U.S. patent application number 09/508535 was filed with the patent office on 2002-01-24 for sulfur-containing organophosphorus compounds.
Invention is credited to HATA, HITOSHI, KOSHIMA, HIROAKI, SONODA, NOBORU, TERADA, IZUMI.
Application Number | 20020010102 09/508535 |
Document ID | / |
Family ID | 17516382 |
Filed Date | 2002-01-24 |
United States Patent
Application |
20020010102 |
Kind Code |
A1 |
KOSHIMA, HIROAKI ; et
al. |
January 24, 2002 |
SULFUR-CONTAINING ORGANOPHOSPHORUS COMPOUNDS
Abstract
New sulfur-containing organophosphorus compounds of general
formulae (I) and (II) and processes for producing the same;
additives for lubricating oils, which contain the sulfur-containing
organophosphorus compounds; and lubricating oil compositions
satisfying requirements of extreme-pressure lubrication and
abrasion resistance under severe conditions of high loads imposed,
on automatic or continuously variable transmissions or the like. In
said formulae, R1 is a hydrocarbon group having 6 to 20 carbon
atoms; R2 is a divalent hydrocarbon group having 1 to 6 carbon
atoms; n is an integer of 1 to 3; p is an integer of 0 to 2; and q
is an integer of 0 or 1, with the proviso that p and q cannot be 0
at the same time.
Inventors: |
KOSHIMA, HIROAKI; (CHIBA,
JP) ; HATA, HITOSHI; (CHIBA, JP) ; SONODA,
NOBORU; (CHIBA, JP) ; TERADA, IZUMI; (CHIBA,
JP) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT
1755 JEFFERSON DAVIS HIGHWAY
FOURTH FLOOR
ARLINGTON
VA
22202
US
|
Family ID: |
17516382 |
Appl. No.: |
09/508535 |
Filed: |
April 4, 2000 |
PCT Filed: |
October 5, 1998 |
PCT NO: |
PCT/JP98/04490 |
Current U.S.
Class: |
508/432 ;
508/433; 508/434; 508/441; 558/186 |
Current CPC
Class: |
C10N 2040/042 20200501;
C10N 2040/044 20200501; C07F 9/4006 20130101; C10M 137/105
20130101; C10M 2223/047 20130101; C07F 9/4075 20130101; C10N
2040/046 20200501; C07F 9/1411 20130101; C10N 2040/04 20130101 |
Class at
Publication: |
508/432 ;
508/441; 508/434; 508/433; 558/186 |
International
Class: |
C10M 137/04; C10M
137/10; C10M 137/14; C10M 137/12 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 6, 1997 |
JP |
9-272613 |
Claims
1. At least one sulfur-containing organophosphorus compound
selected from compounds of a general formula
(I):(R.sup.1--S--R.sup.2--O).sub.n--P--(OH- ).sub.3-n (I)wherein
R.sup.1 represents a hydrocarbon group having from 6 to 20 carbon
atoms; R.sup.2 represents a divalent hydrocarbon group having from
1 to 6 carbon atoms; and n indicates an integer of from 1 to 3, and
a general formula (II): 14wherein R.sup.1 and R.sup.2 have the same
meanings as above; p indicates an integer of from 0 to 2, and q
indicates an integer of 0 or 1, with the proviso that p and q
cannot be 0 at the same time.
2. At least one sulfur-containing organophosphorus compound
selected from compounds of formulae (I) and (II) wherein n=1, those
wherein n=2, those wherein p=1 and q=0, those wherein p=1 and q=1,
and those wherein p=2 and q=0.
3. A method for producing sulfur-containing organophosphorus
compounds of claim 1 or 2, which comprises reacting an
alkylthioalkyl alcohol of a general formula
(III):R.sup.1--S--R.sup.2--OH (III)wherein R.sup.1 and R.sup.2 have
the same meanings as above, with phosphorus trichloride in the
absence of a catalyst or in the presence of a base.
