Phosphorus-containing compounds, their production methods and uses

Abstract

The present invention provides a phosphorus-containing compound, a method for producing the same, and uses thereof. The phosphorus-containing compound of the present invention has the following structure: [Formula 1] JPEG2022553318000129.jpg18169The definition of each group is described in the specification. The phosphorus-containing compound of the present invention has excellent biodegradability and antioxidant properties, and is particularly suitable for promoting the biodegradation of lubricating oil products. Furthermore, the method for producing a phosphorus-containing compound of the present invention allows the phosphorus-containing compound to be produced simply, efficiently, and in high yield.

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to a phosphorus-containing compound, particularly a phosphorus-containing compound capable of promoting the biodegradation of lubricating oils, and a method for producing and using the same.

[0002] [Background technology] Lubricants are a necessary operating medium for the normal operation of machinery and equipment and for the manufacture and processing of materials, and the demand for lubricants is increasing with the rapid development of industry. During the storage, transportation, and use of lubricants, leaks, spills, and improper discharges can inevitably occur, resulting in environmental pollution. Although lubricants have low acute toxicity to living organisms, they have poor biodegradability when they flow into the environment, causing severe pollution of land, rivers, and lakes, and when they accumulate in the environment, they affect the balance of the ecosystem, so there is an urgent need for biodegradation accelerators that can increase the biodegradation rate of lubricants.

[0003] In recent years, the environmental impact of discarded or leaked lubricating oil has been widely noticed, and in order to solve this problem, on the one hand, lubricating oils have been produced using biodegradable vegetable oils or ester-based synthetic oils, for example, CN102408939B reports a biodegradable lubricating oil composition and its production method, and CN105132104A reports a biodegradable industrial gear oil composition, etc. On the other hand, development of lubricating oil biodegradation promoters has also been carried out, for example, CN103642557B reports a compound represented by the chemical formula C 20 H 37 Amide-type lubricant biodegradation accelerators of NO3 have been reported. However, the reality is that there are not many research reports on lubricant biodegradation accelerators.

[0004] [Contents of the invention] As a result of intensive research, the inventors have found that the phosphorus-containing compound having a specific structure as in the present invention can achieve a good effect of promoting the biodegradation of lubricating oil. Furthermore, the phosphorus-containing compound of the present invention has excellent antioxidant properties, and when combined with a lubricating oil, it can also suppress the oxidation of the lubricating oil.

[0005] In particular, the present invention provides the following aspects.

[0006] The present invention provides a phosphorus-containing compound represented by the following formula (I):

[0007] [ka]

[0008] In formula (I), n is an integer of 0 to 50 (preferably an integer of 0 to 20, more preferably an integer of 0 to 10, and even more preferably 0, 1, 2, 3, or 4), and n+1 R groups are the same or different and each independently represent a C1 to C 30 Hydrocarbylene group (preferably C1-C 10 alkylene group, more preferably a C1-C6 alkylene group, and even more preferably a C1-C4 alkylene group), R b The group is H or C1-C 30 Hydrocarbon group (preferably H or C1-C 10 a hydrocarbon group, more preferably H or a C1-C6 linear or branched alkyl group, and even more preferably H or a C1-C4 linear or branched alkyl group; Each R group is the same or different and independently represents H, C1 to C 30 Hydrocarbon groups and

[0009] [ka]

[0010] (Preferably, each independently is H, C1 to C 10 Linear or branched alkyl groups and

[0011] [ka]

[0012] More preferably, H, C1-C4 linear or branched alkyl groups and

[0013] [ka]

[0014] ), preferably at least one R group in formula (I) is

[0015] [ka]

[0016] and

[0017] [ka]

[0018] In the formula, x is an integer of 0 to 5 (preferably an integer of 0 to 4, more preferably 0, 1, 2 or 3), y is an integer of 1 to 5 (preferably an integer of 1 to 4, more preferably 1, 2 or 3), the sum of x+y is ≦ the number of hydrogen atoms that can be substituted on the Ar group, and x R groups are the same or different and each independently represents H, C1 to C 30 Hydrocarbon groups (preferably H, C1-C 10 more preferably H, a C1-C6 linear or branched alkyl group, and even more preferably H, a C1-C4 linear or branched alkyl group, each Ar group being the same or different from the others, and each independently being selected from C3-C 30 Cyclic group (preferably C6-C 15 aromatic ring group, more preferably a benzene ring, a naphthalene ring and an anthracene ring), and R2 is a single bond or a C1-C 10 an alkylene group (preferably a single bond or a C1-C6 alkylene group, more preferably a single bond or a C-C4 alkylene group); each A group is the same or different and each A group is independently

[0019] [ka]

[0020] , OH, optionally

[0021] [ka]

[0022] C1~C substituted with 30 Hydrocarbon groups (preferably optionally

[0023] [ka]

[0024] C1 to C substituted with 10 Linear or branched alkyl groups, more preferably optionally

[0025] [ka]

[0026] C1-C6 linear or branched alkyl group optionally substituted with

[0027] [ka]

[0028] C1-C4 linear or branched alkyl group substituted with

[0029] [ka]

[0030] C1 to C substituted with 30 Alkoxy groups (preferably optionally

[0031] [ka]

[0032] C1~C substituted with 10 A linear or branched alkoxy group, more preferably optionally

[0033] [ka]

[0034] C1-C6 linear or branched alkoxy group optionally substituted with

[0035] [ka]

[0036] and H, wherein in formula (I), at least one A group is selected from

[0037] [ka]

[0038] C1~C substituted with 30 Hydrocarbon groups (preferably

[0039] [ka]

[0040] C1~C substituted with 10 Linear or branched alkyl groups, more preferably

[0041] [ka]

[0042] C1-C6 linear or branched alkyl group substituted with

[0043] [ka]

[0044] C1-C4 linear or branched alkyl group substituted with

[0045] [ka]

[0046] C1~C substituted with 30 Alkoxy groups (preferably

[0047] [ka]

[0048] C1~C substituted with 10 Linear or branched alkoxy groups, more preferably

[0049] [ka]

[0050] C1-C6 linear or branched alkoxy group substituted with

[0051] [ka]

[0052] each X group is independently selected from O or S; a is 0 or 1; each R' is independently selected from C1 to C 30 Hydrocarbon group (preferably C1-C 10 linear or branched alkyl group, more preferably C1 to C6 linear or branched alkyl group, and even more preferably C1 to C4 linear or branched alkyl group), optionally C1 to C 10 C7-C substituted with linear or branched alkyl groups 15 Arylalkyl groups (preferably optionally C1-C 10C7-C substituted with linear or branched alkyl groups 12 Arylalkyl groups, more preferably C1-C 10 benzyl group substituted with a linear or branched alkyl group, optionally C1-C 10 C6-C substituted with linear or branched alkyl groups 15 Aryl groups (preferably optionally C1-C 10 C6-C substituted with linear or branched alkyl groups 10 Aryl groups, more preferably C1-C 10 a phenyl group substituted with a linear or branched alkyl group;

[0053] [ka]

[0054] R'' is selected from C1 to C 30 Hydrocarbon group (preferably C1-C 10 A linear or branched alkyl group, more preferably a C1 to C6 linear or branched alkyl group, and even more preferably a C1 to C4 linear or branched alkyl group), 30 Alkoxy group (preferably C1-C 10 linear or branched alkoxy groups, more preferably C1 to C6 linear or branched alkoxy groups, and further preferably C1 to C4 linear or branched alkyl groups), and each R group, R group, R b The group n is defined as above.

