TECHNICAL FIELD
[0001] The present invention relates to viscosity index improver compositions and lubricating
oil compositions.
BACKGROUND ART
[0002] In recent years, there has been an increasing demand for lower fuel consumption of
vehicles in order to reduce CO
2 emissions and protect petroleum resources. One approach to reduce fuel consumption
is to lower the viscosity of engine oil. However, too low viscosity, especially at
high temperatures, may cause problems such as oil leakage and seizure. Regarding these
problems, the standard for engine oil viscosity (SAE J300) by SAE International (USA)
specifies the minimum guaranteed viscosity. The standard defines grade 0W-20 oil as
having a high temperature high shear (HTHS) viscosity at 150°C (ASTM D4683 or D5481)
of 2.6 mPa·s or higher and grade 0W-16 oil as having an HTHS viscosity at 150°C of
2.3 mPa·s or higher.
[0003] Nowadays, hybrid vehicles and plug-in hybrid vehicles, which use both electricity
and gasoline, and other hardware approaches are also being developed to lower fuel
consumption. Unlike traditional gasoline-driven vehicles, such hybrid vehicles have
low engine oil temperatures during driving. Specifically, the engine oil temperature
during normal driving is usually 80°C to 100°C in gasoline-driven vehicles, while
it is 40°C to 80°C in hybrid vehicles. Thus, engine oils used in hybrid or similar
vehicles require even lower viscosity in the range of 40°C to 80°C. Thus, it is a
common practice to add a viscosity index improver to a lubricating oil to modify the
temperature dependence of the viscosity. Viscosity index improvers that have been
used include methacrylate copolymers (Patent Literatures 1 to 3) and comb copolymers
(Patent Literatures 4 to 6). Comb copolymers are particularly known to have high modifying
effect on the temperature dependence of the viscosity.
[0004] Considering handleability, viscosity index improvers are generally distributed in
the form of viscosity index improver compositions containing high concentrations of
copolymers in base oils. However, viscosity index improver compositions containing
high concentrations of comb copolymers may form gels when exposed to high-temperature
environments in summer or to low-temperature environments in winter or in cold regions.
CITATION LIST
- Patent Literature
SUMMARY OF INVENTION
- Technical Problem
[0006] The present invention aims to provide a viscosity index improver composition that
is less likely to form gels.
- Solution to Problem
[0007] As a result of extensive studies, the present inventors devised the present invention.
[0008] Specifically, the present invention relates to a viscosity index improver composition
containing a copolymer (A) containing, as essential constituent monomers, a polyolefin-based
monomer (a) represented by the following formula (1) and an alkyl (meth)acrylate (b)
having a C1-C4 alkyl group, and a Fischer-Tropsch derived base oil (B) having a kinematic
viscosity at 100°C of 4.0 mm
2/s or less, the copolymer (A) containing the monomer (a) in an amount of 1 to 20 wt%
and the alkyl (meth)acrylate (b) in an amount of 45 to 85 wt% based on the total weight
of the monomers constituting the copolymer (A); and a lubricating oil composition
containing the viscosity index improver composition and at least one additive selected
from the group consisting of a detergent, a dispersant, an antioxidant, an oiliness
improver, a pour point depressant, a friction and wear modifier, an extreme pressure
agent, a defoamer, a demulsifier, a metal deactivator, and a corrosion inhibitor.

[0009] In the formula (1), R
1 is a hydrogen atom or a methyl group; -X
1- is a group represented by -O-, -O(AO)
m-, or - NH-, A is a C2-C4 alkylene group, m is an integer of 1 to 10, and each A may
be the same or different when m is 2 or greater; R
2 is a residue after removal of one hydrogen atom from a hydrocarbon polymer containing
a 1,2-butylene group as a structural unit; and p represents a number of 0 or 1.
- Advantageous Effects of Invention
[0010] The viscosity index improver composition of the present invention is advantageously
less likely to form gels.
DESCRIPTION OF EMBODIMENTS
[0011] The viscosity index improver composition of the present invention contains a copolymer
(A) containing, as essential constituent monomers, a polyolefin-based monomer (a)
represented by the following formula (1) and an alkyl (meth)acrylate (b) having a
C1-C4 alkyl group, and a Fischer-Tropsch derived base oil (B) having a kinematic viscosity
at 100°C of 4.0 mm
2/s or less, the copolymer (A) containing the monomer (a) in an amount of 1 to 20 wt%
and the alkyl (meth)acrylate (b) in an amount of 45 to 85 wt% based on the total weight
of the monomers constituting the copolymer (A).

[0012] In the formula (1), R
1 is a hydrogen atom or a methyl group; -X
1- is a group represented by -O-, -O(AO)
m-, or - NH-, A is a C2-C4 alkylene group, m is an integer of 1 to 10, and each A may
be the same or different when m is 2 or greater; R
2 is a residue after removal of one hydrogen atom from a hydrocarbon polymer containing
a 1,2-butylene group as a structural unit; and p represents a number of 0 or 1.
<Copolymer (A)>
[0013] The copolymer (A) in the present invention contains, as essential constituent monomers,
a polyolefin-based monomer (a) represented by the formula (1) and an alkyl (meth)acrylate
(b) having a C1-C4 alkyl group.
[0014] The polyolefin-based monomer (a) in the present invention is a monomer obtained by
modifying the later-described hydrocarbon polymer and reacting the modified hydrocarbon
polymer with (meth)acrylic acid. The term "(meth)acrylic" means methacrylic or acrylic.
[0015] R
1 in the formula (1) is a hydrogen atom or a methyl group. Of these, a methyl group
is preferred in terms of viscosity index improving effect.
[0016] -X
1- in the formula (1) is a group represented by - O-, -O(AO)
m-, or -NH-.
[0017] A is a C2-C4 alkylene group.
[0018] Examples of the C2-C4 alkylene group include an ethylene group, a 1,2- or 1,3-propylene
group, and a 1,2-, 1,3-, or 1,4-butylene group.
[0019] m is an integer of 1 to 10, and it is preferably an integer of 1 to 4, more preferably
an integer of 1 to 2 in terms of HTHS viscosity in the effective temperature range
(80°C to 150°C).
[0020] Each A may be the same or different when m is 2 or greater, and each AO in the (AO)
m moiety may be bonded in a random form or a block form.
[0021] In terms of HTHS viscosity in the effective temperature range (80°C to 150°C), -X
1- is preferably a group represented by -O- or -O(AO)
m-, more preferably a group represented by -O- or -O(CH
2CH
2O)-.
[0022] p represents a number of 0 or 1.
[0023] R
2 in the formula (1) is a residue after removal of one hydrogen atom from a hydrocarbon
polymer containing a 1,2-butylene group (-CH
2CH(CH
2CH
3)- or CH(CH
2CH
3)CH
2-) as a structural unit.
[0024] Examples of the hydrocarbon polymer containing a 1,2-butylene group as a structural
unit include a polymer containing 1-butene as a constituent monomer and a polymer
obtained by hydrogenating a terminal carbon-carbon double bond of a poly(1,3-butadiene),
which is a product of 1,2-addition of 1,3-butadiene.
[0025] The hydrocarbon polymer may be a block polymer or a random polymer.
[0026] The hydrocarbon polymer containing a 1,2-butylene group as a structural unit may
further contain a structural unit other than the 1,2-butylene group.
[0027] Examples of constituent monomers constituting the hydrocarbon polymer include (1)
aliphatic unsaturated hydrocarbons, (2) alicyclic unsaturated hydrocarbons, and (3)
aromatic-group containing unsaturated hydrocarbons. When the hydrocarbon polymer has
double bonds, the double bonds may be partially or completely hydrogenated by adding
hydrogen.
[0028] Examples of constituent monomers constituting the hydrocarbon polymer include the
following. (1) Aliphatic unsaturated hydrocarbons (e.g., C2-C36 olefins (e.g., ethylene,
propylene, isobutene, 1-butene, 2-butene, pentene, heptene, diisobutylene, octene,
dodecene, octadecene, triacontene, and hexatriacontene) and C2-C36 dienes (e.g., 1,2-butadiene,
1,3-butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, and 1,7-octadiene)) (2) Alicyclic
unsaturated hydrocarbons (e.g., cyclohexene, (di)cyclopentadiene, pinene, limonene,
indene, vinylcyclohexene, and ethylidenebicycloheptene) (3) Aromatic group-containing
unsaturated hydrocarbons (e.g., styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene,
ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene,
crotylbenzene, vinylnaphthalene, divinylbenzene, divinyltoluene, divinylxylene, and
trivinylbenzene)
[0029] The hydrocarbon polymer composed of any of these monomers may be a block polymer
or a random polymer. When the hydrocarbon polymer has double bonds, the double bond
may be partially or completely hydrogenated by adding hydrogen. In one embodiment,
the hydrocarbon polymer in R
2 may be a hydrocarbon polymer containing only a C4 monomer as a constituent monomer.
The C4 monomer may be at least one selected from the group consisting of 1-butene
and 1,3-butadiene or a combination of isobutene and at least one selected from the
group consisting of 1-butene and 1,3-butadiene.
[0030] The monomer (a) preferably has a number average molecular weight (hereinafter abbreviated
as Mn) of 800 to 10,000, more preferably 1,000 to 9,500, still more preferably 1,200
to 9,000, particularly preferably 2,000 to 8,700. An Mn of the monomer (a) of 800
or greater tends to lead to good solubility in the Fischer-Tropsch derived base oil
(B). An Mn of the monomer (a) of 10,000 or less tends to lead to good copolymerizability
with other monomers.
[0031] The weight average molecular weight (hereinafter abbreviated as Mw) and Mn can be
measured by gel permeation chromatography (hereinafter abbreviated as GPC) under the
following conditions.
<Measuring conditions for Mw and Mn>
[0032]
Device: "HLC-8320GPC" (available from Tosoh Corporation)
Column: "TSKgel GMHXL" (available from Tosoh Corporation), two columns
[0033] "TSKgel Multipore H
XL-M", one column
Measurement temperature: 40°C
Sample solution: 0.25 wt% tetrahydrofuran solution
Volume of solution injected: 10.0 µl
Detecting device: refractive index detector
Reference material: standard polystyrene (TS reference material: standard polystyrene
(TSKstandard POLYSTYRENE)) 12 samples (molecular weight: 589, 1,050, 2,630, 9,100,
19,500, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,110,000, 4,480,000) (available
from Tosoh Corporation)
[0034] The monomer (a) can be obtained by esterification of a polymer (Y) having a hydroxy
group at one end with (meth)acrylic acid. The polymer (Y) can be obtained by introducing
a hydroxy group to one end of a hydrocarbon polymer. Alternatively, the monomer (a)
can be obtained by transesterification of a polymer (Y) having a hydroxy group at
one end with an alkyl (preferably C1-C4 alkyl) (meth)acrylate such as methyl (meth)acrylate.
[0035] Specific examples of the polymer (Y) having a hydroxy group at one end include the
following (Y1) to (Y4).
[0036] Alkylene oxide adduct (Y1): Examples include a product obtained by addition of an
alkylene oxide (e.g., ethylene oxide or propylene oxide) to a hydrocarbon polymer
obtained by polymerizing an unsaturated hydrocarbon (x) in the presence of an ionic
polymerization catalyst (e.g., sodium catalyst). In this case, the monomer (a) is
a compound represented by the formula (1) in which -X
1- is - (AO)
m- and p is 0.
[0037] Hydroborated product (Y2): Examples include a product obtained by hydroboration of
a hydrocarbon polymer of an unsaturated hydrocarbon (x) having a double bond at one
end (e.g., those disclosed in
U.S. Patent No. 4,316,973). In this case, the monomer (a) is a compound represented by the formula (1) in which
-X
1- is -O- and p is 0.
[0038] Maleic anhydride-ene-amino alcohol adduct (Y3): Examples include a product obtained
by amino alcohol-mediated imidization of a reaction product obtained by an ene reaction
of a hydrocarbon polymer of an unsaturated hydrocarbon (x) having a double bond at
one end with maleic anhydride. In this case, the monomer (a) is a compound represented
by the formula (1) in which -X
1- is -O- and p is 1.
[0039] Hydroformylated-hydrogenated product (Y4): Examples include a product obtained by
hydroformylation of a hydrocarbon polymer of an unsaturated hydrocarbon (x) having
a double bond at one end, followed by hydrogenation (e.g., those disclosed in
JP S63-175096 A). In this case, the monomer (a) is a compound represented by the formula (1) in which
-X
1- is -O- and p is 0.
[0040] In terms of viscosity index improving effect, preferred among these polymers (Y)
having a hydroxy group at one end are alkylene oxide adducts (Y1) and hydroborated
products (Y2). More preferred are alkylene oxide adducts (Y1).
[0041] In terms of viscosity index improving effect, the proportion of butadiene of all
monomers constituting R
2 in the formula (1) (weight percentage of 1,3-butadiene among all constituent monomers
of the hydrocarbon polymer containing a 1,2-butylene group as a structural unit) is
preferably 50 wt% or more, more preferably 75 wt% or more, still more preferably 85
wt% or more, particularly preferably 90 wt% or more.
[0042] In terms of viscosity index improving effect, the hydrocarbon polymer containing
a 1,2-butylene group as a structural unit in the formula (1) may contain an isobutylene
group.
[0043] In terms of viscosity index improving effect, the total amount of the isobutylene
group and the 1,2-butylene group is preferably 30 mol% or more, more preferably 40
mol% or more, still more preferably 50 mol% or more based on the total number of moles
of the constituent monomers of the hydrocarbon polymer.
[0044] For example, the following methods can be employed to increase the proportion of
the total amount of the isobutylene group and the 1,2-butylene group in the hydrocarbon
polymer. In the case of the alkylene oxide adduct (Y1), for example, the proportion
of the total amount of the isobutylene group and the 1,2-butylene group in the hydrocarbon
polymer can be increased by, in anionic polymerization using 1,3-butadiene, setting
the reaction temperature to be low {e.g., lower than or equal to the boiling temperature
(-4.4°C) of 1,3-butadiene} and adding a polymerization initiator in an amount smaller
than that of 1,3-butadiene. In the case of the hydroborated product (Y2), the maleic
anhydride-ene-amino alcohol adduct (Y3), and the hydroformylated-hydrogenated product
(Y4), the proportion can be increased by increasing the degree of polymerization of
the hydrocarbon polymer having a double bond at one end.