4. Additives for lubricating oils, which contain at least one
sulfur-containing organophosphorus compound selected from compounds
of a general formula
(IV):[R.sup.1--(X--R.sup.2).sub.m--Y].sub.n--P--(OH).sub.- 3-n
(IV)wherein R.sup.1 and R.sup.2 have the same meanings as above; X
and Y each represent S (sulfur) or O (oxygen), and either one of X
and Y is S; m indicates an integer of from 0 to 4 (provided that,
when n=3, m is an integer of from 1 to 4); and n has the same
meaning as above, and a general formula (V): 15wherein m indicates
an integer of from 0 to 4; and X, Y, R.sup.1, R.sup.2, p and q have
the same meanings as above.
5. Additives for lubricating oils, which contain at least one
sulfur-containing organophosphorus compound selected from compounds
of a general formula
(VI):(R.sup.1--S--R.sup.2--Y).sub.n--P--(OH).sub.3-n (VI)wherein
R.sup.1, R.sup.2, Y and n have the same meanings as above, and a
general formula (VII): 16wherein R.sup.1, R.sup.2, Y, p and q have
the same meanings as above.
6. Additives for lubricating oils, which contain at least one
sulfur-containing organophosphorus compound selected from compounds
of the following general formulae (VIII), (IX), (X), (XI) and
(XII):R.sup.1--S--R.sup.2--O--P--(OH).sub.2
(VIII)(R.sup.1--S--R.sup.2--- O).sub.2--P--OH (IX) 17wherein
R.sup.1 and R.sup.2 have the same meanings as above.
7. Lubricating oil compositions comprising base oil and an
effective amount of the sulfur-containing organophosphorus compound
of any one of claims 4 to 6.
Description
TECHNICAL FIELD
[0001] The present invention relates to novel sulfur-containing
organophosphorus compounds and a method for producing them, to
additives for lubricating oils that contain the sulfur-containing
organophosphorus compound, and to lubricating oil compositions
comprising the sulfur-containing organophosphorus compound.
BACKGROUND OF THE INVENTION
[0002] In mechanical devices driving, some parts slide or roll on
others being in contact with them whereby their metal surfaces are
often worn. Lubricating oils are applied to them and are required
to have the ability to prevent or reduce the surface wear. For the
purpose of improving the anti-wear capabilities of lubricating oils
and preventing their capabilities from being degraded so as to
prolong the life of mechanical devices to which they are applied,
additives to lubricating oils take an extremely important role. For
example, base oil alone of lubricating oils could not enjoy many
particular properties satisfying the requirements of transmission
oil compositions and other lubricating oil compositions. Therefore,
additives must be added to lubricating oils so as to improve the
capabilities of the lubricating oil compositions. In that
situation, various attempts have heretofore been made in the art
for finding out novel additives for lubricating oils which have one
or more properties suitable to use in lubricating oil
compositions.
[0003] Known are phosphorus compounds and sulfur compounds as
extreme-pressure agents. Some attempts have been made to produce
novel compounds containing both phosphorus and sulfur atoms in one
molecule and to use them as additives to lubricating oils. For
example, U.S. Pat. Nos. 2,750,342, 2,960,523, 4,511,480, and
Japanese Patent Laid-Open No. 3471/1997 disclose various
phosphates, none of which, however, satisfies the requirements of
extreme-pressure lubricity, wear resistance and frictional
characteristics under severe conditions of high loads.
[0004] Taking the above into consideration, we, the present
inventors have made the invention. The invention is to provide
novel sulfur-containing organophosphorus compounds and a method for
producing them, to provide additives for lubricating oils that
contain the sulfur-containing organophosphorus compounds, and to
provide lubricating oil compositions containing the additive and
capable of satisfying the requirements of extreme-pressure
lubricity, wear resistance and frictional characteristics even
under severe conditions of high loads such as those imposed on
automatic or continuously variable transmissions and the like.
