -CH 2 -(A) n if n is 0, it means -CH 2 -is not substituted by A, and the structural formula is -CH 3 .
  • a hydrocarbyl group refers to a group formed by removing one or more hydrogen atoms from hydrocarbons (hydrocarbons, including but not limited to alkanes, alkenes, alkynes, aromatics, etc.), and hydrocarbyl groups can be divided into monovalent groups
  • the upper limit of the number of hydrogen atoms that can be substituted by the hydrocarbon group is limited to higher valence groups such as divalent groups and trivalent groups as required.
  • monovalent groups CH 3 CH 2 -(ethyl), (isopropyl), CH ⁇ C-CH 2 -(2-propynyl).
  • Trivalent group CH 3 C ⁇ (ethylene ethyl).
  • a C 1 ⁇ C 30 hydrocarbon group refers to the removal of a hydrogen from any carbon atom of a hydrocarbon having 1-30 carbon atoms (including but not limited to alkanes, alkenes, alkynes, aromatics, etc.) Atom or a group derived from two or more hydrogen atoms as required, which can be a monovalent or higher valence linear or branched C 1 ⁇ C 30 alkyl group, a monovalent or higher valence linear or Branched C 2 to C 30 alkenyl, monovalent or higher linear or branched C 2 to C 30 alkynyl, monovalent or higher C 6 to C 30 aromatic hydrocarbon group.
  • a linear or branched C 1 ⁇ C 30 alkyl group it includes a linear or branched C 1 ⁇ C 20 alkyl group, a linear or branched C 1 ⁇ C 10 alkyl group, and a linear or branched C 1 ⁇ C alkyl group. 6 alkyl, straight or branched C 1 -C 4 alkyl. Specific examples of these alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.
  • the alkylene group is a group obtained by further removing one hydrogen atom from the above-mentioned alkyl group.
  • linear or branched C 2 ⁇ C 30 alkenyl group it includes linear or branched C 2 ⁇ C 20 alkenyl, linear or branched C 2 ⁇ C 10 alkenyl, and straight or branched C 2 ⁇ C 6 Alkenyl, straight or branched C 2 to C 4 alkenyl.
  • it is an alkenyl group including 1, 2, 3, or 4 carbon-carbon double bonds.
  • Specific examples of these alkenyl groups include vinyl, propenyl, butenyl, 2-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, and isomers of these groups.
  • it may be a group in which one or two alkenyl groups are included in the specific examples of the above-mentioned alkyl group.
  • a linear or branched C 2 ⁇ C 30 alkynyl group it includes a linear or branched C 2 ⁇ C 20 alkynyl group, a linear or branched C 2 ⁇ C 10 alkynyl group, and a straight or branched C 2 ⁇ C alkynyl group.
  • it is an alkynyl group including 1, 2, 3, or 4 carbon-carbon triple bonds.
  • Specific examples of these alkynyl groups include ethynyl, propynyl, butynyl, and isomers of these groups, but are not limited thereto.
  • the specific examples of the above-mentioned alkyl groups include groups A group derived from 1 or 2 alkynyl groups.
  • the C 6 ⁇ C 30 aromatic hydrocarbon group refers to a group formed by removing one hydrogen atom in an aromatic hydrocarbon containing 6 to 30 carbon atoms without violating the valence .
  • the C 6 ⁇ C 30 aromatic hydrocarbon group includes the case where all the carbon atoms are the ring-forming carbon atoms of the aromatic ring, and also includes the alkyl group, cycloalkyl group, and aryl group bonded to the aromatic ring as the substituent In the case of, as long as it has an aromatic ring in the group structure and the total number of carbon atoms is 6-30.
  • a C 6 to C 30 aromatic hydrocarbon group a C 6 to C 30 aromatic hydrocarbon group, a C 6 to C 20 aromatic hydrocarbon group, a C 6 to C 15 aromatic hydrocarbon group, and a C 6 to C 10 aromatic hydrocarbon group may be included.
  • aryl groups include phenyl, naphthyl, tolyl, xylyl, ethylphenyl, methylnaphthyl, 2-methylnaphthyl, 2-ethylnaphthyl, and cyclohexylphenyl. , Biphenyl, etc., but not limited to this.
  • the C 7 ⁇ C 15 arylalkyl group refers to an arylalkane containing 7-15 carbon atoms, without violating the valence, by removing one hydrogen atom from the alkyl group. Group. It should be noted that in addition to the alkyl moiety where the bond exists, other alkyl, cycloalkyl, and aryl groups may be bonded to the aryl moiety as substituents, as long as the total number of carbon atoms is 7-15. As the C 7 to C 15 aromatic hydrocarbon group, a C 7 to C 12 aryl alkyl group and a C 7 to C 10 aryl alkyl group may be included. Specific examples of these arylalkyl groups include benzyl (benzyl), phenethyl, phenylpropyl, naphthylmethyl, naphthylethyl, etc., but are not limited to these.
  • the C 1 to C 30 hydrocarbylene group refers to a group obtained by removing one more hydrogen atom from any carbon atom of the above C 1 to C 30 hydrocarbylene group without violating the valence.
  • alkylene groups C 1 ⁇ C 30, comprising from above as the C 1 ⁇ C 30 hydrocarbon group and a carbon atom include a group, then a group removed a hydrogen atom from.
  • the hydrocarbon group may also be a divalent, trivalent or higher valence hydrocarbon group.
  • a C 3 ⁇ C 30 ring group means a group having 3-30 atoms selected from C, N, O, and S as ring atoms.
  • the ring group may be saturated or It can be unsaturated (having at least one carbon-carbon double bond and/or at least one carbon-carbon triple bond), and can also be an aromatic group.
  • the C 3 ⁇ C 30 cyclic group includes C 3 ⁇ C 25 cycloalkyl, C 3 ⁇ C 20 cycloalkyl, C 3 ⁇ C 10 cycloalkyl, C 3 ⁇ C 6 cycloalkyl , C 5 ⁇ C 6 cycloalkyl, C 6 ⁇ C 20 aromatic ring group, C 6 ⁇ C 15 aromatic ring group, C 6 ⁇ C 10 aromatic ring group, as the specific ring group Examples include cyclopropane group, cyclobutane group, cyclopentyl group, cyclohexane group, benzene ring group, naphthalene ring group, anthracene ring group, and phenanthrene ring group.
  • the C 1 ⁇ C 30 alkoxy group refers to the group formed after the above-mentioned linear or branched C 1 ⁇ C 30 alkyl group is bonded to an oxygen atom, that is, the linear or branched C 1 ⁇ C 30 alkyl-O- groups. It includes straight or branched C 1 ⁇ C 20 alkoxy, straight or branched C 1 ⁇ C 10 alkoxy, straight or branched C 1 ⁇ C 6 alkoxy, straight or branched C 1 to C 4 alkoxy.
  • the present invention provides a phosphorus-containing compound represented by the following formula (I),
  • n is an integer between 0-50 (preferably an integer between 0-20, more preferably an integer between 0-10, and still more preferably 0, 1, 2, 3 or 4);
  • n+1 R groups are the same or different from each other, and are each independently selected from C 1 to C 30 alkylene groups (preferably C 1 to C 10 alkylene groups, more preferably C 1 to C 6 alkylene groups, and even more preferably C 1 to C 4 alkylene);
  • R b group is H or C 1 to C 30 hydrocarbon group (preferably H or C 1 to C 10 hydrocarbon group, more preferably H or C 1 to C 6 straight or branched chain Alkyl group, more preferably H or C 1 -C 4 straight or branched chain alkyl);
  • Each R 0 group is the same or different from each other, and is independently selected from H, C 1 ⁇ C 30 hydrocarbon group and (Preferably each independently selected from H, C 1 ⁇ C 10 linear or branched alkyl groups and More preferably, each independently selected from H, C 1 to C 4 linear or branched alkyl groups and Preferably at least one of R 0 in formula (I) is Where x is an integer between 0 and 5 (preferably an integer between 0 and 4, more preferably 0, 1, 2 or 3), and y is an integer between 1 and 5 (preferably an integer between 1 and 4) , More preferably 1, 2 or 3), the sum of x+y ⁇ the number of hydrogen atoms that can be substituted on the Ar group; x R 1 groups are the same or different from each other, and are each independently selected from H, C 1 ⁇ C 30 hydrocarbon group (preferably selected from H, C 1 to C 10 linear or branched alkyl, more preferably selected from H, C 1 to C 6 linear or branched alkyl,
  • Each A group is the same or different from each other, and each is independently selected from OH, optional Substituted C 1 ⁇ C 30 hydrocarbon group (preferably optionally by Substituted C 1 ⁇ C 10 linear or branched alkyl, more preferably optionally by The substituted C 1 ⁇ C 6 linear or branched alkyl group is further preferably optionally Substituted C 1 ⁇ C 4 linear or branched alkyl), optionally Substituted C 1 ⁇ C 30 alkoxy (preferably optionally by Substituted C 1 ⁇ C 10 linear or branched alkoxy, more preferably optionally by The substituted C 1 ⁇ C 6 linear or branched alkoxy group is further preferably optionally substituted by Substituted C 1 ⁇ C 4 linear or branched alkoxy) and H, at least one A group in formula (I) is selected from Be Substituted C 1 ⁇ C 30 hydrocarbon group (preferably by The substituted C 1 ⁇ C 10 linear or branched al
  • the present invention also provides a product obtained by partial or complete condensation and dehydration between NH and COOH present in the compound of formula (I).
  • the compound of formula (I) of the present invention may include a pure compound of formula (I), a mixture of two or more compounds of formula (I) with different structures, and two or more compounds of formula (I) with the same structure or different structures. ) The product obtained by dehydration and condensation of a compound. Thus, the compound of the present invention exhibits the form of a mixture.
  • At least one R 0 group represents The group shown.
  • the Ar group is preferably a benzene ring
  • x is preferably 2
  • y is preferably 1
  • OH is preferably located at the para position of the R 2 group
  • the two R 1 are preferably located at the two ortho positions of the OH respectively.
  • each of R 1 is independently selected from C 1 to C 4 linear or branched alkyl groups, preferably selected from C 3 to C 4 branched chain alkyl groups, and more Preferably it is tert-butyl.
  • each A group is independently selected from OH, optional Substituted C 1 ⁇ C 10 linear or branched alkyl groups, optionally A substituted C 1 ⁇ C 10 linear or branched alkoxy group and H, at least one A group is selected from Be Substituted C 1 ⁇ C 10 linear or branched alkyl groups, are Substituted C 1 ⁇ C 10 linear or branched alkoxy, (preferably each A group is independently selected from OH, optional Substituted C 1 ⁇ C 6 linear or branched alkyl groups, optionally Substituted C 1 ⁇ C 6 linear or branched alkoxy group and H, at least one A group is selected from Be Substituted C 1 ⁇ C 6 linear or branched alkyl, is Substituted C 1 -C 6 linear or branched alkoxy, more preferably each A group is independently selected from OH, optional Substituted C 1 ⁇ C 4 linear or branche
  • the group is located at the end of the alkyl group and alkoxy group.
  • At least one A group is p is an integer of 1-4.
  • R' is each independently selected from C 1 ⁇ C 6 linear or branched alkyl, optionally substituted by C 1 ⁇ C 10 linear or branched alkyl Benzyl group, phenyl group optionally substituted by C 1 ⁇ C 10 linear or branched alkyl group.