[0055] The present invention also provides a method for producing a phosphorus-containing compound, comprising the steps of:

[0056] Step (1): reacting a compound represented by formula (II) and / or an inorganic acid salt thereof with a compound represented by formula (III) to produce a product of step (1);

[0057] [ka]

[0058] In formula (II), n is an integer of 0 to 50 (preferably an integer of 0 to 20, more preferably an integer of 0 to 10, and even more preferably 0, 1, 2, 3, or 4), and n+1 R groups are the same or different and each independently represent a C1 to C 30 Hydrocarbylene group (preferably C1-C 10 alkylene group, more preferably a C1-C6 alkylene group, and even more preferably a C1-C4 alkylene group), R b The group is H or C1-C 30 Hydrocarbon group (preferably H or C1-C 10 a hydrocarbon group, more preferably H or a C1-C6 linear or branched alkyl group, and even more preferably H or a C1-C4 linear or branched alkyl group; Each R0′ group is the same or different and independently represents H and C1-C 30 Hydrocarbon groups (preferably each independently H and C1-C 10 linear or branched alkyl groups, more preferably H and C1-C4 linear or branched alkyl groups), preferably at least one R0' group is H; Each A' group is the same or different and independently represents XA'", C1-C 30 Hydrocarbon groups (preferably C1-C optionally substituted with XA''') 10 A linear or branched alkyl group, more preferably a C1 to C6 linear or branched alkyl group optionally substituted with XA''', and even more preferably a C1 to C4 alkyl group optionally substituted with XA''', 30 Alkoxy groups (preferably C1-C optionally substituted with XA''') 10 A'" groups are selected from F, Cl, Br, I, H, and each X group is independently selected from O or S, and at least one A' group is a C1-C alkoxy group substituted with XA'", a C1-C alkoxy group substituted with XA'", and H, and more preferably a C1-C alkoxy group substituted with XA'". 30 Hydrocarbon group (preferably C1-C substituted with XA''') 10A linear or branched alkyl group, more preferably a C1-C6 linear or branched alkyl group substituted with XA''', and even more preferably a C1-C4 alkyl group substituted with XA''', 30 Alkoxy group (preferably C1-C substituted with XA''') 10 linear or branched alkoxy group, more preferably a C1-C6 linear or branched alkoxy group substituted with XA''', and even more preferably a C1-C4 alkoxy group substituted with XA''', The inorganic acid salt of the compound represented by formula (II) is

[0059] [ka]

[0060] wherein M is an inorganic acid radical, j is the absolute value of the charge number of the inorganic acid radical, z is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 1 to 3), and each of the other groups is defined in the same manner as in formula (II) (the inorganic acid salt of the compound represented by formula (II) is preferably a hydrochloride, a nitrate, or a sulfate, and most preferably a hydrochloride); In formula (III), each X group is independently selected from O or S, a is 0 or 1, each R′′ is the same or different from the others, and each R′′ is independently selected from A′′, C1 to C 30 Hydrocarbon group (preferably C1-C 10 linear or branched alkyl group, more preferably C1 to C6 linear or branched alkyl group, and even more preferably C1 to C4 linear or branched alkyl group), optionally C1 to C 10 C7-C substituted with linear or branched alkyl groups 15 Arylalkyl groups (preferably optionally C1-C 10 C7-C substituted with linear or branched alkyl groups 12 Arylalkyl groups, more preferably C1-C 10 benzyl group substituted with a linear or branched alkyl group, optionally C1-C 10 C6-C substituted with linear or branched alkyl groups 15 Aryl groups (preferably optionally C1-C10 C6-C substituted with linear or branched alkyl groups 10 Aryl groups, more preferably C1-C 10 a phenyl group substituted with a linear or branched alkyl group; and, optionally, step (2): reacting the product of step (1) with a compound of formula (IV) to produce the product of step (2);

[0061] [ka]

[0062] In formula (IV), x is an integer of 0 to 5 (preferably an integer of 0 to 4, more preferably 0, 1, 2 or 3), y is an integer of 1 to 5 (preferably an integer of 1 to 4, more preferably 1, 2 or 3), the sum of x+y is ≦ the number of hydrogen atoms that can be substituted on the Ar group, and x R groups are the same or different and each independently represents H, C1 to C 30 Hydrocarbon groups (preferably H, C1-C 10 linear or branched alkyl group, more preferably H, C1-C6 linear or branched alkyl group, and even more preferably H, C1-C4 linear or branched alkyl group), and the Ar group is selected from C3-C 30 Cyclic group (preferably C6-C 15 aromatic ring group, more preferably a benzene ring, a naphthalene ring, or an anthracene ring), and R2 is a single bond or a C1-C 10 It is an alkylene group (preferably a single bond or a C1 to C6 alkylene group, more preferably a single bond or a C1 to C4 alkylene group), and X' is F, Cl, Br, I or OH (preferably Cl, Br).

[0063] The present invention provides use of the phosphorus-containing compound represented by the above formula (I) or the phosphorus-containing compound produced by the above method for producing a phosphorus-containing compound, as a biodegradation agent for lubricating oil.

[0064] The present invention provides a lubricating oil composition containing a lubricating base oil and at least one selected from the group consisting of a phosphorus-containing compound represented by the above formula (I), a phosphorus-containing compound produced by the above method for producing a phosphorus-containing compound, and a product produced by a partial dehydration condensation reaction or a complete dehydration condensation reaction of a phosphorus-containing compound.

[0065] [Effects of the Invention] The phosphorus-containing compound of the present invention has excellent biodegradability and antioxidant properties, and is particularly suitable for promoting the biodegradation of lubricating oil products. Furthermore, the phosphorus-containing compound of the present invention has excellent antioxidant properties, and when combined with a lubricating oil, it can suppress the oxidation of the lubricating oil.

[0066] In addition, the phosphorus-containing compound of the present invention can be produced in high yield by a simple and efficient production method. By the production method of the present invention, it is possible to produce a phosphorus-containing compound having excellent biodegradability and antioxidant properties.

[0067] [Mode for carrying out the invention] Hereinafter, specific embodiments of the present invention will be described in detail, but the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the appended claims.

[0068] All publications, patent applications, patents and other references mentioned herein are hereby incorporated by reference. All technical and scientific terms used herein have the meanings conventionally understood by those skilled in the art unless otherwise defined. In the event of a conflict, the definitions herein shall prevail.

[0069] When the present specification modifies a material, substance, method, process, step, apparatus, or component with "known to those skilled in the art," "prior art," or similar terms, the modified subject matter is intended to be that which is commonly used in the art at the time this application is filed, including, but not limited to, those which are no longer commonly used, but which may hereafter become recognized as suitable for a similar purpose.

[0070] In this specification, matters other than those explicitly described or matters not described are directly applicable to those well known in the art. Furthermore, any embodiment described in this specification can be freely combined with one or more other embodiments described in this specification, and the resulting form or form idea is considered to be part of the original disclosure or original description of the present invention, unless the combination is obviously unreasonable in the opinion of a person skilled in the art, and should not be considered to be new or undisclosed or unanticipated in this specification.

[0071] In the present invention, the term "single bond" may be used in the definition of a group. "Single bond" means that no group is present. For example, in the structural formula -CH2-A-CH3, where the A group is defined as being selected from a single bond and a methyl group, if the A group is a single bond, it means that the A group is not present, and therefore the above structural formula is simplified to -CH2-CH3.

[0072] In the present invention, when the number of groups is 0, it indicates that the group is not present, and the groups attached to both ends of the group are bonded. Alternatively, when the group is located at the terminal, when the number of groups is 0, it indicates that the other group to which the group is bonded is not replaced by the group. For example, in the structural formula -CH2-(A) n Assuming -CH3, if n is 0, the structural formula is -CH2-CH3. Structural formula -CH2-(A) n Assuming that n is 0, this indicates that -CH2- is not replaced with A, and the above structural formula is simplified to -CH3.

[0073] For purposes of the present invention, a hydrocarbon group refers to a group formed by removing one or more hydrogen atoms from a hydrocarbon (including, but not limited to, alkanes, alkenes, alkynes, aromatics, etc.). Hydrocarbon groups can be arbitrarily classified as monovalent, divalent, trivalent, or other high-value groups as needed, subject to an upper limit on the number of hydrogen atoms that the hydrocarbon can substitute. Examples include monovalent groups: CH3CH2-(ethyl), (CH3)2CH-(isopropyl), CH≡C-CH2-(2-propynyl); divalent groups: CH3CH=(ethylidene), -CH=CH-(1,2-vinylidene); trivalent groups: CH3C≡, etc.

[0074] More specifically, in the present invention, C1 to C 30 The hydrocarbon group is a group obtained by removing one hydrogen atom or, if desired, two or more hydrogen atoms from any carbon atom of a hydrocarbon having 1 to 30 carbon atoms (including, but not limited to, alkanes, alkenes, alkynes, aromatic hydrocarbons, etc.), and is, for example, a monovalent or more linear or branched C1-C 30 Alkyl group, linear or branched C2-C with 1 or more valences 30 Alkenyl group, linear or branched C2-C6 with 1 or more valences 30 Alkynyl group, 1 or more C6-C 30 An example of such an alkyl group is an aryl group.