DISCLOSURE OF THE INVENTION
[0005] We, the present inventors have assiduously studied for the
purpose of attaining the object as above, and, as a result, have
found novel sulfur-containing organophosphorus compounds and have
completed the invention.
[0006] Specifically, the first aspect of the invention is to
provide at least one sulfur-containing organophosphorus compound
selected from compounds of a general formula (I):
(R.sup.1--S--R.sup.2--O).sub.n--P--(OH).sub.3-n (I)
[0007] wherein R.sup.1 represents a hydrocarbon group having from 6
to 20 carbon atoms; R.sup.2 represents a divalent hydrocarbon group
having from 1 to 6 carbon atoms; and n indicates an integer of from
1 to 3,
[0008] and a general formula (II): 1
[0009] wherein R.sup.1 and R.sup.2 have the same meanings as above;
p indicates an integer of from 0 to 2, and q indicates an integer
of 0 or 1, with the proviso that p and q cannot be 0 at the same
time.
[0010] The second aspect of the invention is to provide a method
for producing the sulfur-containing organophosphorus compounds of
the first aspect as above, which comprises reacting an
alkylthioalkyl alcohol of a general formula (III):
R.sup.1--S--R.sup.2--OH (III)
[0011] wherein R.sup.1 and R.sup.2 have the same meanings as above,
with phosphorus trichloride in the absence of a catalyst or in the
presence of a base.
[0012] The third aspect of the invention is to provide additives
for lubricating oils, which contain at least one sulfur-containing
organophosphorus compound selected from compounds of a general
formula (IV):
[R.sup.1--(X--R.sup.2).sub.m--Y].sub.n--P--(OH).sub.3-n (IV)
[0013] wherein R.sup.1 and R.sup.2 have the same meanings as above;
X and Y each represent S (sulfur) or O (oxygen), and either one of
X and Y is S; m indicates an integer of from 0 to 4 (provided that,
when n=3, m is an integer of from 1 to 4); and n has the same
meaning as above,
[0014] and a general formula (V): 2
[0015] wherein m indicates an integer of from 0 to 4; and X, Y,
R.sup.1, R.sup.2, p and q have the same meanings as above.
[0016] The fourth aspect of the invention is to provide lubricating
oil compositions comprising an effective amount of the
sulfur-containing organophosphorus compound as above.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is the spectral pattern of the reaction product of
Production Example 1 of the invention, appearing in phosphorus
nuclear magnetic resonance spectrometry of the product; and FIG. 2
is the spectral pattern of the reaction product of Production
Example 1, appearing in proton nuclear magnetic resonance
spectrometry of the product
BEST MODES OF CARRYING OUT THE INVENTION
[0018] Best modes of carrying out the invention are described
below.
[0019] The first aspect of the invention is to provide at least one
sulfur-containing organophosphorus compound selected from compounds
of formulae (I) and (II) noted above.
[0020] In formulae (I) and (II), R.sup.1 represents a hydrocarbon
group having from 6 to 20 carbon atoms, concretely including alkyl
groups such as all types of hexyl groups, all types of heptyl
groups, all types of octyl groups, all types of nonyl groups, all
types of decyl groups, all types of undecyl groups, all types of
dodecyl groups, all types of tridecyl groups, all types of
tetradecyl groups, all types of pentadecyl groups, all types of
hexadecyl groups, all types of heptadecyl groups, all types of
octadecyl groups, all types of nonadecyl groups, all types of
eicodecyl groups; cycloalkyl groups such as cyclohexyl group, all
types of methylcyclohexyl groups, all types of ethylcyclohexyl
groups, all types of propylcycloalkyl group, all types of
dimethylcycloalkyl groups, etc.; aryl groups such as phenyl group,
all types of methylphenyl groups, all types of ethylphenyl groups,
all types of propylphenyl groups, all types of trimethylphenyl
groups, all types of butylphenyl groups, all types of naphthyl
groups, etc.; arylalkyl groups such as benzyl group, all types of
phenylethyl groups, all types of methylbenzyl groups, all types of
phenylpropyl groups, all types of phenylbutyl groups, etc. Of
those, preferred are alkyl groups having from 8 to 16 carbon
atoms.
