JP3429136B2 - Method for analyzing sulfur-containing organometallic complexes in oily substances - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION The present invention relates to an oily substance such as a lubricating oil.
For details on sulfur-containing organometallic complex analysis methods,
Sulfur-containing organic substances contained as additives in oily substances such as oil
Analytical methods that can effectively qualify and quantify metal complexes
You. [0002] 2. Description of the Related Art Dithio contained in oily substances such as lubricating oils
As a method for analyzing a sulfur-containing organometallic complex such as zinc phosphate,
Conventionally, infrared spectroscopy, pyrolysis gas chromatography
ー, thin layer chromatography, distribution paper chromatography
Luffy, nuclear magnetic resonance spectroscopy and the like are known. Only
And sulfur-containing organometallic complexes commonly used in lubricating oils.
Body content is extremely low.
These existing methods are used to avoid interference with components such as additives.
Are all complicated, such as solvent extraction and chromatography.
It is necessary to concentrate the sulfur-containing organometallic complex by pretreatment with operation.
It is important. Therefore, these methods are quick,
Various problems have been pointed out in terms of properties, quantitativeness, and the like. On the other hand, sulfur-containing organic gold such as zinc dithiophosphate
High-performance liquid chromatograph
A method of analyzing by torography has also been proposed (JJ
apan Petrol. Inst. , 27, 21
4 (1984)). This method uses a sulfur-containing organometallic complex or its complex.
It captures the weak UV absorption of the amine salt itself.
You. However, sulfur-containing organometallic complexes do not detect UV absorption
Very low sensitivity to optical detectors such as detectors and fluorescence detectors
Components that have strong ultraviolet absorption, such as lubricating oils (base
A large amount of aromatic components and various additives in oil)
In some cases, these components interfere with each other, and their quantitative
There is a title. [0005] SUMMARY OF THE INVENTION The object of the present invention is to
Sulfur-containing organic substances in oily substances with excellent operability and quantitative properties
An object of the present invention is to provide a method for analyzing a metal complex. [0006] Means for Solving the Problems The inventors of the present invention have developed a lubricant and the like.
Base oils and additives that coexist with sulfur-containing metal complexes in oily substances
Is not affected by the above and does not require pretreatment
After repeated investigations to find a method that can be analyzed directly,
Just react by adding a specific compound to the oily substance
Visible and ultraviolet absorption of sulfur-containing metal complexes in oily substances
And new fluorescent oils
Regardless of the type, analysis can be performed quickly and with excellent operability and quantitativeness.
And found that the present invention was completed.
Was. That is, according to the present invention, a sulfur-containing metal complex is contained.
(A) halo represented by the following formula (1)
Gen-containing organic compounds A-CH_Two−X (1) (Where A is an organic residue having an aromatic ring and 6 to 40 carbon atoms)
X represents a bromine atom, chlorine atom or iodine atom
And (B) a basic compound was added and reacted.
After that, the reaction product was subjected to high performance liquid chromatography,
Characterized in that it is detected by a detector,
A method for analyzing a sulfur-containing organometallic complex is provided. [0008] BEST MODE FOR CARRYING OUT THE INVENTION Analyzing by the analysis method of the present invention
Oily substances containing sulfur-containing metal complexes
As long as it is not particularly limited,
It can be analyzed, especially for sulfur containing metal complexes containing sulfur.
Analysis of lubricating oil can be preferably performed. The analysis can be performed by the analysis method of the present invention.
The type of the lubricating oil is listed in terms of its components and manufacturing method.
For example, mineral oil lubricating oil, synthetic oil lubricating oil,
An oil-based lubricating oil can be used. [0010] As the mineral oil-based lubricating oil, for example, crude oil
The lubricating oil fraction obtained by atmospheric distillation and vacuum distillation of
Agent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic desorption
Purification processing such as wax, hydrorefining, sulfuric acid washing, clay treatment, etc.
Paraffin, naphthenic
And the like as a base oil. As the synthetic oil-based lubricating oil, for example,
Α-olefin (polybutene, 1-octene oligomer
-, 1-decene oligomer, etc.), alkylbenzene,
Lucirnaphthalene, diester (ditridecyl glutare)
Di-ethylhexyl adipate, diisodecyl
Ruadipate, ditridecyl adipate, di-2-ethyl
Lehexyl sebacate, etc.), polyester (trimeric
Acid ester, etc.), polyol ester (trimethylo)
Lupropane caprylate, trimethylolpropanepera
Lugonate, pentaerythritol-P2-ethylhex
Sanoate, pentaerythritol pelargonate
Etc.), polyoxyalkylene glycol, polyphenyl
Examples include those using a synthetic oil such as ether as a base oil. As the semi-synthetic oil-based lubricating oil, for example,
Mixture of mineral oil and synthetic oil in specified proportions
Is mentioned. [0013] In addition, analysis by the analysis method of the present invention.
List the types of lubricating oils that can be made from the viewpoint of their uses.
And gasoline engine oil and diesel
Engine oils such as diesel engine oil; automotive gear oils (automatic
Transmission oil, manual transmission oil, differential oil) and industrial
Gear oil, such as gear oil for use; hydraulic oil; turbine oil; compressor
Oil; refrigerating machine oil; cutting oil, plastic working oil (rolling oil, press
Oil, forging oil, drawing oil, drawing oil, punching oil
Etc.), metal working oils such as heat treatment oils, electric discharge machining oils, etc .;
Surface oil; bearing oil; rust inhibitor oil; heat carrier oil and the like. Further, the analysis method of the present invention can be used for other than lubricating oil.