[0045] Regarding the structure derived from 1-butene and/or 1,3-butadiene in the hydrocarbon
polymer in the formula (1), the proportion of the 1,2-butylene group based on the
total number of moles of the constituent monomers of the hydrocarbon polymer (number
of moles of 1,2-butylene groups/total number of moles of constituent monomers × 100)
is preferably 30 mol% or more, more preferably 30 to 70 mol% in terms of viscosity
index improving effect and copolymerizability with other monomers.
[0046] The proportion of the 1,2-butylene group can be measured by
13C-NMR. Specifically, for example, when only C4 monomers are used, the proportion can
be determined by analyzing the hydrocarbon polymer by
13C-NMR and calculating the molar percentage of the 1,2-butylene group based on the
total number of moles of the structural units of the hydrocarbon polymer by the following
equation (1). In
13C-NMR, a peak derived from the tertiary carbon atom (-CH
2CH(CH
2CH
3)-) of the 1,2-butylene group appears at an integral value of 26 to 27 ppm (integral
value B). The total proportion can be determined from the integral value of the peak
and an integral value (integral value C) of all carbon peaks of the hydrocarbon polymer.
Proportion of 1,2-butylene group (mol%) = {(integral value B) × 4}/(integral value
C) × 100
[0047] The proportion of the 1,2-butylene group can be adjusted as follows: for example,
in the case of anionic polymerization using 1,3-butadiene, the proportion of the 1,2-butylene
group can be increased by setting the reaction temperature to a temperature lower
than or equal to the boiling point (-4.4°C) of 1,3-butadiene and adding a polymerization
initiator in an amount smaller than that of 1,3-butadiene, whereas the proportion
of the 1,2-butylene group can be decreased by setting the reaction temperature to
a temperature higher than or equal to the boiling point of 1,3-butadiene and adding
a polymerization initiator in an amount larger than that of 1,3-butadiene.
[0048] In the hydrocarbon polymer containing a 1,2-butylene group as a structural unit in
the formula (1), the total amount of the isobutylene group and the 1,2-butylene group
can be measured by
13C-NMR. Specifically, for example, when only C4 monomers are used, the proportion can
be determined by analyzing the hydrocarbon polymer by
13C-NMR and calculating the total molar percentage of the isobutylene group and the
1,2-butylene group based on the total number of moles of the structural units of the
hydrocarbon polymer by the following equation (2). In
13C-NMR, a peak derived from the methyl groups of the isobutylene group appears at an
integral value of 30 to 32 ppm (integral value A), and a peak derived from the branched
methylene groups (-CH
2CH(CH
2CH
3)- or -CH(CH
2CH
3)CH
2-) of the 1,2-butylene group appears at an integral value of 26 to 27 ppm (integral
value B). The total molar percentage (mol%) of the isobutylene group and the 1,2-butylene
group based on the total number of moles of the structural units of the hydrocarbon
polymer can be determined from the integral values of the above peaks and an integral
value (integral value C) of all carbon peaks of the hydrocarbon polymer.
Total amount of isobutylene group and 1,2-butylene group (mol%) = 100 × {(integral
value A) × 2 + (integral value B) × 4}/(integral value C)
[0049] When the hydrocarbon polymer in R
2 contains butadiene as a constituent monomer or butadiene and 1-butene as constituent
monomers, in terms of viscosity index improving effect and copolymerizability with
other monomers, the molar ratio of a 1,2-adduct to a 1,4-adduct (1,2-adduct/1,4-adduct)
in a structure derived from butadiene or from butadiene and 1-butene constituting
a part or the whole of R
2 in the formula (1) is preferably 5/95 to 95/5, more preferably 20/80 to 80/20, still
more preferably 30/70 to 70/30.
[0050] When the hydrocarbon polymer in R
2 contains 1,3-butadiene as a constituent monomer or 1,3-butadiene and 1-butene as
constituent monomers, the molar ratio of a 1,2-adduct to a 1,4-adduct in a structure
derived from 1,3-butadiene or from 1,3-butadiene and 1-butene constituting a part
or the whole of R
2 in the formula (1) can be measured by
1H-NMR,
13C-NMR, Raman spectroscopy, or the like.
[0051] In terms of an appropriate solubility parameter (hereinafter abbreviated as SP) of
the copolymer (A) and the solubility in the Fischer-Tropsch derived base oil (B),
the SP of a structural unit derived from the monomer (a) (structure in which the (meth)acryloyl
group of the monomer (a) has reacted to form a single bond) is preferably 7.0 to 9.0
(cal/cm
3)
1/2, more preferably 7.3 to 8.5 (cal/cm
3)
1/
2.
[0052] For example, the SP tends to be smaller when R
2 has a higher degree of branching and a greater carbon number, while it tends to be
greater when R
2 has a lower degree of branching and a smaller carbon number.
[0053] The SP in the present invention means a value calculated by the Fedors method (
Polymer Engineering and Science, February 1974, vol. 14, No. 2, pp. 147 to 154) by substituting numerical values (heat of vaporization and molar volume of atoms
or functional groups at 25°C) on page 152 (Table 5) into formula (28) on page 153
of the same journal. Specifically, the SP can be calculated by substituting, into
the equation below, the numerical values corresponding to the types of atoms and groups
in the molecular structure among the numerical values of Δe
i and v
i (Fedors' parameters) in Table 1 below.
[Table 1]
Fedors' parameters |
|
Atom or group |
 ei [cal/mol] |
vi [cm3/mol] |
|
CH3 |
1125 |
33.5 |
|
CH2 |
1180 |
16.1 |
|
CH |
820 |
-1.0 |
|
C |
350 |
-19.2 |
|
H,C= |
1030 |
28.5 |
|
-CH= |
1030 |
13.5 |
|
C= |
1030 |
-5.5 |
|
HC≡ |
920 |
27.4 |
|
-C≡ |
1690 |
6.5 |
|
Pheny I |
7630 |
71.4 |
|
Pheny I ene (o.m.p) |
7630 |
52.4 |
|
Pheny I (trisubstituted) |
7630 |
33.4 |
|
Pheny I (tetrasubstituted) |
7630 |
14.4 |
|
Pheny I (pentasubstituted) |
7630 |
-4.6 |
|
Pheny I (hexasubstituted) |
7630 |
-23.6 |
|
Ring closure 5 or more atoms |
250 |
16 |
|
Ring closure 3 or 4 atoms |
750 |
18 |
|
CO3 (carbonate) |
4200 |
22.0 |
|
COOH |
6600 |
28.5 |
|
CO2 |
4300 |
18.0 |
|
CO |
4150 |
10.8 |
|
CHO (aldehyde) |
5100 |
22.3 |
|
CO2CO2 (oxalate) |
6400 |
37.3 |
|
C2O3 (anhydride) |
7300 |
30.0 |
|
HCOO (formate) |
4300 |
32.5 |
|
CONH2 |
10000 |
17.5 |
|
CONH |
8000 |
9.5 |
|
CON |
7050 |
-7.7 |
|
HCON |
6600 |
11.3 |
|
HCONH |
10500 |
27.0 |
|
COCl |
5000 |
38.0 |
|
NH2 |
3000 |
19.2 |
|
NH |
2000 |
4.5 |
|
N |
1000 |
-9.0 |
|
-N= |
2800 |
5.0 |
|
CN |
6100 |
24.0 |
|
NO2 (aliphatic) |
7000 |
24.0 |
|
NO2 (aromatic) |
3670 |
32.0 |
|
NO3 |
5000 |
33.5 |
|
NO2 (nitrite) |
2800 |
33.5 |
|
CSN |
4800 |
37.0 |
|
NCO |
6800 |
35.0 |
|
NF2 |
1830 |
33.1 |
|
NF2 |
1210 |
24.5 |
|
O |
800 |
3.8 |
|
OH |
7120 |
10.0 |
|
OH (disubstituted or on adjacent C atoms) |
5220 |
13.0 |
[0054] The SP of the structural unit derived from the monomer (a) can be calculated using
the parameters described above based on the molecular structure of the structural
unit derived from the monomer (a). The SP can be adjusted to a desired range by suitably
adjusting the monomers (unsaturated hydrocarbons (x)) to be used and the weight fractions
of the monomers.
[0055] When the copolymer (A) contains two or more types of monomers (a) in combination,
the SP of each of the structural units derived from the monomers (a) is calculated
by the above method, and the SPs of the structural units derived from the monomers
(a) are used to determine a weighted arithmetic mean based on the weight fractions
of the constituent monomers. The resulting weighted arithmetic mean preferably satisfies
the above SP range for the structural unit derived from the monomer (a).
[0056] Examples of the alkyl (meth)acrylate (b) having a C1-C4 alkyl group (hereinafter
also abbreviated as monomer (b)) include methyl (meth)acrylate, ethyl (meth)acrylate,
n-propyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl
(meth)acrylate, 1-methylpropyl (meth)acrylate, 2-methylpropyl (meth)acrylate, and
1,1-dimethylethyl (meth)acrylate.
[0057] In terms of viscosity index improving effect, preferred among these are ethyl (meth)acrylate,
n-butyl (meth)acrylate, and isobutyl (meth)acrylate. More preferred are ethyl (meth)acrylate
and n-butyl (meth)acrylate. Particularly preferred is n-butyl (meth)acrylate.
[0058] In the present invention, the copolymer (A) may contain a (meth)acryloyl monomer
(c) having a C9-C36 alkyl group and/or a monomer (d) represented by the following
formula (2) as constituent monomer(s).

[0059] In the formula (2), R
3 is a hydrogen atom or a methyl group; -X
2- is a group represented by -O- or -NH-; R
4 is a C2-C4 alkylene group; R
5 is a C1-C18 alkyl group or a C6-C20 aryl group; and q is an integer of 1 to 20, and
each R
4 may be the same or different when q is 2 or greater.
[0060] Examples of the (meth)acryloyl monomer (c) having a C9-C36 alkyl group include alkyl
(meth)acrylates having a straight-chain alkyl group {e.g., n-nonyl (meth)acrylate,
n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl
(meth)acrylate, n-pentadecyl (meth)acrylate, n-hexadecyl (meth)acrylate, n-heptadecyl
(meth)acrylate, n-octadecyl (meth)acrylate, n-icosyl (meth)acrylate, n-docosyl (meth)acrylate,
n-tetracosyl (meth)acrylate, n-triacontyl (meth)acrylate, and n-hexatriacontyl (meth)acrylate},
(meth)acrylamides having a straight-chain alkyl group {e.g., N-nonyl (meth)acrylamide,
N-decyl (meth)acrylamide, N-dodecyl (meth)acrylamide, N-tridecyl (meth)acrylamide,
N-tetradecyl (meth)acrylamide, N-pentadecyl (meth)acrylamide, and N-hexadecyl (meth)acrylamide},
alkyl (meth)acrylates having a branched alkyl group {e.g., 2-methylundecyl (meth)acrylate,
isododecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, isotridecyl (meth)acrylate,
2-methyltridecyl (meth)acrylate, isotetradecyl (meth)acrylate, 2-methyltetradecyl
(meth)acrylate, isopentadecyl (meth)acrylate, 2-methylpentadecyl (meth)acrylate, isohexadecyl
(meth)acrylate, 2-octyldecyl (meth)acrylate, an ester of ethylene glycol mono-2-octylpentadecyl
ether and (meth)acrylic acid, 2-n-octyldodecyl (meth)acrylate, 2-n-decyltetradecyl
(meth)acrylate, 2-n-dodecylhexadecyl (meth)acrylate, 2-n-tetradecyloctadecyl (meth)acrylate,
2-n-dodecylpentadecyl (meth)acrylate, 2-n-tetradecylheptadecyl (meth)acrylate, 2-n-hexadecylheptadecyl
(meth)acrylate, 2-n-heptadecylicosyl (meth)acrylate, 2-n-hexadecyldocosyl (meth)acrylate,
2-n-eicosyldocosyl (meth)acrylate, and 2-n-tetracosylhexacosyl (meth)acrylate}, (meth)acrylamides
having a branched alkyl group {e.g., N-2-methylundecyl (meth)acrylamide, N-isododecyl
(meth)acrylamide, N-2-methyldodecyl (meth)acrylamide, N-isotridecyl (meth)acrylamide,
N-2-methyltridecyl (meth)acrylamide, N-isotetradecyl (meth)acrylamide, N-2-methyltetradecyl
(meth)acrylamide, N-isopentadecyl (meth)acrylamide, N-2-methylpentadecyl (meth)acrylamide,
and N-isohexadecyl (meth)acrylamide}, and an ester of (meth)acrylic acid and an adduct
of 1 to 20 moles of an alkylene oxide (C2-C4) to a C9-C36 alkyl alcohol.
[0061] In terms of viscosity index improving effect, preferred as the monomer (c) are straight-chain
alkyl (meth)acrylates (alkyl (meth)acrylates having a straight-chain alkyl group)
and branched alkyl (meth)acrylates (alkyl (meth)acrylates having a branched alkyl
group).
[0062] The monomer (c) may be a (meth)acrylate of an alkyl alcohol mixture, such as Neodol
® 23 (mixture of C12-C13 straight-chain and branched alkyl alcohols, available from
SHELL) or Neodol
® 45 (mixture of C14-C15 straight-chain and branched alkyl alcohols, available from
SHELL).
[0063] R
3 in the formula (2) is a hydrogen atom or a methyl group. Of these, a methyl group
is preferred in terms of viscosity index improving effect and reduction of HTHS viscosity
at 100°C.
[0064] -X
2- in the formula (2) is a group represented by -O- or -NH-. Of these, a group represented
by -O- is preferred in terms of viscosity index improving effect and reduction of
HTHS viscosity at 100°C.
[0065] R
4 in the formula (2) is a C2-C4 alkylene group.
[0066] Examples of the C2-C4 alkylene group include an ethylene group, an isopropylene group,
a 1,2- or 1,3-propylene group, an isobutylene group, and a 1,2-, 1,3-, or 1,4-butylene
group.
[0067] R
4O is a C2-C4 alkyleneoxy group. Examples include an ethyleneoxy group, a 1,2- or 1,3-propyleneoxy
group, and a 1,2-, 1,3-, or 1,4-butyleneoxy group.
[0068] q in the formula (2) is an integer of 1 to 20. In terms of reduction of HTHS viscosity
at 100°C, preferably, it is an integer of 1 to 5, more preferably 1 to 2.
[0069] Each R
4O may be the same or different when q is 2 or greater, and each R
4O in the (R
4O)
q moiety may be bonded in a random form or a block form.