[0021] In formulae (I) and (II), R.sup.2 represents a divalent
hydrocarbon group having from 1 to 6 carbon atoms, concretely
including divalent aliphatic groups such as methylene group,
ethylene group, 1,2-propylene group, 1,3-propylene group, all types
of butylene groups, all types of pentylene groups, all types of
hexylene groups; alicyclic groups with two bonding sites from
alicyclic hydrocarbons such as cyclohexane, methylcyclopentane,
etc.; all types of phenylene groups, etc. Of those, preferred are
methylene group, ethylene group, and all types of propylene
groups.
[0022] In formula (I), n indicates an integer of from 1 to 3, but
is preferably 1 or 2.
[0023] In formula (II), p indicates an integer of from 0 to 2, and
q indicates an integer of 0 or 1, with the proviso that p and q
cannot be 0 at the same time. Preferably, p=1 and q=0; or p=1 and
q=1; or p=2 and q=0.
[0024] Specific examples of the sulfur-containing organophosphorus
compounds of formulae (I) and (II) include tri(octylthioethoxy)
phosphite, tri(dodecylthioethoxy) phosphite,
tri(hexadecylthioethoxy) phosphite, di(octylthioethoxy) phosphite,
di(dodecylthioethoxy) phosphite, di(hexadecylthioethoxy) phosphite,
mono(octylthioethoxy) phosphite, mono(dodecylthioethoxy) phosphite,
mono(hexadecylthioethoxy) phosphite, octylthioethyl
octylthioethylphosphonate, dodecylthioethyl
dodecylthioethylphosphonate, hexadetylthioethyl
hexadecylthioethylphospho- nate, etc. These di- and mono-esters
include their tautomers.
[0025] The method for producing the sulfur-containing
organophosphorus compounds of formulae (I) and (II) is not
specifically defined. For example, the compounds may be produced by
reacting an alkylthioalkyl alcohol of a general formula (III):
R.sup.1--S--R.sup.2--OH (III)
[0026] wherein R.sup.1 and R.sup.2 have the same meanings as above,
with phosphorus trichloride in the absence of a catalyst or in the
presence of a base.
[0027] Regarding the ratio by mol of the reactants in the method,
the amount of the alkylthioalkyl alcohol to be reacted with
phosphorus trichloride may fall generally between 0.1 and 5.0 mols,
preferably between 1.0 and 3.0 mols, more preferably between 1.5
and 2.5 mols, relative to one mol of phosphorus trichloride.
[0028] The reaction temperature may fall generally between -10 and
100.degree. C., preferably between 0 and 40.degree. C. The base
serving as the catalyst includes, for example, triethylamine,
pyridine, etc. The reaction may be effected in a solvent such as
THF, diethyl ether or the like.
[0029] The third aspect of the invention is to provide additives
for lubricating oils, which contain at least one sulfur-containing
organophosphorus compound selected from compounds of a general
formula (IV):
[R.sup.1--(X--R.sup.2).sub.m--Y].sub.n--P--(OH).sub.3-n (IV)
[0030] wherein R.sup.1 and R.sup.2 have the same meanings as above;
X and Y each represent S (sulfur) or O (oxygen), and either one of
X and Y is S; m indicates an integer of from 0 to 4 (provided that,
when n=3, m is an integer of from 1 to 4); and n has the same
meaning as above,
[0031] and a general formula (V): 3
[0032] wherein m indicates an integer of from 0 to 4; and X, Y,
R.sup.1, R.sup.2, p and q have the same meanings as above.