  • the compound of the specific structure of the phosphorus-containing compound of the present invention includes one or more of the following compounds:
  • the present invention also provides a method for preparing a phosphorus-containing compound, which includes:
  • Step (1) reacting the compound represented by formula (II) and/or its inorganic acid salt with the compound represented by formula (III) to obtain the product of step (1);
  • n is an integer between 0-50 (preferably an integer between 0-20, more preferably an integer between 0-10, and still more preferably 0, 1, 2, 3 or 4);
  • n+1 R groups are the same or different from each other, and are each independently selected from C 1 to C 30 alkylene groups (preferably C 1 to C 10 alkylene groups, more preferably C 1 to C 6 alkylene groups, and even more preferably C 1 to C 4 alkylene);
  • R b group is H or C 1 to C 30 hydrocarbon group (preferably H or C 1 to C 10 hydrocarbon group, more preferably H or C 1 to C 6 straight or branched chain Alkyl group, more preferably H or C 1 -C 4 straight or branched chain alkyl);
  • Each R 0 'group is the same or different from each other, and is each independently selected from H, C 1 ⁇ C 30 hydrocarbon group (preferably each independently selected from H, C 1 ⁇ C 10 linear or branched alkyl group, more preferably Each independently selected from H, C 1 to C 4 linear or branched alkyl), preferably at least one R 0 'is H;
  • Each A'group is the same or different from each other, and each is independently selected from XA"', C 1 to C 30 hydrocarbon groups optionally substituted by XA"' (preferably C 1 to C 10 hydrocarbon groups optionally substituted by XA"' A straight or branched chain alkyl group, more preferably a C 1 to C 6 straight chain or branched alkyl group optionally substituted by XA"', and even more preferably a C 1 to C 4 straight chain optionally substituted by XA"' Or branched chain alkyl), C 1 to C 30 alkoxy optionally substituted by XA"' (preferably C 1 to C 10 linear or branched alkoxy optionally substituted by XA"', more It is preferably a C 1 to C 6 linear or branched alkoxy group optionally substituted by XA"', and more preferably a C 1 to C 4 linear or branched chain alkoxy group optionally substituted by XA"') and H, A"' is
  • X groups are each independently selected from O or S, a is 0 or 1, each R"' is the same or different from each other, and each is independently selected from A"', C 1 ⁇ C 30 hydrocarbon group (Preferably a C 1 to C 10 linear or branched alkyl group, more preferably a C 1 to C 6 linear or branched alkyl group, still more preferably a C 1 to C 4 linear or branched alkyl group), any is selected from straight or branched C 1 ⁇ C 10 alkyl group substituted with a C 7 ⁇ C 15 aryl group (preferably an optionally substituted linear or branched alkyl group of C 1 ⁇ C 10 to C 7 ⁇ C 12 arylalkyl, more preferably optionally substituted straight-chain or branched-chain C 1 ⁇ C 10 alkyl benzyl group) and optionally substituted straight-chain or branched-chain alkyl group of C 1 ⁇ C 10 C 6 ⁇ C 15 aryl group
  • step (2) reacting the product of step (1) with the compound represented by formula (IV) to obtain the product of step (2);
  • x is an integer between 0 and 5 (preferably an integer between 0 and 4, more preferably 0, 1, 2 or 3), and y is an integer between 1 and 5 (preferably an integer between 1 and 4, More preferably 1, 2 or 3), the sum of x+y ⁇ the number of hydrogen atoms that can be substituted on the Ar group;
  • the x R 1 groups are the same or different from each other, and are each independently selected from H, C 1 ⁇ C 30 (Preferably selected from H, C 1 to C 10 linear or branched alkyl, more preferably selected from H, C 1 to C 6 linear or branched alkyl, further preferably selected from H, C 1 ⁇ C 4 linear or branched alkyl),
  • the Ar group is a C 3 to C 30 ring group (preferably a C 6 to C 15 aromatic ring group, more preferably a benzene ring, a naphthalene ring or an anthracene ring)
  • the R 2 group is a single bond or a C 1 to
  • the compound represented by formula (II) and/or its inorganic acid salt can be selected from amino acids, amino acid condensates (polypeptides formed by partial or full condensation), inorganic salts of amino acids, and amino acids.
  • amino acid condensates polypeptides formed by partial or full condensation
  • inorganic salts of amino acids and amino acids.
  • One or more of the inorganic salts of condensates polypeptides formed by partial condensation or complete condensation).
  • the compound represented by formula (II) and/or its inorganic acid salt can be selected from one or more of the following specific compounds: L-serine and/or L-serine ester hydrochloride, L-leucine and/ Or L-leucine ester hydrochloride, L-isoleucine and/or L-isoleucine ester hydrochloride, glycine and/or glycinate hydrochloride, L-phenylalanine and/or L-phenylalanine ester hydrochloride, L-valine and/or L-valine ester hydrochloride.
  • the compound represented by formula (III) can be selected from phosphorous acid, phosphite, thiophosphorous acid, and thiophosphorous acid.
  • specific compounds that can be enumerated include phosphorous acid, phosphorous acid Dimethyl phosphate, diethyl phosphite, dipropyl phosphite, diisopropyl phosphite, di-n-butyl phosphite, diisobutyl phosphite, di-tert-butyl phosphite, phosphorous acid (2- Ethylhexyl) ester, dibenzyl phosphite, diphenyl phosphite, thiophosphorous acid, dimethyl thiophosphite, diethyl thiophosphite, dipropyl thiophosphite, thiophosphite Diisopropyl phosphat
  • step (1) the compound represented by the formula (II) and/or its inorganic acid salt (calculated by XA"') and the compound represented by the formula (III) (calculated by PH)
  • the molar equivalent ratio of the reaction is preferably 1:5 to 5:1, more preferably 1:3 to 3:1; the reaction temperature is preferably -40 to 80°C, more preferably -20 to 40°C; Generally speaking, the longer the time, the better.
  • the reaction time is preferably 0.5 to 30 hours, more preferably 1 to 8 hours.
  • a solvent may or may not be added to the reaction between the compound represented by formula (II) and/or its inorganic acid salt and the compound represented by formula (III).
  • a solvent is added, preferably a solvent.
  • the solvent is preferably one or more of protic solvents, hydrocarbon solvents and furan solvents, for example, one of n-hexane, benzene, toluene, tetrahydrofuran, dichloromethane, methanol, ethanol, isopropanol and water can be selected.
  • more, more preferably a protic solvent for example, one or more of methanol, ethanol, isopropanol and water can be selected.
  • the amount of the solvent added is suitable to promote the smooth progress of the reaction, and is not particularly limited.
  • a catalyst in step (1), in the reaction between the compound represented by formula (II) and/or its inorganic acid salt and the compound represented by formula (III), a catalyst may be added, or No catalyst is added, preferably a catalyst.
  • the catalyst may be a phase transfer catalyst.
  • the phase transfer catalyst may be a quaternary ammonium salt and/or a crown ether, preferably a tetrahydrocarbyl ammonium halide, for example, tetrabutylammonium bromide, trioctylammonium chloride, hexadecylammonium chloride may be used.
  • alkyltrimethylammonium bromide triethylbenzylammonium chloride and 18-crown-6, more preferably tetrabutylammonium bromide.
  • the added amount of the catalyst is preferably 0.1%-10% of the mass of the compound represented by the formula (II) and/or its inorganic acid salt.
  • the compound represented by formula (II) and/or its inorganic acid salt is preferably added with chloride when reacting with the compound represented by formula (III).
  • the chloride is preferably hypochlorite and/or chloroalkane, and the hypochlorite is preferably one or more of sodium hypochlorite, potassium hypochlorite and calcium hypochlorite.
  • the hypochlorite can be used in the form of an aqueous solution.
  • the chloroalkane is preferably chloromethane, for example, one or more of carbon monochloride, carbon dichloride, carbon trichloride and carbon tetrachloride can be selected.
  • the chloride is preferably an aqueous solution of hypochlorite, and its concentration is preferably 5% to 80%, more preferably an aqueous solution of sodium hypochlorite.
  • the added amount of the chloride is preferably 30-100 mL/100 mmol of the compound represented by formula (II) and/or its inorganic acid salt.
  • the reaction between the compound represented by formula (II) and/or its inorganic acid salt and the compound represented by formula (III) is preferably at a pH of 8-10 (Preferably 8.5 to 9.5) conditions.
  • the pH value can be adjusted by adding an alkaline medium.
  • the alkaline medium is preferably an alkaline solution, and the alkaline solution is preferably one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide.
  • Aqueous solution is preferably one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide.
  • step (1) after the reaction of the compound represented by formula (II) and/or its inorganic acid salt with the compound represented by formula (III), the reaction product is optionally Extraction treatment, optional drying treatment and optional sonication treatment. Preferably, ultrasonic treatment is performed.
  • the solvent is preferably one or more of ether solvents, ester solvents, chlorinated alkane solvents and hydrocarbon solvents.
  • ether solvents preferably one or more of ether solvents, ester solvents, chlorinated alkane solvents and hydrocarbon solvents.
  • the extraction treatment is preferably 1 to 3 times.
  • the acidic environment is obtained by adding an acid solution to adjust the pH of the system where the reaction product is located.
  • the pH is preferably 2 to 5, more preferably 2.5 to 3.5; the acid solution is preferably one of hydrochloric acid, acetic acid, nitric acid and sulfuric acid.
  • an inorganic salt is added during the extraction process to improve the extraction efficiency.
  • the inorganic salt is preferably one or more of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate.
  • a desiccant is preferably added to dry the reaction product.
  • the desiccant can be anhydrous magnesium chloride and/or anhydrous sodium sulfate.
  • the reaction product of step (1) is subjected to ultrasonic treatment
  • the solvent is preferably one of furan solvents, halogenated alkane solvents, ketone solvents, ester solvents and nitrile solvents.
  • the solvent is preferably one of furan solvents, halogenated alkane solvents, ketone solvents, ester solvents and nitrile solvents.
  • Multiple types for example, one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate and acetonitrile can be selected, more preferably one or more of tetrahydrofuran, dichloromethane and acetonitrile.
  • the time for the ultrasonic treatment is preferably 1-10h, more preferably 2-8h.
  • step (1) after the reaction of the compound represented by formula (II) and/or its inorganic acid salt with the compound represented by formula (III), the reaction of step (1)
  • the product undergoes further purification treatment.
  • the purification treatment includes one or more of drying, evaporation, washing, distillation, recrystallization, and centrifugal separation methods known in the prior art.
  • the structure compound represented by formula (IV) can be prepared by a method known in the prior art, and is not particularly limited.
  • the Ar group is preferably a benzene ring, x is preferably 2, and y is preferably 1, OH is preferably located at the para position of the R 2 group, two R 1 are preferably located at two ortho positions of OH, and X'is preferably Cl or Br.
  • R 1 is each independently selected from C 1 to C 4 linear or branched chain alkyl groups, preferably selected from C 3 to C 4 branched chain alkyl groups, more preferably It is tert-butyl.
  • each of R"' is independently selected from C 1 to C 6 linear or branched alkyl, optionally C 1 to C 10 linear or branched alkyl A substituted benzyl group, a phenyl group optionally substituted by a C 1 to C 10 linear or branched alkyl group.
  • the XA"' group is located at the end of the alkyl group or alkoxy group.
  • At least one A'group is p is an integer of 1-4.
  • the compound of formula (IV) can be synthesized by a method known in the art, or it can be a commercially available product.
  • one or more of the following specific compounds can be selected: 3,5-bis(tert-butyl)-4-hydroxyphenylacetyl chloride, 3,5-bis(tert-butyl) -Butyl)-4-hydroxyphenylpropionyl chloride, p-hydroxyphenylacetyl chloride, 3-hydroxyphenylacetyl chloride, 2-hydroxyphenylacetyl chloride, 3,4-dihydroxyphenylacetyl chloride, 3,5-dihydroxyphenylethyl Acid chloride, 3-methyl-4-hydroxyphenylacetyl chloride, 3,5-dimethyl-4-hydroxyphenylacetyl chloride, 2,4-dihydroxyphenylpropionyl chloride, 3,4-dihydroxyphenylpropionyl chloride, 2 -Hydroxy-naphthalene acetyl chloride.
  • step (2) the reaction mole between the compound represented by formula (IV) (calculated as X') and the reaction product (calculated as NH) of step (1)
  • the equivalent ratio is preferably 5:1 to 1:5, more preferably 1:2 to 2:1
  • the reaction temperature is preferably -40 to 60°C, more preferably -20 to 20°C
  • the reaction time is generally longer The longer the better, in order to improve the reaction efficiency, the reaction time is preferably 1 to 20 hours, more preferably 3 to 8 hours.
  • a solvent may be added or not, and a solvent is preferably added.
  • the solvent is preferably one or more of protic solvents, ether solvents, ester solvents, chlorinated alkane solvents, furan solvents, ketone solvents, and hydrocarbon solvents.
  • protic solvents e.g., water, methanol, ethanol, and other solvents can be selected.
  • the amount of the solvent added is suitable to promote the smooth progress of the reaction, and is not particularly limited.
  • step (2) between the compound represented by formula (IV) (calculated as X′) and the reaction product of step (1) (calculated as NH)
  • the reaction product of step (2) is washed to improve the purity of the reaction product.
  • an acid solution is used to wash the reaction product of step (2).
  • the acid solution is preferably one acid or an aqueous solution of multiple acids among hydrochloric acid, sulfuric acid and nitric acid, and the concentration of the acid solution is preferably 1-12 mol/L.
  • step (2) between the compound represented by formula (IV) (calculated as X′) and the reaction product of step (1) (calculated as NH) After the reaction, the reaction product of step (2) is further purified.
  • the purification treatment includes one or more of washing, distillation, recrystallization and centrifugal separation methods known in the prior art.
  • the phosphorus-containing compound of the present invention can be used as a biodegradation agent for lubricating oil.
  • the phosphorus-containing compound prepared by the production method of the phosphorus-containing compound of the present invention can be used as a biodegradation agent for lubricating oil.
  • the present invention also provides a phosphorous-containing compound composition, which comprises the above-mentioned phosphorous compound of the present invention or the phosphorous-containing compound prepared according to the above-mentioned method of the present invention, one or all of the products obtained by condensation dehydration reaction. A variety of mixtures.
  • the present invention also provides a lubricating oil composition
  • a lubricating oil composition comprising a lubricating oil base oil selected from the above-mentioned phosphorus-containing compound of the present invention, the phosphorus-containing compound prepared according to the above-mentioned method of the present invention, and the above-mentioned phosphorus-containing compound of the present invention At least one of the composition.