Also, organic solvents containing sulfur-containing metal complexes, such as mineral oil-based
Suitable for oily substances such as organic solvents and synthetic oil organic solvents.
Is available. [0015] Qualitative and quantitative analysis is performed by the analysis method of the present invention.
The components that can be used are sulfur-containing
It is an organometallic complex. As the sulfur-containing organometallic complex, lubricating oils
Metal dithiophosphoes commonly used as additives
Compounds called metal or metal dithiocarbamate
I can do it. Specific examples of metal dithiophosphates include
Specifically, a compound represented by the following formula (2) may be mentioned.
it can. On the other hand, as metal dithiocarbamate,
Specifically, a compound represented by the following formula (3) may be mentioned.
it can. [0018] Embedded imageIn the above formula (2), R¹, R^Two, R^Threeas well as
R^Four, And R in formula (3)^Five, R⁶, R⁷And R⁸
Are the same or different groups, each having 1 to 24 carbon atoms
Represents a hydrogen group, and represents Y in the formula (2) and in the formula (3)
Z represents zinc, copper, nickel, lead or molybdenum.
You. Further, in a, b and c in the formula (2), Y
For lead, copper, nickel or lead, a = 1, b = c = 0
Yes, when Y is molybdenum, a = 2, b = 0-4, c
= 0 to 4 and b + c = 4;
In (3), d, e and f are such that Z is zinc, copper, nickel
For lead or lead, d = 1 and e = f = 0, and Z is
In the case of budene, d = 2, e = 0 to 4, f = 0 to 4
And e is an integer such that e + f = 4. The above R¹~ R⁸Are preferably the same or different
Linear or branched alkyl having 1 to 24 carbon atoms
A kill group, a linear or branched alkenyl having 3 to 24 carbon atoms
Group, cycloalkyl group having 5 to 13 carbon atoms or alkyl
A cycloalkyl group, an aryl group having 6 to 18 carbon atoms or
Alkylaryl group, arylalkyl having 7 to 19 carbon atoms
It is preferably a group. Here, the alkyl group
A primary alkyl group, a secondary alkyl group or a tertiary alkyl group
included. The linear or branched C1 to C24 alkyl group
As the alkyl group, specifically, methyl group, ethyl
Group, n-propyl group, isopropyl group, n-butyl group,
Isobutyl group, sec-butyl group, tert-butyl
Group, linear or branched pentyl group, linear or branched hexyl
Group, straight-chain or branched heptyl group, straight-chain or branched octyl
A straight-chain or branched nonyl group, a straight-chain or branched decyl group,
Chain or branched undecyl, straight or branched dodecyl, straight
Chain or branched tridecyl group, straight or branched tetradecyl
Group, straight-chain or branched pentadecyl group, straight-chain or branched hexa
Decyl group, straight-chain or branched heptadecyl group, straight-chain or branched
Octadecyl group, straight-chain or branched nonadecyl group, straight-chain or
Branched icosyl group, straight-chain or branched henicosyl group, straight-chain or
Is a branched docosyl group, a linear or branched tricosyl group, a linear or
Is preferably a branched tetracosyl group or the like.
You. The straight-chain or branched-chain C 3 -C 24
Specific examples of the alkenyl group include a propenyl group and an alkenyl group.
Sopropenyl group, linear or branched butenyl group, butadienyl
Group, straight-chain or branched pentenyl group, straight-chain or branched hexene
Nyl group, straight or branched heptenyl group, straight or branched octyl group
Thenyl group, straight-chain or branched nonenyl group, straight-chain or branched
Nyl group, straight-chain or branched undecenyl group, straight-chain or branched
Decenyl group, straight-chain or branched tridecenyl group, straight-chain or branched
Branched tetradecenyl group, straight-chain or branched pentadecenyl group,
Straight-chain or branched hexadecenyl group, straight-chain or branched heptadene
Straight-chain or branched octadecenyl such as senyl group and oleyl group
Group, linear or branched nonadecenyl group, linear or branched
Nil group, straight-chain or branched henicocenyl group, straight-chain or branched
Docosenyl group, straight-chain or branched tricosenyl group, straight-chain or
Preferred are branched tetracosenyl groups and the like.
You. The cycloalkyl group having 5 to 13 carbon atoms;
Specifically, specifically, cyclopentyl group, cyclohexyl
And a cycloheptyl group.