[0033] In formulae (IV) and (V), R.sup.1, R.sup.2, n, p and q are
the same as those in the first aspect of the invention. In formulae
(IV) and (V), m is preferably an integer falling between 1 and
4.
[0034] More preferably, the third aspect of the invention provides
additives for lubricating oils, which contain at least one
sulfur-containing organophosphorus compound selected from compounds
of a general formula (VI):
(R.sup.1--S--R.sup.2--Y).sub.n--P--(OH).sub.3-n (VI)
[0035] wherein R.sup.1, R.sup.2, Y and n have the same meanings as
above, and a general formula (VII): 4
[0036] wherein R.sup.1, R.sup.2, Y, p and q have the same meanings
as above.
[0037] Even more preferably, the additives for lubricating oils
contain at least one sulfur-containing organophosphorus compound
selected from compounds of the following general formulae (VIII),
(IX), (X), (XI) and (XII):
R.sup.1--S--R.sup.2--O--P--(OH).sub.2 (VIII)
(R.sup.1--S--R.sup.2--O).sub.2--P--OH (IX)
[0038] 5
[0039] wherein R.sup.1 and R.sup.2 have the same meanings as
above.
[0040] Where the sulfur-containing organophosphorus compounds are
used as additives to lubricating oils, (1) they are used as they
are, or (2) they are diluted with base oil of lubricating oils,
before added to lubricating oils, or (3) they are combined with
other additives, which will be mentioned hereinunder, into packages
for use in lubricating oils. Therefore, the content of the
sulfur-containing organophosphorus compound to be in the additives
for lubricating oils may fall generally between 0.1 and 100% by
weight.
[0041] The lubricating oils to which the additives of the third
aspect of the invention are added are not specifically defined,
including, for example, transmission oils for automatic or
continuous variable transmissions, gear oils, engine oils for
internal-combustion engines, bearing oils, shock absorber oils,
cutting fluids, forming lubricants, rolling oils and other various
lubricating oils for industrial use.
[0042] The fourth aspect of the invention is to provide lubricating
oil compositions comprising base oil and an effective amount of at
least one sulfur-containing organophosphorus compound as above.
[0043] As the base oil, usable is any of mineral oils and synthetic
oils. Known are various mineral oils and synthetic oils, from which
may be selected appropriate ones for use in the invention,
depending on their applications. For example, mineral oils include
paraffinic mineral oils, naphthenic mineral oils, and mineral,
intermediate base crude oils. As their specific examples, mentioned
are solvent-purified or hydrogenated, light neutral oils,
medium-gravity neutral oils, heavy neutral oils, bright stocks,
etc.
[0044] Synthetic oils include, for example, poly-.alpha.-olefins,
.alpha.-olefin copolymers, polybutenes, alkylbenzenes,
polyolesters, esters of dibasic acids, esters of polyalcohols,
polyoxyalkylene glycols, esters of polyoxyalkylene glycols,
polyalkylene glycol ethers, cycloalkane compounds, etc.
[0045] These base oils can be used either singly or as combined. As
the case may be, mineral oils and synthetic oils can be combined
for use in the invention.
[0046] The effective amount of the sulfur-containing
organophosphorus compound to be in the lubricating oil compositions
varies, depending on the use of the compositions, but may fall
generally between 0.01 and 10% by weight, preferably between 0.1
and 5% by weight of the composition.
[0047] In addition to the additive noted above, the lubricating oil
compositions of the invention may optionally contain any additional
additives which have heretofore been used in ordinary lubricating
oil compositions, such as detergent dispersants, antioxidants, rust
inhibitors, defoaming agents, viscosity index improvers, pour point
depressants, demulsifying agents, other extreme-pressure
lubrication improvers, other anti-wear additives, etc., so far as
the additional additives do not detract from the object of the
invention.
[0048] The lubricating oil compositions of the invention can be
used, for example, as lubricating oils for power transmissions,
lubricating oils for internal-combustion engines, gear oils,
bearing oils, shock absorber oils, and lubricating oils for
industrial machines.
