U.S. patent application number 11/426356 was filed with the patent office on 2007-01-04 for lubricants for refrigeration systems.
Invention is credited to Elizabeth Dixon, Kaoru Matsumura.
Application Number | 20070004605 11/426356 |
Document ID | / |
Family ID | 37067610 |
Filed Date | 2007-01-04 |
United States Patent
Application |
20070004605 |
Kind Code |
A1 |
Matsumura; Kaoru ; et
al. |
January 4, 2007 |
LUBRICANTS FOR REFRIGERATION SYSTEMS
Abstract
A lubricating composition which comprises: (A) a
polyalkyleneglycol of the general formula (I):
RO(R.sup.aO).sub.x(R.sup.bO).sub.y(R.sup.cO).sub.zR.sup.d (I)
wherein: R is a C.sub.4 to C.sub.6 substituent comprising a
heterocyclic ring, in which the heteroatom(s) in said ring(s) is
(are) oxygen and/or sulphur, R.sup.a is a C.sub.2 alkylene group,
R.sup.b is a C.sub.3 alkylene group, R.sup.c is a C.sub.4 alkylene
group, R.sup.d is the same as R, or is a hydrogen atom or a
C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 acyl group, x, y, z are
each independently 0 or an integer in the range of from 1 to 100,
and x+y+z=4 to 100; and (B) an ester of a alcohol containing two or
more hydroxyl groups with a mono- or dicarboxylic acid, or an ester
of an dicarboxylic acid with an alcohol containing one hydroxyl
group.
Inventors: |
Matsumura; Kaoru; (Troy,
OH) ; Dixon; Elizabeth; (Hampshire, GB) |
Correspondence
Address: |
COGNIS CORPORATION;PATENT DEPARTMENT
300 BROOKSIDE AVENUE
AMBLER
PA
19002
US
|
Family ID: |
37067610 |
Appl. No.: |
11/426356 |
Filed: |
June 26, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60693779 |
Jun 27, 2005 |
|
|
|
Current U.S.
Class: |
508/577 |
Current CPC
Class: |
C10M 2207/287 20130101;
C10M 2207/304 20130101; C10M 2209/103 20130101; C10M 2207/2875
20130101; C10M 2209/1075 20130101; C10M 2207/3025 20130101; C10M
2209/1045 20130101; C10M 171/008 20130101; C10N 2020/097 20200501;
C10M 2209/109 20130101; C10M 2207/302 20130101; C10M 2207/3045
20130101; C10M 2209/104 20130101; C10M 2209/106 20130101; C10M
2209/1085 20130101; C10M 2207/289 20130101; C10M 2209/108 20130101;
C10N 2020/103 20200501; C10N 2030/06 20130101; C10M 111/04
20130101; C10M 2209/1065 20130101; C10M 2221/04 20130101; C10M
2209/1055 20130101; C10N 2020/099 20200501; C10M 2209/105 20130101;
C10M 2209/10 20130101; C10M 2207/288 20130101; C10M 2207/301
20130101; C10M 2207/044 20130101; C10M 2221/0405 20130101; C10N
2020/106 20200501; C10M 2207/282 20130101; C10M 2209/107 20130101;
C10M 2207/2835 20130101; C10M 2209/1095 20130101; C10N 2020/101
20200501; C10M 2207/283 20130101; C10M 2207/30 20130101; C10N
2020/105 20200501; C10M 2207/2885 20130101; C10M 2209/1033
20130101; C10N 2040/30 20130101; C10M 2207/2825 20130101; C10M
2207/2895 20130101 |
Class at
Publication: |
508/577 |
International
Class: |
C10M 171/00 20060101
C10M171/00 |
Claims
1. A lubricating composition which comprises: (A) a
polyalkyleneglycol of the general formula (I):
RO(R.sup.aO),(R.sup.bO).sub.y(R.sup.cO).sub.zR.sup.d (I) wherein: R
is a C.sub.4 to C.sub.6 substituent comprising a heterocyclic ring,
in which the heteroatom(s) in said ring(s) is (are) oxygen and/or
sulphur, R.sup.a is a C.sub.2 alkylene group, R.sup.b is a C.sub.3
alkylene group, R.sup.c is a C.sub.4 alkylene group, R.sup.d is the
same as R, or is a hydrogen atom or a C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 acyl group, x, y, z are each independently 0 or an
integer in the range of from 1 to 100, and X+y+z=4 to 100; and (B)
an ester of a alcohol containing two or more hydroxyl groups with a
mono- or dicarboxylic acid, or an ester of an dicarboxylic acid
with an alcohol containing one hydroxyl group.