And an alkylcycloalkyl group having 5 to 13 carbon atoms
Specifically, specifically, a methylcyclopentyl group (all
Dimethylcyclopentyl group (including substituted isomers of
All substituted isomers), ethylcyclopentyl group
(Including all substituted isomers), straight or branched propyl
Cyclopentyl group (including all substituted isomers), ethyl
Methylcyclopentyl group (including all substituted isomers)
), Trimethylcyclopentyl group (all substitution isomers)
Body), diethylcyclopentyl group (all substitutions
Isomer), ethyldimethylcyclopentyl group (including
All substituted isomers), straight-chain or branched propylmethyl
Rucyclopentyl group (including all substituted isomers),
Chain or branched propylethylcyclopentyl group (all
Including substituted isomers), di-linear or branched propylcyclo
Pentyl group (including all substituted isomers), linear or branched
Branched propylethylmethylcyclopentyl group (all
Methylcyclohexyl group (including all isomers)
Dimethylcyclohexyl group (including substituted isomers)
All substituted isomers), ethylcyclohexyl group (including
All substituted isomers), straight-chain or branched propylcycl
Rohexyl group (including all substituted isomers), ethyl
Tylcyclohexyl group (including all substituted isomers),
Trimethylcyclohexyl group (including all substituted isomers)
), Diethylcyclohexyl group (all substituted isomers)
), Ethyldimethylcyclohexyl group (all
Including substituted isomers), linear or branched propylmethylcyclyl
Rohexyl group (including all substituted isomers), straight chain or
Branched propylethylcyclohexyl (all substitutions
Di-linear or branched propylcyclohexyl)
(Including all substituted isomers), linear or branched
Pyrethylmethylcyclohexyl group (all substitution isomers
Methylcycloheptyl group (including all substitution variants)
Dimethylcycloheptyl group (including all
Including isomers), ethylcycloheptyl group (all
Including substituted isomers), linear or branched propylcyclohep
Tyl group (including all substituted isomers),
Chloheptyl group (including all substituted isomers), trime
Tylcycloheptyl group (including all substituted isomers),
Diethylcycloheptyl group (including all substituted isomers)
), Ethyldimethylcycloheptyl group (all substitutions
Isomers), linear or branched propylmethylcyclo
Butyl group (including all substituted isomers), straight chain or branched
Propylethylcycloheptyl group (all substituted isomers
), Di-linear or branched propylcycloheptyl group
(Including all substituted isomers), straight or branched propyl
Ethylmethylcycloheptyl group (all substituted isomers
Including cycloalkyl groups or alkylcycloalkyl
And a phenyl group. As the aryl group having 6 to 18 carbon atoms,
Is preferably a phenyl group, a naphthyl group or the like.
And the alkyl ant having 6 to 18 carbon atoms.
Specific examples of the tolyl group include a tolyl group (all substituted
Isomer), xylyl group (including all substituted isomers)
), Ethylphenyl group (including all substituted isomers)
), Linear or branched propylphenyl group (all substitutions
Isomer), ethylmethylphenyl group (all
Trimethylphenyl group (including all isomers)
Butylphenyl group (including
All substituted isomers), straight-chain or branched propylmethyl
Ruphenyl group (including all substituted isomers), diethyl
Phenyl group (including all substituted isomers), ethyldimethyl
Tylphenyl group (including all substituted isomers), tetra
Methylphenyl group (including all substituted isomers), straight chain
Or a branched pentylphenyl group (including all substituted isomers)
), Linear or branched hexylphenyl group (all substitutions
Isomers), linear or branched heptylphenyl groups (including
All substituted isomers), linear or branched octylfe
Nyl group (including all substituted isomers), linear or branched
Nylphenyl group (including all substituted isomers), straight chain or
Is a branched decylphenyl group (including all substituted isomers)
), Straight-chain or branched undecylphenyl groups (all
Straight-chain or branched dodecylphenyl group
(Including all substituted isomers)
To form an arylalkyl group having 7 to 19 carbon atoms.
Specifically, specifically, benzyl group, methylbenzyl group (all
Dimethylbenzyl group (including all substituted isomers)
Phenethyl group, methylphenetici
(Including all substituted isomers), dimethylphenethyl
(Including all substituted isomers)
be able to. Of these, R¹~ R⁸Are the same or different
Linear or branched having 1 to 18 carbon atoms
Compounds that are alkyl groups or aryls having 6 to 18 carbon atoms
Compound that is a phenyl group or an alkylaryl group is a lubricating oil
Commonly used as sulfur-containing organometallic complex as an additive
And especially an alkyl group having 4 to 12 carbon atoms.