[0049] The invention is described in more detail with reference to
the following Examples, which, however, are not intended to
restrict the scope of the invention.
Production Example 1
[0050] 38.1 g (0.2 mols) of n-octylthioethanol, 20.2 g (0.2 mols)
of triethylamine and 250 ml of THF were put into a 500 ml flask and
stirred to give a uniform liquid. With cooling the liquid with ice,
13.7 g (0.1 mols) of phosphorus trichloride was dropwise added
thereto in a nitrogen atmosphere, and stirred at room temperature
for 1 hour. The side product, triethylamine hydrochloride was
removed through filtration. 1.8 g (0.1 mols) of water was dropwise
added to the reaction mixture, and stirred at room temperature for
one full day. Then, THF was evaporated away under reduced pressure,
using an evaporator. The yield of the thus-obtained reaction
product was 42 g.
[0051] By its phosphorus nuclear magnetic resonance spectrometry
(FIG. 1) and proton nuclear magnetic resonance spectrometry (FIG.
2), the reaction product was identified as the compound of the
following formula (XIII): 6
Production Example 2
[0052] 13.7 g (0.1 mols) of phosphorus trichloride and 50 ml of THF
were put into a 500 ml flask and stirred to give a uniform liquid.
With cooling the liquid with ice, a mixture of 38.1 g (0.2 mols) of
n-octylthioethanol, 20.2 g (0.2 mols) of triethylamine and 250 ml
of THF was dropwise added thereto in a nitrogen atmosphere, and
stirred at room temperature for 1 hour. The side product,
triethylamine hydrochloride was removed through filtration. 1.8 g
(0.1 mols) of water was dropwise added to the reaction mixture, and
stirred at room temperature for one full day. Then, THF was
evaporated away under reduced pressure, using an evaporator. The
yield of the thus-obtained reaction product was 41 g.
[0053] By its phosphorus nuclear magnetic resonance spectrometry
and proton nuclear magnetic resonance spectrometry, the reaction
product was identified as the compound of above formula (XIII).
Production Example 3
[0054] The same process as in Production Example 2 was repeated,
except that 38.6 g (0.2 mols) of n-dodecylthioethanol was used in
place of octylthioethanol. The yield of the reaction product
obtained herein was 51 g.
[0055] By its phosphorus nuclear magnetic resonance spectrometry
and proton nuclear magnetic resonance spectrometry, the reaction
product was identified as the compound of the following formula
(XIV). 7
Production Example 4
[0056] The same process as in Production Example 2 was repeated,
except that 60.5 g (0.2 mols) of n-hexadecylthioethanol was used in
place of n-octylthioethanol. The yield of the reaction product
obtained herein was 65 g. By its phosphorus nuclear magnetic
resonance spectrometry and proton nuclear magnetic resonance
spectrometry, the reaction product was identified as the compound
of the following formula (XV). 8
Production Example 5
[0057] The same process as in Production Example 2 was repeated,
except that the amount of n-octylthioethanol to be used was varied
to 28.5 g (0.15 mols) and that of water was to 2.7 g (0.15 mols).
The yield of the reaction product obtained herein was 33 g.
[0058] By its phosphorus nuclear magnetic resonance spectrometry
and proton nuclear magnetic resonance spectrometry, the reaction
product was identified as a mixture of compounds of the following
formula (XVI) and the above formula (XIII). 9
[0059] The mixture was subjected to liquid chromatography (through
a reversed-phase column with a solvent of acetonitrile, equipped
with a differential refractiometer serving as a detector) The data
confirmed that the mixture was comprised of 44% by weight of the
compound of formula (XVI) and 56% by weight of the compound of
formula (XIII).
Production Example 6
[0060] The same process as in Production Example 2 was repeated,
except that the amount of n-octylthioethanol to be used was varied
to 47.6 g (0.25 mols), that of triethylamine was to 25.3 g (0.25
mols) and that of water was to 0.9 g (0.05 mols) . The yield of the
reaction product obtained herein was 52 g.