2. A composition as claimed in claim 1, in which R represents a
5-membered oxygen-containing heterocycle linked to the rest of the
molecule either directly or via a CH.sub.2 group.
3. A composition as claimed in claim 2, in which R represents a
tetrahydrofurfuryl group.
4. A composition as claimed in claim 1, in which either z is 0 or z
and x are both 0.
5. A composition as claimed in claim 1, in which the sum of x, y
and z is equal to a number in the range of from 5 to 80.
6. A composition as claimed in claim 1, in which R.sup.d represents
a hydrogen atom or a C.sub.1-4 alkyl group.
7. A composition as claimed in claim 6, in which R.sup.d represents
a methyl group.
8. A composition as claimed in claim 1, in which the compound of
the formula I has the formula Ia:
R.sup.1O--(R.sup.2O).sub.m--R.sup.3 (Ia) in which R.sup.1 is a
tetrahydrofurfuryl group; R.sup.2 is a mix of C.sub.2 and C.sub.3
alkylene groups, the number ratio of C.sub.2 to C.sub.3 groups
preferably being in the range of from 27:75 to 75:25, or R.sup.2 is
a C.sub.3 alkylene group; m is from 5 to 80; and R.sup.3 is a
hydrogen atom or a C.sub.1-4 alkyl group.
9. A composition as claimed in claim 1, in which the acid from
which the ester component (B) is derived is an alkanoic or
alkandioic acid, and the alcohol is a mono-, di- or poly-hydroxyl
alkanol.
10. A composition as claimed in claim 9, in which the ester is an
ester of neopentyl glycol, monopentaerythritol, dipentaerythritol
and/or trimethylolpropane with a C.sub.2-18 mono- or di-alkanoic
acid.
11. A composition as claimed in claim 10, in which the ester is an
ester of neopentyl glycol and/or monopentaerythritol with a
C.sub.2-10 mono alkanoic acid or a C.sub.6 dialkanoic acid, or a
dipentaerythritol ester of a C.sub.2-10 mono alkanoic acid or a
C.sub.8-9 dialkanoic acid.
12. A composition as claimed in claim 11, in which the ester is an
ester of monopentaerythritol with a C.sub.5-9 mono alkanoic acid or
a C.sub.6 dialkanoic acid.
13. A refrigerant composition for refrigeration apparatus which
comprises a lubricant composition comprising: (A) a
polyalkyleneglycol of the general formula (I):
RO(R.sup.aO).sub.x(R.sup.bO).sub.y(R.sup.cO).sub.zR.sup.d (I)
wherein: R is a C.sub.4 to C.sub.6 substituent comprising a
heterocyclic ring, in which the heteroatom(s) in said ring(s) is
(are) oxygen and/or sulphur, R.sup.a is a C.sub.2 alkylene group,
R.sup.b is a C.sub.3 alkylene group, R.sup.c is a C.sub.4 alkylene
group, R.sup.d is the same as R, or is a hydrogen atom or a
C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 acyl group, x, y, z are
each independently 0 or an integer in the range of from 1 to 100,
and X+y+z=4 to 100; and (B) an ester of a alcohol containing two or
more hydroxyl groups with a mono- or dicarboxylic acid, or an ester
of an dicarboxylic acid with an alcohol containing one hydroxyl
group; together with a refrigerant.
14. A refrigerant composition as claimed in claim 13, in which the
refrigerant is selected from fluorocarbons, hydrofluorocarbons,
hydrocarbons, ammonia, and carbon dioxide.
15. A refrigerant composition as claimed in claim 14, in which the
refrigerant is selected from 1,1,1,2-tetrafluoroethane or carbon
dioxide.