Or an alkylaryl group having 10 to 15 carbon atoms
Certain compounds are more commonly used. The metal dithiophos represented by the above formula (2)
As the fate, specifically, zinc diethyldithiopho
Sulfate, zinc dipropyldithiophosphate, zinc
Dibutyl dithiophosphate, zinc dipentyl dithiopho
Sulfate, zinc dihexyl dithiophosphate, zinc
Dioctyldithiophosphate, zinc didecyldithiopho
Sulfate, zinc didodecyl dithiophosphate, zinc
Di (butylphenyl) dithiophosphate, zinc di
Nylphenyl) dithiophosphate, molybdenum sulfide
Ethyl dithiophosphate, molybdenum dipropyl sulfide
Dithiophosphate, molybdenum dibutyl dithiopho sulfide
Sulfate, molybdenum dipentyl dithiophosphate
Molybdenum dihexyl dithiophosphate,
Molybdenum dioctyl dithiophosphate, molybdenum sulfide
Molybdenum sulfide, molybdenum sulfide
Didodecyldithiophosphate, molybdenum sulfide
Tylphenyl) dithiophosphate, molybdenum sulfide
(Nonylphenyl) dithiophosphate, oximo sulfide
Lybdenum diethyldithiophosphate, oxymori sulfide
Budene dipropyl dithiophosphate, oxymori sulfide
Budene dibutyl dithiophosphate, oxymolybdenum sulfide
Dendipentyl dithiophosphate, oxymolybdenum sulfide
Dendihexyl dithiophosphate, oxymolybdenum sulfide
Dendiooctyl dithiophosphate, oxymolybdenum sulfide
Dendidecyl dithiophosphate, oxymolybdenum sulfide
Ndidodecyl dithiophosphate, oxymolybdenum sulfide
Di (butylphenyl) dithiophosphate, sulfurized oxy
Simolybdenum di (nonylphenyl) dithiophosphate
And the like. The metal dithiocarba represented by the above formula (3)
As the mate, specifically, zinc diethyldithiocar
Bamate, zinc dipropyl dithiocarbamate, zinc di
Butyl dithiocarbamate, zinc dipentyl dithiocar
Bamate, zinc dihexyl dithiocarbamate, zinc di
Octyl dithiocarbamate, zinc didecyl dithiocar
Bamate, zinc didodecyl dithiocarbamate, zinc di
(Butylphenyl) dithiocarbamate, zinc di (noni
Ruphenyl) dithiocarbamate, molybdenum sulfide
Tildithiocarbamate, molybdenum dipropyldisulfide
Thiocarbamate, molybdenum dibutyl dithiocar
Bamate, molybdenum sulfide dipentyl dithiocarbamate
G, molybdenum dihexyl dithiocarbamate, sulfuric acid
Molybdenum dioctyl dithiocarbamate, molybdenum sulfide
Budene decyl dithiocarbamate, molybdenum sulfide
Dodecyl dithiocarbamate, molybdenum sulfide
Ruphenyl) dithiocarbamate, molybdenum sulfide
(Nonylphenyl) dithiocarbamate, oximo sulfide
Libdene diethyldithiocarbamate, oxymori sulfide
Budene dipropyl dithiocarbamate, oxymori sulfide
Budene dibutyl dithiocarbamate, oxymolybdenum sulfide
Dendipentyl dithiocarbamate, oxymolybdenum sulfide
Dendihexyl dithiocarbamate, oxymolybdenum sulfide
Dendiooctyl dithiocarbamate, oxymolybdenum sulfide
Dendidecyl dithiocarbamate, oxymolybdenum sulfide
Ndidodecyl dithiocarbamate, oxymolybdenum sulfide
Di (butylphenyl) dithiocarbamate, sulfide oxy
Simolybdenum di (nonylphenyl) dithiocarbamate
And the like. The sulfur-containing metal complex is a single compound.
Metal dithiophosphate and metal dithiophosphate
Of two or more compounds selected from thiocarbamates
It may be a mixture. In the analysis method of the present invention, the sulfur-containing metal complex
(A) specific halogen-containing
Organic compound (hereinafter abbreviated as (A) component) and (B) salt
Addition of basic compound (hereinafter abbreviated as component (B))
Let it. The component (A) is represented by the above formula (1).
Therefore, a single compound may be used for use.
And two or more compounds represented by the formula (1)
Is also good. By adding the component (A),
Of the sulfur-containing organometallic complex of (A) and the component (A)
Sulfur-Containing Organometallic Complexes with Aromatic Rings with Strong Absorption Coefficients in the Range
Can be introduced. In the above formula (1), A has an aromatic ring.
Organic residues having 6 to 40 carbon atoms,
As the aromatic ring, specifically, benzene ring, naphthalene
Ring, anthracene ring, phenanthrene ring, benzo [a]
Anthracene ring, chrysene ring, fluoranthene ring, pyre
Ring, 5,6-cyclopentanobenzo [a] anthracene
Ring, 6,7-cyclopentanobenzo [a] anthracene
Ring, benzo [e] acephenanthrylene ring, benzo
[J] fluoranthene ring, dibenzo [a, i] fluor
Ring, benzo [a] pyrene ring, benzo [e] pyrene ring,
Dibenzo [a, h] anthracene ring, perylene ring,
Deno [1,2,3-c, d] pyrene ring, dibenzo [a,
h] pyrene ring, dibenzo [a, i] pyrene ring, dibenzo
[A, l] pyrene ring, anthranthracene ring, benzo
[G, h, i] perylene ring, benzoperylene ring, diben
Azo [a, c] pyrene ring, coronene ring, dibenzo [a,
h] acridine ring, dibenzo [a, j] acridine ring,
Anthantrone ring, phenalen-9-one ring, xan
Ten-9-one ring, 7H-benzo [d, e] anthrace
And a 7-7-one ring.
Ring, naphthalene ring, anthracene ring, phenanthrene
Rings and the like are preferred. These aromatic rings are represented by the following formula:
Any constituent hydrogen atom is a substituent, specifically
For example, hydroxyl group; thiol group; amino group; chlorine atom, bromine atom
Halogen atom such as iodine atom, nitro group, nitroso
Group; nitrile group; aldehyde group; carboxyl group;
Alkyl having 1 to 5 carbon atoms such as
A group having 1 to 1 carbon atoms represented by a methoxy group, an ethoxy group, etc.
5 may be substituted with an alkoxy group or the like. The aromatic ring and methyl in component (A)
Len group (-CH_TwoBonding with-) is optional, direct bonding
In addition to the above, other groups may intervene and bind,
The component (A) includes an aromatic ring and a methylene group of the formula (1).