[0075] Linear or branched C1-C 30 The alkyl group is a straight or branched C1-C 20 Alkyl group, linear or branched C1-C 10 The alkyl group includes a linear or branched C1-C6 alkyl group, and a linear or branched C1-C4 alkyl group. Specific examples of these alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cetyl, octadecyl, eicosyl, docosyl, and isomers of these groups. The alkylene group includes a group obtained by further removing one hydrogen atom from the above alkyl groups.

[0076] Linear or branched C2-C30 The alkenyl group is a straight or branched C2-C 20 Alkenyl group, linear or branched C2-C 10 Alkenyl groups include linear or branched C2-C6 alkenyl groups and linear or branched C2-C4 alkenyl groups. Alkenyl groups containing one, two, three or four carbon-carbon double bonds are preferred. Specific examples of these alkenyl groups include, but are not limited to, vinyl, propenyl, butenyl, 2-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl and isomers thereof. For example, the alkenyl groups may be groups obtained by adding one or two carbon-carbon double bonds to the specific examples of the alkyl groups listed above.

[0077] Linear or branched C2-C 30 The alkynyl group is a straight or branched C2-C 20 Alkynyl group, linear or branched C2-C 10 Alkynyl groups include linear or branched C2-C6 alkynyl groups and linear or branched C2-C4 alkynyl groups. Alkynyl groups containing one, two, three or four carbon-carbon triple bonds are preferred. Specific examples of these alkynyl groups include, but are not limited to, ethynyl groups, propargyl groups, butynyl groups and isomers thereof. For example, groups obtained by adding one or two carbon-carbon triple bonds to the specific examples of the above alkyl groups are included.

[0078] In the present invention, C6 to C 30 The aromatic hydrocarbon group (aryl group) is a group formed by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 30 carbon atoms without violating the chemical valence. 30 The aryl group includes a group in which all carbon atoms are ring-forming carbon atoms of an aromatic ring, an alkyl group, a cycloalkyl group as a substituent, and a group that bonds an aryl group to an aromatic ring, and may have an aromatic ring in its structure and a total of 6 to 30 carbon atoms. 30 The aryl group is C6-C 30 Aryl groups, C6-C 20 Aryl groups, C6-C 15 Aryl groups, C6-C10 Aryl groups may be included, specific examples of which include, but are not limited to, phenyl, naphthyl, tolyl, dimethylphenyl, ethylphenyl, methylnaphthyl, 2-methylnaphthyl, 2-ethylnaphthyl, cyclohexylphenyl, biphenyl, and the like.

[0079] In the present invention, C7 to C 15 An arylalkyl group is a group formed by removing one hydrogen atom from the alkyl portion of an arylalkane having 7 to 15 carbon atoms without violating the chemical valence. In addition to the alkyl portion, other alkyl groups, cycloalkyl groups, and aryl groups can be bonded to the aromatic ring as substituents, as long as the total number of carbon atoms is 7 to 15. C7 to C 15 Aryl alkyl groups are C7-C 12 Arylalkyl groups, C7-C 10 Specific examples of the arylalkyl group include, but are not limited to, benzyl (phenylmethyl), phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, and the like.

[0080] C1~C 30 The hydrocarbylene group may be any of the above C1 to C6 groups without violating the chemical valence. 30 A group obtained by removing one hydrogen atom from any carbon atom of a hydrocarbon group. C1-C 30 Examples of the hydrocarbylene group include the above C1 to C 30 Examples of the hydrocarbon group include groups obtained by removing one hydrogen atom from a carbon atom of the groups listed as the hydrocarbon group. 30 When the hydrocarbon group carries other substituents, the hydrocarbon group may be a divalent, trivalent or higher valent hydrocarbon group.

[0081] In the present invention, C3 to C 30The cyclic group refers to a group having 3 to 30 atoms selected from C, N, O, and S as ring-forming atoms, and may be saturated or unsaturated (having at least one carbon-carbon double bond and / or at least one carbon-carbon triple bond), and may be non-directional or aromatic. 30 The cyclic group is preferably C3 to C 25 Cycloalkyl groups, C3-C 20 Cycloalkyl groups, C3-C 10 Cycloalkyl groups, C3-C6 cycloalkyl groups, C5-C6 cycloalkyl groups, C6-C 20 Aromatic ring group, C6~C 15 Aromatic ring group, C6~C 10 Specific examples of aromatic ring groups include a group derived from cyclopropane, a group derived from cyclobutane, a group derived from cyclopentene, a group derived from cyclohexane, a group derived from benzene, a group derived from naphthalene, a group derived from anthracene, and a group derived from phenanthrene.

[0082] In the present invention, C1 to C 30 The alkoxy group is the above-mentioned linear or branched C1-C 30 A group formed by bonding an alkyl group to an oxygen atom, i.e., a linear or branched C1-C 30 Alkyl-O- group. Linear or branched C1-C 20 Alkoxy, linear or branched C1-C 10 Alkoxy, straight or branched C1 to C6 alkoxy, straight or branched C1 to C4 alkoxy and the like are included.

[0083] The present invention provides a phosphorus-containing compound represented by the following formula (I):

[0084] [ka]

[0085] In formula (I), n is an integer of 0 to 50 (preferably an integer of 0 to 20, more preferably an integer of 0 to 10, and even more preferably 0, 1, 2, 3, or 4), and n+1 R groups are the same or different and each independently represent a C1 to C 30 Hydrocarbylene group (preferably C1-C 10 alkylene group, more preferably a C1-C6 alkylene group, and even more preferably a C1-C4 alkylene group), R b The group is H or C1-C 30 Hydrocarbon group (preferably H or C1-C 10 a hydrocarbon group, more preferably H or a C1-C6 linear or branched alkyl group, and even more preferably H or a C1-C4 linear or branched alkyl group; Each R group is the same or different and independently represents H, C1 to C 30 Hydrocarbon groups and

[0086] [ka]

[0087] (Preferably, each independently is H, C1 to C 10 Linear or branched alkyl groups and

[0088] [ka]

[0089] More preferably, H, C1-C4 linear or branched alkyl groups and

[0090] [ka]

[0091] ), preferably at least one R group in formula (I) is

[0092] [ka]

[0093] and

[0094] [ka]

[0095] In the formula, x is an integer of 0 to 5 (preferably an integer of 0 to 4, more preferably 0, 1, 2 or 3), y is an integer of 1 to 5 (preferably an integer of 1 to 4, more preferably 1, 2 or 3), the sum of x+y is ≦ the number of hydrogen atoms that can be substituted on the Ar group, and x R groups are the same or different and each independently represents H, C1 to C 30 Hydrocarbon groups (preferably H, C1-C 10 more preferably H, a C1-C6 linear or branched alkyl group, and even more preferably H, a C1-C4 linear or branched alkyl group, each Ar group being the same or different from the others, and each independently being selected from C3-C 30 Cyclic group (preferably C6-C 15 aromatic ring group, more preferably a benzene ring, a naphthalene ring and an anthracene ring), and R2 is a single bond or a C1-C 10 an alkylene group (preferably a single bond or a C1-C6 alkylene group, more preferably a single bond or a C-C4 alkylene group); each A group is the same or different and each A group is independently

[0096] [ka]

[0097] , OH, optionally

[0098] [ka]

[0099] C1~C substituted with 30 Hydrocarbon groups (preferably optionally

[0100] [ka]

[0101] C1~C substituted with 10 Linear or branched alkyl groups, more preferably optionally

[0102] [ka]

[0103] C1-C6 linear or branched alkyl group optionally substituted with

[0104] [ka]

[0105] C1-C4 linear or branched alkyl group substituted with

[0106] [ka]

[0107] C1~C substituted with 30 Alkoxy groups (preferably optionally

[0108] [ka]

[0109] C1~C substituted with 10 A linear or branched alkoxy group, more preferably optionally

[0110] [ka]

[0111] C1-C6 linear or branched alkoxy group optionally substituted with

[0112] [ka]