  • the phosphorus-containing compound and the product obtained by the partial or complete condensation dehydration reaction relative to the total mass of the lubricating oil composition are 0.001-30%, preferably 0.01-20%, more preferably 0.1- 10%.
  • the phosphorus-containing compound of the present invention has very excellent biodegradability and anti-oxidation properties, and is particularly suitable for promoting the biodegradation of lubricating oil products.
  • the preparation method of the phosphorus-containing compound of the invention is simple, efficient and high in yield.
  • the preparation method of 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride in step (2) is: 3,5-bis(tert-butyl)-4-hydroxyphenylpropionic acid (81mmol , 22.5g) dissolved in 150mL chloroform, added thionyl chloride (124mmol, 14.8g), refluxed for 4 hours, rotary evaporation to remove the solvent and excess thionyl chloride, a light yellow solid (ie 3,5-bis( Tert-Butyl)-4-hydroxyphenylpropionyl chloride).
  • the synthesized compound is indeed the target compound O-dimethyloxophosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (see structural formula I-a).
  • the preparation method of 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride in step (2) is: 3,5-bis(tert-butyl)-4-hydroxyphenylpropionic acid (81mmol , 22.5g) dissolved in 150mL chloroform, added thionyl chloride (124mmol, 14.8g), refluxed for 4 hours, rotary evaporation to remove the solvent and excess thionyl chloride, a light yellow solid (ie 3,5-bis( Tert-Butyl)-4-hydroxyphenylpropionyl chloride).
  • the compound synthesized after structural identification is indeed the target compound O-diisopropyloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (see structural formula Ib) .
  • the preparation method of 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride in step (2) is: 1) 3,5-bis(tert-butyl)-4-hydroxyphenylpropionic acid (81mmol, 22.5g) was dissolved in 150mL of chloroform, added with thionyl chloride (124mmol, 14.8g), refluxed for 4 hours, rotary evaporation to remove the solvent and excess thionyl chloride, a light yellow solid (ie 3,5- Bis(tert-butyl)-4-hydroxyphenylpropionyl chloride).
  • the synthesized compound is indeed the target compound O-benzyloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (see structural formula Ic) .
  • the preparation method of 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride in step (2) is: 3,5-bis(tert-butyl)-4-hydroxyphenylpropionic acid (81mmol , 22.5g) dissolved in 150mL chloroform, added thionyl chloride (124mmol, 14.8g), refluxed for 4 hours, rotary evaporation to remove the solvent and excess thionyl chloride, a light yellow solid (ie 3,5-bis( Tert-Butyl)-4-hydroxyphenylpropionyl chloride).
  • the compound synthesized after structural identification is indeed the target compound O-dimethyloxophosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine methyl ester (see structural formula Id ).
  • Example 1 Example 2
  • Example 3 Example 4 Blank group HVI 350 63.9% 75.8% 77.4% 64.6% 23.5% PAO4 68.1% 80.4% 81.4% 66.2% 25.7% PAO10 61.2% 72.1% 75.9% 60.3% 22.3%
  • the phosphorus-containing compound of the present invention can improve the biodegradability of lubricating oil.
  • the phosphorus-containing compound of the present invention has excellent oxidation resistance, and can inhibit the oxidation of the lubricating oil when it is blended with lubricating oil.

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Abstract

本发明提供了一种含磷化合物及其制备方法、和其用途。本发明的含磷化合物的结构为（I）。其中各基团的定义见说明书。本发明的含磷化合物具有非常优异的生物降解性能和抗氧化性能，特别适于促进润滑油产品的生物降解。另外，本发明含磷化合物的制备方法简单、高效，产率高。

Description

一种含磷化合物及其制备方法、用途 技术领域
本发明涉及一种含磷化合物，特别涉及一种具有促进润滑油生物降解的含磷化合物及其制备方法和用途。
背景技术
润滑油是机械设备正常运转及材料制造加工过程中必要的工作介质，随着工业的高速发展，润滑油的需求量也越来越大。在润滑油的储存、运输和使用过程中，也不可避免有泄漏、溢出及不恰当排放、污染环境的情况。虽然润滑油对生物的急性毒性很小，但是进入环境的润滑油由于生物降解能力差，会严重污染陆地及江河湖泊，同时在环境中的集聚也会影响生态平衡，因而急需一种生物降解促进剂来提高润滑油的生物降解率。
近年来，废弃及泄漏润滑油对环境的影响已经引起了人们广泛的关注，为解决这一问题，一方面是利用可生物降解的植物油及酯类合成油制备润滑油，如CN 102408939B中报道的可生物降解的润滑油组合物及其制备方法、CN 105132104A报道的可生物降解的工业齿轮油组合物；另一方面是开展润滑油生物降解促进剂的研制，如专利CN 103642557B中报道了化学式为C 20H 37NO 3酰胺型润滑油生物降解促进剂，但是，目前润滑油生物降解促进剂的研究报道尚不多见。
发明内容
本发明的发明人经过深入地研究，结果发现，通过本发明这样的具有特定结构的含磷化合物，可以实现良好的促进润滑油生物降解的效果。并且，本发明的含磷化合物的抗氧化性能优异，在配合于润滑油时，可以抑制润滑油的氧化。
具体而言，本发明提供以下的技术方案。
本发明提供了一种下式(I)所示的含磷化合物，
Figure PCTCN2020122396-appb-000001
在式(I)中，n为0～50之间的整数(优选0～20之间的整数，更优选0～10之间的整数，进一步优选为0、1、2、3或4)；n+1个R基团彼此相同或不同，各自独立地选自C 1～C 30的亚烃基(优选C 1～C 10亚烷基，更优选C 1～C 6亚烷基，进一步优选C 1～C 4亚烷基)；R b基团为H或C 1～C 30的烃基(优选H或C 1～C 10的烃基，更优选H或C 1～C 6的直链或支链烷基，进一步优选H或C 1～C 4的直链或支链烷基)；
各个R 0基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基和
Figure PCTCN2020122396-appb-000002
(优选各自独立地选自H、C 1～C 10的直链或支链烷基和
Figure PCTCN2020122396-appb-000003
更优选各自独立地选自H、C 1～C 4的直链或支链烷基和
Figure PCTCN2020122396-appb-000004
优选式(I)中至少其中一个R 0为
Figure PCTCN2020122396-appb-000005
Figure PCTCN2020122396-appb-000006
中，x为0～5之间的整数(优选0～4之间的整数，更优选0、1、2或3)，y为1～5之间的整数(优选1～4之间的整数，更优选1、2或3)，x+y之和≤Ar基团上可被取代的氢原子数目；x个R 1基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基(优选选自H、C 1～C 10的直链或支链烷基，更优选选自H、C 1～C 6的直链或支链烷基，进一步优选选自H、C 1～C 4的直链或支链烷基)，各个Ar基团彼此相同或不同，各自独立地选自C 3～C 30的环基团(优选选自C 6～C 15的芳香环基团，更优选选自苯环、萘环和蒽环)，R 2基团为单键或C 1～C 10的亚烷基(优选单键或C 1～C 6的亚烷基，更优选单键或C 1～C 4的亚烷基)；
各个A基团彼此相同或不同，各自独立地选自
Figure PCTCN2020122396-appb-000007
OH、任选被
Figure PCTCN2020122396-appb-000008
取代的C 1～C 30的烃基(优选任选被
Figure PCTCN2020122396-appb-000009
取代的C 1～C 10的直链或支链烷基，更优选任选被
Figure PCTCN2020122396-appb-000010
取代的C 1～C 6的直链或支链烷基，进一步优选任选被
Figure PCTCN2020122396-appb-000011
取代的C 1～C 4的直链或支链烷基)、任选被
Figure PCTCN2020122396-appb-000012
取代的C 1～C 30的烷氧基(优选任选被
Figure PCTCN2020122396-appb-000013
取代的C 1～C 10的直链或支链烷氧基，更优选任选被
Figure PCTCN2020122396-appb-000014
取代的C 1～C 6的直链或支链烷氧基，进一步优选任选被
Figure PCTCN2020122396-appb-000015
取代的C 1～C 4的直链或支链烷氧基)和H，式(I)中至少一个A基团选自
Figure PCTCN2020122396-appb-000016
被
Figure PCTCN2020122396-appb-000017
取代的C 1～C 30的烃基(优选被
Figure PCTCN2020122396-appb-000018
取代的C 1～C 10的直链或支链烷基，更优选被
Figure PCTCN2020122396-appb-000019
取代的C 1～C 6的直链或支链烷基，进一步优选被
Figure PCTCN2020122396-appb-000020
取代的C 1～C 4的直链或支链烷基)、被
Figure PCTCN2020122396-appb-000021