(-CH_Two-) Is directly bonded to
Via a group containing a carbonyl group or a carbonyl group
Are preferred. Preferred examples of the component (A) include the following
A compound represented by the formula (4), the formula (5) or the formula (6)
Can be mentioned. [0035] Embedded image In the above (4) to (6), Ar¹,
Ar^TwoAnd Ar^ThreeIs, specifically, a carbon number of 6 to
40 aromatic rings, preferably benzene rings, naphthalene
A ring, a phenanthrene ring or an anthracene ring,
B¹, B^TwoAnd B^ThreeIs a hydroxyl group; a thiol group; an amino group; a salt
A halogen atom such as an element atom, a bromine atom and an iodine atom;
B group; nitroso group; nitrile group; aldehyde group;
Xyl group; carbon number 1 represented by methyl group, ethyl group, etc.
To 5 alkyl groups; represented by methoxy group, ethoxy group, etc.
A substituent such as an alkoxy group having 1 to 5 carbon atoms,
¹, X^TwoAnd X^ThreeRepresents a bromine, chlorine or iodine atom
And g, h and i are integers of 0-5. As the compound represented by the above formula (4),
Specifically, benzyl bromide, benzyl chloride, benzene iodide
Jill, p-nitrobenzyl bromide, p-nitrobenzyl chloride
, P-nitrobenzyl iodide, 3,5-dinitro bromide
Benzyl, 3,5-dinitrobenzyl chloride, iodide 3,
5-dinitrobenzyl, 9-methylphenanthrome
9-methylphenanthrene, 9-methyl iodide
Phenanthrene, 9-methylmethylanthracene, 9-salt
Methyl anthracene, 9-methyl anthracene iodide
And the like. The compound represented by the formula (5) includes
Specifically, phenacyl bromide, phenacyl chloride, iodide
Phenacyl, p-bromophenacyl bromide, p-bromo chloride
Mofenacyl, p-bromophenacyl iodide, p-bromide
Nitrophenacyl, p-nitrophenacyl chloride, iodide
p-Nitrophenacyl, 2-naphthacyl bromide, 2-chloride
Naphthasil, 2-naphthacyl iodide and the like can be mentioned.
Wear. Phenacyl is a group represented by the following formula (7)
And 2-naphthacyl is a group represented by the following formula (8).
Shown respectively. [0039] Embedded image The compound represented by the above formula (6) includes
Specifically, compounds represented by the following formulas (9) to (11)
And the like. [0041] Embedded image On the other hand, (B) used in the analysis method of the present invention.
The component may be an organic basic compound or an inorganic basic compound.
Or a mixture of both. Add component (B)
By adding the component (B), the sulfur-containing component in the oily substance
Acts as a catalyst in the reaction between metal complex and component (A)
And a sulfur-containing aromatic ring with a strong extinction coefficient in the ultraviolet region.
Reaction to be introduced into the metal complex. Specific examples of the inorganic basic compound include
Means sodium hydroxide, potassium hydroxide, calcium hydroxide
Metal water such as magnesium, magnesium hydroxide, barium hydroxide
Oxides; metal oxides such as calcium oxide; sodium carbonate
Metal carbonates such as potassium carbonate, magnesium carbonate, etc .;
Basic sodium carbonate, basic magnesium carbonate, base
Zinc chloride, basic iron chloride, basic sodium acetate, etc.
Basic metal salts; ammonia, mixtures thereof, and the like.
I can do it. As the organic basic compound, a nitrogen-containing compound is used.
Specific examples include alkylamines and cycloamines.
Loalkylamine, alkanolamine, heterocyclic amine
Min, polyamine, quaternary organic ammonium compound and
These mixtures can be mentioned. The alkylamine has 1 to 1 carbon atoms.
Having 1 to 3 linear or branched alkyl groups of 18
Things. Preferred alkylamines include
Specifically, monomethylamine, dimethylamine, trime
Tylamine, monoethylamine, diethylamine, tri
Ethylamine, monopropylamine, dipropylamido
, Tripropylamine, monobutylamine, dibutyl
Amine, tributylamine, monopentylamine, dipe
Methylamine, tripentylamine, monohexylamine
, Dihexylamine, trihexylamine, monohepta
Tylamine, diheptylamine, triheptylamine,
Monooctylamine, dioctylamine, trioctyl
Amine, monononylamine, dinonylamine, trinoni
Ruamine, monodecylamine, didecylamine, tride
Silamine, monododecylamine, didodecylamine,
Tridodecylamine, monotetradecylamine, ditet
Radecylamine, tritetradecylamine, monohexa
Decylamine, dihexadecylamine, trihexadeci
Luamine, monooctadecylamine, dioctadecylua
Min, trioctadecylamine and the like. As the cycloalkylamine, 5 to 5
And those having 1 to 3 7-membered cycloalkyl groups.
It is. 1 to 2 hydrogen atoms constituting the saturated aliphatic ring
The atom may be substituted by an alkyl group having 1 to 6 carbon atoms.