[0113] and H, wherein in formula (I), at least one A group is selected from

[0114] [ka]

[0115] C1~C substituted with 30 Hydrocarbon groups (preferably

[0116] [ka]

[0117] C1~C substituted with 10 Linear or branched alkyl groups, more preferably

[0118] [ka]

[0119] C1-C6 linear or branched alkyl group substituted with

[0120] [ka]

[0121] C1-C4 linear or branched alkyl group substituted with

[0122] [ka]

[0123] C1~C substituted with 30Alkoxy groups (preferably

[0124] [ka]

[0125] C1~C substituted with 10 Linear or branched alkoxy groups, more preferably

[0126] [ka]

[0127] C1-C6 linear or branched alkoxy group substituted with

[0128] [ka]

[0129] each X group is independently selected from O or S; a is 0 or 1; each R' is independently selected from C1 to C 30 Hydrocarbon group (preferably C1-C 10 linear or branched alkyl group, more preferably C1 to C6 linear or branched alkyl group, and even more preferably C1 to C4 linear or branched alkyl group), optionally C1 to C 10 C7-C substituted with linear or branched alkyl groups 15 Arylalkyl groups (preferably optionally C1-C 10 C7-C substituted with linear or branched alkyl groups 12 Arylalkyl groups, more preferably C1-C 10 benzyl group substituted with a linear or branched alkyl group, optionally C1-C 10 C6-C substituted with linear or branched alkyl groups 15 Aryl groups (preferably optionally C1-C 10 C6-C substituted with linear or branched alkyl groups 10 Aryl groups, more preferably C1-C 10a phenyl group substituted with a linear or branched alkyl group;

[0130] [ka]

[0131] R'' is selected from C1 to C 30 Hydrocarbon group (preferably C1-C 10 A linear or branched alkyl group, more preferably a C1 to C6 linear or branched alkyl group, and even more preferably a C1 to C4 linear or branched alkyl group), 30 Alkoxy group (preferably C1-C 10 linear or branched alkoxy groups, more preferably C1 to C6 linear or branched alkoxy groups, and further preferably C1 to C4 linear or branched alkyl groups), and each R group, R group, R b The group n is defined as above.

[0132] Furthermore, NH and COOH are present in the compound represented by formula (I) of the present invention, and therefore the present invention provides a product produced by a partial dehydration condensation reaction or a complete dehydration condensation reaction between NH and COOH present in the compound represented by formula (I).

[0133] Therefore, the compound represented by formula (I) of the present invention includes a pure compound represented by formula (I), a mixture of two or more compounds represented by formula (I) having different structures, and a product produced by a dehydration condensation reaction of two or more compounds represented by formula (I) having the same or different structures. Thus, the compound of the present invention (compound represented by formula (I)) exhibits the form of a mixture.

[0134] In the compounds of formula (I), preferably at least one R group is

[0135] [ka]

[0136] It represents a group represented by the following formula:

[0137] In the compound represented by formula (I),

[0138] [ka]

[0139] In the formula (I), 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 R2 group, and the two R1 are preferably located at the two ortho-positions of the OH, respectively.

[0140] In the compound represented by formula (I), preferably, each R1 is independently selected from a C1 to C4 linear or branched alkyl group, preferably a C3 to C4 branched alkyl group, more preferably a tert-butyl group.

[0141] In compounds of formula (I), preferably each A group is independently

[0142] [ka]

[0143] , OH, optionally

[0144] [ka]

[0145] C1~C substituted with 10 A linear or branched alkyl group, optionally

[0146] [ka]

[0147] C1~C substituted with 10At least one A group is selected from linear or branched alkoxy groups and H.

[0148] [ka]

[0149] C1~C substituted with 10 Linear or branched alkyl groups,

[0150] [ka]

[0151] C1~C substituted with 10 A is selected from linear or branched alkoxy groups (preferably each A group is independently

[0152] [ka]

[0153] , OH, optionally

[0154] [ka]

[0155] C1-C6 linear or branched alkyl group optionally substituted with

[0156] [ka]

[0157] and H, wherein at least one A group is selected from a C1-C6 linear or branched alkoxy group substituted with

[0158] [ka]

[0159] C1-C6 linear or branched alkyl group substituted with

[0160] [ka]

[0161] More preferably, each A group is independently selected from a C1 to C6 straight or branched alkoxy group substituted with

[0162] [ka]

[0163] , OH, optionally

[0164] [ka]

[0165] C1-C4 linear or branched alkyl group optionally substituted with

[0166] [ka]

[0167] and H, wherein at least one A group is selected from C1-C4 linear or branched alkoxy groups substituted with

[0168] [ka]

[0169] C1-C4 linear or branched alkyl group substituted with

[0170] [ka]

[0171] substituted with C1 to C4 linear or branched alkoxy groups).

[0172] In the compound represented by formula (I), preferably, the A group is an alkyl group or an alkoxy group.

[0173] [ka]

[0174] If replaced with

[0175] [ka]

[0176] is located at the terminal of the alkyl group or alkoxy group.

[0177] In the compounds of formula (I), preferably at least one A group is

[0178] [ka]

[0179] and p is an integer from 1 to 4.

[0180] In the compound of formula (I), preferably, R' is each independently a C1 to C6 linear or branched alkyl group, optionally a C1 to C 10 Benzyl group substituted with a linear or branched alkyl group, optionally C1-C 10 It may be selected from phenyl groups substituted with straight or branched alkyl groups.

[0181] In the present invention, the phosphorus-containing compound may be one or more of the compounds shown below.

[0182] [ka]

[0183] The present invention also provides a method for producing a phosphorus-containing compound, comprising the steps of:

[0184] Step (1): reacting a compound represented by formula (II) and / or an inorganic acid salt thereof with a compound represented by formula (III) to produce a product of step (1);

[0185] [ka]

[0186] In formula (II), n is an integer of 0 to 50 (preferably an integer of 0 to 20, more preferably an integer of 0 to 10, and even more preferably 0, 1, 2, 3, or 4), and n+1 R groups are the same or different and each independently represent a C1 to C 30 Hydrocarbylene group (preferably C1-C 10 alkylene group, more preferably a C1-C6 alkylene group, and even more preferably a C1-C4 alkylene group), R b The group is H or C1-C 30 Hydrocarbon group (preferably H or C1-C 10 a hydrocarbon group, more preferably H or a C1-C6 linear or branched alkyl group, and even more preferably H or a C1-C4 linear or branched alkyl group; Each R0′ group is the same or different and independently represents H and C1-C 30 Hydrocarbon groups (preferably each independently H and C1-C 10 linear or branched alkyl groups, more preferably H and C1-C4 linear or branched alkyl groups), preferably at least one R0' group is H; Each A' group is the same or different and independently represents XA'", C1-C 30 Hydrocarbon groups (preferably C1-C optionally substituted with XA''') 10 A linear or branched alkyl group, more preferably a C1 to C6 linear or branched alkyl group optionally substituted with XA''', and even more preferably a C1 to C4 alkyl group optionally substituted with XA''',30 Alkoxy groups (preferably C1-C optionally substituted with XA''') 10 A'" groups are selected from F, Cl, Br, I, H, and each X group is independently selected from O or S, and at least one A' group is a C1-C alkoxy group substituted with XA'", a C1-C alkoxy group substituted with XA'", and H, and more preferably a C1-C alkoxy group substituted with XA'". 30 Hydrocarbon group (preferably C1-C substituted with XA''') 10 A linear or branched alkyl group, more preferably a C1-C6 linear or branched alkyl group substituted with XA''', and even more preferably a C1-C4 alkyl group substituted with XA''', 30 Alkoxy group (preferably C1-C substituted with XA''') 10 linear or branched alkoxy group, more preferably a C1-C6 linear or branched alkoxy group substituted with XA''', and even more preferably a C1-C4 alkoxy group substituted with XA''', The inorganic acid salt of the compound represented by formula (II) is

[0187] [ka]