取代的C 1～C 30的烷氧基(优选被
Figure PCTCN2020122396-appb-000022
取代的C 1～C 10的直链或支链烷氧基，更优选被
Figure PCTCN2020122396-appb-000023
取代的C 1～C 6的直链或支链烷氧基，进一步优选被
Figure PCTCN2020122396-appb-000024
取代的C 1～C 4的直链或支链烷氧基)，X基团各自独立地选自O或S，a为0或1，R’各自独立地选自C 1～C 30的烃基(优选C 1～C 10的直链或支链烷基，更优选C 1～C 6的直链或支链烷基，进一步优选C 1～C 4的直链或支链烷基)、任选被C 1～C 10的直链或支链烷基取代的C 7～C 15芳基烷基(优选任选被C 1～C 10的直链或支链烷基取代的C 7～C 12芳基烷基、更优选任选被C 1～C 10的直链或支链烷基取代的苄基)、任选被C 1～C 10的直链或支链烷基取代的C 6～C 15芳基(优选任选被C 1～C 10的直链或支链烷基取代的C 6～C 10芳基、更优选任选被C 1～C 10的直链或支链烷基取代的苯基)、
Figure PCTCN2020122396-appb-000025
R”选自C 1～C 30的烃基(优选C 1～C 10的直链或支链烷基，更优选C 1～C 6的直链或支链烷基，进一步优选C 1～C 4的直链或支链烷基)、C 1～C 30的烷氧基(优选C 1～C 10的直链或支链烷氧基，更优选C 1～C 6的直链或支链烷氧基，进一步优选C 1～C 4的直链或支链烷氧基)，其中各个R 0、R、R b、n的定义同前所述。
本发明还提供一种含磷化合物的制备方法，其包括：
第(1)步骤：使式(II)所示化合物和/或其无机酸盐与式(III)所示化合物发生反应，获得第(1)步骤的产物；
Figure PCTCN2020122396-appb-000026
在式(II)中，n为0～50之间的整数(优选0～20之间的整数，更优选0～10之间的整数，进一步优选为0、1、2、3或4)；n+1个R基团彼此相同或不同，各自独立地选自C 1～C 30的亚烃基(优选C 1～C 10亚烷基，更优选C 1～C 6亚烷基，进一步优选C 1～C 4亚烷基)；R b基团为H或C 1～C 30的烃基(优 选H或C 1～C 10的烃基，更优选H或C 1～C 6的直链或支链烷基，进一步优选H或C 1～C 4的直链或支链烷基)；
各个R 0’基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基(优选各自独立地选自H、C 1～C 10的直链或支链烷基，更优选各自独立地选自H、C 1～C 4的直链或支链烷基)，优选至少一个R 0’为H；
各个A’基团彼此相同或不同，各自独立地选自XA”’、任选被XA”’取代的C 1～C 30的烃基(优选任选被XA”’取代的C 1～C 10的直链或支链烷基，更优选任选被XA”’取代的C 1～C 6的直链或支链烷基，进一步优选任选被XA”’取代的C 1～C 4的直链或支链烷基)、任选被XA”’取代的C 1～C 30的烷氧基(优选任选被XA”’取代的C 1～C 10的直链或支链烷氧基，更优选任选被XA”’取代的C 1～C 6的直链或支链烷氧基，进一步优选任选被XA”’取代的C 1～C 4的直链或支链烷氧基)和H，A”’选自F、Cl、Br、I、H，X基团各自独立地选自O或S，其中至少一个A’基团选自XA”’、被XA”’取代的C 1～C 30的烃基(优选被XA”’取代的C 1～C 10的直链或支链烷基，更优选被XA”’取代的C 1～C 6的直链或支链烷基，进一步优选被XA”’取代的C 1～C 4的直链或支链烷基)、被XA”’取代的C 1～C 30的烷氧基(优选被XA”’取代的C 1～C 10的直链或支链烷氧基，更优选被XA”’取代的C 1～C 6的直链或支链烷氧基，进一步优选被XA”’取代的C 1～C 4的直链或支链烷氧基)；式(II)所示化合物的无机酸盐的结构为
Figure PCTCN2020122396-appb-000027
其中M为无机酸根，j为所述无机酸根电荷数的绝对值，z为1～10之间的整数(优选1～6之间的整数，更优选1～3之间的整数)，其它各基团的定义同式(II)(所述式(II)所示化合物的无机酸盐优选其盐酸盐、其硝酸盐、或其硫酸盐，最优选其盐酸盐)；
在式(III)中，X基团各自独立地选自O或S，a为0或1，各个R”’彼此相同或不同，各自独立地选自A”’、C 1～C 30的烃基(优选C 1～C 10的直链或支链烷基、更优选C 1～C 6的直链或支链烷基，进一步优选C 1～C 4的直链或支链烷基)、任选被C 1～C 10的直链或支链烷基取代的C 7～C 15芳基烷基(优选任选被C 1～C 10的直链或支链烷基取代的C 7～C 12芳基烷基、更优选 任选被C 1～C 10的直链或支链烷基取代的苄基)和任选被C 1～C 10的直链或支链烷基取代的C 6～C 15芳基(优选任选被C 1～C 10的直链或支链烷基取代的C 6～C 10芳基、更优选任选被C 1～C 10的直链或支链烷基取代的苯基)；
及任选的第(2)步骤：使步骤(1)的产物与式(IV)所示化合物发生反应，得到第(2)步骤产物；
Figure PCTCN2020122396-appb-000028
其中x为0～5之间的整数(优选0～4之间的整数，更优选0、1、2或3)，y为1～5之间的整数(优选1～4之间的整数，更优选1、2或3)，x+y之和≤Ar基团上可被取代的氢原子数目；x个R 1基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基(优选选自H、C 1～C 10的直链或支链烷基，更优选选自H、C 1～C 6的直链或支链烷基，进一步优选选自H、C 1～C 4的直链或支链烷基)，Ar基团为C 3～C 30的环基团(优选C 6～C 15的芳香环基团，更优选苯环、萘环或蒽环)，R 2基团为单键或C 1～C 10的亚烷基(优选单键或C 1～C 6的亚烷基，更优选单键或C 1～C 4的亚烷基)，X’为F、Cl、Br、I或OH(优选Cl、Br)。
本发明还提供上述式(I)所示的含磷化合物或通过上述含磷化合物的制备方法制得的含磷化合物用作润滑油的生物降解剂的用途。
本发明还提供一种润滑油组合物，其包含润滑油基础油、选自上述式(I)所示的含磷化合物、通过上述含磷化合物的制备方法制得的含磷化合物和它们的部分或全部缩合脱水反应所得的产物中的至少一种。
发明效果
本发明的含磷化合物具有非常优异的生物降解性能和抗氧化性能，特别适于促进润滑油产品的生物降解。并且，本发明的含磷化合物的抗氧化性能优异，在配合于润滑油时，可以抑制润滑油的氧化。
另外，本发明的含磷化合物的制备方法简单、高效，产率高。可以制备出本发明的生物降解性能和抗氧化性能均优异的含磷化合物。
具体实施方式
下面对本发明的具体实施方式进行详细说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时，该词头导出的对象涵盖本申请提出时本领域常规使用的那些，但也包括目前还不常用，却将变成本领域公认为适用于类似目的的那些。
在本说明书的上下文中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此而形成的技术方案或技术思想均视为本发明原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合是明显不合理的。
本发明中，在基团的定义中有时使用术语“单键”。所谓“单键”，指的是该基团不存在。举例而言，假定结构式-CH 2-A-CH 3，其中基团A被定义为选自单键和甲基。鉴于此，若A是单键，则代表该基团A不存在，此时所述结构式即被相应简化为-CH 2-CH 3。
本发明中，某一基团数目为0，表示该基团部分不存在，此时，连接于该基团两端的基团彼此键合。另外，当该基团位于末端时，该基团数目为0则表示被该基团连接的其他基团未被该基团取代。举例而言，假定结构式-CH 2-(A) n-CH 3，若n为0，则该结构式为-CH 2-CH 3。假定结构式-CH 2-(A) n，若n为0，则表明-CH 2-未被A取代，则该结构式为-CH 3。
本发明中，烃基指的是由烃(碳氢化合物，包括但不限于烷烃、烯烃、炔烃、芳烃等)中去掉一个或多个氢原子而成的基团，烃基可分为一价基、二价基、三价基等根据需要的更高价的基团，以烃基所能被取代的氢原子的数目的上限为限。例如，一价基：CH 3CH 2-(乙基)、(异丙基)、CH≡C-CH 2-(2-丙炔基)。二价基：CH 3CH＝(亚乙基)、-CH＝CH-(1，2- 亚乙烯基)。三价基：CH 3C≡(次乙基)。
更具体而言，本发明中，C 1～C 30烃基是指从具有1-30个碳原子的烃(包括但不限于烷烃、烯烃、炔烃、芳烃等)的任意一个碳原子去除一个氢原子或者根据需要的二个以上的氢原子而得的基团，其可以为一价或更高价态的直链或支链C 1～C 30烷基、一价或更高价态的直链或支链C 2～C 30烯基、一价或更高价态的直链或支链C 2～C 30炔基、一价或更高价态的C 6～C 30芳族烃基。
作为直链或支链C 1～C 30烷基，包括直链或支链C 1～C 20烷基、直链或支链C 1～C 10烷基、直链或支链C 1～C 6烷基、直链或支链C 1～C 4烷基。作为这些烷基的具体例，可以列举甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十六烷基、十八烷基、二十烷基、二十二烷基以及这些基团的异构体等。作为亚烷基，为从上述烷基中进一步去除一个氢原子而得的基团。
作为直链或支链C 2～C 30烯基，包括直链或支链C 2～C 20烯基、直链或支链C 2～C 10烯基、直链或支链C 2～C 6烯基、直链或支链C 2～C 4烯基。优选为包括1个、2个、3个或4个碳碳双键的烯基。作为这些烯基的具体例，可以列举乙烯基、丙烯基、丁烯基、2-戊烯基、1-己烯基、1-庚烯基、1-辛烯基以及这些基团的异构体等，但不限于此，例如还可以为上述烷基的具体例的基团中包括1个或2个烯基而得的基团。
作为直链或支链C 2～C 30炔基，包括直链或支链C 2～C 20炔基、直链或支链C 2～C 10炔基、直链或支链C 2～C 6炔基、直链或支链C 2～C 4炔基。优选为包括1个、2个、3个或4个碳碳三键的炔基。作为这些炔基的具体例，可以列举乙炔基、丙炔基、丁炔基以及这些基团的异构体等，但不限于此，例如还可以为上述烷基的具体例的基团中包括1个或2个炔基而得的基团。
本发明中，作为C 6～C 30芳族烃基(芳基)，是指在含有6-30个碳原子的芳香烃中，在不违反化合价的情况下，去除一个氢原子而成的基团。需要说明的是，C 6～C 30芳族烃基包括所有碳原子均为芳香环的成环碳原子的情况，还包括在芳香环上键合有烷基、环烷基、芳基作为取代基的情况，只要在基团结构中具有芳香环且碳原子总数为6-30即可。作为C 6～C 30芳族烃基，可以包括C 6～C 30芳族烃基、C 6～C 20芳族烃基、C 6～C 15 芳族烃基、C 6～C 10芳族烃基。作为这些芳基的具体例，可以列举苯基、萘基、甲苯基、二甲苯基、乙苯基、甲基萘基、2-甲基萘基、2-乙基萘基、环己基苯基、联苯基等，但不限于此。
本发明中，作为C 7～C 15芳基烷基，是指在含有7-15个碳原子的芳基烷烃中，在不违反化合价的情况下，从烷基部分去除一个氢原子而成的基团。需要说明的是，除了存在结合键的烷基部分之外，在芳基部分还可以键合有其他烷基、环烷基、芳基作为取代基，只要碳原子总数为7-15即可。作为C 7～C 15芳族烃基，可以包括C 7～C 12芳基烷基、C 7～C 10芳基烷基。作为这些芳基烷基的具体例，可以列举苄基(苯甲基)、苯乙基、苯丙基、萘甲基、萘乙基等，但不限于此。
C 1～C 30亚烃基是指，在不违反化合价的情况下，从上述C 1～C 30亚烃基的任意碳原子再去除一个氢原子而得的基团。作为C 1～C 30亚烃基的实例，包括从上述作为C 1～C 30烃基而列举的基团的碳原子上，再去除一个氢原子而得的基团。另外，在C 1～C 30烃基上具有其他取代基时，该烃基还可以为二价、三价或更高价态的烃基。
本发明中，C 3～C 30的环基团表示具有3-30个选自C、N、O、S中原子作为成环原子而得的基团，该环基团可以为饱和的，也可以为不饱和的(具有至少一个碳碳双键和/或至少一个碳碳三键)，还可以是芳香性基团。该C 3～C 30的环基团包括C 3～C 25的环烷基、C 3～C 20的环烷基、C 3～C 10的环烷基、C 3～C 6的环烷基、C 5～C 6的环烷基、C 6～C 20的芳香环基团、C 6～C 15的芳香环基团、C 6～C 10的芳香环基团，作为该环基团具体例，可以列举环丙烷基团、环丁烷基团、环戊烷基团、环己烷基团、苯环基团、萘环基团、蒽环基团、菲环基团。
本发明中，C 1～C 30的烷氧基是指，上述直链或支链C 1～C 30烷基与氧原子键合以后形成的基团，即直链或支链C 1～C 30烷基-O-基团。其包括直链或支链C 1～C 20烷氧基、直链或支链C 1～C 10烷氧基、直链或支链C 1～C 6烷氧基、直链或支链C 1～C 4烷氧基。
本发明提供了一种下式(I)所示的含磷化合物，
Figure PCTCN2020122396-appb-000029
在式(I)中，n为0～50之间的整数(优选0～20之间的整数，更优选0～10 之间的整数，进一步优选为0、1、2、3或4)；n+1个R基团彼此相同或不同，各自独立地选自C 1～C 30的亚烃基(优选C 1～C 10亚烷基，更优选C 1～C 6亚烷基，进一步优选C 1～C 4亚烷基)；R b基团为H或C 1～C 30的烃基(优选H或C 1～C 10的烃基，更优选H或C 1～C 6的直链或支链烷基，进一步优选H或C 1～C 4的直链或支链烷基)；
各个R 0基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基和
Figure PCTCN2020122396-appb-000030
(优选各自独立地选自H、C 1～C 10的直链或支链烷基和