[0070] R
5 in the formula (2) is a C1-C18 alkyl group or a C6-C20 aryl group. Examples of R
5 include C1-C4 alkyl groups (C1-C4 straight-chain or branched alkyl groups) {e.g.,
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups},
C5-C18 alkyl groups {e.g., pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl,
dodecyl, tetradecyl, hexadecyl, and octadecyl groups}, and C6-C20 aryl groups {e.g.,
phenyl, benzyl, phenylethyl, toluyl, naphthyl, naphthylmethyl, anthracenyl, phenanthrenyl,
and fluorenyl groups}.
[0071] Preferred among these in terms of reduction of HTHS viscosity at 100°C are C1-C4
straight-chain alkyl groups, more preferred is a C4 straight-chain alkyl group (n-butyl
group).
[0072] Specific examples of the monomer (d) include methoxyethyl (meth)acrylate, ethoxyethyl
(meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate {e.g., 2-(n-butyloxy)ethyl
(meth)acrylate, 2-(tert-butyloxy)ethyl (meth)acrylate, 2-(sec-butyloxy)ethyl (meth)acrylate,
and 2-(isobutyloxy)ethyl (meth)acrylate}, phenoxyethyl (meth)acrylate, benzyl oxyethyl
(meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, propoxypropyl
(meth)acrylate, butoxypropyl (meth)acrylate {e.g., 2-(n-butyloxy)propyl (meth)acrylate,
2-(tert-butyloxy)propyl (meth)acrylate, 2-(sec-butyloxy)propyl (meth)acrylate, and
2-(isobutyloxy)propyl (meth)acrylate}, phenoxypropyl (meth)acrylate, benzyloxypropyl
(meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, propoxybutyl
(meth)acrylate, butoxybutyl (meth)acrylate, phenoxybutyl (meth)acrylate, benzyloxybutyl
(meth)acrylate, as well as esters of (meth)acrylic acid and an adduct of 2 to 20 moles
of at least one selected from the group consisting of ethylene oxide, propylene oxide,
and butylene oxide to a C1-C18 straight-chain or branched alkyl alcohol or a hydroxy
group-containing aromatic compound (e.g., phenol or benzyl alcohol).
[0073] Preferred among the monomers (d) in terms of viscosity index improving effect and
reduction of HTHS viscosity at 100°C are ethoxyethyl (meth)acrylate and butoxyethyl
(meth)acrylate. More preferred is n-butoxyethyl (meth)acrylate.
[0074] The copolymer (A) in the present invention may further contain, as constituent monomers,
other monomers such as a nitrogen atom-containing monomer (e), a hydroxy group-containing
monomer (f), a phosphorus atom-containing monomer (g), an aromatic ring-containing
vinyl monomer (h), and monomers (i) to (m), in addition to the monomers (a) to (d)
.
[0075] One or more of each of monomers (e) to (m) may be used.
[0076] Examples of the nitrogen atom-containing monomer (e) include the following monomers
(e1) to (e4), excluding the monomers (a) to (d).
Amide group-containing monomer (e1):
[0077] Examples include (meth)acrylamides, N-(N'-monoalkylaminoalkyl) (meth)acrylamides
(those having an aminoalkyl group (C2-C6) in which one C1-C4 alkyl group is bonded
to a nitrogen atom, such as N-(N'-methylaminoethyl) (meth)acrylamide, N-(N'-ethylaminoethyl)
(meth)acrylamide, N-(N'-isopropylamino-n-butyl) (meth)acrylamide, N-(N'-n-butylamino-n-butyl)
(meth)acrylamide, and N-(N'-isobutylamino-n-butyl) (meth)acrylamide); dialkyl (meth)acrylamides
(those in which two C1-C4 alkyl groups are bonded to a nitrogen atom, such as N,N-dimethyl
(meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-diisopropyl (meth)acrylamide,
and N,N-di-n-butyl (meth)acrylamide); N-(N',N'-dialkylaminoalkyl) (meth)acrylamides
(those having an aminoalkyl group (C2-C6) in which two C1-C4 alkyl groups are bonded
to a nitrogen atom of an aminoalkyl group, such as N-(N',N'-dimethylaminoethyl) (meth)acrylamide,
N-(N',N'-diethylaminoethyl) (meth)acrylamide, N-(N',N'-dimethylaminopropyl) (meth)acrylamide,
and N-(N',N'-di-n-butylaminobutyl) (meth)acrylamide); and N-vinyl carboxylic acid
amides, such as N-vinylformamide, N-vinylacetamide, N-vinyl-n- or isopropionic acid
amide, and N-vinylhydroxyacetamide.
Nitro group-containing monomer (e2):
Examples include 4-nitrostyrene.
Primary to tertiary amino group-containing monomer (e3):
[0078] Examples include primary amino group-containing monomers {C3-C6 alkenylamines (e.g.,
(meth)allylamine and crotylamine) and aminoalkyl (C2-C6) (meth)acrylates (e.g., aminoethyl
(meth)acrylate)}; secondary amino group-containing monomers {monoalkylaminoalkyl (meth)acrylates
(e.g., those having an aminoalkyl group (C2-C6) in which one C1-C6 alkyl group is
bonded to a nitrogen atom, such as N-t-butylaminoethyl (meth)acrylate and N-methylaminoethyl
(meth)acrylate), and C6-C12 dialkenylamines (e.g., di(meth)allylamine)}; tertiary
amino group-containing monomers {dialkylaminoalkyl (meth)acrylates (e.g., those having
an aminoalkyl group (C2-C6) in which two C1-C6 alkyl groups are bonded to a nitrogen
atom, such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate),
alicyclic (meth)acrylates having a nitrogen atom such as morpholinoethyl (meth)acrylate,
and aromatic monomers such as N-(N',N'-diphenylaminoethyl) (meth)acrylamide, N,N-dimethylaminostyrene,
4-vinylpyridine, 2-vinylpyridine, N-vinylpyrrole, N-vinylpyrrolidone, and N-vinylthiopyrrolidone};
and hydrochlorides, sulfates, phosphates, and lower alkyl (C1-C8) monocarboxylic acid
(e.g., acetic acid and propionic acid) salts of these monomers.
Nitrile group-containing monomer (e4):
Examples include (meth)acrylonitrile.
[0079] Preferred among the monomers (e) are the amide group-containing monomers (e1) and
the primary to tertiary amino group-containing monomers (e3). More preferred are N-(N',N'-diphenylaminoethyl)
(meth)acrylamide, N-(N',N'-dimethylaminoethyl) (meth)acrylamide, N-(N',N'-diethylaminoethyl)
(meth)acrylamide, N-(N',N'-dimethylaminopropyl) (meth)acrylamide, N,N-dimethylaminoethyl
(meth)acrylate, and N,N-diethylaminoethyl (meth)acrylate.
Hydroxy group-containing monomer (f):
[0080] Examples include hydroxy group-containing aromatic monomers (e.g., p-hydroxystyrene),
hydroxyalkyl (C2-C6) (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate and 2- or
3-hydroxypropyl (meth)acrylate), mono- or bis-hydroxyalkyl (C1-C4) substituted (meth)acrylamides
(e.g., N,N-bis(hydroxymethyl) (meth)acrylamide, N,N-bis(hydroxypropyl) (meth)acrylamide,
and N,N-bis(2-hydroxybutyl) (meth)acrylamide), vinyl alcohol, C3-C12 alkenols (e.g.,
(meth)allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-octenol, and 1-undecenol),
C4-C12 alkene monools or alkene diols (e.g., 1-buten-3-ol, 2-buten-1-ol, and 2-butene-1,4-diol),
hydroxyalkyl (C1-C6) alkenyl (C3-C10) ethers (e.g., 2-hydroxyethylpropenyl ether),
and alkenyl (C3-C10) ethers or (meth)acrylates of polyhydric (tri- to octahydric)
alcohols (e.g., glycerol, pentaerythritol, sorbitol, sorbitan, diglycerol, sugars,
and sucrose) (e.g., (meth)allylether of sucrose). Examples also include mono(meth)acrylates
of polyoxyalkylene glycols (carbon number of the alkylene group: C2-C4; polymerization
degree: 2 to 50), polyoxyalkylene polyols (polyoxyalkylene ethers (carbon number of
the alkylene group: C2-C4; polymerization degree: 2 to 100) of the tri- to octahydric
alcohols), or alkyl (C1-C4) ethers of polyoxyalkylene glycols or polyoxyalkylene polyols
(e.g., polyethylene glycol (Mn: 100 to 300) mono(meth)acrylate, polypropylene glycol
(Mn: 130 to 500) mono(meth)acrylate, methoxy polyethylene glycol (Mn: 110 to 310)
(meth)acrylate, lauryl alcohol ethylene oxide adduct (2 to 30 moles) (meth)acrylate,
and polyoxyethylene (Mn: 150 to 230) sorbitan mono(meth)acrylate).
[0081] Examples of the phosphorus atom-containing monomer (g) include the following monomers
(g1) and (g2).
Phosphate ester group-containing monomer (g1):
[0082] Examples include (meth)acryloyloxyalkyl (C2-C4) phosphate esters ((meth)acryloyloxyethyl
phosphate and (meth)acryloyloxy isopropyl phosphate) and alkenyl phosphate esters
(e.g., vinyl phosphate, allyl phosphate, propenyl phosphate, isopropenyl phosphate,
butenyl phosphate, pentenyl phosphate, octenyl phosphate, decenyl phosphate, and dodecenyl
phosphate). The term "(meth)acryloyloxy" means acryloyloxy or methacryloyloxy.
Phosphono group-containing monomer (g2):
[0083] Examples include (meth)acryloyloxy alkyl (C2-C4) phosphonic acids (e.g., (meth)acryloyloxyethyl
phosphonic acid) and alkenyl (C2-C12) phosphonic acids (e.g., vinylphosphonic acid,
allylphosphonic acid, and octenylphosphonic acid).
[0084] Preferred among the monomers (g) are the monomers (g1). More preferred is (meth)acryloyloxyalkyl
(C2-C4) phosphate esters. Particularly preferred is (meth)acryloyloxyethyl phosphate.
Aromatic ring-containing vinyl monomer (h):
[0085] Examples include styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, 4-ethylstyrene,
4-isopropylstyrene, 4-butylstyrene, 4-phenylstyrene, 4-cyclohexylstyrene, 4-benzylstyrene,
4-crotylbenzene, indene, and 2-vinylnaphthalene.
[0086] Preferred among the monomers (h) are styrene and α-methylstyrene. More preferred
is styrene.
Monomer containing two or more unsaturated groups (i) (sometimes abbreviated as monomer
(i)):
[0087] Examples include divinylbenzene, C4-C12 alkadienes (e.g., butadiene, isoprene, 1,4-pentadiene,
1,6-heptadiene, and 1,7-octadiene), (di)cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene,
limonene, ethylene di(meth)acrylate, polyalkylene oxide glycol di(meth)acrylate, pentaerythritol
triallyl ether, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,
trimethylolpropane tri(meth)acrylate, and esters disclosed in
WO 01/009242 such as an ester of an unsaturated carboxylic acid having a Mn of 500 or more and
glycol and an ester of an unsaturated alcohol and a carboxylic acid.
Vinyl esters, vinyl ethers, vinyl ketones (j) (sometimes abbreviated as the monomer
(j)):
[0088] Examples include vinyl esters of C2-C12 saturated fatty acids (e.g., vinyl acetate,
vinyl propionate, vinyl butyrate, and vinyl octanoate), C1-C12 alkyl, aryl, or alkoxyalkyl
vinyl ethers (e.g., methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl
vinyl ether, 2-ethylhexyl vinyl ether, phenyl vinyl ether, vinyl-2-methoxyethyl ether,
and vinyl-2-butoxyethyl ether), and C1-C8 alkyl or aryl vinyl ketones (e.g., methyl
vinyl ketone, ethyl vinyl ketone, and phenyl vinyl ketone).
Epoxy group-containing monomer (k) (sometimes abbreviated as the monomer (k)):
[0089] Examples include glycidyl (meth)acrylate and glycidyl (meth)allyl ether.
Halogen-containing monomer (1) (sometimes abbreviated as the monomer (l)):
[0090] Examples include vinyl chloride, vinyl bromide, vinylidene chloride, (meth)allyl
chloride, and halogenated styrenes (e.g., dichlorostyrene).
Ester of unsaturated polycarboxylic acid (m) (sometimes abbreviated as the monomer
(m)):
[0091] Examples include alkyl, cycloalkyl, or aralkyl esters of unsaturated polycarboxylic
acids (C1-C8 alkyl diesters (dimethyl maleate, dimethyl fumarate, diethyl maleate,
and dioctylmaleate) of unsaturated dicarboxylic acids (e.g., maleic acid, fumaric
acid, and itaconic acid)).
[0092] In the copolymer (A), in terms of gelation prevention, the weight percentage of the
monomer (a) among the constituent monomers of the copolymer (A) is 1 to 20 wt%, preferably
5 to 20 wt%, more preferably 8 to 18 wt%, particularly preferably 10 to 17 wt% based
on the total weight of the monomers constituting the copolymer (A). A weight percentage
of the monomer (a) of less than 1 wt% tends to lead to a lower viscosity index improving
effect. A weight percentage of the monomer (a) of more than 20 wt% tends to lead to
easy gelation of the viscosity index improver composition.
[0093] In the copolymer (A), in terms of gelation prevention and solubility in base oil,
the weight percentage of the monomer (b) among the constituent monomers of the copolymer
(A) is 45 to 85 wt%, preferably 50 to 85 wt%, more preferably 55 to 80 wt% based on
the total weight of the monomers constituting the copolymer (A). A weight percentage
of the monomer (b) of less than 45 wt% tends to lead to easy gelation of the viscosity
index improver composition. A weight percentage of the monomer (b) of more than 85
wt% tends to lead to poor solubility of the copolymer (A) in base oil (Fischer-Tropsch
derived base oil (B) and other base oils).
[0094] In the copolymer (A), in terms of reduction of HTHS viscosity at 100°C and viscosity
index improving effect, the weight percentage of the monomer (c) among the constituent
monomers of the copolymer (A) is preferably 1 to 54 wt%, more preferably 1 to 53 wt%,
further preferably 1 to 45 wt%, even further preferably 1 to 37 wt%, still more preferably
1 to 35 wt%, particularly preferably 2 to 30 wt% based on the total weight of the
monomers constituting the copolymer (A).
[0095] In the copolymer (A), in terms of reduction of HTHS viscosity at 100°C and viscosity
index improving effect, the weight percentage of the monomer (d) among the constituent
monomers of the copolymer (A) is preferably 1 to 35 wt%, more preferably 1 to 20 wt%,
particularly preferably 5 to 15 wt% based on the total weight of the monomers constituting
the copolymer (A).