[0188] wherein M is an inorganic acid radical, j is the absolute value of the charge number of the inorganic acid radical, z is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 1 to 3), and each of the other groups is defined in the same manner as in formula (II) (the inorganic acid salt of the compound represented by formula (II) is preferably a hydrochloride, a nitrate, or a sulfate, and most preferably a hydrochloride); In formula (III), each X group is independently selected from O or S, a is 0 or 1, each R′′ is the same or different from the others, and each R′′ is independently selected from A′′, C1 to C 30 Hydrocarbon group (preferably C1-C 10linear or branched alkyl group, more preferably C1 to C6 linear or branched alkyl group, and even more preferably C1 to C4 linear or branched alkyl group), optionally C1 to C 10 C7-C substituted with linear or branched alkyl groups 15 Arylalkyl groups (preferably optionally C1-C 10 C7-C substituted with linear or branched alkyl groups 12 Arylalkyl groups, more preferably C1-C 10 benzyl group substituted with a linear or branched alkyl group, optionally C1-C 10 C6-C substituted with linear or branched alkyl groups 15 Aryl groups (preferably optionally C1-C 10 C6-C substituted with linear or branched alkyl groups 10 Aryl groups, more preferably C1-C 10 a phenyl group substituted with a linear or branched alkyl group; and, optionally, step (2): reacting the product of step (1) with a compound of formula (IV) to produce the product of step (2);

[0189] [ka]

[0190] In formula (IV), x is an integer of 0 to 5 (preferably an integer of 0 to 4, more preferably 0, 1, 2 or 3), y is an integer of 1 to 5 (preferably an integer of 1 to 4, more preferably 1, 2 or 3), the sum of x+y is ≦ the number of hydrogen atoms that can be substituted on the Ar group, and x R groups are the same or different and each independently represents H, C1 to C 30 Hydrocarbon groups (preferably H, C1-C 10 linear or branched alkyl group, more preferably H, C1-C6 linear or branched alkyl group, and even more preferably H, C1-C4 linear or branched alkyl group), and the Ar group is selected from C3-C 30 Cyclic group (preferably C6-C 15 aromatic ring group, more preferably a benzene ring, a naphthalene ring, or an anthracene ring), and R2 is a single bond or a C1-C 10It is an alkylene group (preferably a single bond or a C1 to C6 alkylene group, more preferably a single bond or a C1 to C4 alkylene group), and X' is F, Cl, Br, I or OH (preferably Cl, Br).

[0191] According to the production method of the present invention, the inorganic acid salt of the compound represented by the formula (II) can be produced by reacting the compound represented by the formula (II) with an inorganic acid.

[0192] According to the production method of the present invention, the compound represented by the formula (II) and / or its inorganic acid salt is at least one selected from an amino acid, an amino acid condensate (polypeptide formed by partial or complete condensation), an amino acid inorganic salt, and an amino acid condensate (polypeptide formed by partial or complete condensation). The compound represented by the formula (II) and / or its inorganic acid salt can be at least one selected from 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 glycine ester hydrochloride, L-phenylalanine and / or L-phenylalanine ester hydrochloride, and L-valine and / or L-valine ester hydrochloride.

[0193] According to the production method of the present invention, the compound represented by formula (III) can be selected from phosphorous acid, phosphite, thiophosphorous acid, and thiophosphite, and specific examples thereof include one or more of phosphorous acid, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, diisopropyl phosphite, di-n-butyl phosphite, diisobutyl phosphite, di-tert-butyl phosphite, di(2-ethylhexyl) phosphite, dibenzyl phosphite, diphenyl phosphite, thiophosphorous acid, dimethyl thiophosphite, diethyl thiophosphite, dipropyl thiophosphite, diisopropyl thiophosphite, di-n-butyl thiophosphite, diisobutyl thiophosphite, di-tert-butyl thiophosphite, di(2-ethylhexyl) thiophosphite, dibenzyl thiophosphite, and diphenyl thiophosphite.

[0194] In the production method according to the present invention, in step (1), the reaction molar equivalent ratio of the compound represented by formula (II) and / or its inorganic acid salt (in terms of XA″) to the compound represented by formula (III) (in terms of PH) 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. In order to increase the reaction efficiency, the reaction time is generally as long as possible, preferably 0.5 to 30 hours, more preferably 1 to 8 hours.

[0195] In the production method according to the present invention, in step (1), 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). The solvent is preferably at least one selected from protic solvents, hydrocarbon solvents, and furan solvents, such as at least one selected from hexane, benzene, toluene, tetrahydrofuran, methylene chloride, methanol, ethanol, isopropanol, and water, and more preferably at least one protic solvent, such as at least one of methanol, ethanol, isopropanol, and water. The amount of the solvent added is not particularly limited as long as it is added so that the reaction proceeds smoothly.

[0196] In the production method according to the present invention, in step (1), a catalyst 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). The catalyst may be a phase transfer catalyst. The phase transfer catalyst is one or more selected from quaternary ammonium salts and / or crown ethers, preferably tetrahydrocarbonylammonium halides, such as tetrabutylammonium bromide, trioctylammonium chloride, cetyltrimethylammonium bromide, triethylbenzylammonium chloride, and 18-crown-6, and more preferably tetrabutylammonium bromide. The catalyst is preferably added in an amount of 0.1% by mass to 10% by mass with respect to the compound represented by formula (II) and / or its inorganic acid salt.

[0197] In the production method according to the present invention, in step (1), it is preferable to add a chloride when the compound represented by formula (II) and / or its inorganic acid salt is reacted with the compound represented by formula (III). The chloride is preferably a hypochlorite and / or a chloroalkane, and the hypochlorite is more 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 chlorinated alkane is preferably chloromethane, and for example, one or more of carbon monochloride, carbon dichloride, carbon trichloride, and carbon tetrachloride can be used. The chloride is preferably an aqueous solution of hypochlorite, and the concentration of the aqueous solution is preferably 5% to 80%, more preferably an aqueous solution of sodium hypochlorite. The chloride is preferably added in an amount of 30 to 100 mL / 100 mmol to the compound represented by formula (II) and / or its inorganic acid salt.

[0198] In the step (1) of the production method according to the present invention, the reaction between the compound represented by formula (II) and / or its inorganic acid salt and the compound represented by formula (III) is preferably carried out at a pH of 8 to 10 (preferably 8.5 to 9.5). The pH can be adjusted by adding an alkaline substance, and the alkaline substance is preferably an alkaline solution, and the alkaline solution is preferably an aqueous solution of one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide.

[0199] In the production method according to the present invention, in step (1), the compound represented by formula (II) and / or its inorganic acid salt is reacted with the compound represented by formula (III), and the reaction product may then be subjected to any extraction treatment, any drying treatment, and any ultrasonic treatment, preferably ultrasonic treatment.

[0200] When the reaction product of step (1) is extracted, the reaction product is preferably extracted with a solvent, more preferably under an acidic environment. The solvent is preferably one or more selected from ether solvents, ester solvents, chloroalkane solvents, and hydrocarbon solvents, and examples thereof include one or more selected from petroleum ether, ethyl ether, ethyl acetate, methylene chloride, chloroform, and toluene. The extraction treatment is preferably performed 1 to 3 times. The acidic environment is obtained by adjusting the pH of the system in which the reaction product exists by adding an acid solution, and the pH is preferably 2 to 5, more preferably 2.5 to 3.5, and the acid solution is preferably an aqueous solution of one or more of hydrochloric acid, acetic acid, nitric acid, and sulfuric acid, and the concentration of the acid solution is preferably 1 to 10 mol / L. Preferably, an inorganic salt is added when the extraction treatment is performed in order to improve the extraction efficiency. The inorganic salt is preferably one or more selected from sodium chloride, potassium chloride, sodium sulfate, and potassium sulfate.

[0201] If the reaction product of step (1) is dried, it is preferably dried by adding a drying agent, which may be anhydrous magnesium chloride and / or anhydrous sodium sulfate.

[0202] When the reaction product of step (1) is subjected to ultrasonic treatment, it is preferably treated in the presence of a solvent. The solvent is, for example, one or more selected from furan solvents, chloroalkane solvents, ketone solvents, ester solvents, and nitrile solvents, more preferably one or more selected from tetrahydrofuran, methylene chloride, chloroform, acetone, ethyl acetate, and acetonitrile. It is more preferably one or more selected from tetrahydrofuran, dichloromethane, and acetonitrile. The time of the ultrasonic treatment is preferably 1 to 10 hours, more preferably 2 to 8 hours.