Figure PCTCN2020122396-appb-000031
更优选各自独立地选自H、C 1～C 4的直链或支链烷基和
Figure PCTCN2020122396-appb-000032
优选式(I)中至少其中一个R 0为
Figure PCTCN2020122396-appb-000033
Figure PCTCN2020122396-appb-000034
中，x为0～5之间的整数(优选0～4之间的整数，更优选0、1、2或3)，y为1～5之间的整数(优选1～4之间的整数，更优选1、2或3)，x+y之和≤Ar基团上可被取代的氢原子数目；x个R 1基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基(优选选自H、C 1～C 10的直链或支链烷基，更优选选自H、C 1～C 6的直链或支链烷基，进一步优选选自H、C 1～C 4的直链或支链烷基)，各个Ar基团彼此相同或不同，各自独立地选自C 3～C 30的环基团(优选选自C 6～C 15的芳香环基团，更优选选自苯环、萘环和蒽环)，R 2基团为单键或C 1～C 10的亚烷基(优选单键或C 1～C 6的亚烷基，更优选单键或C 1～C 4的亚烷基)；
各个A基团彼此相同或不同，各自独立地选自
Figure PCTCN2020122396-appb-000035
OH、任选被
Figure PCTCN2020122396-appb-000036
取代的C 1～C 30的烃基(优选任选被
Figure PCTCN2020122396-appb-000037
取代的C 1～C 10的直链或支链烷基，更优选任选被
Figure PCTCN2020122396-appb-000038
取代的C 1～C 6的直链或支链烷基，进一步优选任选被
Figure PCTCN2020122396-appb-000039
取代的C 1～C 4的直链或支链烷基)、任选被
Figure PCTCN2020122396-appb-000040
取代的C 1～C 30的烷氧基(优选任选被
Figure PCTCN2020122396-appb-000041
取代的C 1～C 10的直链或支链烷氧基，更优选任选被
Figure PCTCN2020122396-appb-000042
取代的C 1～C 6的直链或支链烷氧基，进一步优选任选被
Figure PCTCN2020122396-appb-000043
取代的C 1～C 4的直链或支链烷氧基)和H，式(I)中至少一个A基团选自
Figure PCTCN2020122396-appb-000044
被
Figure PCTCN2020122396-appb-000045
取代的C 1～C 30的烃基(优选被
Figure PCTCN2020122396-appb-000046
取代的C 1～C 10的直链或支链烷基，更优选被
Figure PCTCN2020122396-appb-000047
取代的C 1～C 6的直链或支链烷基，进一步优选被
Figure PCTCN2020122396-appb-000048
取代的C 1～C 4的直链或支链烷基)、被
Figure PCTCN2020122396-appb-000049
取代的C 1～C 30的烷氧基(优选被
Figure PCTCN2020122396-appb-000050
取代的C 1～C 10的直链或支链烷氧基，更优选被
Figure PCTCN2020122396-appb-000051
取代的C 1～C 6的直链或支链烷氧基，进一步优选被
Figure PCTCN2020122396-appb-000052
取代的C 1～C 4的直链或支链烷氧基)，X基团各自独立地选自O或S，a为0或1，R’各自独立地选自C 1～C 30的烃基(优选C 1～C 10的直链或支链烷基，更优选C 1～C 6的直链或支链烷基，进一步优选C 1～C 4的直链或支链烷基)、任选被C 1～C 10的直链或支链烷基取代的C 7～C 15芳基烷基(优选任选被C 1～C 10的直链或支链烷基取代的C 7～C 12芳基烷基、更优选任选被C 1～C 10的直链或支链烷基取代的苄基)、任选被C 1～C 10的直链或支链烷基取代的C 6～C 15芳基(优选任选被C 1～C 10的直链或支链烷基取代的C 6～C 10芳基、更优选任选被C 1～C 10的直链或支链烷基取代的苯基)、
Figure PCTCN2020122396-appb-000053
R”选自C 1～C 30的烃基(优选C 1～C 10的直链或支链烷基，更优选C 1～C 6的直链或支链烷基，进一步优选C 1～C 4的直链或支链烷基)、C 1～C 30的烷氧基(优选C 1～C 10的直链或支链烷氧基，更优选C 1～C 6的直链或支链烷氧基，进一步优选C 1～C 4的直链或支链烷氧基)，其中各个R 0、R、R b、n的定义同前所述。
进而，本发明的式(I)化合物中存在NH和COOH，因此，本发明还提供一种式(I)结构化合物中存在的NH与COOH之间发生部分或全部缩合脱水反应所得的产物。
因此，在本发明的式(I)化合物中，可以包括纯式(I)化合物，不同结构的两种以上的式(I)化合物的混合物，以及相同结构或不同结构的两个以上式(I)化合物发生脱水缩合而得的产物。从而使得本发明的化合物表现出混合物的形式。
在式(I)结构化合物中，优选地，至少一个R 0基团表示
Figure PCTCN2020122396-appb-000054
所示的基团。
在式(I)结构化合物中，优选地，在
Figure PCTCN2020122396-appb-000055
基团中，Ar基团优选苯环，x优选为2，y优选为1，OH优选位于R 2基团的对位，两个R 1优选分别位于OH的两个邻位。
在式(I)所示的化合物中，优选地，R 1各自独立地选自C 1～C 4的直链或支链烷基，优选选自C 3～C 4的支链烷基，更优选为叔丁基。
在式(I)结构化合物中，优选地，各个A基团各自独立地选自
Figure PCTCN2020122396-appb-000056
OH、任选被
Figure PCTCN2020122396-appb-000057
取代的C 1～C 10的直链或支链烷基、任选被
Figure PCTCN2020122396-appb-000058
取代的C 1～C 10的直链或支链烷氧基和H，至少一个A基团选自
Figure PCTCN2020122396-appb-000059
被
Figure PCTCN2020122396-appb-000060
取代的C 1～C 10的直链或支链烷基、被
Figure PCTCN2020122396-appb-000061
取代的C 1～C 10的直链或支链烷氧基，(优选各个A基团各自独立地选自
Figure PCTCN2020122396-appb-000062
OH、任选被
Figure PCTCN2020122396-appb-000063
取代的C 1～C 6的直链或支链烷基、任选被
Figure PCTCN2020122396-appb-000064
取代的C 1～C 6的直链或支链烷氧基和H，至少一个A基团选自
Figure PCTCN2020122396-appb-000065
被
Figure PCTCN2020122396-appb-000066
取代的C 1～C 6的直链或支链烷基、被
Figure PCTCN2020122396-appb-000067
取代的C 1～C 6的直链或支链烷氧基，更优选各个A基团各自独立地选自
Figure PCTCN2020122396-appb-000068
OH、任选被
Figure PCTCN2020122396-appb-000069
取代的C 1～C 4的直链或支链烷 基、任选被
Figure PCTCN2020122396-appb-000070
取代的C 1～C 4的直链或支链烷氧基和H，至少一个A基团选自
Figure PCTCN2020122396-appb-000071
被
Figure PCTCN2020122396-appb-000072
取代的C 1～C 4的直链或支链烷基、被
Figure PCTCN2020122396-appb-000073
取代的C 1～C 4的直链或支链烷氧基)。
在式(I)结构化合物中，优选地，A基团中，当烷基、烷氧基被
Figure PCTCN2020122396-appb-000074
取代时，
Figure PCTCN2020122396-appb-000075
基团位于烷基、烷氧基的末端。
在式(I)结构化合物中，优选地，至少一个A基团为
Figure PCTCN2020122396-appb-000076
p为1-4的整数。
在式(I)结构化合物中，优选地，R’各自独立地选自C 1～C 6的直链或支链烷基、任选被C 1～C 10的直链或支链烷基取代的苄基、任选被C 1～C 10的直链或支链烷基取代的苯基。
本发明的含磷化合物的具体结构的化合物包括如下所示化合物中的一种或多种：
Figure PCTCN2020122396-appb-000077
本发明还提供一种含磷化合物的制备方法，其包括：
第(1)步骤：使式(II)所示化合物和/或其无机酸盐与式(III)所示化合物发生反应，获得第(1)步骤的产物；
Figure PCTCN2020122396-appb-000078
在式(II)中，n为0～50之间的整数(优选0～20之间的整数，更优选0～10之间的整数，进一步优选为0、1、2、3或4)；n+1个R基团彼此相同或不同，各自独立地选自C 1～C 30的亚烃基(优选C 1～C 10亚烷基，更优选C 1～C 6亚烷基，进一步优选C 1～C 4亚烷基)；R b基团为H或C 1～C 30的烃基(优选H或C 1～C 10的烃基，更优选H或C 1～C 6的直链或支链烷基，进一步优选H或C 1～C 4的直链或支链烷基)；
各个R 0’基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基(优选各自独立地选自H、C 1～C 10的直链或支链烷基，更优选各自独立地选自H、C 1～C 4的直链或支链烷基)，优选至少一个R 0’为H；
各个A’基团彼此相同或不同，各自独立地选自XA”’、任选被XA”’取代的C 1～C 30的烃基(优选任选被XA”’取代的C 1～C 10的直链或支链烷基，更优选任选被XA”’取代的C 1～C 6的直链或支链烷基，进一步优选任选被XA”’取代的C 1～C 4的直链或支链烷基)、任选被XA”’取代的C 1～C 30的烷氧基(优选任选被XA”’取代的C 1～C 10的直链或支链烷氧基，更优选任选被XA”’取代的C 1～C 6的直链或支链烷氧基，进一步优选任选被XA”’取代的C 1～C 4的直链或支链烷氧基)和H，A”’选自F、Cl、Br、I、H，X基团各自独立地选自O或S，其中至少一个A’基团选自XA”’、被XA”’取代的C 1～C 30的烃基(优选被XA”’取代的C 1～C 10的直链或支链烷基，更优选被XA”’取代的C 1～C 6的直链或支链烷基，进一步优选被XA”’取代的C 1～C 4的直链或支链烷基)、被XA”’取代的C 1～C 30的烷氧基(优选被XA”’取代的C 1～C 10的直链或支链烷氧基，更优选被XA”’取代的C 1～C 6的直链或支链烷氧基，进一步优选被XA”’取代的C 1～C 4的直链或支链烷氧基)；式(II)所示化合物的无机酸盐的结构为
Figure PCTCN2020122396-appb-000079
其中M为无机酸根，j为所述无机酸根电荷数的绝对值，z为1～10之间的整数(优选1～6之间的整数，更优选1～3 之间的整数)，其它各基团的定义同式(II)(所述式(II)所示化合物的无机酸盐优选其盐酸盐、其硝酸盐、或其硫酸盐，最优选其盐酸盐)；
在式(III)中，X基团各自独立地选自O或S，a为0或1，各个R”’彼此相同或不同，各自独立地选自A”’、C 1～C 30的烃基(优选C 1～C 10的直链或支链烷基、更优选C 1～C 6的直链或支链烷基，进一步优选C 1～C 4的直链或支链烷基)、任选被C 1～C 10的直链或支链烷基取代的C 7～C 15芳基烷基(优选任选被C 1～C 10的直链或支链烷基取代的C 7～C 12芳基烷基、更优选任选被C 1～C 10的直链或支链烷基取代的苄基)和任选被C 1～C 10的直链或支链烷基取代的C 6～C 15芳基(优选任选被C 1～C 10的直链或支链烷基取代的C 6～C 10芳基、更优选任选被C 1～C 10的直链或支链烷基取代的苯基)；
及任选的第(2)步骤：使步骤(1)的产物与式(IV)所示化合物发生反应，得到第(2)步骤产物；
Figure PCTCN2020122396-appb-000080
其中x为0～5之间的整数(优选0～4之间的整数，更优选0、1、2或3)，y为1～5之间的整数(优选1～4之间的整数，更优选1、2或3)，x+y之和≤Ar基团上可被取代的氢原子数目；x个R 1基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基(优选选自H、C 1～C 10的直链或支链烷基，更优选选自H、C 1～C 6的直链或支链烷基，进一步优选选自H、C 1～C 4的直链或支链烷基)，Ar基团为C 3～C 30的环基团(优选C 6～C 15的芳香环基团，更优选苯环、萘环或蒽环)，R 2基团为单键或C 1～C 10的亚烷基(优选单键或C 1～C 6的亚烷基，更优选单键或C 1～C 4的亚烷基)，X’为F、Cl、Br、I或OH(优选Cl、Br)。根据本发明的制备方法，所述式(II)所示化合物的无机酸盐可以通过将式(II)所示化合物与无机酸发生成盐反应而得。
根据本发明的制备方法，所述式(II)所示化合物和/或其无机酸盐可以选用氨基酸、氨基酸的缩合物(部分缩合或全部缩合而形成的多肽)、氨基酸的无机盐、氨基酸的缩合物(部分缩合或全部缩合而形成的多肽)的无机盐中的一种或多种。所述式(II)所示化合物和/或其无机酸盐可以选用以下具体化合物中的一种或多种：L-丝氨酸和/或L-丝氨酸酯盐酸盐、L-亮氨酸和/或L-亮氨酸酯盐酸盐、L-异亮氨酸和/或L-异亮氨酸酯 盐酸盐、甘氨酸和/或甘氨酸酯盐酸盐、L-苯丙氨酸和/或L-苯丙氨酸酯盐酸盐、L-缬氨酸和/或L-缬氨酸酯盐酸盐。