Preferred cycloalkylamines include, specifically,
No (cyclopentyl) amine, mono (methylcyclopentene)
Tyl) amine, mono (dimethylcyclopentyl) ami
Dicyclopentylamine, di (methylcyclopentene)
L) amine, di (dimethylcyclopentyl) amine,
No (cyclohexyl) amine, mono (methylcyclohexyl)
Sil) amine, mono (dimethylcyclohexyl) ami
Dicyclohexylamine, di (methylcyclohexyl)
L) amine, di (dimethylcyclohexyl) amine,
No (cycloheptyl) amine, mono (methylcyclohep
Tyl) amine, mono (dimethylcycloheptyl) amido
Di (cycloheptyl) amine, di (methylcyclo
(Butyl) amine, di (dimethylcycloheptyl) amine
And the like. The alkanolamine includes carbon atoms
1 to 18 linear or branched alkanol groups
Straight-chain or branched alkyl having 1 to 18 carbon atoms
Those having 0 to 2 kill groups are exemplified. Preferred a
Monoethanolamine, diethanolamine
Methanolamine, trimethanolamine, monoethano
Amine, diethanolamine, triethanolamine
, Monopropanolamine, dipropanolamine,
Tripropanolamine, monobutanolamine, jib
Tanolamine, tributanolamine, monopentano
Amine, dipentanolamine, tripentanol
Amine, monohexanolamine, dihexanolamine
, Trihexanolamine, monoheptanolamine
, Diheptanolamine, triheptanolamine,
Monooctanolamine, dioctanolamine, tri
Octanolamine, monononanolamine, dinonano
Amine, trinonanolamine, monodecanolamine
Min, didecanolamine, tridecanolamine,
Nododecanolamine, didodecanolamine, trido
Decanolamine, monotetradecanolamine, dite
Tradecanolamine, tritetradecanolamine,
Monohexadecanolamine, dihexadecanolamine
, Trihexadecanolamine, monooctadecano
Luamine, dioctadecanolamine, trioctadeca
Nolamine and the like. As the heterocyclic amine, nitrogen-containing
Membered heterocyclic compounds, nitrogen-containing 6-membered heterocyclic compounds, or these
A nitrogen-containing 5-membered heterocyclic ring or a nitrogen-containing 6-membered heterocyclic ring as a structural unit.
And a condensed heterocyclic compound. Preferred heterocyclic amines include
Pyrrolidine, pyrroline, pyrrole, pyrrolenine,
Quinuclidine, imidazolidin, imidazoline, imida
Sol, pyrazolidine, pyrazoline, pyrazole, fura
Zan, isothiazole, isoxazole, piperidi
Pyridine, piperazine, morpholine, pyrazine,
Lidazine, pyrimidine, indoline, indole, ind
Dorizine, isoindole, anthralin, pudding, ki
Norin, isoquinoline, cinnoline, naphthyridine,
Tarazine, pteridine, quinazoline, quinolidine, quino
Xaline, acridine, carbazole, carbazoleni
, Β-carboline, phenanthridine, phenanthro
Phosphorus, phenazine, phenothiazine, phenoxazine,
And one or two waters constituting a heterocycle of these compounds
Compounds in which an elementary atom is substituted by an alkyl group having 1 to 6 carbon atoms
And the like. The polyamine includes 2 to 6 carbon atoms.
Polyamines having 1 to 10 alkylene groups include
You. Preferred examples of the polyamine include, specifically,
Is ethylenediamine, diethylenetriamine, triethyl
Lentramine, tetraethylenepentamine, pentae
Tylenehexamine, propylenediamine, dipropylene
Triamine, tripropylenetetramine, tetrapropyl
Lenpentamine, pentapropylenehexamine, trime
Tylenediamine di (trimethylene) triamine, tri
(Trimethylene) tetramine, tetra (trimethylene)
Pentamine, penta (trimethylene) hexamine, etc.
I can do it. As the quaternary organic ammonium compound,
Is a linear or branched alkyl group having 1 to 18 carbon atoms.
Contains 4 or is linear or branched having 1 to 18 carbon atoms
Containing 1 to 3 alkanol groups and having 1 to 1 carbon atoms
Contains 0 to 3 linear or branched alkyl groups
And quaternary organic ammonium hydroxides. Preferred quaternary organic ammonium compounds
Therefore, specifically, tetramethyl ammonium hydroxide
Sid, tetraethylammonium hydroxide, tetra
Propyl ammonium hydroxide, tetrabutylan
Monium hydroxide, tetrapentylammonium arsenic
Droxide, tetrahexylammonium hydroxy
, Tetraheptyl ammonium hydroxide, tetra
Octyl ammonium hydroxide, tetranonylan
Monium hydroxide, tetradecyl ammonium hydride
Loxide, tetradodecyl ammonium hydroxide,
Tetratetradecyl ammonium hydroxide, tetra
Hexadecyl ammonium hydroxide, tetraocta
Decyl ammonium hydroxide and the like. Among these, the component (B) of the present invention
As basic compounds, organic basic compounds are preferred.
Especially alkylamines, alkanolamines, quaternary
Organic ammonium compounds and mixtures thereof are more preferred.
It is used well. Reaction operation between component (A) and component (B)
In the above, the addition amount of the component (A) and the component (B) is optional.
However, the amount of the component (A) is usually
0.5-5 parts by weight, preferably 1-4 parts by weight
Parts by weight, more preferably 2-3 parts by weight.
On the other hand, the amount of the component (B) is 100% by weight of the oily substance.
0.5 to 5 parts by weight, preferably 1 to 4 parts by weight
Parts, more preferably 2-3 parts by weight. Also, the temperature and reaction time for the reaction are determined.
Usually, the reaction temperature is 30 to 100 ° C., preferably
50 to 90 ° C, more preferably 70 to 80 ° C, reaction
Time is 5-60 minutes, preferably 5-40 minutes, more preferred
It is preferably 10 to 20 minutes. This reaction may be carried out without a solvent.