[0203] In the production method according to the present invention, after reacting the compound represented by formula (II) and / or its inorganic acid salt with the compound represented by formula (III) in step (1), the reaction product of step (1) is preferably subjected to a purification step, which includes one or a combination of drying, evaporating, washing, distilling, recrystallizing and centrifugation methods known in the prior art.

[0204] In the optional step (2) of the production method of the present invention, the compound represented by the formula (IV) can be produced by a method known in the prior art, and is not particularly limited.

[0205] Preferably, in the compound represented by formula (IV),

[0206] [ka]

[0207] 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 R2 group, the two R1 are respectively located at the two ortho-positions of OH, and X' is preferably Cl or Br.

[0208] Preferably, in the compound represented by formula (IV), R1 is independently selected from C1 to C4 linear or branched alkyl groups, preferably C3 to C4 branched alkyl groups, more preferably a tert-butyl group.

[0209] In the compound of formula (III), preferably, R''' is each independently a C1 to C6 linear or branched alkyl group, optionally a C1 to C 10 Benzyl group substituted with a linear or branched alkyl group, optionally C1-C 10 A phenyl group substituted with a straight-chain or branched alkyl group is selected from the group consisting of phenyl groups substituted with straight-chain or branched alkyl groups.

[0210] In the compound represented by formula (II), preferably, when the A' group is an alkyl group or an alkoxy group substituted with a XA''' group, the XA''' group is located at the terminal of the alkyl or alkoxy group.

[0211] In compounds of formula (II), preferably at least one A' group is

[0212] [ka]

[0213] and p is an integer from 1 to 4.

[0214] Compounds of formula (IV) may be synthesised using methods known in the art or may be commercially available.

[0215] Specific examples of the compound represented by formula (IV) include one or more selected from 3,5-bis(tert-butyl)-4-hydroxyphenylacetyl chloride, 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride, p-hydroxyphenylacetyl chloride, 3-hydroxyphenylacetyl chloride, 2-hydroxyphenylacetyl chloride, 3,4-dihydroxyphenylacetyl chloride, 3,5-dihydroxyphenylacetyl chloride, 3-methyl-4-hydroxyphenylacetyl chloride, 3,5-dimethyl-4-hydroxyphenylacetyl chloride, 2,4-dihydroxyphenylpropionyl chloride, 3,4-dihydroxyphenylpropionyl chloride, and 2-hydroxy-naphthylacetyl chloride.

[0216] In the production method of the present invention, in the optional step (2), the reaction molar equivalent ratio of the compound represented by the formula (IV) (as calculated as X') to the reaction product of step (1) (as calculated as NH) is preferably 5:1 to 1:5, more preferably 1:2 to 2:1, and the reaction temperature is preferably -40 to 60°C, more preferably -20 to 20°C. In order to improve the reaction efficiency, the reaction time is preferably 1 to 20 hours, more preferably 3 to 8 hours.

[0217] In the production method of the present invention, in the optional step (2), a solvent may or may not be added to the reaction between the compound represented by formula (IV) (as calculated as X') and the reaction product of step (1) (as calculated as NH), and preferably a solvent is added. The solvent is preferably at least one selected from proton-based solvents, ether-based solvents, ester-based solvents, chloroalkane-based solvents, furan-based solvents, ketone-based solvents, and hydrocarbon-based solvents, such as at least one selected from water, methanol, ethanol, isopropanol, methylene chloride, chloroform, ethyl ether, tetrahydrofuran, ethyl acetate, acetone, and toluene, and more preferably at least one selected from water, ethanol, ethyl ether, tetrahydrofuran, and acetone. The amount of the solvent added is not particularly limited as long as it is added so that the reaction proceeds smoothly.

[0218] In the optional step (2) of the production method of the present invention, after the reaction of the compound represented by formula (IV) (in terms of X') with the reaction product of step (1) (in terms of NH), the reaction product of step (2) can be subjected to a washing treatment in order to improve the purity of the reaction product. Preferably, the reaction product of step (2) is washed with an acid solution. The acid solution is preferably an aqueous solution of one or more selected from hydrochloric acid, sulfuric acid, and nitric acid, and the concentration of the acid solution is preferably 1 to 12 mol / l. In the optional step (2) of the production method of the present invention, after the reaction of the compound represented by formula (IV) (in terms of X') with the reaction product of step (1) (in terms of NH), the reaction product of step (2) can be subjected to a purification treatment. The purification step can include one or a combination of a washing method, a distillation method, a recrystallization method, and a centrifugation method known in the prior art.

[0219] The phosphorus-containing compounds of the present invention can be used as biodegradants for lubricating oils.

[0220] The phosphorus-containing compound produced by the method for producing a phosphorus-containing compound of the present invention can be used as a biodegradation agent for lubricating oil.

[0221] The present invention provides a composition of phosphorus-containing compounds comprising one or a mixture of two or more selected from the phosphorus-containing compounds of the present invention, the phosphorus-containing compounds produced by the production method of the present invention, and products produced by a partial dehydration condensation reaction or a complete dehydration condensation reaction of the phosphorus-containing compounds.

[0222] The present invention provides a lubricating oil composition comprising at least one selected from the phosphorus-containing compound of the present invention, the phosphorus-containing compound produced by the production method of the present invention, and the composition of the phosphorus-containing compound of the present invention, and a lubricating oil base oil.

[0223] In the lubricating oil composition of the present invention, the phosphorus-containing compound or the product produced by the partial dehydration condensation reaction or the complete dehydration condensation reaction of the phosphorus-containing compound is contained in an amount of 0.001 to 30%, preferably 0.01 to 20%, and more preferably 0.1 to 10%, based on the total mass of the lubricating oil composition.

[0224] The phosphorus-containing compound of the present invention has excellent biodegradability and antioxidation properties, and is particularly suitable for promoting the biodegradation of lubricating oil products. The method for producing a phosphorus-containing compound of the present invention makes it possible to produce the phosphorus-containing compound simply, efficiently, and in high yield.

[0225] [Example] The present invention will be described below with reference to specific examples, but the present invention is not limited to these.

[0226] The experimental methods described in the following examples are conventional unless otherwise limited, and reagents and materials are commercially available unless otherwise limited.

[0227] The meanings of the abbreviations used in the examples are shown below.

[0228] Me: Methyl iPr: Isopropyl Bn: Benzyl Example 1 Synthesis of O-dimethyloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (1) L-serine (formula II-a) (100 mmol, 10.5 g) and 40 mL of water were added to the reactor in sequence, cooled to 0 ° C., adjusted to pH = 9.0 with sodium hydroxide, added dimethyl phosphite (formula III-a) (130 mmol, 14.3 g) and tetrabutylammonium bromide (1 mmol, 0.32 g), and added dropwise with stirring 50 mL of 12% sodium hypochlorite solution. After 4 hours, the reaction product was extracted twice with ether, the aqueous layer was adjusted to pH = 3 with hydrochloric acid, 8 g of sodium chloride was added, the organic phase was extracted twice with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium chloride, and the solvent was removed by distillation under reduced pressure to obtain a colorless oil. The colorless oil was dissolved in 60 mL of acetonitrile, sonicated at room temperature for 5 hours, and then filtered to obtain a white solid.

[0229] (2) A mixture of the above white solid (47.6 mmol, 10.2 g), 40 mL acetone, 20 mL water, and sodium hydroxide (95.2 mmol, 10 g) was cooled to 0°C, and 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride (47.6 mmol, 14.1 g) was added. After 5 hours, the mixture was acidified to pH 2 using 6 mol / l aqueous hydrochloric acid, and a large amount of white solid appeared. The solid was filtered, and the resulting cake was washed with water and petroleum ether to obtain the reaction product of step (2). Its structure and reaction scheme are shown below, and the reaction product of step (2) is shown by formula Ia in the reaction scheme.

[0230] [ka]

[0231] 3,5-Bis(tert-butyl)-4-hydroxyphenylpropionic acid (81 mmol, 22.5 g) was dissolved in 150 mL of chloroform, dichlorosulfoxide (124 mmol, 14.8 g) was added, and the mixture was refluxed for 4 hours. The solvent and excess dichlorosulfoxide were removed by rotary evaporation to obtain a pale yellow solid (i.e., 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride used in step (2)).