根据本发明的制备方法，式(III)所示化合物可以选用亚磷酸、亚磷酸酯、硫代亚磷酸、硫代亚磷酸酯，具体而言，可以举出的具体的化合物包括亚磷酸、亚磷酸二甲酯、亚磷酸二乙酯、亚磷酸二丙酯、亚磷酸二异丙酯、亚磷酸二正丁酯、亚磷酸二异丁酯、亚磷酸二叔丁酯、亚磷酸(2-乙基己基)酯、亚磷酸二苄酯、亚磷酸二苯酯、硫代亚磷酸、硫代亚磷酸二甲酯、硫代亚磷酸二乙酯、硫代亚磷酸二丙酯、硫代亚磷酸二异丙酯、硫代亚磷酸二正丁酯、硫代亚磷酸二异丁酯、硫代亚磷酸二叔丁酯、硫代亚磷酸(2-乙基己基)酯、硫代亚磷酸二苄酯、硫代亚磷酸二苯酯中的一种或多种。
根据本发明的制备方法，在步骤(1)中，所述式(II)所示化合物和/或其无机酸盐(以XA”’计)与式(III)所示化合物(以P-H计)之间的反应摩尔当量比优选为1∶5～5∶1，更优选为1∶3～3∶1；所述反应的温度优选为-40～80℃，更优选-20～40℃；反应时间一般来说越长越好，为提高反应效率，反应时间优选为0.5～30小时，更优选1～8小时。
根据本发明的制备方法，在步骤(1)中，在所述式(II)所示化合物和/或其无机酸盐与式(III)所示化合物发生的反应中可以加入溶剂，也可以不加入溶剂，优选加入溶剂。所述溶剂优选质子性溶剂、烃类溶剂和呋喃类溶剂中的一种或多种，例如可以选用正己烷、苯、甲苯、四氢呋喃、二氯甲烷、甲醇、乙醇、异丙醇和水中的一种或多种，更优选质子性溶剂，例如可以选用甲醇、乙醇、异丙醇和水中的一种或多种。所述溶剂的加入量以促进反应顺利进行为宜，并没有特别的限定。
根据本发明的制备方法，在步骤(1)中，在所述式(II)所示化合物和/或其无机酸盐与式(III)所示化合物发生的反应中，可以加入催化剂，也可以不加入催化剂，优选加入催化剂。所述催化剂可以为相转移催化剂，所述相转移催化剂可以选用季铵盐和/或冠醚，优选四烃基卤化铵，例如可以选用四丁基溴化铵、三辛基氯化铵、十六烷基三甲基溴化铵、三乙基苄基氯化铵和18-冠-6中的一种或多种，更优选四丁基溴化铵。所述催化剂的加入量优选为所述式(II)所示化合物和/或其无机酸盐质量的0.1％～10％。
根据本发明的制备方法，在步骤(1)中，所述式(II)所示化合物和/ 或其无机酸盐与式(III)所示化合物反应时优选加入氯化物。所述氯化物优选次氯酸盐和/或氯代烷，所述次氯酸盐优选次氯酸钠、次氯酸钾和次氯酸钙中的一种或多种。该次氯酸盐可以以水溶液的形式使用。所述氯代烷优选氯代甲烷，例如可以选用一氯化碳、二氯化碳、三氯化碳和四氯化碳中的一种或多种。所述氯化物优选次氯酸盐的水溶液，其浓度优选为5％～80％，更优选次氯酸钠的水溶液。所述氯化物的加入量优选为30～100mL/100mmol式(II)所示化合物和/或其无机酸盐。
根据本发明的制备方法，在步骤(1)中，在所述式(II)所示化合物和/或其无机酸盐与式(III)所示化合物发生的反应优选在pH值为8～10(优选8.5～9.5)的条件下进行。可以通过加入碱性介质来调节pH值，所述碱性介质优选碱性溶液，所述碱性溶液优选氢氧化钠、氢氧化钾、氢氧化锂和氢氧化钙中的一种或多种碱的水溶液。
根据本发明的制备方法，在步骤(1)中，在所述式(II)所示化合物和/或其无机酸盐与式(III)所示化合物的反应之后，对反应产物进行任选的萃取处理、任选的干燥处理和任选的超声处理。优选进行超声处理。
对步骤(1)的反应产物进行萃取处理时，优选利用溶剂对反应产物进行萃取处理，更优选利用溶剂在酸性环境下对反应产物进行萃取处理。所述溶剂优选醚类溶剂、酯类溶剂、氯代烷溶剂和烃类溶剂中的一种或多种，例如可以选用石油醚、乙醚、乙酸乙酯、二氯甲烷、氯仿和甲苯中的一种或多种。所述萃取处理优选1～3次。所述的酸性环境是通过加入酸液调节反应产物所在体系的pH值而得，所述pH优选为2～5，更优选2.5～3.5；所述酸液优选盐酸、醋酸、硝酸和硫酸中的一种酸或多种酸的水溶液，所述酸液的浓度优选为1～10摩尔/升。优选地，在进行所述萃取处理时加入无机盐，以提高萃取效率。所述无机盐优选氯化钠、氯化钾、硫酸钠和硫酸钾中的一种或多种。
对步骤(1)的反应产物进行干燥处理时，优选地加入干燥剂对反应产物进行干燥处理。所述干燥剂可以选用无水氯化镁和/或无水硫酸钠。
对步骤(1)的反应产物进行超声处理时，，优选在溶剂存在下进行超声处理，所述溶剂优选呋喃类溶剂、卤代烷溶剂、酮类溶剂、酯类溶剂和腈类溶剂中的一种或多种，例如可以选用四氢呋喃、二氯甲烷、氯仿、丙酮、乙酸乙酯和乙腈中的一种或多种，更优选四氢呋喃、二氯甲烷和乙腈中的一种或多种。所述超声处理的时间优选1～10h，更优 选2～8h。
根据本发明的制备方法，在步骤(1)中，在所述式(II)所示化合物和/或其无机酸盐与式(III)所示化合物的反应之后，对步骤(1)的反应产物进行进一步的提纯处理。所述提纯处理包括现有技术中已知的干燥、蒸发、洗涤、蒸馏、重结晶和离心分离方法中的一种或多种。
根据本发明的制备方法，在任选的步骤(2)中，所述式(IV)所示结构化合物可以采用现有技术中已知的方法制备得到，并没有特别的限定。
优选的是，在式(IV)结构化合物中，
Figure PCTCN2020122396-appb-000081
Ar基团优选苯环，x优选为2，y优选为1，OH优选位于R 2基团的对位，两个R 1优选分别位于OH的两个邻位，X’优选为Cl或Br。
优选的是，在式(IV)结构化合物中，R 1各自独立地选自C 1～C 4的直链或支链烷基，优选选自C 3～C 4的支链烷基，更优选为叔丁基。
在式(III)结构化合物中，优选地，R”’各自独立地选自C 1～C 6的直链或支链烷基、任选被C 1～C 10的直链或支链烷基取代的苄基、任选被C 1～C 10的直链或支链烷基取代的苯基。
在式(II)结构化合物中，优选地，A’基团中，当烷基、烷氧基被XA”’取代时，XA”’基团位于烷基、烷氧基的末端。
在式(II)结构化合物中，优选地，至少一个A’基团为
Figure PCTCN2020122396-appb-000082
p为1-4的整数。
式(IV)结构化合物可以采用本领域已知的方法进行合成，也可以是市售品。
作为所述式(IV)所示化合物，可以选用以下具体化合物中的一种或多种：3，5-双(叔-丁基)-4-羟基苯乙酰氯、3，5-双(叔-丁基)-4-羟基苯丙酰氯、对羟基苯乙酰氯、3-羟基苯乙酰氯、2-羟基苯乙酰氯、3，4-二羟基苯乙酰氯、3，5-二羟基苯乙酰氯、3-甲基-4-羟基苯乙酰氯、3，5-二甲基-4-羟基苯乙酰氯、2，4-二羟基苯丙酰氯、3，4-二羟基苯丙酰氯、2-羟基-萘乙酰氯。
根据本发明的制备方法，在任选的步骤(2)中，所述式(IV)所示化合物(以X’计)与步骤(1)的反应产物(以NH计)之间的反应摩尔当量比优选为5∶1～1∶5，更优选为1∶2～2∶1；所述反应的温度优选为-40～60℃，更优选-20～20℃；反应时间一般来说越长越好，为提高反应效率，反应时间优选1～20小时，更优选3～8小时。
根据本发明的制备方法，在任选的步骤(2)中，在所述式(IV)所示化合物(以X’计)与步骤(1)的反应产物(以其中的NH计)之间的反应中可以加入溶剂，也可以不加入溶剂，优选加入溶剂。所述溶剂优选质子性溶剂、醚类溶剂、酯类溶剂、氯代烷溶剂、呋喃类溶剂、酮类溶剂和烃类溶剂中的一种或多种，例如可以选用水、甲醇、乙醇、异丙醇、二氯甲烷、氯仿、乙醚、四氢呋喃、乙酸乙酯、丙酮和甲苯，更优选水、乙醇、乙醚、四氢呋喃和丙酮中的一种或多种。所述溶剂的加入量以促进反应顺利进行为宜，并没有特别的限定。
根据本发明的制备方法，在任选的步骤(2)中，在所述式(IV)所示化合物(以X’计)与步骤(1)的反应产物(以其中的NH计)之间的反应之后，对第(2)步骤的反应产物进行洗涤处理，以提高反应产物的纯度。优选采用酸液对第(2)步骤的反应产物进行洗涤处理。所述酸液优选盐酸、硫酸和硝酸中的一种酸或多种酸的水溶液，所述酸液的浓度优选1～12摩尔/升。根据本发明的制备方法，在任选的步骤(2)中，在所述式(IV)所示化合物(以X’计)与步骤(1)的反应产物(以其中的NH计)之间的反应之后，对第(2)步骤的反应产物进行进一步的提纯处理。所述提纯处理包括现有技术中已知的洗涤、蒸馏、重结晶和离心分离方法中的一种或多种。
本发明的含磷化合物能够用作润滑油的生物降解剂。
通过本发明的含磷化合物的制造方法制备的得到的含磷化合物能够用作润滑油的生物降解剂。
本发明还提供一种含磷化合物的组合物，其包含本发明上述的含磷化合物或按照本发明上述方法制得的含磷化合物，其部分或全部缩合脱水反应所得的产物中的一种或多种混合物。
本发明还提供一种润滑油组合物，其包含润滑油基础油，选自本发明上述的含磷化合物、按照本发明上述的方法制得的含磷化合物、和本发明上述的含磷化合物的组合物中的至少一种。
本发明的润滑油组合物中，所述含磷化合物、其部分或全部缩合脱水反应所得的产物相对于润滑油组合物总质量，为0.001-30％，优选0.01-20％，更优选0.1-10％。
本发明的含磷化合物具有非常优异的生物降解性能和抗氧化性能，特别适于促进润滑油产品的生物降解。本发明含磷化合物的制备方法简单、高效，产率高。
实施例
下面通过具体实施例对本发明的方法进行说明，但本发明并不局限于此。
下述实施例中所述实验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例中的缩写符号含义如下所示：
Me：甲基
iPr：异丙基
Bn：苄基
实施例1
合成O-二甲基氧磷酰基-N-3，5-双(叔-丁基)-4-羟基苯丙酰-L-丝氨酸
(1)向反应器中依次加入L-丝氨酸(式II-a所示)(100mmol，10.5g)，40mL水，降温至0℃，用氢氧化钠调节至pH＝9.0，加入亚磷酸二甲酯(式III-a所示)(130mmol，14.3g)和四丁基溴化铵(1mmol，0.32g)，搅拌下滴加12％的次氯酸钠溶液50mL。反应4小时后用乙醚萃取2次，水层用盐酸调节pH＝3，加入8g氯化钠，用乙酸乙酯萃取2次，合并有机相，用无水氯化镁干燥，减压蒸馏除去溶剂得到无色油状物。将无色油状物溶于60mL乙腈中，室温超声5小时，过滤得到白色固体；
(2)将上述白色固体(47.6mmol，10.2g)，40mL丙酮，20mL水，氢氧化钠(95.2mmol，10g)，降温至0℃，加入3，5-双(叔-丁基)-4-羟基苯丙酰氯(47.6mmol，14.1g)。反应5小时后使用6摩尔/升盐酸溶液酸化至pH值为2，出现大量白色固体，抽滤，滤饼用水及石油醚洗涤，得到第(2)步骤的反应产物，其结构及示例反应式如下所示，第(2)步骤 反应产物的结构为示例反应式中的式I-a。
Figure PCTCN2020122396-appb-000083
其中步骤(2)中3，5-双(叔-丁基)-4-羟基苯丙酰氯的制备方法是：将3，5-双(叔-丁基)-4-羟基苯丙酸(81mmol，22.5g)溶于150mL氯仿，加入二氯亚砜(124mmol，14.8g)，回流4小时，旋转蒸发除去溶剂和多余的二氯亚砜，得到淡黄色固体(即为3，5-双(叔-丁基)-4-羟基苯丙酰氯)。
第(2)步骤反应产物的结构的表征结果如下： 1H NMR(400MHz，CDCl 3)δ12.19(br，1H)，8.71(s，1H)，6.96(s，2H)，5.97(br，1H)，4.66(d，J＝6.4Hz，2H)，4.07(t，J＝6.8Hz，1H)，3.79(s，6H)，2.87(t，J＝6.8Hz，2H)，2.49(t，J＝6.8Hz，2H)，1.31(s，18H)；HRMS(FT-ICRMS)calcd for C 22H 35NO 8P -(M-H)：472.2106，found：472.2109.
经结构鉴定所合成的化合物确为目标化合物O-二甲基氧磷酰基-N-3，5-双(叔-丁基)-4-羟基苯丙酰-L-丝氨酸(见结构式I-a)。
实施例2
合成O-二异丙基氧磷酰基-N-3，5-双(叔-丁基)-4-羟基苯丙酰-L-丝氨酸
(1)向反应器中依次加入L-丝氨酸(式II-a所示)(100mmol，10.5g)，40mL水，降温至0℃，用氢氧化钠调节至pH＝9.0，加入亚磷酸二异丙酯(式III-b所示)(130mmol，21.7g)和四丁基溴化铵(1mmol，0.32g)，搅拌下滴加12％次氯酸钠溶液50mL。反应4小时后用乙醚萃取2次，水层用盐酸调节pH＝3，加入8g氯化钠，用乙酸乙酯萃取2次，合并有机相，用无水氯化镁干燥，减压蒸馏除去溶剂得到无色油状物。将无色油状物溶于60mL乙腈中，室温超声5小时，过滤得到白色固体；
(2)将上述白色固体(47.6mmol，12.8g)，40mL丙酮，20mL水，氢氧化钠(95.2mmol，10g)，降温至0℃，加入3，5-双(叔-丁基)-4-羟基苯丙酰氯(47.6mmol，14.1g)。反应5小时后使用6摩尔/升盐酸溶液 酸化至pH值为2，出现大量白色固体，抽滤，滤饼用水及石油醚洗涤，得到第(2)步骤的反应产物，其结构及示例反应式如下所示，第(2)步骤反应产物的结构为示例反应式中的式I-b。
Figure PCTCN2020122396-appb-000084
其中步骤(2)中3，5-双(叔-丁基)-4-羟基苯丙酰氯的制备方法是：将3，5-双(叔-丁基)-4-羟基苯丙酸(81mmol，22.5g)溶于150mL氯仿，加入二氯亚砜(124mmol，14.8g)，回流4小时，旋转蒸发除去溶剂和多余的二氯亚砜，得到淡黄色固体(即为3，5-双(叔-丁基)-4-羟基苯丙酰氯)。
第(2)步骤反应产物的结构的表征结果如下： 1H NMR(400MHz，CDCl 3)δ12.10(br，1H)，8.55(s，1H)，6.88(s，2H)，5.85(br，1H)，4.61(d，J＝6.4Hz，2H)，4.09(t，J＝6.8Hz，1H)，3.99-3.89(m，2H)，2.81(t，J＝6.8Hz，2H)，2.44(t，J＝6.8Hz，2H)，1.31(s，18H)，1.25(s，12H)；HRMS(FT-ICRMS)calcd for C 26H 43NO 8P -(M-H)：528.2732，found：528.2737.