16. Refrigeration apparatus which includes a refrigerant
composition which comprises: (A) a polyalkyleneglycol of the
general formula (I):
RO(R.sup.aO).sub.x(R.sup.bO).sub.y(R.sup.cO).sub.zR.sup.d (I)
wherein: R is a C.sub.4 to C.sub.6 substituent comprising a
heterocyclic ring, in which the heteroatom(s) in said ring(s) is
(are) oxygen and/or sulphur, R.sup.a is a C.sub.2 alkylene group,
R.sup.b is a C.sub.3 alkylene group, R.sup.c is a C.sub.4 alkylene
group, R.sup.d is the same as R, or is a hydrogen atom or a
C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 acyl group, x, y, z are
each independently 0 or an integer in the range of from 1 to 100,
and X+y+z=4 to 100; and (B) an ester of a alcohol containing two or
more hydroxyl groups with a mono- or dicarboxylic acid, or an ester
of an dicarboxylic acid with an alcohol containing one hydroxyl
group; together with a refrigerant.
17. A composition as claimed in claim 8, in which the acid from
which the ester component (B) is derived is an alkanoic or
alkandioic acid, and the alcohol is a mono-, di- or poly-hydroxyl
alkanol.
18. A composition as claimed in claim 17, in which the ester is an
ester of neopentyl glycol, monopentaerythritol, dipentaerythritol
and/or trimethylolpropane with a C.sub.2-18 mono- or di-alkanoic
acid.
19. A composition as claimed in claim 18, in which the ester is an
ester of neopentyl glycol and/or monopentaerythritol with a
C.sub.2-10 mono alkanoic acid or a C.sub.6 dialkanoic acid, or a
dipentaerythritol ester of a C.sub.2-10 mono alkanoic acid or a
C.sub.8-9 dialkanoic acid.
20. A composition as claimed in claim 19, in which the ester is an
ester of monopentaerythritol with a C.sub.5-9 mono alkanoic acid or
a C.sub.6 dialkanoic acid.
Description
RELATED APPLICATIONS
[0001] This application claims priority from U.S. Provisional
Application No. 60/693,779, filed Jun. 27, 2005.
FIELD OF THE INVENTION
[0002] The present invention relates to lubricating compositions
for use in refrigeration apparatus, particularly compression-type
refrigerators.
BACKGROUND INFORMATION
[0003] In a compression-type refrigerator, a mixture of a
refrigerant and a lubricating oil is circulated through a number of
units including a compressor, which exerts pressure on the gaseous
refrigerant to convert it into a liquid. Such units comprise moving
parts, and the lubricating oil is necessary to reduce friction
between these parts. In addition to such lubricating properties, to
ensure maximum system efficiency it is necessary for the lubricant
to have appropriate miscibility characteristics with the
refrigerant across the system's temperature operating range
(commonly within the region of -50 to +80.degree. C.).
[0004] Polyalkylene glycols ("PAGs") and esters are well known as
lubricants, and lubricants containing mixtures of PAGs with esters
are known. For example, U.S. Pat. No. 4,302,343 discloses a defined
mix of PAGs with esters for use in rotary screw compressors, while
U.S. Pat. No. 4,751,012 discloses mixtures for use in reciprocating
air compressors. EP 913457 discloses a liquid refrigeration
composition comprising a defined fluorine-containing refrigerant
and a lubricant comprising a defined ester of a carboxylic acid and
a polyhydroxy compound together with a defined alkoxylated alcohol
or an alkoxylated glycol. U.S. Pat. No. 4,851,144 discloses
lubricant compositions miscible in hydrofluorocarbon and
hydrochlorofluorocarbon refrigerants in the range from -20.degree.
C. to greater than 65.degree. C. and having a viscosity greater
than 75 centistokes at 38.degree. C., comprising about 5 to 95% of
a defined polyether polyol together with about 95 to 5% of an ester
made from a polyhydric alcohols with an alkanoic acid, or an ester
made from an alkanedioic acid with an alkanol. EP 980416 discloses
the use of particular PAGs in carbon dioxide refrigeration systems,
and states that the lubricant composition may also contain
neopentylpolyol esters.
SUMMARY OF THE INVENTION
[0005] Briefly described, according to one aspect of the invention,
a lubricating composition which includes (A) a polyalkyleneglycol
of the general formula (I):
RO(R.sup.aO).sub.x(R.sup.bO).sub.y(R.sup.cO).sub.zR.sup.d (I)
[0006] in which R is a C.sub.4 to C.sub.6 substituent including a
heterocyclic ring, in which the heteroatom(s) in said ring(s) is
(are) oxygen and/or sulphur, R.sup.a is a C.sub.2 alkylene group,
R.sup.b is a C.sub.3 alkylene group, R.sup.c is a C.sub.4 alkylene
group, R.sup.d is the same as R, or is a hydrogen atom or a
C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 acyl group, x, y, z are
each independently 0 or an integer in the range of from 1 to 100,
and X+y+z=4 to 100; and (B) an ester of a alcohol containing two or
more hydroxyl groups with a mono- or dicarboxylic acid, or an ester
of an dicarboxylic acid with an alcohol containing one hydroxyl
group is provided.