[0096] In the copolymer (A), in terms of reduction of HTHS viscosity at 100°C and viscosity
index improving effect, the total weight percentage of the monomers (e) to (m) among
the constituent monomers of the copolymer (A) is preferably 5 wt% or less, more preferably
1 wt% or less based on the total weight of the monomers constituting the copolymer
(A).
[0097] The weight percentage of each of the monomers (b) to (m) in the copolymer (A) can
be measured by a method such as pyrolysis GC/MS. The weight percentage of the monomer
(a) in the copolymer (A) can be determined, for example, as the weight percentage
of the remainder after subtracting the weight of monomers other than monomer (a) measured
by a method such as pyrolysis GC/MS from the weight of the entire copolymer (A).
[0098] In terms of HTHS viscosity in the effective temperature range and low-temperature
viscosity, the copolymer (A) preferably has an Mw of 5,000 to 2,000,000. More preferred
ranges vary depending on the application of the viscosity index improver composition
and the lubricating oil composition containing the viscosity index improver composition.
Table 2 shows the ranges.
[Table 2]
Application |
More preferably |
Still more preferably |
Particularly preferably |
Engine oil |
150,000 to 1,000,000 |
230,000 to 1,000,000 |
300,000 to 800,000 |
ATF* |
5,000 to 150,000 |
10,000 to 80,000 |
12,000 to 55,000 (most preferably 15,000 to 50,000) |
Belt-CVTF** |
Gear oil, MFT*** |
Traction fluids |
10,000 to 600,000 |
12,000 to 230,000 |
15,000 to 150,000 |
*: Automatic transmission fluid
**: Belt-continuously variable transmission fluid
***: Manual transmission fluid |
[0099] The copolymer (A) preferably has a molecular weight distribution (Mw/Mn) of 1.0 to
4.0, more preferably 1.5 to 3.5 in terms of shear stability.
[0100] Conditions for measuring the Mw and molecular weight distribution (Mw/Mn) of the
copolymer (A) are the same as the conditions for measuring the Mw and Mn of the monomer
(a).
[0101] In terms of solubility in base oil (Fischer-Tropsch derived base oil (B) and other
base oils) and viscosity index improving effect, the copolymer (A) preferably has
a SP of 8.0 to 10.0 (cal/cm
3)
1/2, more preferably 9.0 to 9.5 (cal/cm
3)
1/2.
[0102] The SP of the copolymer (A) means a value obtained by calculating the SPs of the
structural units (structures in which vinyl groups have polymerized to form a single
bond) derived from the monomers constituting the copolymer (A) using the SP calculation
method described above, and calculating a weighted arithmetic mean based on the weight
fractions of the constituent monomers at the time of preparation. For example, when
the monomer is methyl methacrylate, the structural unit derived from methyl methacrylate
consists of two CH
3 groups, one CH
2 group, one C atom, and one CO
2 group. Thus, the SP of the structural unit derived from methyl methacrylate is determined
from the following equations to be 9.933 (cal/cm
3)
1/2. By a similar calculation, the SP of a structural unit derived from ethyl methacrylate
is determined to be 9.721 (cal/cm
3)
1/2.

[0103] When the copolymer is a polymer of 50 wt% methyl methacrylate and 50 wt% ethyl methacrylate,
the SP of the copolymer is determined by calculating a weighted arithmetic mean of
the SPs of the monomer-derived structural units based on the weight fractions as shown
below.

[0104] The SP of the copolymer (A) can be adjusted to a desired range by suitably adjusting
the monomers to be used or the weight fractions. Specifically, use of many monomers
having a high-carbon number alkyl group can result in a lower SP, and use of many
monomers having a low-carbon number alkyl group can result in a higher SP.
[0105] The viscosity index improver composition of the present invention can be obtained
by a known production method. Specific examples include a method involving solution
polymerization of the monomers described above in a base oil (e.g., Fischer-Tropsch
derived base oil (B) and/or a base oil other than the Fischer-Tropsch derived base
oil (B) described later) in the presence of a polymerization catalyst.
[0106] When the base oil for polymerization includes the Fischer-Tropsch derived base oil
(B), in terms of gelation prevention, the weight percentage of the Fischer-Tropsch
derived base oil (B) in the base oil is preferably 20 to 100 wt%, more preferably
50 to 100 wt% based on the weight of the base oil.
[0107] Examples of the polymerization catalyst include azo catalysts (e.g., 2,2'-azobis(2-methylbutyronitrile)
and 2,2'-azobis(2,4-dimethylvaleronitrile)), peroxide catalysts (e.g., benzoyl peroxide,
cumyl peroxide, and lauryl peroxide), and redox catalysts (e.g., mixtures of benzoyl
peroxide and tertiary amines). A known chain transfer agent (e.g., C2-C20 alkylmercaptans)
can also be used in order to further adjust the molecular weight, if necessary.
[0108] The polymerization temperature is preferably 25°C to 140°C, more preferably 50°C
to 120°C. The viscosity index improver composition can also be obtained by preparing
the copolymer (A) by bulk polymerization, emulsion polymerization, or suspension polymerization
instead of the solution polymerization in the base oil, and then dissolving the copolymer
(A) in the base oil including the Fischer-Tropsch derived base oil (B) as necessary.
[0109] The polymerization form of the copolymer (A) in the viscosity index improver composition
may be a random addition polymer, or an alternating copolymer, and may be a graft
copolymer, or a block copolymer.
<Fischer-Tropsch derived base oil (B)>
[0110] The viscosity index improver composition of the present invention contains a Fischer-Tropsch
derived base oil (B) having a kinematic viscosity at 100°C of 4.0 mm
2/s or less. "Fischer-Tropsch derived" means that the base oil is a synthetic product
obtained by the Fischer-Tropsch process or the base oil is derived from a synthetic
product obtained by the Fischer-Tropsch process. The Fischer-Tropsch process first
produces synthesis gas (or "syngas") containing carbon monoxide and hydrogen and then
converts the gas into hydrocarbons using Fischer-Tropsch catalysts. For example, oils
obtained by producing synthesis gas from natural gas and converting it into hydrocarbons
using Fischer-Tropsch catalysts are called gas-to-liquids (GTL) oils. Oils obtained
by producing synthesis gas from coal and converting it into hydrocarbons using Fischer-Tropsch
catalysts are called coal-to-liquids (CTL) oils. Oils obtained by producing synthesis
gas from biomass and converting it into hydrocarbons using Fischer-Tropsch catalysts
are called biomass-to-liquids (BTL) oils. These are all hydrocarbons with narrow molecular
weight distributions produced by rearranging the molecular structure of synthesis
gas, and have in common that they contain very low amounts of aromatics, nitrogen-
or sulfur-based compounds, and other compounds found in oils such as mineral oils.
[0111] In the present invention, the viscosity index improver composition contains the copolymer
(A) in the base oil including the aforementioned Fischer-Tropsch derived base oil
(B) that has a relatively low viscosity (low carbon number). The components in the
Fischer-Tropsch derived base oil (B) are considered to reduce the formation of gels
derived from the copolymer (A) in the viscosity index improver composition.
[0112] The Fischer-Tropsch derived base oil (B) may be at least one base oil selected from
the group consisting of a GTL oil, a CTL oil, and a BTL oil. The Fischer-Tropsch derived
base oil (B) may be a GTL oil and/or a CTL oil or may be a GTL oil.
[0113] The Fischer-Tropsch derived base oil (B) has a kinematic viscosity at 100°C (measured
according to JIS-K2283 (2000)) (unit: mm
2/s, hereinafter omitted) of 4.0 or less. With the kinematic viscosity at 100°C of
the Fischer-Tropsch derived base oil (B) being 4.0 or less, the resulting viscosity
index improver composition is less likely to form gels.
[0114] In terms of gelation prevention, the kinematic viscosity at 100°C of the Fischer-Tropsch
derived base oil (B) is preferably 2.0 to 3.9, more preferably 2.4 to 3.5, particularly
preferably 2.7 to 3.5.
[0115] In terms of gelation prevention, the Fischer-Tropsch derived base oil (B) preferably
has a kinematic viscosity at 40°C (measured according to JIS-K2283 (2000)) (unit:
mm
2/s, hereinafter omitted) of 5.0 to 15.0, more preferably 6.0 to 12.0.
[0116] In terms of viscosity index and low-temperature fluidity of the lubricating oil composition,
the Fischer-Tropsch derived base oil (B) preferably has a viscosity index (measured
according to JIS-K2283 (2000)) of 100 or greater.
[0117] The fact that the viscosity index improver composition contains a Fischer-Tropsch
derived base oil (B) can be confirmed by the following method, for example.
[0118] First, only the base oil is isolated from the viscosity index improver composition
by membrane separation, column treatment, or other processes. The isolated base oil
is then analyzed using a mass spectrometer and NMR to determine the amounts of paraffin,
naphthene, aromatic compounds, and the like therein, whereby whether the base oil
is a Fischer-Tropsch derived base oil or a base oil other than a Fischer-Tropsch derived
base oil, such as a mineral oil, can be determined. The kinematic viscosity at 100°C
of the Fischer-Tropsch derived base oil isolated by the above method is measured according
to the method of JIS-K2283 (2000), and whether the kinematic viscosity at 100°C is
4.0 mm
2/s or less is determined, whereby the fact that the viscosity index improver composition
contains a Fischer-Tropsch derived base oil (B) can be confirmed.
[0119] The viscosity index improver composition of the present invention may contain, in
addition to the copolymer (A) and the Fischer-Tropsch derived base oil (B), a base
oil other than the Fischer-Tropsch derived base oil (e.g., hydrocarbon oils {e.g.,
mineral oils (e.g., solvent refined oils, paraffin oils, isoparaffin-containing high-viscosity-index
oils, high-viscosity-index oils obtained by hydrocracking isoparaffins, and naphthene
oils), poly α-olefin-based synthetic lubricating oils}, and ester oils), an alkyl
(meth)acrylate (co)polymer (C) other than copolymer (A), or the like.
[0120] In terms of solubility of the copolymer (A), the base oil other than the Fischer-Tropsch
derived base oil (B) is preferably a base oil of API (the American Petroleum Institute)
Groups I to V.
[0121] In terms of viscosity index and HTHS viscosity at the effective temperature, the
base oil other than the Fischer-Tropsch derived base oil (B) preferably has a kinematic
viscosity at 100°C (measured according to JIS-K2283 (2000)) (unit: mm
2/s, hereinafter omitted) of 1.5 to 6.0, more preferably 2.0 to 5.0.
[0122] In terms of HTHS viscosity in the effective temperature range, the base oil other
than the Fischer-Tropsch derived base oil (B) preferably has a viscosity index (measured
according to JIS-K2283 (2000)) of 100 or greater, more preferably 110 or greater.
[0123] In terms of viscosity index and HTHS viscosity at the effective temperature, the
base oil other than the Fischer-Tropsch derived base oil (B) preferably has a kinematic
viscosity at 40°C (measured according to JIS-K2283 (2000)) (unit: mm
2/s, hereinafter omitted) of 5.0 to 38.0, more preferably 7.0 to 25.0.
[0124] When the viscosity index improver composition contains a base oil other than the
Fischer-Tropsch derived base oil (B), in terms of gelation prevention, the entire
base oil (entire base oil including the Fischer-Tropsch derived base oil (B) and the
base oil other than the Fischer-Tropsch derived base oil (B)) in the viscosity index
improver composition preferably has a kinematic viscosity at 100°C (measured according
to JIS-K2283 (2000)) (unit: mm
2/s, hereinafter omitted) of 1.5 to 5.0, more preferably 2.0 to 4.5, particularly preferably
2.4 to 4.3.
[0125] When the viscosity index improver composition contains a base oil other than the
Fischer-Tropsch derived base oil (B), in terms of gelation prevention, the entire
base oil (entire base oil including the Fischer-Tropsch derived base oil (B) and the
base oil other than the Fischer-Tropsch derived base oil (B)) in the viscosity index
improver composition preferably has a kinematic viscosity at 40°C (measured according
to JIS-K2283 (2000)) (unit: mm
2/s, hereinafter omitted) of 5.0 to 15.0, more preferably 6.0 to 12.0.
<(Co)polymer (C)>
[0126] In terms of reduction of low-temperature viscosity, the viscosity index improver
composition preferably contains an alkyl (meth)acrylate (co)polymer (C).
[0127] Examples of the (co)polymer (C) include a (co)polymer containing no monomer (a),
for example, a (co)polymer containing, as an essential constituent monomer, the (meth)acryloyl
monomer (c) having a C9-C36 alkyl group. Specific examples include a n-dodecyl (meth)acrylate/n-tetradecyl
(meth)acrylate/n-hexadecyl (meth)acrylate/n-octadecyl (meth)acrylate copolymer, a
n-octadecyl (meth)acrylate/n-dodecyl (meth)acrylate (molar ratio of 10-30/90-70) copolymer,
a n-tetradecyl (meth)acrylate/n-dodecyl (meth)acrylate (molar ratio: 10-30/90-70)
copolymer, a n-hexadecyl (meth)acrylate/n-dodecyl (meth)acrylate/methyl (meth)acrylate
(molar ratio: 20-40/55-75/0-10)copolymer, and a n-dodecyl acrylate/n-dodecyl methacrylate
(molar ratio: 10-40/90-60) copolymer. These may be used alone or in combination of
two or more.
[0128] In terms of lower pour point temperature, the (co)polymer (C) preferably has an Mw
of 5,000 to 100,000, more preferably 10,000 to 80,000.
[0129] In terms of solubility in the Fischer-Tropsch derived base oil (B), the (co)polymer(C)
preferably has a SP of 7.0 to 10, more preferably 8.0 to 9.5.
[0130] Conditions for measuring the Mw of the (co)polymer (C) are the same as the conditions
for measuring the Mw of the monomer (a).
<Viscosity index improver composition>
[0131] The viscosity index improver composition of the present invention contains the copolymer
(A) and the Fischer-Tropsch derived base oil (B) having a kinematic viscosity at 100°C
of 4.0 mm
2/s or less.
[0132] In terms of handleability, the amount of the copolymer (A) in the viscosity index
improver composition of the present invention is preferably 10 to 30 wt%, more preferably
15 to 25 wt% based on the weight of the viscosity index improver composition.