经结构鉴定所合成的化合物确为目标化合物O-二异丙基氧磷酰基-N-3，5-双(叔-丁基)-4-羟基苯丙酰-L-丝氨酸(见结构式I-b)。
实施例3
合成O-二苯甲基氧磷酰基-N-3，5-双(叔-丁基)-4-羟基苯丙酰-L-丝氨酸
(1)向反应器中依次加入L-丝氨酸(式II-a所示)(100mmol，10.5g)，40mL水，降温至0℃，用氢氧化钠调节至pH＝9.0，加入亚磷酸二苄酯(式III-c所示)(130mmol，34.0g)和四丁基溴化铵(1mmol，0.32g)，搅拌下滴加12％次氯酸钠溶液50mL。反应4小时后用乙醚萃取2次，水层用盐酸调节pH＝3，加入8g氯化钠，用乙酸乙酯萃取2次，合并有机相，用无水氯化镁干燥，减压蒸馏除去溶剂得到无色油状物。将无色油状物溶于60mL乙腈中，室温超声5小时，过滤得到白色固体；
(2)将上述白色固体(47.6mmol，17.4g)，40mL丙酮，20mL水， 氢氧化钠(95.2mmol，10g)，降温至0℃，加入3，5-双(叔-丁基)-4-羟基苯丙酰氯(47.6mmol，14.1g)。反应5小时后使用6摩尔/升盐酸溶液酸化至pH值为2，出现大量白色固体，抽滤，滤饼用水及石油醚洗涤，得到第(2)步骤的反应产物，其结构及示例反应式如下所示，第(2)步骤反应产物的结构为示例反应式中的式I-c。
Figure PCTCN2020122396-appb-000085
其中步骤(2)中3，5-双(叔-丁基)-4-羟基苯丙酰氯的制备方法是：1)将3，5-双(叔-丁基)-4-羟基苯丙酸(81mmol，22.5g)溶于150mL氯仿，加入二氯亚砜(124mmol，14.8g)，回流4小时，旋转蒸发除去溶剂和多余的二氯亚砜，得到淡黄色固体(即为3，5-双(叔-丁基)-4-羟基苯丙酰氯)。
第(2)步骤反应产物的表征确证结果如下： 1H NMR(400MHz，CDCl 3)δ12.27(br，1H)，8.64(s，1H)，7.55-7.26(m，10H)，6.91(s，2H)，5.71(br，1H)，5.17(s，4H)，4.61(d，J＝6.4Hz，2H)，4.01(t，J＝6.8Hz，1H)，2.81(t，J＝6.8Hz，2H)，2.44(t，J＝6.8Hz，2H)，1.32(s，18H)；HRMS(FT-ICRMS)calcd for C 34H 43NO 8P -(M-H)：624.2732，found：624.2730.
经结构鉴定所合成的化合物确为目标化合物O-二苯甲基氧磷酰基-N-3，5-双(叔-丁基)-4-羟基苯丙酰-L-丝氨酸(见结构式I-c)。
实施例4
合成O-二甲基氧磷酰基-N-3，5-双(叔-丁基)-4-羟基苯丙酰-L-丝氨酸甲酯
(1)向反应器中依次加入L-丝氨酸甲酯盐酸盐(式II-b所示)(100mmol，15.5g)，40mL水，降温至0℃，用氢氧化钠调节至pH＝9.0，加入亚磷酸二甲酯(式III-a所示)(130mmol，14.3g)和四丁基溴化铵(1mmol，0.32g)，搅拌下滴加12％次氯酸钠溶液50mL。反应4小时后用 乙醚萃取2次，水层用盐酸调节pH＝3，加入8g氯化钠，用乙酸乙酯萃取2次，合并有机相，用无水氯化镁干燥，减压蒸馏除去溶剂得到白色固体。将白色固体溶于60mL乙腈中，室温超声5小时，过滤得到白色固体；
(2)将上述白色固体(47.6mmol，10.8g)，40mL丙酮，20mL水，氢氧化钠(95.2mmol，10g)，降温至0℃，加入3，5-双(叔-丁基)-4-羟基苯丙酰氯(47.6mmol，14.1g)。反应5小时后使用6摩尔/升盐酸溶液酸化至pH值为2，出现大量白色固体，抽滤，滤饼用水及石油醚洗涤，得到第(2)步骤的反应产物，其结构及示例反应式如下所示，第(2)步骤反应产物的结构为示例反应式中的式I-d。
Figure PCTCN2020122396-appb-000086
其中步骤(2)中3，5-双(叔-丁基)-4-羟基苯丙酰氯的制备方法是：将3，5-双(叔-丁基)-4-羟基苯丙酸(81mmol，22.5g)溶于150mL氯仿，加入二氯亚砜(124mmol，14.8g)，回流4小时，旋转蒸发除去溶剂和多余的二氯亚砜，得到淡黄色固体(即为3，5-双(叔-丁基)-4-羟基苯丙酰氯)。
第(2)步骤反应产物的结构表征结果如下： 1H NMR(400MHz，CDCl 3)δ8.54(s，1H)，6.91(s，2H)，5.77(br，1H)，4.60(d，J＝6.4Hz，2H)，4.11(t，J＝6.8Hz，1H)，3.73(s，6H)，3.61(s，3H)，2.80(t，J＝6.8Hz，2H)，2.52(t，J＝6.8Hz，2H)，1.35(s，18H)；HRMS(FT-ICRMS)calcd for C 23H 37NO 8P -(M-H)：486.2262，found：486.2268.
经结构鉴定所合成的化合物确为目标化合物O-二甲基氧磷酰基-N-3，5-双(叔-丁基)-4-羟基苯丙酰-L-丝氨酸甲酯(见结构式I-d)。
实施例5
分别将上述含磷化合物以1质量％的比例加入到不同种类的润滑油中，根据OECD302B方法测定生物降解性能，测定结果见表1。
表1生物降解性能
润滑油名称 实施例1 实施例2 实施例3 实施例4 空白组
HVI 350 63.9％ 75.8％ 77.4％ 64.6％ 23.5％
PAO4 68.1％ 80.4％ 81.4％ 66.2％ 25.7％
PAO10 61.2％ 72.1％ 75.9％ 60.3％ 22.3％
分别将上述含磷化合物以1质量％的比例加入不同种类的润滑油中，在氧气压力500kPa，200℃条件下，使用差式扫描量热法(PDSC法)对润滑油氧化诱导期进行测定，测定结果见表2。
表2氧化诱导期试验
润滑油名称 实施例1 实施例2 实施例3 实施例4 空白组
HVI 350 24.7min 22.9min 25.1min 25.9min 6.7min
PAO4 36.1min 34.2min 37.4min 38.8min 15.4min
PAO10 33.4min 33.1min 34.2min 35.5min 14.9min
以上结果表明，本发明的含磷化合物可以提高润滑油的生物降解性能。并且，本发明的含磷化合物的抗氧化性能优异，在配合于润滑油时，可以抑制润滑油的氧化。
本领域技术人员应当注意的是，本发明所描述的实施方式仅仅是示范性的，可在本发明的范围内作出各种其他替换、改变和改进。因而，本发明不限于上述实施方式，而仅由权利要求限定。

Claims (15)

  1. 一种含磷化合物，其结构为下式(I)所示：
    Figure PCTCN2020122396-appb-100001
    在式(I)中，n为0～50之间的整数(优选0～20之间的整数，更优选0～10之间的整数，进一步优选为0、1、2、3或4)；n+1个R基团彼此相同或不同，各自独立地选自C 1～C 30的亚烃基(优选C 1～C 10亚烷基，更优选C 1～C 6亚烷基，进一步优选C 1～C 4亚烷基)；R b基团为H或C 1～C 30的烃基(优选H或C 1～C 10的烃基，更优选H或C 1～C 6的直链或支链烷基，进一步优选H或C 1～C 4的直链或支链烷基)；
    各个R 0基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基和
    Figure PCTCN2020122396-appb-100002
    (优选各自独立地选自H、C 1～C 10的直链或支链烷基和
    Figure PCTCN2020122396-appb-100003
    更优选各自独立地选自H、C 1～C 4的直链或支链烷基和
    Figure PCTCN2020122396-appb-100004
    )，优选式(I)中至少其中一个R 0为
    Figure PCTCN2020122396-appb-100005
    Figure PCTCN2020122396-appb-100006
    中，x为0～5之间的整数(优选0～4之间的整数，更优选0、1、2或3)，y为1～5之间的整数(优选1～4之间的整数，更优选1、2或3)，x+y之和≤Ar基团上可被取代的氢原子数目；x个R 1基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基(优选选自H、C 1～C 10的直链或 支链烷基，更优选选自H、C 1～C 6的直链或支链烷基，进一步优选选自H、C 1～C 4的直链或支链烷基)，各个Ar基团彼此相同或不同，各自独立地选自C 3～C 30的环基团(优选选自C 6～C 15的芳香环基团，更优选选自苯环、萘环和蒽环)，R 2基团为单键或C 1～C 10的亚烷基(优选单键或C 1～C 6的亚烷基，更优选单键或C 1～C 4的亚烷基)；
    各个A基团彼此相同或不同，各自独立地选自
    Figure PCTCN2020122396-appb-100007
    OH、任选被
    Figure PCTCN2020122396-appb-100008
    取代的C 1～C 30的烃基(优选任选被
    Figure PCTCN2020122396-appb-100009
    取代的C 1～C 10的直链或支链烷基，更优选任选被
    Figure PCTCN2020122396-appb-100010
    取代的C 1～C 6的直链或支链烷基，进一步优选任选被
    Figure PCTCN2020122396-appb-100011
    取代的C 1～C 4的直链或支链烷基)、任选被
    Figure PCTCN2020122396-appb-100012
    取代的C 1～C 30的烷氧基(优选任选被
    Figure PCTCN2020122396-appb-100013
    取代的C 1～C 10的直链或支链烷氧基，更优选任选被
    Figure PCTCN2020122396-appb-100014
    取代的C 1～C 6的直链或支链烷氧基，进一步优选任选被
    Figure PCTCN2020122396-appb-100015
    取代的C 1～C 4的直链或支链烷氧基)和H，式(I)中至少一个A基团选自
    Figure PCTCN2020122396-appb-100016
    被
    Figure PCTCN2020122396-appb-100017
    取代的C 1～C 30的烃基(优选被
    Figure PCTCN2020122396-appb-100018
    取代的C 1～C 10的直链或支链烷基，更优选被
    Figure PCTCN2020122396-appb-100019
    取代的C 1～C 6的直链或支链烷基，进一步优选被
    Figure PCTCN2020122396-appb-100020
    取代的C 1～C 4的直链或支链烷基)、被
    Figure PCTCN2020122396-appb-100021
    取代的C 1～C 30的烷氧基(优选被
    Figure PCTCN2020122396-appb-100022
    取代的C 1～C 10的直链或支链烷氧基，更优选被
    Figure PCTCN2020122396-appb-100023
    取代的C 1～C 6的直链或支链烷氧基，进一步优选被
    Figure PCTCN2020122396-appb-100024
    取代的C 1～C 4的直链或支链烷氧基)，X基团各自独立地选自O或S，a为0或1，R’各自独立地选自C 1～C 30的烃基(优选C 1～C 10的直链或支链烷基，更优选C 1～C 6的直链或支链烷基，进一步优选C 1～C 4的直链或支链烷基)、任选被C 1～C 10的直链或支链烷基取代的C 7～C 15芳基烷基(优选任选被C 1～C 10的直链或支链烷基取代的C 7～C 12芳基烷基、更优选任选被C 1～C 10的直链或支链烷基取代的苄基)、任选被C 1～C 10的直链或支链烷基取代的C 6～C 15芳基(优选任选被C 1～C 10的直链或支链烷基取代的C 6～C 10芳基、更优选任选被C 1～C 10的直链或支链烷基取代的苯基)、
    Figure PCTCN2020122396-appb-100025
    R”选自C 1～C 30的烃基(优选C 1～C 10的直链或支链烷基，更优选C 1～C 6的直链或支链烷基，进一步优选C 1～C 4的直链或支链烷基)、C 1～C 30的烷氧基(优选C 1～C 10的直链或支链烷氧基，更优选C 1～C 6的直链或支链烷氧基，进一步优选C 1～C 4的直链或支链烷氧基)，其中各个R 0、R、R b、n的定义同前所述。