[0061] By its phosphorus nuclear magnetic resonance spectrometry
and proton nuclear magnetic resonance spectrometry, the reaction
product was identified as a mixture of compounds of the following
formula (XVII) and the above formula (XIII). 10
[0062] The mixture was subjected to liquid chromatography (through
a reversed-phase column with a solvent of acetonitrile, equipped
with a differential refractiometer serving as a detector). The data
confirmed that the mixture was comprised of 51% by weight of the
compound of formula (XVII) and 49% by weight of the compound of
formula (XIII).
Production Example 7
[0063] 13.7 g (0.1 mols) of phosphorus trichloride and 100 ml of
diethyl ether were put into a 500 ml flask, and stirred to give a
uniform liquid. With cooling the liquid with ice, a solution in
diethyl ether of 27.7 g (0.1 mols) of n-octylthioethylmagnesium
bromide was dropwise added thereto in a nitrogen atmosphere, and
stirred at a temperature not higher than 10.degree. C. for 1 hour.
Then, this was further stirred at room temperature for 1 hour. The
reaction mixture was poured into an aqueous 5% hydrochloric acid
solution cooled with ice, to stop the reaction. This was extracted
with diethyl ether, and the resulting extract was dried with
anhydrous magnesium sulfate. Then, diethyl ether was evaporated
away, and 21 g (yield: 75%) of n-octylthioethyldichlorophosphine
was obtained.
[0064] 13.7 g (0.05 mols of the thus-obtained
n-octylthioethyldichlorophos- phine and 50 ml of THF were put into
a 500 ml flask, and stirred to give a uniform liquid. With cooling
the liquid with ice, a mixture of 9.5 g (0.05 mols) of
n-octylthioethanol, 5.1 g (0.05 mols) of triethylamine and 100 ml
of THF was dropwise added thereto in a nitrogen atmosphere, and
stirred at room temperature for 1 hour. The side product,
triethylamine hydrochloride was removed through filtration. 0.9 g
(0.05 mols) of water was dropwise added to the reaction mixture,
and stirred at room temperature for one full day. Then, THF was
evaporated away under reduced pressure, using an evaporator. The
yield of the thus-obtained reaction product was 20 g.
[0065] By its phosphorus nuclear magnetic resonance spectrometry
and proton nuclear magnetic resonance spectrometry, the reaction
product was identified as the compound of the following formula
(XVIII): 11
Production Example 8
[0066] The same process as in Production Example 1 was repeated,
except that 21.2 g (0.2 mols) of ethylthioethanol was used in place
of n-octylthioethanol. The yield of the reaction product obtained
herein was 33 g.
[0067] By its phosphorus nuclear magnetic resonance spectrometry
and proton nuclear magnetic resonance spectrometry, the reaction
product was identified as the compound of the following formula
(XIX). 12
Production Example 9
[0068] The same process as in Production Example 1 was repeated,
except that 15.3 g (0.1 mols) of phosphorus oxychloride was used in
place of phosphorus trichloride. The yield of the reaction product
obtained herein was 44 g.
[0069] By its phosphorus nuclear magnetic resonance spectrometry
and proton nuclear magnetic resonance spectrometry, the reaction
product was identified as the compound of the following formula
(XX). 13
Examples 1 to 7
Comparative Examples 1 to 4, and Reference Example 1
[0070] To a cycloalkane-type, synthetic base oil, added were 1% by
weight (based on the total weight of the resulting composition--the
same shall apply hereunder) of the sulfur-containing
organophosphorus compound prepared in any of Production Examples
mentioned above, or a commercial product, phosphite or
thiophosphite, 1% by weight of a detergent dispersant, 0.5% by
weight of an antioxidant, 0.1% by weight of a rust inhibitor, and
0.1% by weight of a defoaming agent to prepare different
lubricating oil compositions. The compositions were subjected to a
Falex block on ring test (frictional wear test, according to ASTM
D-3704) under the conditions mentioned below, to evaluate their
properties. The data obtained are in Table 1. Apart from those,
prepared was another lubricating oil composition containing none of
the sulfur-containing organophosphorus compounds of the invention
and the commercial products of phosphite and thiophosphite, as
Reference Example 1. This was also subjected to the same test.