Hexane, benzene, toluene, volatile oil for extraction, stone
Oil ether, petroleum benzine, ligroin, mineral spirits
Lit, methanol, acetone, tetrahydrofuran,
Acetonitrile, dimethylformamide, chloroform
And the like, or an organic solvent such as water or the like. What
The amount when the solvent is used is also arbitrary, but is usually an oily substance.
100-700 parts by weight, preferably 100 parts by weight
150 to 500 parts by weight, more preferably 200 to 3 parts by weight.
It is desirable to use an amount of 00 parts by weight of solvent. In the analysis method of the present invention,
The reaction product is subjected to high performance liquid chromatography.
It is detected by an optical detector. Generally, high performance liquid chromatography is
Chromatography usually uses a liquid as the mobile phase.
For example, partition chromatography
(Liquid-liquid chromatography: LLC) and adsorption chromatography
For chromatography (liquid-solid chromatography: LSC)
LLC can be broadly classified, and LLC is a liquid stationary phase-non-polar mobile phase liquid
Normal phase LLC and non-polar stationary phase-polar mobile phase liquid
It can be classified as a reversed phase LLC of a body combination. Book
High-speed liquid crystal that can be used in the analysis method of the invention
The chromatography is not particularly limited.
These various types of chromatography can be used.
You. Apparatus for the high performance liquid chromatography
Although there is no particular limitation, the liquid supply section (liquid supply port) is usually basically
Pump), sample injection section, separation section (separation column), detection section
(Detector) or the like can be used. The liquid feed pump is not particularly limited.
However, the normal discharge pressure is 50-500kg / cm^TwoOf the degree
Can be used. The sample injection section is not particularly limited.
Usually, however, a sample is taken in a microsyringe, etc.
Syringe method for injection through the system or filling the loop with the sample
The valve loop method for switching the valve and injecting
Can be used. As a sample injection method
Is not particularly limited, but is usually about 1 to 100 μl.
Can do it. The separation column is not particularly limited.
However, usually 10 to 70 cm in length and 1 to 60 mm in inner diameter (min.
For stainless steel or glass)
Can be used and filled with filler for separation
can do. The filler is not particularly limited.
However, for example, commonly used surface porous particles, total porosity
Use various kinds of fine particles or porous particles
be able to. Of these, those of all porous fine particles
Is generally used. The surface porous particles usually have a particle size.
Inner core and thickness without particles, about 20 to 50 μm in size
What consists of a porous outer core of about 1-2 μm
And the total porous fine particles usually have a particle size of about 2 to 10 μm.
It is possible to mention that the whole consists of porous fine particles.
And the total porous particles usually have a particle size of 20 to 50 μm.
It is possible to mention that the whole is made of porous particles.
it can. As described above for the high performance liquid chromatography,
When performing LLC, as a stationary phase, usually a chemically bonded type
Fillers can be used. The chemical bond type filler and
Although there is no particular limitation, a fully porous silicon
Using Kagel, for the silanol group on the surface,
Aminopropyl group, cyanopropyl group, nitrophenol
Organosilicon compounds having polar groups such as
Obtained by reacting the product (for normal phase LLC),
Octyl, octadecyl, phenylmethyl
Organosilicon having a hydrophobic group such as
Obtained by reacting a kon compound (for reversed-phase LLC)
And the like. As described above for the high performance liquid chromatography,
When performing the LSC, the stationary phase (adsorbent)
But not limited to silica gel, alumina, porous silica
Rimmer (polysterene gel, polyvinyl acetate gel, poly
Hydrophobic gels such as methyl methacrylate gel and polyhydro
Xyethyl methacrylate gel, polyvinyl alcohol
Hydrophilic gels such as gels) can be used. The liquid for the mobile phase is not particularly limited.
Not usually, but a variety of polar solvents can be used.
You. As the polar solvent, in order from the largest polarity
To list, for example, water, formaldehyde, acetonit
Ril, methanol, acetic acid, ethanol, isopropanol
, Acetone, dioxane, tetrahydrofuran, t-
Butanol, methyl ethyl ketone, phenol, n-butyl
Tanol, n-pentanol, ethyl acetate, ethyl
Toluene, n-butyl acetate, nitromethane,
Sopropyl ether, dichloromethane, chloroform,
1,2-dichloroethane, phenyl bromide, ethyl bromide,
Benzene, propyl chloride, toluene, xylene, tetrachloride
Carbon, carbon disulfide, cyclohexane, hexane, hepta
Solvents such as ketone and kerosene.
Can be used alone or as a mixture of two or more
You. In the above high performance liquid chromatography
The flow rate (elution rate) of the mobile phase is arbitrary and is particularly limited.
It also varies greatly depending on the column inner diameter, etc.
For example, when using a column with an inner diameter for analysis,
It can be performed at about 3 ml / min. In the above high performance liquid chromatography
The column temperature is not particularly limited.
It can be in the range of the boiling point of the phase liquid. In particular, stationary phases
Considering the effects on the environment, it is preferable that the temperature range from room temperature to about 80 ° C.
New The method used for the high performance liquid chromatography
Any optical detector can be used.
However, usually, an ultraviolet absorption detector or a fluorescence detector is preferably used.
Can be The detection wavelength of the detector is usually
Ultraviolet spectrum of the reaction product of the genus complex with the component (A) or
Measures the fluorescence spectrum and determines its peak position
Can be determined by In the above high performance liquid chromatography
Is the unreacted component (A) previously contained in the reactant,
Although the component (B) may be removed, the unreacted component is usually removed.