[0007] According to another aspect of the invention, a refrigerant
composition for refrigeration apparatus which includes a lubricant
composition including: (A) a polyalkyleneglycol of the general
formula (I):
RO(R.sup.aO).sub.x(R.sup.bO).sub.y(R.sup.cO).sub.zR.sup.d (I)
[0008] in which R is a C.sub.4 to C.sub.6 substituent comprising a
heterocyclic ring, in which the heteroatom(s) in said ring(s) is
(are) oxygen and/or sulphur, R.sup.a is a C.sub.2 alkylene group,
R.sup.b is a C.sub.3 alkylene group, R.sup.c is a C.sub.4 alkylene
group, R.sup.d is the same as R, or is a hydrogen atom or a
C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 acyl group, x, y, z are
each independently 0 or an integer in the range of from 1 to 100,
and X+y+z=4 to 100; and (B) an ester of a alcohol containing two or
more hydroxyl groups with a mono- or dicarboxylic acid, or an ester
of an dicarboxylic acid with an alcohol 10 containing one hydroxyl
group; together with a refrigerant is provided.
[0009] According to another embodiment of the invention, a
refrigeration apparatus which includes a refrigerant composition
which includes: (A) a polyalkyleneglycol of the general formula
(I): RO(R.sup.aO).sub.x(R.sup.bO).sub.y(R.sup.cO).sub.zR.sup.d
(I)
[0010] in which R is a C.sub.4 to C.sub.6 substituent comprising a
heterocyclic ring, in which the heteroatom(s) in said ring(s) is
(are) oxygen and/or sulphur, R.sup.a is a C.sub.2 alkylene group,
R.sup.b is a C.sub.3 alkylene group, R.sup.c is a C.sub.4 alkylene
group, R.sup.d is the same as R, or is a hydrogen atom or a
C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 acyl group, x, y, z are
each independently 0 or an integer in the range of from 1 to 100,
and X+y+z=4 to 100; and (B) an ester of a alcohol containing two or
more hydroxyl groups with a mono- or dicarboxylic acid, or an ester
of an dicarboxylic acid with an alcohol containing one hydroxyl
group; together with a refrigerant is provided.
DETAILED DESCRIPTION OF THE INVENTION
[0011] We have now found that selection of a particular class of
PAG in a mixture of PAG with ester, gives a lubricant oil for
refrigeration apparatus with particularly useful properties.
[0012] Accordingly, the present invention provides a lubricating
composition which comprises:
[0013] (A) a polyalkyleneglycol of the general formula (I):
RO(R.sup.aO).sub.x(R.sup.bO).sub.y(R.sup.cO).sub.zR.sup.d (I)
[0014] wherein:
[0015] R is a C.sub.4 to C.sub.6 substituent comprising a
heterocyclic ring, in which the heteroatom(s) in said ring(s) is
(are) oxygen and/or sulphur,
[0016] R.sup.a is a C.sub.2 alkylene group,
[0017] R.sup.b is a C.sub.3 alkylene group,
[0018] R.sup.c is a C.sub.4 alkylene group,
[0019] R.sup.d is the same as R, or is a hydrogen atom or a
C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 acyl group,
[0020] x, y, z are each independently 0 or an integer in the range
of from 1 to 100, and
[0021] x+y+z=4 to 100; and
[0022] (B) an ester of a alcohol containing two or more hydroxyl
groups with a mono- or dicarboxylic acid, or an ester of an
dicarboxylic acid with an alcohol containing one hydroxyl
group.
[0023] In the compound of the general formula I, R is a substituent
comprising a C.sub.4 to C.sub.6 heterocyclic species, in which the
heteroatom (s) in the heterocyclic ring is oxygen and/or sulphur.
Preferably, the heterocyclic ring comprises oxygen or sulphur. The
heterocyclic ring may be saturated or unsaturated. For example, R
may comprise a saturated cyclic ether or saturated cyclic
thioether. Such cyclic compounds may or may not be substituted.