[0133] In terms of handleability, the amount of the Fischer-Tropsch derived base oil (B)
in the viscosity index improver composition of the present invention is preferably
2 wt% or more, more preferably 5 wt% or more, still more preferably 20 wt% or more,
particularly preferably 25 wt% or more based on the weight of the viscosity index
improver composition. The upper limit of the amount is preferably 90 wt% or less,
more preferably 85 wt% or less. The amount is preferably in the range of 2 to 90 wt%,
more preferably 5 to 90 wt%, still more preferably 20 to 90 wt%, particularly preferably
25 to 90 wt%.
[0134] In terms of handleability, the amount of the base oil other than the Fischer-Tropsch
derived base oil (B) in the viscosity index improver composition of the present invention
is preferably 78 wt% or less, more preferably 68 wt% or less based on the weight of
the viscosity index improver composition.
[0135] In terms of handleability, the ratio of the weight of the copolymer (A) to the weight
of the Fischer-Tropsch derived base oil (B) {(A)/(B)} in the viscosity index improver
composition of the present invention is preferably 0.05 to 10, more preferably 0.1
to 4.0, still more preferably 0.1 to 2.5, particularly preferably 0.1 to 1.1, most
preferably 0.1 to 1.0.
[0136] In terms of handleability, the amount of the Fischer-Tropsch derived base oil (B)
in the viscosity index improver composition of the present invention is preferably
5 wt% or more, more preferably 25 wt% or more, particularly preferably 50 wt% or more
based on the total weight of the base oils in the viscosity index improver composition.
[0137] In terms of handleability, the amount of the base oil other than the Fischer-Tropsch
derived base oil (B) in the viscosity index improver composition of the present invention
is preferably 95 wt% or less, more preferably 75 wt% or less, particularly preferably
50 wt% or less based on the total weight of the base oils in the viscosity index improver
composition.
[0138] In terms of reduction of the low-temperature viscosity, the amount of the (co)polymer
(C) in the viscosity index improver composition of the present invention is preferably
0.01 to 30 wt%, more preferably 0.01 to 10 wt% based on the weight of the copolymer
(A).
[0139] The viscosity index improver composition of the present invention is less likely
to form gels. A lubricating oil composition containing the viscosity index improver
composition of the present invention can be suitably used in gear oils (e.g., differential
oil and industrial gear oil), MTF, transmission fluids (e.g., ATF, DCTF, and belt-CVTF),
traction fluids (e.g., toroidal-CVTF), shock absorber fluids, power steering fluids,
hydraulic oils (e.g., construction machinery hydraulic oil and industrial hydraulic
oil), and engine oils (for gasoline and diesel), particularly suitably used as a lubricating
oil composition for internal combustion engines, particularly a lubricating oil composition
for hybrid vehicles.
<Lubricating oil composition>
[0140] The lubricating oil composition of the present invention contains the viscosity index
improver composition of the present invention and at least one additive selected from
the group consisting of a detergent, a dispersant, an antioxidant, an oiliness improver,
a pour point depressant, a friction and wear modifier, an extreme pressure agent,
a defoamer, a demulsifier, a metal deactivator, and a corrosion inhibitor.
[0141] With the use of the viscosity index improver composition of the present invention,
the components present in the Fischer-Tropsch derived base oil (B) are considered
to affect the dimensions of the side chains derived from the monomer (a), a constituent
monomer of the copolymer (A), and thereby further increases the viscosity index of
the lubricating oil composition.
[0142] In terms of viscosity index and HTHS viscosity, the amount of the viscosity index
improver composition in the lubricating oil composition is preferably 1.5% to 30 wt%,
more preferably 2 to 20 wt% based on the weight of the lubricating oil composition.
[0143] In terms of viscosity index improving effect and cost, the amount of the copolymer
(A) in the lubricating oil composition of the present invention is preferably 0.1
wt% or more and less than 10 wt%, more preferably 0.5 to 3 wt% based on the weight
of the lubricating oil composition.
[0144] In terms of reduction of fuel consumption and cost, the amount of the Fischer-Tropsch
derived base oil (B) in the lubricating oil composition is preferably 0.4% to 27 wt%,
more preferably 1 to 20 wt% based on the weight of the lubricating oil composition.
[0145] In terms of reduction of the low-temperature viscosity, the amount of the (co)polymer
(C) in the lubricating oil composition of the present invention is preferably 0.01
to 5 wt% based on the weight of the lubricating oil composition.
[0146] In terms of reduction of fuel consumption and cost, the amount of the base oil other
than the Fischer-Tropsch derived base oil (B) in the lubricating oil composition is
preferably 43% to 94 wt%, more preferably 57 to 93 wt% based on the weight of the
lubricating oil composition.
[0147] Examples of the additives in the present invention include the following.
(1) Detergent:
[0148] Examples include basic, overbased, or neutral metal salts (e.g., overbased metal
salts or alkaline earth metal salts of sulfonates such as petroleum sulfonate, alkylbenzene
sulfonate, and alkylnaphthalene sulfonate), salicylates, phenates, naphthenates, carbonates,
phosphonates, and mixtures of detergents.
(2) Dispersant:
[0149] Examples include succinimides (bis- or mono-polybutenyl succinimides), Mannich condensates,
and borates.
(3) Antioxidant:
[0150] Examples include hindered phenols and aromatic secondary amines.
(4) Oiliness improver:
[0151] Examples include long-chain fatty acids and their esters (e.g., oleic acid and its
ester), long-chain amines and their amides (e.g., oleylamine and oleylamide).
(5) Pour point depressant:
[0152] Examples include polyalkylmethacrylates and ethylenevinyl acetate copolymers.
(6) Friction and wear modifier:
[0153] Examples include molybdenum-based compounds and zinc-based compounds (e.g., molybdenum
dithiophosphate, molybdenum dithiocarbamate, and zinc dialkyldithiophosphate).
(7) Extreme pressure agent:
[0154] Examples include sulfur-based compounds (mono- or disulfide, sulfoxide, and sulfur
phosphide compounds), phosphide compounds, and chlorinated compounds (e.g., chlorinated
paraffin).
(8) Defoamer:
[0155] Examples include silicone oils, metallic soap, fatty acid esters, and phosphate compounds.
(9) Demulsifier:
[0156] Examples include quaternary ammonium salts (e.g., tetraalkyl ammonium salt), sulfonated
oil and phosphates (e.g., phosphates of polyoxyethylene-containing nonionic surfactant),
and hydrocarbon-based solvents (toluene, xylene, and ethyl benzene).
(10) Metal deactivator
[0157] Examples include nitrogen atom-containing compounds (e.g., benzotriazole), nitrogen
atom-containing chelate compounds (e.g., N,N'-disalicylidene-1,2-diaminopropane),
and nitrogen/sulfur atom-containing compounds (e.g., 2-(n-dodecylthio)benzimidazole).
(11) Corrosion inhibitor:
[0158] Examples include nitrogen-containing compounds (e.g., benzotriazole and 1,3,4-thiadiazolyl-2,5-bisdialkyldithiocarbamate).
[0159] Only one of these additives may be added, or two or more additives may be added if
necessary. A mixture of these additives, which may be referred to as a performance
additive or a package additive, may be added.
[0160] The amount of each of these additives is preferably 0.1 to 15 wt% based on the total
amount of the lubricating oil composition. The total amount of the additives is preferably
0.1 to 30 wt%, more preferably 0.3 to 20 wt%, still more preferably 3 to 10 wt% based
on the total amount of the lubricating oil composition.
[0161] When the lubricating oil composition is used as an engine oil (0W-16), in terms of
fuel economy, the lubricating oil composition preferably has a viscosity index (measured
according to JIS-K2283 (2000)) of 250 to 290, more preferably 260 to 280.
[0162] When the lubricating oil composition is used as an engine oil (0W-20), in terms of
fuel economy, the lubricating oil composition preferably has a viscosity index (measured
according to JIS-K2283 (2000)) of 300 to 330, more preferably 310 to 325.
[0163] Here, "0W-16" and "0W-20" mean that the oil has a viscosity corresponding to 0W-16
and 0W-20 respectively in the SAE standards {"0W" denotes a viscosity index under
low-temperature/cold conditions (at start of engine) (winter grade), and "16" and
"20" denote the viscosity of the engine oil when the engine has warmed up}.
[0164] When the lubricating oil composition is used as an engine oil (0W-16), in terms of
fuel economy, the lubricating oil composition preferably has a HTHS viscosity (100°C)
(according to ASTM D4683) of 3.50 to 4.50 mPa·s, more preferably 3.60 to 4.30 mPa·s.
[0165] When the lubricating oil composition is used as an engine oil (0W-20), in terms of
fuel economy, the lubricating oil composition preferably has a HTHS viscosity (100°C)
(according to ASTM D4683) of 4.00 to 5.00 mPa·s, more preferably 4.10 to 4.70 mPa·s.
[0166] When the lubricating oil composition is used as an engine oil (0W-16), in terms of
fuel economy, the lubricating oil composition preferably has a kinematic viscosity
(100°C) (measured according to JIS-K2283 (2000)) of 6.00 to 6.70 mm
2/s, more preferably 6.10 to 6.60 mm
2/s.
[0167] When the lubricating oil composition is used as an engine oil (0W-20), in terms of
fuel economy, the lubricating oil composition preferably has a kinematic viscosity
(100°C) (measured according to JIS-K2283 (2000)) of 7.40 to 7.80 mm
2/s, still more preferably 7.50 to 7.70 mm
2/s.
[0168] When the lubricating oil composition is used as an engine oil (0W-16), in terms of
fuel economy, the lubricating oil composition preferably has a kinematic viscosity
(40°C) (measured according to JIS-K2283 (2000)) of 21.0 to 23.5 mm
2/s, more preferably 21.2 to 23.0 mm
2/s.
[0169] When the lubricating oil composition is used as an engine oil (0W-20), in terms of
fuel economy, the lubricating oil composition preferably has a kinematic viscosity
(40°C) (measured according to JIS-K2283 (2000)) of 22.0 to 25.0 mm
2/s, more preferably 22.2 to 24.5 mm
2/s.
[0170] The lubricating oil composition of the present invention is suitably used in gear
oils (e.g., differential oil and industrial gear oil), MTF, transmission fluids (e.g.,
ATF, DCTF, and belt-CVTF), traction fluids (e.g., toroidal-CVTF), shock absorber fluids,
power steering fluids, hydraulic oils (e.g., construction machinery hydraulic oil
and industrial hydraulic oil), and engine oils (for gasoline and diesel), particularly
suitably used as a lubricating oil composition for internal combustion engines, particularly
a lubricating oil composition for hybrid vehicles.
[0171] The following matters are disclosed herein.
[0172] The disclosure (1) relates to a viscosity index improver composition containing:
a copolymer (A) containing, as essential constituent monomers, a polyolefin-based
monomer (a) represented by the following formula (1) and an alkyl (meth)acrylate (b)
having a C1-C4 alkyl group; and a Fischer-Tropsch derived base oil (B) having a kinematic
viscosity at 100°C of 4.0 mm
2/s or less, the copolymer (A) containing the monomer (a) in an amount of 1 to 20 wt%
and the alkyl (meth)acrylate (b) in an amount of 45 to 85 wt% based on the total weight
of the monomers constituting the copolymer (A):

wherein R
1 is a hydrogen atom or a methyl group; -X
1- is a group represented by -O-, -O(AO)
m-, or -NH-, A is a C2-C4 alkylene group, m is an integer of 1 to 10, and each A may
be the same or different when m is 2 or greater; R
2 is a residue after removal of one hydrogen atom from a hydrocarbon polymer containing
a 1,2-butylene group as a structural unit; and p represents a number of 0 or 1.
[0173] The disclosure (2) relates to the viscosity index improver composition according
to the disclosure (1), wherein a ratio {(A)/(B)} of the weight of the copolymer (A)
to the weight of the Fischer-Tropsch derived base oil (B) in the viscosity index improver
composition is 0.05 to 10.
[0174] The disclosure (3) relates to the viscosity index improver composition according
to the disclosure (1) or (2), wherein the copolymer (A) has a solubility parameter
of 8.0 to 10.0 (cal/cm
3)
1/2.
[0175] The disclosure (4) relates to the viscosity index improver composition according
to any one of the disclosures (1) to (3), wherein the copolymer (A) is a copolymer
containing, as a constituent monomer, a (meth)acryloyl monomer (c) having a C9-C36
alkyl group.
[0176] The disclosure (5) relates to the viscosity index improver composition according
to the disclosure (4), wherein the copolymer (A) is a copolymer containing a monomer
(d) represented by the following formula (2) as a constituent monomer:

wherein R
3 is a hydrogen atom or a methyl group; -X
2- is a group represented by -O- or -NH-; R
4 is a C2-C4 alkylene group; R
5 is a C1-C18 alkyl group or a C6-C20 aryl group; and q is an integer of 1 to 20, and
each R
4 may be the same or different when q is 2 or greater.
[0177] The disclosure (6) relates to the viscosity index improver composition according
to the disclosure (5), wherein the copolymer (A) is a copolymer containing, as constituent
monomers, the monomer (c) in an amount of 1 to 53 wt% and the monomer (d) in an amount
of 1 to 35 wt% based on the total weight of the monomers constituting the copolymer
(A).
[0178] The disclosure (7) relates to the viscosity index improver composition according
to any one of the disclosures (1) to (6), wherein the copolymer (A) has a weight average
molecular weight of 5,000 to 2,000,000.
[0179] The disclosure (8) relates to the viscosity index improver composition according
to any one of the disclosures (1) to (7), further comprising a base oil of API Groups
I to V other than the Fischer-Tropsch derived base oil (B).
[0180] The disclosure (9) relates to a lubricating oil composition containing: the viscosity
index improver composition according to any one of the disclosures (1) to (8); and
at least one additive selected from the group consisting of a detergent, a dispersant,
an antioxidant, an oiliness improver, a pour point depressant, a friction and wear
modifier, an extreme pressure agent, a defoamer, a demulsifier, a metal deactivator,
and a corrosion inhibitor.
EXAMPLES
[0181] The present invention is described in further detail below with reference to examples
and comparative examples, but the present invention should not be limited to these
examples.
<Production Example 1>
[0182] A SUS pressure-resistant reaction vessel equipped with a temperature adjuster and
a stirrer was charged with degassed and dehydrated hexane (400 parts by weight), tetrahydrofuran
(1 part by weight), 1,3-butadiene (75 parts by weight), and n-butyllithium (2 parts
by weight), followed by polymerization at a polymerization temperature of 70°C.