Conditions for Frictional Wear Test
[0071] Ring: made of SAE 4620 steel.
[0072] Block: made of SAE 01 steel.
[0073] Temperature: 130.degree. C.
[0074] Rotation Speed: 0.367 m/sec.
[0075] Load: 1500 N.
[0076] Time: 60 minutes.
[0077] Matters checked: appearance of ring, degree of ring wear,
width of block wear, degree of block wear, change in coefficient of
friction.
1 TABLE 1-1 Frictional Wear Test Data Degree of Width of Appearance
of Ring Wear Block Wear Additive Ring*1 (mg) (mm) Example 1
Production .smallcircle. 0.2 0.743 Example 1 Example 2 Production
.smallcircle. 0.1 0.686 Example 2 Example 3 Production
.smallcircle. 0.1 0.669 Example 3 Example 4 Production
.smallcircle. 0.1 0.706 Example 4 Example 5 Production
.smallcircle. 0.0 0.654 Example 5 Example 6 Production
.smallcircle. 0.2 0.735 Example 6 Example 7 Production
.smallcircle. 0.1 0.725 Example 7 Comparative Production .DELTA.
0.5 0.934 Example 1 Example 8 Comparative Substance A*2 .DELTA. 0.3
0.846 Example 2 Comparative Substance B*3 x 4.4 0.872 Example 3
Comparative Production x 4.7 1.037 Example 4 Example 9 Reference --
x 3.9 1.016 Example 1 *1: .smallcircle. indicates that the ring
surface was smooth. .DELTA. indicates that the ring surface changed
gray. x indicates that the ring surface changed black. *2:
Di(dodecyl) phosphite. *3: Tridodecyl trithiophosphite.
[0078]
2 TABLE 1-2 Frictional Wear Test Data Degree of Block Wear Change
in Coefficient (mg) of Friction*4 Example 1 0.1 .smallcircle.
Example 2 0.0 .smallcircle. Example 3 0.0 .smallcircle. Example 4
0.0 .smallcircle. Example 5 0.0 .smallcircle. Example 6 0.1
.smallcircle. Example 7 0.0 .smallcircle. Comparative Example 1 0.1
x Comparative Example 2 0.1 x Comparative Example 3 0.2 x
Comparative Example 4 0.2 x Reference Example 1 0.3 x *4:
.smallcircle. indicates that the change was smaller than 0.01. x
indicates that the change was 0.01 or above.
[0079] From the data in Table 1, it is understood that the
lubricating oil compositions containing any of the
sulfur-containing organophosphorus compounds of the invention are
all good in that they have no negative influence on the ring in the
test, that they wear little the ring and the block, that the width
of the block tested with them is reduced little, and that their
coefficient of friction changes little.
[0080] It is also understood therefrom that the lubricating oil
compositions containing any of the compounds of Production Examples
8 and 9 (though their structures are similar to the structures of
the sulfur-containing organophosphorus compounds of the invention)
and the commercial products, phosphite and thiophosphite are all
inferior to the compositions of the invention with respect to all
the matters checked in the test.
INDUSTRIAL APPLICABILITY
[0081] The lubricating oil compositions that contain the
sulfur-containing organophosphorus compound of the invention
satisfy the requirements of extreme-pressure lubrication, wear
resistance and frictional characteristics even under severe
conditions of high loads such as those imposed on automatic or
continuous variable transmissions and the like. Therefore, they
have many applications in the field of lubricating oils.
* * * * *