[0232] Identification of the reaction product of step (2): 1 H NMR(400MHz,CDCl3)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 22 H 35 NO8P - (MH):472.2106,found:472.2109. As a result of identification, the reaction product was found to be O-dimethyloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (formula Ia).

[0233] Example 2 Synthesis of O-diisopropyloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (1) L-serine (formula II-a) (100 mmol, 10.5 g) and 40 mL of water were added to a reactor, cooled to 0°C, adjusted to pH=9.0 with sodium hydroxide, diisopropyl phosphite (formula III-b) (130 mmol, 21.7 g) and tetrabutylammonium bromide (1 mmol, 0.32 g) were added, and 50 mL of 12% sodium hypochlorite solution was added dropwise with stirring. After 4 hours, the reaction product was extracted twice with ether, the aqueous layer was adjusted to pH=3 with hydrochloric acid, 8 g of sodium chloride was added, the organic phase was extracted twice with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium chloride, and the solvent was removed by distillation under reduced pressure to obtain a colorless oil. The colorless oil was dissolved in 60 mL of acetonitrile, sonicated at room temperature for 5 hours, and then filtered to obtain a white solid.

[0234] (2) A mixture of the above white solid (47.6 mmol, 12.8 g), 40 mL acetone, 20 mL water, and sodium hydroxide (95.2 mmol, 10 g) was cooled to 0°C, and 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride (47.6 mmol, 14.1 g) was added. After 5 hours, the mixture was acidified to pH 2 using 6 mol / l aqueous hydrochloric acid, and a large amount of white solid appeared. The solid was filtered, and the resulting cake was washed with water and petroleum ether to obtain the reaction product of step (2). Its structure and reaction scheme are shown below, and the reaction product of step (2) is shown by formula Ib in the reaction scheme.

[0235] [ka]

[0236] 3,5-Bis(tert-butyl)-4-hydroxyphenylpropionic acid (81 mmol, 22.5 g) was dissolved in 150 mL of chloroform, dichlorosulfoxide (124 mmol, 14.8 g) was added, and the mixture was refluxed for 4 hours. The solvent and excess dichlorosulfoxide were removed by rotary evaporation to obtain a pale yellow solid (i.e., 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride used in step (2)).

[0237] Identification of the reaction product of step (2): 1 H NMR(400MHz,CDCl3)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 26 H 43 NO8P - (MH):528.2732,found:528.2737. As a result of identification, the reaction product was found to be O-diisopropyloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (formula Ib).

[0238] Example 3 Synthesis of O-diphenylmethoxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (1) L-serine (formula II-a) (100 mmol, 10.5 g) and 40 mL of water were added to a reactor, cooled to 0°C, adjusted to pH=9.0 with sodium hydroxide, dibenzyl phosphite (formula III-c) (130 mmol, 34.0 g) and tetrabutylammonium bromide (1 mmol, 0.32 g) were added, and 50 mL of 12% sodium hypochlorite solution was added dropwise with stirring. After 4 hours, the reaction product was extracted twice with ether, the aqueous layer was adjusted to pH=3 with hydrochloric acid, 8 g of sodium chloride was added, the organic phase was extracted twice with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium chloride, and the solvent was removed by distillation under reduced pressure to obtain a colorless oil. The colorless oil was dissolved in 60 mL of acetonitrile, sonicated at room temperature for 5 hours, and then filtered to obtain a white solid.

[0239] (2) A mixture of the above white solid (47.6 mmol, 17.4 g), 40 mL acetone, 20 mL water, and sodium hydroxide (95.2 mmol, 10 g) was cooled to 0°C, and 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride (47.6 mmol, 14.1 g) was added. After 5 hours, the mixture was acidified to pH 2 using 6 mol / l aqueous hydrochloric acid, and a large amount of white solid appeared. The solid was filtered, and the resulting cake was washed with water and petroleum ether to obtain the reaction product of step (2). Its structure and reaction scheme are shown below, and the reaction product of step (2) is shown by formula Ic in the reaction scheme.

[0240] [ka]

[0241] 3,5-Bis(tert-butyl)-4-hydroxyphenylpropionic acid (81 mmol, 22.5 g) was dissolved in 150 mL of chloroform, dichlorosulfoxide (124 mmol, 14.8 g) was added, and the mixture was refluxed for 4 hours. The solvent and excess dichlorosulfoxide were removed by rotary evaporation to obtain a pale yellow solid (i.e., 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride used in step (2)).

[0242] Identification of the reaction product of step (2): 1 H NMR(400MHz,CDCl3)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,4 H),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 34 H 43 NO8P - (MH):624.2732,found:624.2730. As a result of identification, the reaction product was found to be O-diphenylmethoxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine (formula Ic).

[0243] Example 4 Synthesis of O-dimethyloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine-methyl ester (1) L-serine methyl ester hydrochloride (formula II-b) (100 mmol, 15.5 g) and 40 mL of water were added to a reactor, cooled to 0°C, adjusted to pH=9.0 with sodium hydroxide, dimethyl phosphite (formula III-a) (130 mmol, 14.3 g) and tetrabutylammonium bromide (1 mmol, 0.32 g) were added, and 50 mL of 12% sodium hypochlorite solution was added dropwise with stirring. After 4 hours, the reaction product was extracted twice with ether, the aqueous layer was adjusted to pH=3 with hydrochloric acid, 8 g of sodium chloride was added, the organic phase was extracted twice with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium chloride, and the solvent was removed by distillation under reduced pressure to obtain a white solid. The white solid was dissolved in 60 mL of acetonitrile, sonicated at room temperature for 5 hours, and then filtered to obtain a white solid.

[0244] (2) A mixture of the above white solid (47.6 mmol, 10.8 g), 40 mL acetone, 20 mL water, and sodium hydroxide (95.2 mmol, 10 g) was cooled to 0°C, and 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride (47.6 mmol, 14.1 g) was added. After 5 hours, the mixture was acidified to pH 2 using 6 mol / l aqueous hydrochloric acid, and a large amount of white solid appeared. The solid was filtered, and the resulting cake was washed with water and petroleum ether to obtain the reaction product of step (2). Its structure and reaction scheme are shown below, and the reaction product of step (2) is shown by formula Id in the reaction scheme.

[0245] [ka]

[0246] 3,5-Bis(tert-butyl)-4-hydroxyphenylpropionic acid (81 mmol, 22.5 g) was dissolved in 150 mL of chloroform, dichlorosulfoxide (124 mmol, 14.8 g) was added, and the mixture was refluxed for 4 hours. The solvent and excess dichlorosulfoxide were removed by rotary evaporation to obtain a pale yellow solid (i.e., 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride used in step (2)).

[0247] Identification of the reaction product of step (2): 1 H NMR(400MHz,CDCl3)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 23 H 37 NO8P - (MH):486.2262,found:486.2268. Identification revealed that the reaction product was O-dimethyloxyphosphoryl-N-3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl-L-serine-methyl ester (formula Id).

[0248] Example 5 The above phosphorus-containing compounds were each added at a ratio of 1 mass % to different types of lubricating oil, and the biodegradability was measured according to OECD302B method. The results are shown in Table 1.

[0249] [Table 1]

[0250] The above phosphorus-containing compounds were each added at a ratio of 1 mass% to different types of lubricating oil, and the oxidation induction period of the lubricating oil was measured using a differential scanning calorimeter (PDSC method) under conditions of an oxygen pressure of 500 kPa and 200°C. The results are shown in Table 2.

[0251] [Table 2]

[0252] As is clear from the above results, the phosphorus-containing compound of the present invention can improve the biodegradability of lubricating oil. Furthermore, the phosphorus-containing compound of the present invention has excellent antioxidant properties, and when combined with a lubricating oil, can suppress the oxidation of the lubricating oil.

[0253] It should be understood by those skilled in the art that the embodiments described herein are merely exemplary, and that various other substitutions, modifications, and improvements can be made within the scope of the present invention. Therefore, the present invention is not limited to the above-described embodiments, but is limited only by the scope of the claims.