  2. 按照权利要求1所述的含磷化合物，其特征在于，在式(I)结构化合物中，在
    Figure PCTCN2020122396-appb-100026
    基团中，Ar基团为苯环(x优选为2，y优选 为1，OH优选位于R 2基团的对位，两个R 1优选分别位于OH的两个邻位，优选两个R 1各自独立地选自C 1～C 4的直链或支链烷基(优选选自C 3～C 4的支链烷基，更优选为叔丁基))。
  3. 按照权利要求1或2所述的含磷化合物，其特征在于，在式(I)结构化合物中，各个A基团各自独立地选自
    Figure PCTCN2020122396-appb-100027
    OH、任选被
    Figure PCTCN2020122396-appb-100028
    取代的C 1～C 10的直链或支链烷基、任选被
    Figure PCTCN2020122396-appb-100029
    取代的C 1～C 10的直链或支链烷氧基和H，至少一个A基团选自
    Figure PCTCN2020122396-appb-100030
    被
    Figure PCTCN2020122396-appb-100031
    取代的C 1～C 10的直链或支链烷基、被
    Figure PCTCN2020122396-appb-100032
    取代的C 1～C 10的直链或支链烷氧基，(优选各个A基团各自独立地选自
    Figure PCTCN2020122396-appb-100033
    OH、任选被
    Figure PCTCN2020122396-appb-100034
    取代的C 1～C 6的直链或支链烷基、任选被
    Figure PCTCN2020122396-appb-100035
    取代的C 1～C 6的直链或支链烷氧基和H，至少一个A基团选自
    Figure PCTCN2020122396-appb-100036
    被
    Figure PCTCN2020122396-appb-100037
    取代的C 1～C 6的直链或支链烷基、被
    Figure PCTCN2020122396-appb-100038
    取代的C 1～C 6的直链或支链烷氧基，更优选各个A基团各自独立地选自
    Figure PCTCN2020122396-appb-100039
    OH、 任选被
    Figure PCTCN2020122396-appb-100040
    取代的C 1～C 4的直链或支链烷基、任选被
    Figure PCTCN2020122396-appb-100041
    取代的C 1～C 4的直链或支链烷氧基和H，至少一个A基团选自
    Figure PCTCN2020122396-appb-100042
    被
    Figure PCTCN2020122396-appb-100043
    取代的C 1～C 4的直链或支链烷基、被
    Figure PCTCN2020122396-appb-100044
    取代的C 1～C 4的直链或支链烷氧基)。
  4. 按照权利要求1-3任一项所述的含磷化合物，其特征在于，所述含磷化合物选自如下所示化合物中的一种或多种：
    Figure PCTCN2020122396-appb-100045
  5. 一种含磷化合物的制备方法，其包括：
    第(1)步骤：使式(II)所示化合物和/或其无机酸盐与式(III)所示化合物发生反应，获得第(1)步骤的产物；
    Figure PCTCN2020122396-appb-100046
    在式(II)中，n为0～50之间的整数(优选0～20之间的整数，更优选0～10之间的整数，进一步优选为0、1、2、3或4)；n+1个R基团彼此相同或不同，各自独立地选自C 1～C 30的亚烃基(优选C 1～C 10亚烷基，更优选 C 1～C 6亚烷基，进一步优选C 1～C 4亚烷基)；R b基团为H或C 1～C 30的烃基(优选H或C 1～C 10的烃基，更优选H或C 1～C 6的直链或支链烷基，进一步优选H或C 1～C 4的直链或支链烷基)；
    各个R 0’基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基(优选各自独立地选自H、C 1～C 10的直链或支链烷基，更优选各自独立地选自H、C 1～C 4的直链或支链烷基)，优选至少一个R 0’为H；
    各个A’基团彼此相同或不同，各自独立地选自XA”’、任选被XA”’取代的C 1～C 30的烃基(优选任选被XA”’取代的C 1～C 10的直链或支链烷基，更优选任选被XA”’取代的C 1～C 6的直链或支链烷基，进一步优选任选被XA”’取代的C 1～C 4的直链或支链烷基)、任选被XA”’取代的C 1～C 30的烷氧基(优选任选被XA”’取代的C 1～C 10的直链或支链烷氧基，更优选任选被XA”’取代的C 1～C 6的直链或支链烷氧基，进一步优选任选被XA”’取代的C 1～C 4的直链或支链烷氧基)和H，A”’选自F、Cl、Br、I、H，X基团各自独立地选自O或S，其中至少一个A’基团选自XA”’、被XA”’取代的C 1～C 30的烃基(优选被XA”’取代的C 1～C 10的直链或支链烷基，更优选被XA”’取代的C 1～C 6的直链或支链烷基，进一步优选被XA”’取代的C 1～C 4的直链或支链烷基)、被XA”’取代的C 1～C 30的烷氧基(优选被XA”’取代的C 1～C 10的直链或支链烷氧基，更优选被XA”’取代的C 1～C 6的直链或支链烷氧基，进一步优选被XA”’取代的C 1～C 4的直链或支链烷氧基)；式(II)所示化合物的无机酸盐的结构为
    Figure PCTCN2020122396-appb-100047
    其中M为无机酸根，j为所述无机酸根电荷数的绝对值，z为1～10之间的整数(优选1～6之间的整数，更优选1～3之间的整数)，其它各基团的定义同式(II)(所述式(II)所示化合物的无机酸盐优选其盐酸盐、其硝酸盐、或其硫酸盐，最优选其盐酸盐)；
    在式(III)中，X基团各自独立地选自O或S，a为0或1，各个R”’彼此相同或不同，各自独立地选自A”’、C 1～C 30的烃基(优选C 1～C 10的直链或支链烷基、更优选C 1～C 6的直链或支链烷基，进一步优选C 1～C 4的直链或支链烷基)、任选被C 1～C 10的直链或支链烷基取代的C 7～C 15芳基烷基 (优选任选被C 1～C 10的直链或支链烷基取代的C 7～C 12芳基烷基、更优选任选被C 1～C 10的直链或支链烷基取代的苄基)和任选被C 1～C 10的直链或支链烷基取代的C 6～C 15芳基(优选任选被C 1～C 10的直链或支链烷基取代的C 6～C 10芳基、更优选任选被C 1～C 10的直链或支链烷基取代的苯基)；
    及任选的第(2)步骤：使步骤(1)的产物与式(IV)所示化合物发生反应，得到第(2)步骤产物；
    Figure PCTCN2020122396-appb-100048
    其中x为0～5之间的整数(优选0～4之间的整数，更优选0、1、2或3)，y为1～5之间的整数(优选1～4之间的整数，更优选1、2或3)，x+y之和≤Ar基团上可被取代的氢原子数目；x个R 1基团彼此相同或不同，各自独立地选自H、C 1～C 30的烃基(优选选自H、C 1～C 10的直链或支链烷基，更优选选自H、C 1～C 6的直链或支链烷基，进一步优选选自H、C 1～C 4的直链或支链烷基)，Ar基团为C 3～C 30的环基团(优选C 6～C 15的芳香环基团，更优选苯环、萘环或蒽环)，R 2基团为单键或C 1～C 10的亚烷基(优选单键或C 1～C 6的亚烷基，更优选单键或C 1～C 4的亚烷基)，X’为F、Cl、Br、I或OH(优选Cl、Br)。
  6. 按照权利要求5的制备方法，其特征在于，所述式(II)所示化合物和/或其无机酸盐为氨基酸、氨基酸的缩合物(部分缩合或全部缩合而形成的多肽)、氨基酸的无机盐、氨基酸的缩合物(部分缩合或全部缩合而形成的多肽)的无机盐中的一种或多种。
  7. 按照权利要求5或6的制备方法，其特征在于，所述式(II)所示化合物和/或其无机酸盐选自以下化合物中的一种或多种：L-丝氨酸和/或L-丝氨酸酯盐酸盐、L-亮氨酸和/或L-亮氨酸酯盐酸盐、L-异亮氨酸和/或L-异亮氨酸酯盐酸盐、甘氨酸和/或甘氨酸酯盐酸盐、L-苯丙氨酸和/或L-苯丙氨酸酯盐酸盐、L-缬氨酸和/或L-缬氨酸酯盐酸盐，所述式(III)所示化合物选自亚磷酸、亚磷酸酯、硫代亚磷酸、硫代亚磷酸酯(优选选自亚磷酸、亚磷酸二甲酯、硫代亚磷酸二甲酯、亚磷酸二乙酯、亚磷酸二丙酯、亚磷酸二异丙酯、亚磷酸二正丁酯、亚磷酸二异丁酯、亚磷酸二叔丁酯、亚磷酸(2-乙基己基)酯、亚磷酸二苄酯、亚磷酸二苯 酯、硫代亚磷酸、硫代亚磷酸二甲酯、硫代亚磷酸二乙酯、硫代亚磷酸二丙酯、硫代亚磷酸二异丙酯、硫代亚磷酸二正丁酯、硫代亚磷酸二异丁酯、硫代亚磷酸二叔丁酯、硫代亚磷酸(2-乙基己基)酯、硫代亚磷酸二苄酯、硫代亚磷酸二苯酯中的一种或多种)。
  8. 按照权利要求5-7任一项所述的制备方法，其特征在于，在步骤(1)中，所述式(II)所示化合物和/或其无机酸盐(以XA”’计)与式(III)所示化合物(以P-H计)之间的反应摩尔当量比为1∶5～5∶1(优选为1∶3～3∶1)；所述反应的温度为-40～80℃(优选-20～40℃)。
  9. 按照权利要求5-8任一项所述的制备方法，其特征在于，在步骤(1)中，在所述式(II)所示化合物和/或其无机酸盐与式(III)所示化合物发生的反应中，加入溶剂(所述溶剂优选质子性溶剂、烃类溶剂和呋喃类溶剂中的一种或多种)，
    任选地加入催化剂(所述催化剂优选相转移催化剂(更优选季铵盐和/或冠醚)，
    任选地加入氯化物(所述氯化物优选次氯酸盐和/或氯代烷)，
    任选地反应在pH值为8～10(优选8.5～9.5)的条件下进行。
  10. 按照权利要求5-9任一项所述的制备方法，其特征在于，在步骤(1)中，在所述式(II)所示化合物和/或其无机酸盐与式(III)所示化合物的反应之后，对反应产物进行萃取处理、干燥处理和超声处理中的一种或多种，
    对步骤(1)的反应产物进行萃取处理时，利用溶剂对反应产物进行萃取处理(优选利用溶剂(所述溶剂优选醚类溶剂、酯类溶剂、氯代烷溶剂和烃类溶剂中的一种或多种)在酸性环境下对反应产物进行萃取处理)，
    对步骤(1)的反应产物进行干燥处理时，对反应产物进行超声处理，所述超声处理的时间为1～10h(优选2～8h)，
    对步骤(1)的反应产物进行超声处理时，在溶剂存在下对反应产物进行超声处理(所述溶剂优选呋喃类溶剂、卤代烷溶剂、酮类溶剂、酯类溶剂和腈类溶剂中的一种或多种)。
  11. 按照权利要求5-10任一项所述的制备方法，其特征在于，在任选的步骤(2)中，所述式(IV)所示化合物选自以下化合物中的一种或多种：3，5-双(叔-丁基)-4-羟基苯乙酰氯、3，5-双(叔-丁基)-4-羟基苯丙酰氯、 对羟基苯乙酰氯、3-羟基苯乙酰氯、2-羟基苯乙酰氯、3，4-二羟基苯乙酰氯、3，5-二羟基苯乙酰氯、3-甲基-4-羟基苯乙酰氯、3，5-二甲基-4-羟基苯乙酰氯、2，4-二羟基苯丙酰氯、3，4-二羟基苯丙酰氯、2-羟基-萘乙酰氯。
  12. 按照权利要求5-11任一项所述的制备方法，其特征在于，在任选的步骤(2)中，所述式(IV)所示化合物(以X’计)与步骤(1)的反应产物(以NH计)之间的反应摩尔当量比为5∶1～1∶5(优选为1∶2～2∶1)；所述反应的温度为-40～60℃(优选-20～20℃)。
  13. 含磷化合物的组合物，其包含权利要求1～4任一项所述的含磷化合物或按照权利要求5～12任一项的方法制得的含磷化合物，其部分或全部缩合脱水反应所得的产物中的一种或多种混合物。
  14. 权利要求1～4任一项所述的含磷化合物或按照权利要求5～12任一项的方法制得的含磷化合物用作润滑油的生物降解剂用途。
  15. 润滑油组合物，其包含润滑油基础油，选自权利要求1～4任一项所述的含磷化合物、按照权利要求5～12任一项的方法制得的含磷化合物、和权利要求13所述的含磷化合物的组合物中的至少一种，所述含磷化合物、其部分或全部缩合脱水反应所得的产物相对于润滑油组合物总质量，为0.001-30％，优选0.01-20％，更优选0.1-10％。
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