Even without removal,
Unreacted components can be separated at the same time
Thus, without employing such a removing operation, the component (A)
The reaction product obtained by adding component (B) and reacting
It can be used as a sample for high performance liquid chromatography.
Wear. Thus, (A) without any separation operation, etc.
The reaction product obtained by adding the component and the component (B) and reacting
It can be used as a sample for high performance liquid chromatography
Perform analysis operations quickly and easily
Can be. If necessary, further use this reactant.
Dilution with organic solvent and then try high performance liquid chromatography
It may be used as a fee. Examples of the organic solvent include (A)
Used when reacting by adding component and component (B)
The same solvents as those listed as possible solvents are listed.
I can do it. Obtained by the above high performance liquid chromatography
Chromatograms usually contain sulfur-containing metal complexes.
One or more peaks of the substance in which the body and component (1) are bound
Appears. This peak is compared with the chromatogram of the standard.
Quantify the amount of sulfur-containing metal complex in oily substances by comparing
Can be analyzed qualitatively and qualitatively. Also, sulfur-containing metals
There are two or more substances in which the complex and the component (1) are bonded.
In this case, by appropriately selecting the elution conditions,
Separate peaks can also be obtained, from which oily
Analysis of sulfur-containing metal complexes in materials
it can. In particular, said metal dithiophosphate and / or
When analyzing metal dithiocarbamates,
The component is preserved without changing the hydrocarbon group part of
Analyze them quantitatively and qualitatively because they bind to (1)
Then, their structures, quantitative ratios, and the like can be analyzed. [0072] The analysis method of the present invention comprises the steps of:
The contained oily substance may contain certain halogen-containing organic compounds and
And basic compounds are added and reacted.
Since it is an analysis method to be provided for matography, (1) Easy operation and sulfur-containing organic under mild conditions
A reaction between the metal complex and the component (A) can be performed. (2) High reaction rate between sulfur-containing organometallic complex and component (A)
And good reproducibility (3) Good separation of sulfur-containing organometallic complexes in oily substances
Quantify the structure, quantitative ratio, etc. of sulfur-containing organometallic complexes
・ Can be analyzed qualitatively (4) Improve existing high-performance liquid chromatography equipment
Can be used without modification Analysis with excellent operability and quantitativeness
It can be performed conveniently. [0073] The present invention will now be described with reference to Examples and Comparative Examples.
The present invention will be described in more detail below.
It is not limited. [0074] Example 1 City containing zinc dithiophosphate
9-Methyl chloride
Add 2 parts by weight of anthracene and 2 parts by weight of triethylamine
After the addition, the system was kept at 70 ° C. and reacted for 20 minutes. Thereafter, the reaction product was added to an organic solvent (chlorophore).
The sample was prepared by diluting 10 times the volume with
High performance liquid chromatography set to conditions
When 0 μl was injected, the chromatogram shown in FIG.
Obtained. Equipment: Waters 840 Operation
System Separation column: YMC's chemically bonded reverse-phase partitioning A304
(Silica gel surface treated with octadecylsilane
of) Eluent; special grade methanol Flow rate: 0.8ml / min Detector; UV absorption detector Detection wavelength: 252 nm From the comparison with the elution time of the standard sample,
The peaks shown are the unreacted 9-methyl chloride of CMA.
Anthracene peak, and a is an isopropyl group
Only b is isopropyl and 1,3-dimethylbutyl
And c represents only a 1,3-dimethylbutyl group, respectively.
Zinc dialkyldithiophosphate having alkyl group
Reaction product of the salt with 9-methylanthracene chloride,
Are the same as the peaks of the compounds represented by the following formulas.
I was able to determine. [0077] Embedded image Therefore, from this result, this engine oil
Zinc dithiophosphate used for is isopropyl
Mixture of alcohol and 1,3-dimethylbutyl alcohol
Zinc dialkyldiene synthesized from synthetic alcohol
It was found to be a mixture of thiophosphates. [0079] Comparative Example 1 Commercially available engine oil used in Example 1 was dissolved in an organic solvent.
Sample diluted 10 times with medium (chloroform)
The high-performance liquid chromatograph was set to the same conditions as in Example 1.
When 10 μl of the injection was injected into the
No peak appears in the chromatogram, and zinc dithiophosphate
No identification was possible.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a chromatogram showing the results of the chromatography of Example 1.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kiyoshi Nakiaki 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Japan Inside the Central Research Laboratory of Petroleum Corporation (56) References JP-A-5-149940 (JP, A) JP-A-9-236593 (JP, A) JP-A-3-267758 (JP, A) JP-A-9-184832 (JP, A) JP-A-6-230002 (JP, A) (58) Int.Cl. ⁷ , DB name) G01N 30/88 G01N 30/06 G01N 30/74 G01N 31/00

Claims (1)

(57) [Claim 1] An oily substance containing a sulfur-containing metal complex,
(A) a halogen-containing organic compound A-CH ₂ -X (1) represented by the following formula (1) (where A represents an organic residue having an aromatic ring and having 6 to 40 carbon atoms, and X represents bromine (Indicating an atom, a chlorine atom or an iodine atom) and (B) a basic compound, and after reacting, subjecting the reaction product to high performance liquid chromatography and detecting with an optical detector, an oily property A method for analyzing a sulfur-containing organometallic complex in a substance.