[0183] After the polymerization proceeded to almost 100%, ethylene oxide (2 parts by weight)
was added. The mixture was reacted at 50°C for three hours. To terminate the reaction,
water (50 parts by weight) and a 1N aqueous hydrochloric acid solution (25 parts by
weight) were added to the mixture, followed by stirring at 80°C for one hour. The
organic phase of the reaction solution was collected using a separating funnel, and
heated to 70°C. Then, the solvent was removed under reduced pressure of 0.027 to 0.040
MPa over two hours.
[0184] The resulting polybutadiene having a hydroxy group at one end was transferred to
a reaction vessel equipped with a temperature adjuster, a stirrer, and a hydrogen
inlet tube, and tetrahydrofuran (150 parts by weight) was added to uniformly dissolve
the polybutadiene therein. To the resulting solution was added a suspension obtained
in advance by mixing palladium on carbon (10 parts by weight) and tetrahydrofuran
(50 parts by weight). Then, the mixture was reacted at room temperature for eight
hours while hydrogen was supplied at a flow rate of 30 mL/min through the hydrogen
inlet tube into the solution. Subsequently, the palladium on carbon was filtered out.
[0185] The resulting filtrate was heated to 70°C, and tetrahydrofuran was removed under
reduced pressure of 0.027 to 0.040 MPa. Thus, a hydrogenated polybutadiene polymer
having a hydroxy group at one end (Y1-1) (total proportion of the isobutylene group
and the 1,2-butylene group: 45 mol%; 1,2-adduct/1,4-adduct (molar ratio): 45/55; hydroxy
value: 8.0 mgKOH/g; crystallization temperature: -60°C or lower) was obtained.
[0186] A reaction vessel was charged with the hydrogenated polybutadiene polymer having
a hydroxy group at one end (Y1-1) (245 parts by weight), methacrylic acid (245 parts
by weight), and a sulfonic acid group-carrying inorganic porous material (acid value
45 mgKOH/g; particle size: 240 µm) (98 parts by weight), followed by esterification
at 120°C. Then, the sulfonic acid group-carrying inorganic porous material was filtered
out, and excess methacrylic acid was removed from the reaction solution under reduced
pressure (0.027 to 0.040 MPa). Thus, a monomer (a-1) was obtained. The molecular weight
of the resulting monomer (a-1) was measured by GPC, and the proportion of the 1,2-butylene
group was measured by
13C-NMR. The results were as follows: Mw = 6,900, Mn = 6,800, the proportion of the
1,2-butylene group = 45 mol%, -X
1- in the formula (1) was a group represented by -O(CH
2CH
2O)
1-, and p = 0.
<Production Example 2>
[0187] A 1-L SUS pressure-resistant reaction vessel equipped with a temperature adjuster
and a stirrer was charged with degassed and dehydrated hexane (400 parts by weight),
tetrahydrofuran (1 part by weight), and n-butyllithium (0.4 parts by weight), followed
by cooling to -40°C. 1,3-Butadiene (90 parts by weight) liquefied at -40°C was added
thereto, and the mixture was polymerized at a polymerization temperature of -40°C.
The rest of the process was performed as in Production Example 1, whereby a hydrogenated
polybutadiene polymer having a hydroxy group at one end (Y1-2) (total proportion of
the isobutylene group and the 1,2-butylene group: 65 mol%; 1,2-adduct/1,4-adduct (molar
ratio): 65/35; hydroxy value: 13.1 mgKOH/g; crystallization temperature: -60°C or
lower) was obtained. The polymer (Y1-2) and methacrylic acid were esterified to give
a monomer (a-2). The molecular weight of the resulting monomer (a-2) was measured
by GPC, and the proportion of the 1,2-butylene group was measured by
13C-NMR. The results were as follows: Mw = 6,900, Mn = 6,800, the proportion of the
1,2-butylene group = 65 mol%, -X
1- in the formula (1) was a group represented by -O(CH
2CH
2O)
1-, and p = 0.
<Example 1>
[0188] In Example 1, a viscosity index improver composition (R-1) shown in Table 4, containing
a copolymer (A-1) shown in Table 3, was obtained by the following method. First, a
reaction vessel equipped with a stirrer, a heating and cooling device, a thermometer,
and a nitrogen inlet tube was charged with a monomer blend for copolymer (A) production
(100 parts by weight in total) shown in Table 3 and a base oil for polymerization
(200 parts by weight in total) shown in Table 4. After purging with nitrogen (gas
phase oxygen concentration: 100 ppm), the mixture was heated to 76°C with stirring
under hermetically sealed conditions, and a polymerization catalyst (2,2'-azobis(2-methylbutyronitrile))
in an amount shown in Table 3 was added, whereby the mixture was polymerized at the
same temperature for four hours. The mixture was heated to 90°C and reacted for two
hours, and then heated to 120°C to 130°C. To the mixture was added a diluent base
oil shown in Table 4, whereby a viscosity index improver composition (R-1) containing
a copolymer (A-1) was obtained. The SP of the obtained copolymer (A-1) was calculated
according to the method described above, and the Mw and the Mn were measured according
to the methods described above. Table 4 shows the results. Here, KV 100 in Tables
4 to 12 denotes the kinematic viscosity at 100°C.
<Examples 2 to 17, Comparative Examples 1 to 13>
[0189] Viscosity index improver compositions (R-2 to R-17, S-1 to S-13) containing copolymers
(A) were obtained as in Example 1, except that the amounts of the monomer blends and
the polymerization catalysts were as shown in Table 3, and that the amounts of the
base oils for polymerization and the diluent base oils were as shown in Table 4 to
12.
[Table 3]
Copolymer (A) |
SP of structural unit |
A-1 |
A-2 |
A-3 |
A-4 |
A-5 |
Monomer blend for copolymer (A) production |
(a-1): Methacrylic acid ester of (Y1-1) |
8.41 |
7.5 |
6 |
8 |
5 |
11 |
(a-2): Methacrylic acid ester of (Y1-2) |
8.33 |
7.5 |
6 |
8 |
5 |
11 |
(b-1): Methyl methacrylate |
9.93 |
- |
- |
- |
10 |
- |
(b-2): Ethyl methacrylate |
9.72 |
- |
- |
- |
10 |
- |
(b-3): n-Butyl methacrylate |
9.45 |
63 |
60 |
76 |
30 |
40 |
(c-1): n-Dodecyl methacrylate |
9.02 |
- |
11 |
6 |
27 |
- |
(c-2): Methacrylate of Neodol 23 |
8.99 |
10 |
- |
- |
10 |
20 |
(parts by weight) |
(c-3): Methacrylate of Neodol 45 |
8.94 |
2 |
- |
- |
- |
8 |
(c-4): n-Hexadecyl methacrylate |
8.93 |
- |
4 |
1 |
- |
- |
(c-5): n-Octadecyl methacrylate |
8.90 |
- |
1 |
1 |
- |
- |
(d-1): n-Butoxy ethyl methacrylate |
9.43 |
10 |
12 |
- |
3 |
10 |
Total |
|
100 |
100 |
100 |
100 |
100 |
Polymerization catalyst (parts by weight) |
2,2-Azobis(2,4-dimethylvaleronitrile) |
- |
- |
- |
0.03 |
- |
2,2'-Azobis(2-methylbutyronitrile) |
0.12 |
0.10 |
0.12 |
0.12 |
0.12 |
[Table 4]
|
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Example 5 |
Comparative Example 1 |
Comparative Example 2 |
Comparative Example 3 |
Type of copolymer (A) |
A-1 |
A-1 |
A-1 |
A-1 |
A-1 |
A-1 |
A-1 |
A-1 |
Copolymer (A) (parts by weight) |
100.0 |
100.0 |
100.0 |
100.0 |
100.0 |
100.0 |
100.0 |
100.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
200.0 |
15.0 |
- |
15.0 |
200.0 |
- |
- |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
- |
- |
- |
- |
- |
200.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
- |
- |
- |
- |
- |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
- |
- |
- |
200.0 |
120.0 |
- |
Base oil for polymerization (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
- |
185.0 |
200.0 |
- |
- |
- |
- |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
- |
- |
- |
- |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
- |
- |
- |
- |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
- |
185.0 |
- |
- |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
- |
- |
- |
- |
- |
- |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
- |
- |
- |
- |
- |
- |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
- |
- |
- |
- |
- |
30.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
- |
- |
- |
- |
280.0 |
170.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
- |
- |
- |
200.0 |
- |
- |
Diluent base oil (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
- |
200.0 |
200.0 |
- |
- |
- |
- |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
200.0 |
- |
- |
- |
- |
- |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
- |
- |
- |
- |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
- |
200.0 |
200.0 |
- |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
- |
- |
- |
- |
- |
- |
Total charge |
500.0 |
500.0 |
500.0 |
500.0 |
500.0 |
500.0 |
500.0 |
500.0 |
Viscosity index improver composition |
R-1 |
R-2 |
R-3 |
R-4 |
R-5 |
S-1 |
S-2 |
S-3 |
|
Copolymer (A) |
20.0 |
20.0 |
20.0 |
20.0 |
20.0 |
20.0 |
20.0 |
20.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
40.0 |
3.0 |
0.0 |
3.0 |
40.0 |
0.0 |
0.0 |
0.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
46.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
56.0 |
34.0 |
Amount in viscosity index improver composition (wt%) |
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
80.0 |
24.0 |
0.0 |
|
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
0.0 |
77.0 |
80.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
40.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
0.0 |
0.0 |
0.0 |
77.0 |
40.0 |
0.0 |
0.0 |
0.0 |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
|
Total |
100.0 |
100.0 |
100.0 |
100.0 |
100.0 |
100.0 |
100.0 |
100.0 |
Copolymer (A) |
Amount of monomer (a) in copolymer (A) (wt%) |
15.0 |
15.0 |
15.0 |
15.0 |
15.0 |
15.0 |
15.0 |
15.0 |
Amount of monomer (b) in copolymer (A) (wt%) |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
SP (cal/cm3)1/2 of copolymer (A) |
9.23 |
9.23 |
9.23 |
9.23 |
9.23 |
9.23 |
9.23 |
9.23 |
Mw of copolymer (A) (×104) |
51 |
51 |
51 |
51 |
51 |
51 |
51 |
51 |
Mw/Mn of copolymer (A) |
2.62 |
2.62 |
2.62 |
2.62 |
2.62 |
2.62 |
2.62 |
2.62 |
Base oil |
Amount of Fischer-Tropsch derived base oil (B) having kinematic viscosity at 100°C
of 4.0 mm2/s or less in entire viscosity index improver composition (wt%) |
40.0 |
77.0 |
80.0 |
77.0 |
40.0 |
0.0 |
0.0 |
0.0 |
Properties of entire base oil in composition |
Kinematic viscosity at 100°C (mm2/s) |
2.94 |
2.75 |
2.70 |
3.00 |
3.53 |
4.08 |
2.71 |
2.70 |
Kinematic viscosity at 40°C (mm2/s) |
10.73 |
10.05 |
9.80 |
11.43 |
14.63 |
18.22 |
10.05 |
10.11 |
Weight ratio (A)/(B) in viscosity index improver composition |
0.50 |
0.26 |
0.25 |
0.26 |
0.50 |
- |
- |
- |
Property evaluation of viscosity index improver composition |
DissoMng time of sample after gelation test (min) |
30 |
15 |
15 |
15 |
30 |
255 |
240 |
255 |
[Table 5]
|
Example 6 |
Example 7 |
Comparative Example 4 |
Type of copolymer (A) |
A-1 |
A-1 |
A-1 |
Copolymer (A) (parts by weight) |
100.0 |
100.0 |
100.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
100.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
100.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
- |
Base oil for polymerization (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
- |
150.0 |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
200.0 |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
100.0 |
- |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
100.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
50.0 |
Diluent base oil (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
- |
200.0 |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
50.0 |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
50.0 |
50.0 |
50.0 |
Total charge |
500.0 |
500.0 |
500.0 |
Viscosity index improver composition |
R-6 |
R-7 |
S-4 |
|
Copolymer (A) |
20.0 |
20.0 |
20.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
20.0 |
0.0 |
0.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
0.0 |
0.0 |
20.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
0.0 |
0.0 |
40.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
0.0 |
0.0 |
10.0 |
Amount in viscosity index improver composition (wt%) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
0.0 |
70.0 |
0.0 |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
50.0 |
0.0 |
0.0 |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
10.0 |
10.0 |
10.0 |
|
Total |
100.0 |
100.0 |
100.0 |
Copolymer (A) |
Amount of monomer (a) in copolymer (A) (wt%) |
15.0 |
15.0 |
15.0 |
Amount of monomer (b) in copolymer (A) (wt%) |
63.0 |
63.0 |
63.0 |
SP of copolymer (A) (cal/cm3)1/2 |
9.23 |
9.23 |
9.23 |
Mw of copolymer (A) (×104) |
51 |
51 |
51 |
Mw/Mn of copolymer (A) |
2.62 |
2.62 |
2.62 |
Base oil |
Amount of Fischer-Tropsch derived base oil (B) having kinematic viscosity at 100°C
of 4.0 mm2/s or less in entire viscosity index improver composition (wt%) |
50.0 |
70.0 |
0.0 |
Properties of entire base oil in composition |
Kinematic viscosity at 100°C (mm2/s) |
2.31 |
2.45 |
2.44 |
Kinematic viscosity at 40°C (mm2/s) |
8.72 |
100.0 |
10.19 |
Weight ratio (A)/(B) in viscosity index improver composition |
0.40 |
0.29 |
- |
Property evaluation of viscosity index improver composition |
Dissolving time of sample after gelation test (min) |
30 |
30 |
270 |
[Table 6]
|
Example 8 |
Example 9 |
Comparative Example 5 |
Type of copolymer (A) |
A-1 |
A-1 |
A-1 |
Copolymer (A) (parts by weight) |
100.0 |
100.0 |
100.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
15.0 |
177.0 |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
177.0 |
Base oil for polymerization (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
- |
- |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
162.0 |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
177.0 |
Diluent base oil (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
- |
- |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
177.0 |
177.0 |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
- |
Total charge |
454.0 |
454.0 |
454.0 |
Viscosity index improver composition |
R-8 |
R-9 |
S-5 |
|
Copolymer (A) |
22.0 |
22.0 |
22.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
3.3 |
39.0 |
0.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
0.0 |
0.0 |
78.0 |
Amount in viscosity index improver composition (wt%) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
74.7 |
39.0 |
0.0 |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
0.0 |
0.0 |
0.0 |
|
Total |
100.0 |
100.0 |
100.0 |
Copolymer (A) |
Amount of monomer (a) in copolymer (A) (wt%) |
15.0 |
15.0 |
15.0 |
Amount of monomer (b) in copolymer (A) (wt%) |
63.0 |
63.0 |
63.0 |
SP of copolymer (A) (cal/cm3)1/2 |
9.23 |
9.23 |
9.23 |
Mw of copolymer (A) (×104) |
51 |
51 |
51 |
Mw/Mn of copolymer (A) |
2.62 |
2.62 |
2.62 |
Base oil |
Amount of Fischer-Tropsch derived base oil (B) having kinematic viscosity at 100°C
of 4.0 mm2/s or less in entire viscosity index improver composition (wt%) |
74.7 |
39.0 |
0.0 |
Properties of entire base oil in composition |
Kinematic viscosity at 100°C (mm2/s) |
3.00 |
3.53 |
4.08 |
Kinematic viscosity at 40°C (mm2/s) |
11.46 |
14.63 |
18.22 |
Weight ratio (A)/(B) in viscosity index improver composition |
0.29 |
0.56 |
- |
Property evaluation of viscosity index improver composition |