Claims

1. A phosphorus-containing compound represented by the following formula (I): 【Chemistry 1】 In formula (I), n is 0, 1, 2, 3 or 4, and n+1 R groups are the same or different and each independently represents C １ ~C ６ alkylene groups; R ｂ The group is H or C １ ~C ６ is a linear or branched alkyl group, Each R ０ The groups are the same or different and each independently represents H, C １ ~C １０ Linear or branched alkyl groups and 【Chemistry 2】 At least one R in formula (I) is selected from ０ The basis is 【Chemistry 3】 and 【Chemistry 4】 In the formula, x is 0, 1, 2, or 3, y is 1, 2, or 3, and the sum of x+y is ≦ the number of hydrogen atoms that can be substituted on the Ar group; １ The groups are the same or different and each independently represents H, C １ ~C ６ linear or branched alkyl groups, each Ar group may be the same or different from the others, and may be selected from benzene rings; R ２ The group is C １ ~C ６ is an alkylene group, each A group is the same or different and each A group is independently 【Chemistry 5】 、 【Chemistry 6】 C substituted with １ ~C ６ Selected from linear or branched alkyl groups, each X group is independently selected from O; a is 1; each R′ is independently selected from C １ ~C ６ It is selected from linear or branched alkyl groups.

2. In the compound of formula (I), x is 2, y is 1 and OH is R ２ The two R １ are located at the two ortho-positions of OH, and R １ are each independently １ ~C ４ 2. The phosphorus-containing compound according to claim 1, characterized in that the alkyl group is selected from linear or branched alkyl groups.

3. In the compound of formula (I), each A group is independently 【Chemistry 7】 、 【Chemistry 8】 C substituted with １ ~C ４ 3. The phosphorus-containing compound according to claim 1, wherein the alkyl group is selected from linear and branched alkyl groups.

4. The phosphorus-containing compound, 【Chemistry 9】 The phosphorus-containing compound according to any one of claims 1 to 3, which is one or more selected from the following:

5. A method for producing a phosphorus-containing compound, comprising the steps of: Step (1): reacting a compound represented by formula (II) and / or an inorganic acid salt thereof with a compound represented by formula (III) to produce a product of step (1); 【Chemistry 10】 、 【Chemistry 11】 In formula (II), n is 0, 1, 2, 3 or 4, and n+1 R groups are the same or different and each independently represent C １ ~C ６ alkylene groups; R ｂ The group is H or C １ ~C ６ is a linear or branched alkyl group, Each R ０ ' groups are the same or different and each independently represents H and C １ ~C １０ At least one R is selected from linear or branched alkyl groups. ０ ' group is H, Each A′ group is the same or different, and each independently represents XA′″, C substituted with XA′″ １ ~C ６ A'" groups are selected from H, and each X group is independently selected from O, and at least one A' group is selected from XA'", C substituted with XA'". １ ~C ６ Selected from linear or branched alkyl groups, The inorganic acid salt of the compound represented by formula (II) is 【Chemistry 12】 wherein M is an inorganic acid radical, j is the absolute value of the charge number of the inorganic acid radical, z is an integer of 1 to 3, and each other group is defined as in formula (II), and the inorganic acid salt of the compound represented by formula (II) is a hydrochloride, a nitrate, or a sulfate; In formula (III), each X group is independently selected from O, a is 1, each R′′ is the same or different from the others, and each independently represents C １ ~C ６ Selected from linear or branched alkyl groups, and step (2): reacting the product of step (1) with a compound represented by formula (IV) to produce a product of step (2); 【Chemistry 13】 In formula (IV), x is 0, 1, 2 or 3, y is 1, 2 or 3, the sum of x + y is ≦ the number of hydrogen atoms that can be substituted on the Ar group, and x R １ The groups are the same or different and each independently represents H, C １ ~C ６ A linear or branched alkyl group is selected from the group consisting of an Ar group and a benzene ring; R ２ The group is C １ ~C ６ A method for producing a phosphorus-containing compound, wherein X' is an alkylene group and X' is F, Cl, Br, I or OH.

6. The method for producing a phosphorus-containing compound according to claim 5, characterized in that the compound represented by formula (II) and / or its inorganic acid salt is at least one selected from the group consisting of an amino acid, an amino acid condensate, an inorganic salt of an amino acid, and an inorganic salt of an amino acid condensate.

7. The compound represented by formula (II) and / or its inorganic acid salt is at least one selected from 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 glycine ester hydrochloride, L-phenylalanine and / or L-phenylalanine ester hydrochloride, and L-valine and / or L-valine ester hydrochloride; The method for producing a phosphorus-containing compound according to claim 5 or 6, characterized in that the compound represented by formula (III) is one or more selected from phosphorous acid, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, diisopropyl phosphite, di-n-butyl phosphite, diisobutyl phosphite, di-tert-butyl phosphite, di(2-ethylhexyl) phosphite, dibenzyl phosphite, diphenyl phosphite, thiophosphorous acid, dimethyl thiophosphite, diethyl thiophosphite, dipropyl thiophosphite, diisopropyl thiophosphite, di-n-butyl thiophosphite, diisobutyl thiophosphite, di-tert-butyl thiophosphite, di(2-ethylhexyl) thiophosphite, dibenzyl thiophosphite, and diphenyl thiophosphite.

8. The method for producing a phosphorus-containing compound according to any one of claims 5 to 7, characterized in that in step (1), the reaction molar equivalent ratio of the compound represented by formula (II) and / or its inorganic acid salt (in terms of XA″) to the compound represented by formula (III) (in terms of P-H) is 1:5 to 5:1, and the reaction temperature is −40 to 80° C.

9. In step (1), a solvent is added to the reaction of the compound represented by formula (II) and / or an inorganic acid salt thereof with the compound represented by formula (III); A catalyst is added, Chloride is added, The method for producing a phosphorus-containing compound according to any one of claims 5 to 8, characterized in that the reaction is carried out at a pH of 8 to 10.

10. In step (1), the compound represented by formula (II) and / or its inorganic acid salt is reacted with the compound represented by formula (III), and then the reaction product of step (1) is subjected to at least one treatment selected from an extraction treatment, a drying treatment, and an ultrasonic treatment; When extracting the reaction product of step (1), the reaction product is extracted with a solvent in an acidic environment; The method for producing a phosphorus-containing compound according to any one of claims 5 to 9, characterized in that when the reaction product of step (1) is subjected to ultrasonic treatment, the treatment is performed for 1 to 10 hours in the presence of one or more solvents selected from a furan solvent, a chloroalkane solvent, a ketone solvent, an ester solvent, and a nitrile solvent.

11. The method for producing a phosphorus-containing compound according to any one of claims 5 to 10, characterized in that in step (2), the compound represented by formula (IV) is one or more selected from the group consisting of 3,5-bis(tert-butyl)-4-hydroxyphenylacetyl chloride, 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride, p-hydroxyphenylacetyl chloride, 3-hydroxyphenylacetyl chloride, 2-hydroxyphenylacetyl chloride, 3,4-dihydroxyphenylacetyl chloride, 3,5-dihydroxyphenylacetyl chloride, 3-methyl-4-hydroxyphenylacetyl chloride, 3,5-dimethyl-4-hydroxyphenylacetyl chloride, 2,4-dihydroxyphenylpropionyl chloride, 3,4-dihydroxyphenylpropionyl chloride, and 2-hydroxy-naphthylacetyl chloride.

12. The method for producing a phosphorus-containing compound according to any one of claims 5 to 11, characterized in that in step (2), the reaction molar equivalent ratio of the compound represented by formula (IV) (in terms of X') to the reaction product of step (1) (in terms of NH) is 5:1 to 1:5, and the reaction temperature is -40 to 60°C.

13. A composition of phosphorus-containing compounds comprising the phosphorus-containing compound according to any one of claims 1 to 4.

14. Use of the phosphorus-containing compound according to any one of claims 1 to 4 as a biodegradation agent for lubricating oils.

15. A lubricating oil composition comprising at least one selected from the phosphorus-containing compound according to any one of claims 1 to 4 and the composition of the phosphorus-containing compound according to claim 13 and a lubricating base oil, The lubricating oil composition contains the phosphorus-containing compound or the product produced by the partial dehydration condensation reaction or the complete dehydration condensation reaction of the phosphorus-containing compound in an amount of 0.001 to 30% based on the total mass of the lubricating oil composition.

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