Dissolving time of sample after gelation test (min) |
17 |
35 |
360 |
[Table 7]
|
Example 10 |
Example 11 |
Comparative Example 6 |
Type of copolymer (A) |
A-1 |
A-1 |
A-1 |
Copolymer (A) (parts by weight) |
100.0 |
100.0 |
100.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
15.0 |
158.0 |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
158.0 |
Base oil for polymerization (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
- |
- |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
143.0 |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
158.0 |
Diluent base oil (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
- |
- |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
158.0 |
158.0 |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
- |
Total charge |
416.0 |
416.0 |
416.0 |
Viscosity index improver composition |
R-10 |
R-11 |
S-6 |
|
Copolymer (A) |
24.0 |
24.0 |
24.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
3.6 |
38.0 |
0.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
0.0 |
0.0 |
76.0 |
Amount in viscosity index improver composition (wt%) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
72.4 |
38.0 |
0.0 |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
0.0 |
0.0 |
0.0 |
|
Total |
100.0 |
100.0 |
100.0 |
Copolymer (A) |
Amount of monomer (a) in copolymer (A) (wt%) |
15.0 |
15.0 |
15.0 |
Amount of monomer (b) in copolymer (A) (wt%) |
63.0 |
63.0 |
63.0 |
SP of copolymer (A) (cal/cm3)1/2 |
9.23 |
9.23 |
9.23 |
Mw of copolymer (A) (×104) |
51 |
51 |
51 |
Mw/Mn of copolymer (A) |
2.62 |
2.62 |
2.62 |
Base oil |
Amount of Fischer-Tropsch derived base oil (B) having kinematic viscosity at 100°C
of 4.0 mm2/s or less in entire viscosity index improver composition (wt%) |
72.4 |
38.0 |
0.0 |
Properties of entire base oil in composition |
Kinematic viscosity at 100°C (mm2/s) |
3.01 |
3.53 |
4.08 |
Kinematic viscosity at 40°C (mm2/s) |
11.49 |
14.63 |
18.22 |
Weight ratio (A)/(B) in viscosity index improver composition |
0.33 |
0.63 |
- |
Property evaluation of viscosity index improver composition |
Dissolving time of sample after gelation test (min) |
19 |
40 |
400 |
[Table 8]
|
Example 12 |
Example 13 |
Comparative Example 7 |
Type of copolymer (A) |
A-1 |
A-1 |
A-1 |
Copolymer (A) (parts by weight) |
100.0 |
100.0 |
100.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
30.0 |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
140.0 |
150.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
30.0 |
50.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
- |
Base oil for polymerization (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
200.0 |
- |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
- |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
70.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
30.0 |
Diluent base oil (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
100.0 |
30.0 |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
60.0 |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
10.0 |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
- |
Total charge |
400.0 |
400.0 |
400.0 |
Viscosity index improver composition |
R-12 |
R-13 |
S-7 |
|
Copolymer (A) |
25.0 |
25.0 |
25.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
0.0 |
7.5 |
0.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
0.0 |
35.0 |
37.5 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
0.0 |
7.5 |
30.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
0.0 |
0.0 |
7.5 |
Amount in viscosity index improver composition (wt%) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
75.0 |
7.5 |
0.0 |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
0.0 |
15.0 |
0.0 |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
0.0 |
2.5 |
0.0 |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
0.0 |
0.0 |
0.0 |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
0.0 |
0.0 |
0.0 |
|
Total |
100.0 |
100.0 |
100.0 |
Copolymer (A) |
Amount of monomer (a) in copolymer (A) (wt%) |
15.0 |
15.0 |
15.0 |
Amount of monomer (b) in copolymer (A) (wt%) |
63.0 |
63.0 |
63.0 |
SP of copolymer (A) (cal/cm3)1/2 |
9.23 |
9.23 |
9.23 |
Mw of copolymer (A) (×104) |
51 |
51 |
51 |
Mw/Mn of copolymer (A) |
2.62 |
2.62 |
2.62 |
Base oil |
Amount of Fischer-Tropsch derived base oil (B) having kinematic viscosity at 100°C
of 4.0 mm2/s or less in entire viscosity index improver composition (wt%) |
75.0 |
25.0 |
0.0 |
Properties of entire base oil in composition |
Kinematic viscosity at 100°C (mm2/s) |
2.70 |
2.72 |
2.80 |
Kinematic viscosity at 40°C (mm2/s) |
9.80 |
9.95 |
10.64 |
Weight ratio (A)/(B) in viscosity index improver composition |
0.33 |
1.00 |
- |
Property evaluation of viscosity index improver composition |
Dissolving time of sample after gelation test (min) |
20 |
50 |
360 |
[Table 9]
|
Example 14 |
Comparative Example 8 |
Type of copolymer (A) |
A-1 |
A-1 |
Copolymer (A) (parts by weight) |
100.0 |
100.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
200.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
Base oil for polymerization (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
150.0 |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
50.0 |
- |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
255.6 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
Diluent base oil (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
255.6 |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
Total charge |
555.6 |
555.6 |
Viscosity index improver composition |
R-14 |
S-8 |
|
Copolymer (A) |
18.0 |
18.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
0.0 |
0.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
0.0 |
82.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
0.0 |
0.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
0.0 |
0.0 |
Amount in viscosity index improver composition (wt%) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
73.0 |
0.0 |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
0.0 |
0.0 |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
0.0 |
0.0 |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
0.0 |
0.0 |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
9.0 |
0.0 |
|
Total |
100.0 |
100.0 |
Copolymer (A) |
Amount of monomer (a) in copolymer (A) (wt%) |
15.0 |
15.0 |
Amount of monomer (b) in copolymer (A) (wt%) |
63.0 |
63.0 |
SP of copolymer (A) (cal/cm3)1/2 |
9.23 |
9.23 |
Mw of copolymer (A) (×104) |
51 |
51 |
Mw/Mn of copolymer (A) |
2.62 |
2.62 |
Base oil |
Amount of Fischer-Tropsch derived base oil (B) having kinematic viscosity at 100°C
of 4.0 mm2/s or less in entire viscosity index improver composition (wt%) |
73.0 |
0.0 |
Properties of entire base oil in composition |
Kinematic viscosity at 100°C (mm2/s) |
2.48 |
3.06 |
Kinematic viscosity at 40°C (mm2/s) |
9.98 |
12.25 |
Weight ratio (A)/(B) in viscosity index improver composition |
0.25 |
- |
Property evaluation of viscosity index improver composition |
Dissolving time of sample after gelation test (min) |
30 |
270 |
[Table 10]
|
Example 15 |
Comparative Example 9 |
Type of copolymer (A) |
A-2 |
A-2 |
Copolymer (A) (parts by weight) |
100.0 |
100.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
200.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
Base oil for polymerization (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
150.0 |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
50.0 |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
200.0 |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
100.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
100.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
Diluent base oil (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
- |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
Total charge |
500.0 |
500.0 |
Viscosity index improver composition |
R-15 |
S-9 |
|
Copolymer (A) |
20.0 |
20.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
40.0 |
40.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
0.0 |
20.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
0.0 |
20.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
0.0 |
0.0 |
Amount in viscosity index improver composition (wt%) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
30.0 |
0.0 |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
10.0 |
0.0 |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
0.0 |
0.0 |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
0.0 |
0.0 |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
0.0 |
0.0 |
|
Total |
100.0 |
100.0 |
Copolymer (A) |
Amount of monomer (a) in copolymer (A) (wt%) |
12.0 |
12.0 |
Amount of monomer (b) in copolymer (A) (wt%) |
60.0 |
60.0 |
SP of copolymer (A) (cal/cm3)1/2 |
9.24 |
9.24 |
Mw of copolymer (A) (×104) |
55 |
55 |
Mw/Mn of copolymer (A) |
2.55 |
2.55 |
Base oil |
Amount of Fischer-Tropsch derived base oil (B) having kinematic viscosity at 100°C
of 4.0 mm2/s or less in entire viscosity index improver composition (wt%) |
40.0 |
0.0 |
Properties of entire base oil in composition |
Kinematic viscosity at 100°C (mm2/s) |
3.26 |
3.33 |
Kinematic viscosity at 40°C (mm2/s) |
12.88 |
13.67 |
Weight ratio (A)/(B) in viscosity index improver composition |
0.50 |
- |
Property evaluation of viscosity index improver composition |
Dissolving time of sample after gelation test (min) |
45 |
300 |
[Table 11]
|
Example 16 |
Comparative Example 10 |
Type of copolymer (A) |
A-3 |
A-3 |
Copolymer (A) (parts by weight) |
100.0 |
100.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
200.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
100.0 |
- |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
100.0 |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
Base oil for polymerization (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
- |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
100.0 |
200.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
Diluent base oil (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
50.0 |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
50.0 |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
Total charge |
500.0 |
500.0 |
Viscosity index improver composition |
R-16 |
S-10 |
|
Copolymer (A) |
20.0 |
20.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
20.0 |
80.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
20.0 |
0.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
20.0 |
0.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
0.0 |
0.0 |
Amount in viscosity index improver composition (wt%) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
10.0 |
0.0 |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
10.0 |
0.0 |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
0.0 |
0.0 |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
0.0 |
0.0 |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
0.0 |
0.0 |
|
Total |
100.0 |
100.0 |
Copolymer (A) |
Amount of monomer (a) in copolymer (A) (wt%) |
16.0 |
16.0 |
Amount of monomer (b) in copolymer (A) (wt%) |
76.0 |
76.0 |
SP of copolymer (A) (cal/cm3)1/2 |
9.24 |
9.24 |
Mw of copolymer (A) (×104) |
51 |
51 |
Mw/Mn of copolymer (A) |
2.62 |
2.62 |
Base oil |
Amount of Fischer-Tropsch derived base oil (B) having kinematic viscosity at 100°C
of 4.0 mm2/s or less in entire viscosity index improver composition (wt%) |
20.0 |
0.0 |
Properties of entire base oil in composition |
Kinematic viscosity at 100°C (mm2/s) |
2.88 |
4.21 |
Kinematic viscosity at 40°C (mm2/s) |
10.88 |
19.12 |
Weight ratio (A)/(B) in viscosity index improver composition |
1.00 |
- |
Property evaluation of viscosity index improver composition |
Dissolving time of sample after gelation test (min) |
60 |
340 |
[Table 12]
|
Example 17 |
Comparative Example 11 |
Comparative Example 12 |
Comparative Example 13 |
Type of copolymer (A) |
A-4 |
A-4 |
A-5 |
A-5 |
Copolymer (A) (parts by weight) |
100.0 |
100.0 |
100.0 |
100.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
- |
200.0 |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
150.0 |
- |
- |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
50.0 |
- |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
- |
- |
200.0 |
Base oil for polymerization (parts by weight) |
Base oilBase oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
200.0 |
- |
- |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
- |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
- |
- |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
- |
- |
- |
- |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
- |
- |
- |
- |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
- |
70.0 |
- |
- |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
- |
30.0 |
- |
200.0 |
Diluent base oil (parts by weight) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
100.0 |
- |
- |
- |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
- |
- |
200.0 |
- |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
- |
- |
- |
- |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
- |
- |
- |
- |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
- |
- |
- |
- |
Total charge |
400.0 |
400.0 |
500.0 |
500.0 |
Viscosity index improver composition |
R-17 |
S-11 |
S-12 |
S-13 |
|
Copolymer (A) |
25.0 |
25.0 |
20.0 |
20.0 |
|
|
Hydrocarbon oil-1 |
KV100 = 4.21 mm2/s |
0.0 |
0.0 |
40.0 |
0.0 |
|
|
Hydrocarbon oil-2 |
KV100 = 3.06 mm2/s |
0.0 |
37.5 |
0.0 |
0.0 |
|
|
Hydrocarbon oil-3 |
KV100 = 2.28 mm2/s |
0.0 |
30.0 |
0.0 |
0.0 |
|
|
GTL oil-1 |
KV100 = 4.08 mm2/s |
0.0 |
7.5 |
0.0 |
80.0 |
Amount in viscosity index improver composition (wt%) |
Base oil |
GTL oil-2 |
KV100 = 2.70 mm2/s |
75.0 |
0.0 |
0.0 |
0.0 |
|
|
GTL oil-3 |
KV100 = 2.05 mm2/s |
0.0 |
0.0 |
40.0 |
0.0 |
|
|
GTL oil-4 |
KV100 = 1.32 mm2/s |
0.0 |
0.0 |
0.0 |
0.0 |
|
|
CTL oil-1 |
KV100 = 2.96 mm2/s |
0.0 |
0.0 |
0.0 |
0.0 |
|
|
Ester oil-1 |
KV100 = 3.23 mm2/s |
0.0 |
0.0 |
0.0 |
0.0 |
|
Total |
100.0 |
100.0 |
100.0 |
100.0 |
Copolymer (A) |
Amount of monomer (a) in copolymer (A) (wt%) |
10.0 |
10.0 |
22.0 |
22.0 |
Amount of monomer (b) in copolymer (A) (wt%) |
50.0 |
50.0 |
40.0 |
40.0 |
SP of copolymer (A) (cal/cm3)1/2 |
9.25 |
9.25 |
9.08 |
9.08 |
Mw of copolymer (A) (×104) |
45 |
45 |
51 |
51 |
Mw/Mn of copolymer (A) |
2.55 |
2.55 |
2.62 |
2.62 |
Base oil |
Amount of Fischer-Tropsch derived base oil (B) having kinematic viscosity at 100°C
of 4.0 mm2/s or less in entire viscosity index improver composition (wt%) |
75.0 |
0.0 |
40.0 |
0.0 |
Properties of entire base oil in composition |
Kinematic viscosity at 100°C (mm2/s) |
2.70 |
2.80 |
2.94 |
4.08 |
Kinematic viscosity at 40°C (mm2/s) |
9.80 |
10.64 |
10.73 |
18.22 |
Weight ratio (A)/(B) in viscosity index improver composition |
0.33 |
- |
0.50 |
- |
Property evaluation of viscosity index improver composition |
Dissolving time of sample after gelation test (min) |
75 |
390 |
390 |
405 |
[0190] The monomers (a) to (d) in Table 3 are as follows.
(a-1): Methacrylic acid ester (Mn: 6800) of (Y1-1)
(a-2): Methacrylic acid ester (Mn: 6800) of (Y1-2)
(b-1): Methyl methacrylate
(b-2): Ethyl methacrylate
(b-3): n-Butyl methacrylate
(c-1): n-Dodecyl methacrylate
(c-2): C12-C13 straight-chain and branched alkyl methacrylate mixture (ester of methacrylic
acid and Neodol 23 (mixture with weight ratio = straight-chain C12:branched C12:straight-chain
C13:branched C13 = 40:10:40:10) available from SHELL)
(c-3): C14-C15 straight-chain and branched alkyl methacrylate mixture (ester of methacrylic
acid and Neodol 45 (mixture with weight ratio = straight-chain C14:branched C14:straight-chain
C15:branched C15 = 40:10:40:10) available from SHELL)
(c-4): n-Hexadecyl methacrylate
(c-5): n-Octadecyl methacrylate
(d-1): n-Butoxy ethyl methacrylate
[0191] The SPs of the structural units (structures in which carbon-carbon double bonds have
reacted to form a single bond) derived from the monomers (a-1), (a-2), (c-2), and
(c-3) were calculated based on the following formulas. Structural unit derived from
(a-1)
ΣΔei = 1125 (CH3) + 1180 (CH2) + 350 (C) + 4300 (CO2) = 6955
Σvi = 33.5 (CH3) + 16.1 (CH2) - 19.2 (C) + 18.0 (CO2) = 48.4
ΣΔei = 1180 (CH2) × 2 + 800 (O) = 3160
Σvi = 16.1 (CH2) × 2 + 3.8 (O) = 36
ΣΔei = 1180 (CH2) × 2 + 1125 (CH3) + 820 (CH) = 4305
Σvi = 16.1 (CH2) × 2 + 33.5 (CH3) - 1.0 (CH) = 64.7
ΣΔei = 1180 (CH2) × 4 = 4720
Σvi = 16.1 (CH2) × 4 = 64.4
[0192] Here, the total number of 1,2-butylene and 1,4-butylene groups is as follows.
Total number of 1,2-butylene and 1,4-butylene groups = (6800 - 85 - 44)/56 = 119.125
[0193] Accordingly, the parameters of the structural unit derived from (a-1) are as follows.
ΣΔei = 6955 + 3160 + 4305 × 119.125 × 0.45 + 4720 × 119.125 × 0.55 = 550138.4
Σvi = 48.4 + 36 + 64.7 × 119.125 × 0.45 + 64.4 × 119.125 × 0.55 = 7772.132

[0194] Structural unit derived from (a-2)
Total number of 1,2-butylene and 1,4-butylene groups = (6800 - 85 - 44)/56 = 119.125
ΣΔei = 6955 + 3160 + 4305 × 119.125 × 0.65 + 4720 × 119.125 × 0.35 = 540251
Σvi = 48.4 + 36 + 64.7 × 119.125 × 0.65 + 64.4 × 119.125 × 0.35 = 7779.279

[0197] The base oils shown in Tables 4 to 12 are as follows.
Hydrocarbon oil-1: available from SK Lubricants, product name "Yubase 4", API Group
III (kinematic viscosity at 100°C: 4.21 mm2/s, kinematic viscosity at 40°C: 19.12 mm2/s)
Hydrocarbon oil-2: available from SK Lubricants, product name "Yubase 3", API Group
III (kinematic viscosity at 100°C: 3.06 mm2/s, kinematic viscosity at 40°C: 12.25 mm2/s)
Hydrocarbon oil-3: available from S-OIL, product name "Ultra S-2", API Group II (kinematic
viscosity at 100°C: 2.28 mm2/s, kinematic viscosity at 40°C: 7.79 mm2/s)
GTL oil-1: available from Shell, XHVI4, kinematic viscosity at 100°C: 4.08 mm2/s, kinematic viscosity at 40°C: 18.22 mm2/s
GTL oil-2: available from Shell, Ondina X415, kinematic viscosity at 100°C: 2.70 mm2/s, kinematic viscosity at 40°C: 9.80 mm2/s
GTL oil-3: available from Shell Chemicals, GS310, kinematic viscosity at 100°C: 2.05
mm2/s, kinematic viscosity at 40°C: 6.02 mm2/s
GTL oil-4: available from Shell Chemicals, GS270, kinematic viscosity at 100°C: 1.32
mm2/s, kinematic viscosity at 40°C: 3.38 mm2/s
CTL oil-1: available from Shanxi Lu'an Taihang Lubricant Technology, ICCSYN3, kinematic
viscosity at 100°C: 2.96 mm2/s, kinematic viscosity at 40°C: 11.20 mm2/s
Ester oil-1: API Group V (bis(2-ethylhexyl) sebacate, kinematic viscosity at 100°C:
3.23 mm2/s, kinematic viscosity at 40°C: 11.53 mm2/s)
[0198] Of the base oils shown in Tables 4 to 12, GTL oil-2, GTL oil-3, GTL oil-4, and CTL
oil-1 fall within the category of the Fischer-Tropsch derived base oil (B) having
a kinematic viscosity at 100°C of 4.0 mm
2/s or less. In Table 4 to 12, "Amount (wt%) of Fischer-Tropsch derived base oil (B)
having kinematic viscosity at 100°C of 4.0 mm
2/s or less in entire viscosity index improver composition" refers to the total amount
of GTL oil-2, GTL oil-3, GTL oil-4, and CTL oil-1.
<Method of measuring kinematic viscosity of entire base oil blend>
[0199] For each of the viscosity index improver compositions of Examples 1 to 17 and Comparative
Examples 1 to 13, a base oil blend was separately prepared by mixing only the base
oil for polymerization and the diluent base oil. The kinematic viscosity at 40°C and
100°C of the base oil blend were measured according to the method of JIS-K2283 (2000).
Similarly, the viscosity index was calculated according to the method of JIS-K2283
(2000).
<Gelation test of viscosity index improver composition - rheometer>
[0200] The gelation test of the viscosity index improver compositions herein was performed
using a rheometer ("Physica MCR302" available from Anton paar) under the following
conditions.
Measurement fixture: parallel plates (diameter 50 mm)
Temperature control: Peltier system
Gap: 0.5 mm
Strain: 1%
Frequency: 1 Hz
Heating rate 5°C/min (from 10°C to 100°C)
Cooling rate 2°C/min (from 100°C to 10°C)
Heating/cooling pattern before determination of gelation: heating → cooling → heating
→ cooling
<Weight ratio (A)/(B) in viscosity index improver composition>
[0201] Tables 4 to 12 show the ratio of the weight of the copolymer (A) to the weight of
the Fischer-Tropsch derived base oil (B) in each of the viscosity index improver compositions.
<Solubility test of sample after gelation test>
[0202] A reaction vessel equipped with a stirrer, a heating and cooling device, and a thermometer
was charged with the sample (30.0 g) after the gelation test and hydrocarbon oil-1
(Yubase 4, kinematic viscosity at 100°C: 4.21 mm
2/s, kinematic viscosity at 40°C: 19.12 mm
2/s). The stirring rate was 50 rpm, and the temperature was adjusted to 50°C. The mixture
was sampled at 15-minute intervals (3 g). The kinematic viscosity (40°C) of each sample
was measured, and the time when the difference between two measurements was within
0.5% was defined as the end of dissolution. The time from the start of stirring to
sampling of the first of the two samples with a kinematic viscosity difference within
0.5% was defined as the sample dissolving time after the gelation test. Tables 4 to
12 show the dissolving time. A shorter sample dissolving time after the gelation test
is considered to indicate less gel formation in the viscosity index improver composition.
[0203] The kinematic viscosity (40°C) was measured according to the method of ASTM D 7042
using a Stabinger viscometer (SVM3001) available from Anton Paar.
<Examples 18 to 25, Comparative Example 14 (evaluation as 0W-16 grade)>
[0204] A stainless steel vessel equipped with a stirrer was charged with Yubase 4 (kinematic
viscosity at 100°C: 4.21 mm
2/s, kinematic viscosity at 40°C: 19.12 mm
2/s)), Yubase 3 (3.06 mm
2/s, kinematic viscosity at 40°C: 12.25 mm
2/s), and an engine oil package additive (Infineum P-5741, 10 wt% of the entire lubricating
oil composition) in accordance with the formulation shown in Table 13. One of the
viscosity index improver compositions (R-1) to (R-9), (R-12), and (S-1) was added
to the mixture such that the resulting lubricating oil composition had a kinematic
viscosity at 100°C of 6.5 mm
2/s and a NOACK evaporation loss of 22%. In this manner, lubricating oil compositions
(V-1) to (V-8) and (W-1) were obtained.
[0205] The lubricating oil compositions (V-1) to (V-8) and (W-1) were subjected to measurements
of shear stability, HTHS viscosity (150°C, 100°C), kinematic viscosity (40°C, 100°C),
viscosity index, and solubility in additive-containing base oil by the following methods.
Table 13 shows the results.
<Method of measuring NOACK evaporation loss of lubricating oil composition>
[0206] The NOACK evaporation loss was measured according to the method of ASTM D 5800 (measurement
conditions: 250°C, one hour).
<Method of measuring HTHS viscosity of lubricating oil composition>
[0207] The HTHS viscosity was measured at 150°C and 100°C according to the method of ASTM
D 4683.
<Method of measuring viscosity of lubricating oil composition>
[0208] The kinematic viscosity at 40°C and 100°C was measured according to the method of
JIS-K2283 (2000). The viscosity index was calculated according to the method of JIS-K2283
(2000). A higher viscosity index indicates a higher viscosity index improving effect.
<Methods of measuring and calculating shear stability of lubricating oil composition>
[0209] The shear stability was measured according to the method of ASTM D 6278 and calculated
according to the method of ASTM D 6022. A lower value indicates a higher shear stability.
<Method of evaluating solubility of copolymer in additive-containing base oil>
[0210] The appearance of the lubricating oil compositions (V-1) to (V-8) and (W-1) was visually
observed, and the solubility in base oil was evaluated according to the following
criteria.
Evaluation criteria
[0211]
∘ (Good): The appearance was uniform, and no undissolved matter was observed.
× (Poor): The appearance was not uniform, and undissolved matter was observed.
[Table 13]
|
Example |
Comparative Example |
18 |
19 |
20 |
21 |
22 |
23 |
24 |
25 |
14 |
Lubricating oil composition |
V-1 |
V-2 |
V-3 |
V-4 |
V-5 |
V-6 |
V-7 |
V-8 |
W-1 |
Viscosity index improver composition |
R-1 |
R-2 |
R-3 |
R-6 |
R-7 |
R-8 |
R-9 |
R-12 |
S-1 |
Composition of lubricating oil composition (wt%) |
Viscosity index improver composition |
11.0 |
11.2 |
11.2 |
10.7 |
11.0 |
10.2 |
10.1 |
9.0 |
11.0 |
Yubase 4 |
50.0 |
52.1 |
52.4 |
51.9 |
51.4 |
47.3 |
45.8 |
52.3 |
42.7 |
Yubase 3 |
29.0 |
26.7 |
26.4 |
27.4 |
27.6 |
32.5 |
34.1 |
28.7 |
36.3 |
Package additive for engine oil |
10.0 |
10.0 |
10.0 |
10.0 |
10.0 |
10.0 |
10.0 |
10.0 |
10.0 |
Evaluation results |
HTHS viscosity (150°C) (mPa·s) |
2.41 |
2.40 |
2.40 |
2.35 |
2.40 |
2.40 |
2.41 |
2.41 |
2.39 |
HTHS viscosity (100°C) (mPa·s) |
4.23 |
4.21 |
4.20 |
4.23 |
4.19 |
4.19 |
4.21 |
4.22 |
4.29 |
Kinematic viscosity at 100°C (mm2/s) |
6.50 |
6.50 |
6.50 |
6.50 |
6.50 |
6.50 |
6.50 |
6.50 |
6.50 |
Kinematic viscosity at 40°C (mm2/s) |
22.9 |
22.4 |
22.3 |
22.6 |
22.1 |
22.0 |
22.6 |
22.5 |
23.9 |
Viscosity index |
265 |
274 |
275 |
270 |
279 |
281 |
270 |
272 |
250 |
Shear stability (%) |
1 |
1 |
1 |
1 |
1 |
1 |
1 |
1 |
2 |
Solubility of copolymer in additive-containing base oil |
∘ |
∘ |
∘ |
∘ |
∘ |
∘ |
∘ |
∘ |
∘ |
[0212] As obvious from the results in Tables 4 to 12, the following viscosity index improver
composition is less likely to form gels and dissolves fast in preparation of a lubricating
oil: a viscosity index improver composition containing a copolymer (A) containing,
as essential constituent monomers, a polyolefin-based monomer (a) represented by the
formula (1) and an alkyl (meth)acrylate (b) having a C1-C4 alkyl group, and a Fischer-Tropsch
derived base oil (B) having a kinematic viscosity at 100°C of 4.0 mm
2/s or less, the copolymer (A) containing the monomer (a) in an amount of 1 to 20 wt%
and the monomer (b) in an amount of 45 to 85 wt%.
[0213] Moreover, the results in Table 13 show that the viscosity index improver composition
of the present invention has a high viscosity index improving effect when added to
a lubricating oil composition, and thus is highly excellent as a viscosity index improver
composition.
INDUSTRIAL APPLICABILITY
[0214] The viscosity index improver composition of the present invention is less likely
to form gels. A lubricating oil composition containing the viscosity index improver
composition of the present invention can be suitably used in gear oils (e.g., differential
oil and industrial gear oil), MTF, transmission fluids (e.g., ATF, DCTF, and belt-CVTF),
traction fluids (e.g., toroidal-CVTF), shock absorber fluids, power steering fluids,
hydraulic oils (e.g., construction machinery hydraulic oil and industrial hydraulic
oil), and engine oils (for gasoline and diesel), particularly suitably used as a lubricating
oil composition for internal combustion engines, particularly a lubricating oil composition
for hybrid vehicles.