When substituted, the heterocycle may be linked to the rest of the
molecule via the ring or via a substituent, which in such a case
may be a hydrocarbyl linkage, e.g. --CH.sub.2--, --C.sub.2H.sub.4--
or --C.sub.3H.sub.6--. R preferably comprises a C.sub.4 to C.sub.6
heterocyclic moiety which is attached to the rest of the molecule
either directly or via a hydrocarbyl linkage. For example, the
heterocyclic moiety may be a furan or a thiophene ring. The
heterocyclic moiety may alternatively be furfuryl, or a furfuryl
derivative such as tetrahydrofurfuryl, attached to the rest of the
molecule either directly or via a hydrocarbyl linkage. Examples of
compounds from which R may be derived include tetrahydrofuran,
methyltetrahydrofuran, tetrahydrothiophene or
methyltetrahydrothiophene substituents. In a preferred embodiment
of the invention, R represents a 5-membered oxygen-containing
heterocycle linked to the rest of the molecule either directly or
via a CH.sub.2 group. An especially preferred example of R is
derivable from 2-hydroxymethyltetrahydrofuran, which may be
regarded as having the formula R--OH according to the above
definition, such that R is a tetrahydrofuranmethyl
(tetrahydrofurfuryl) group.
[0024] Each of R.sup.a, R.sup.b and R.sup.c may be represented by
the general formula II:
[--C(R.sup.e)(R.sup.f)-C(R.sup.g)R.sup.h)--] (II)
[0025] In the case of R.sup.a, each of R.sup.e, R.sup.f, R.sup.g,
and R.sup.h is hydrogen. In the case of R.sup.b, one of R.sup.e,
R.sup.f, R.sup.g, and R.sup.h is methyl and the others are
hydrogen. In the case of R.sup.c, either one of R.sup.e, R.sup.f,
R.sup.g, and R.sup.h is ethyl or two of R.sup.a, R.sup.f, R.sup.g,
and R.sup.h are methyl, the remainder being hydrogen. For example,
R.sup.c may be a butylene group or an iso-butylene group.
[0026] Preferably, only one or two of R.sup.a, R.sup.b, and R.sup.c
are present in the compound of Formula I. In other words, in
preferred embodiments of the invention one or two of x, y and z is
0. For example, x may be zero, and/or z may be 0. Preferably,
either z is 0 or z and x are both 0, i.e. the compound of Formula I
is a polyalkylene glycol based upon propylene oxide, or upon a
mixture of ethylene oxide and propylene oxide. If more than one of
x, y and z is present, the compound of Formula I may be either a
block copolymer or a random copolymer. The use of random copolymers
is preferred. Preferably, the sum of x, y and z is equal to a
number in the range of from 5 to 80, more preferably from 7 to
65.
[0027] R.sup.d may be the same as R, or may be a hydrogen atom or a
C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 acyl group. Where
R.sup.d is a C.sub.1-C.sub.20 alkyl or a C.sub.1-C.sub.20 acyl
group, it preferably has 1 to 15 carbon atoms, more preferably 1 to
10 carbon atoms, and most preferably, 1 to 6 carbon atoms. When
R.sup.d is a C.sub.1-C.sub.20 alkyl group, the alkyl group may be a
straight chain, branched chain, or cyclic alkyl group. Suitable
alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and
hexyl groups. When R.sup.d is a C.sub.1-C.sub.20 acyl group, the
acyl group may be straight chain, branched chain or cyclic. The
acyl group may have one or more further substituents, for example
alkyl substituents, which may be a straight chain, branched chain
or cyclic alkyl substituent. Such alkyl substituents include
methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Preferably
R.sup.d represents a hydrogen atom or, especially, a C.sub.1-4
alkyl group, preferably a methyl group.
[0028] In an especially preferred embodiment of the invention, the
compound of the formula I has the following formula Ia:
R.sup.1O--(R.sup.2O).sub.m--R.sup.3 (Ia)
[0029] in which R.sup.1 is a tetrahydrofurfuryl group; R.sup.2is a
mix of C.sub.2 and C.sub.3 alkylene groups, the number ratio of
C.sub.2 to C.sub.3 groups preferably being in the range of from
27:75 to 75:25, especially 40:60 to 60:40, or R.sup.2 is a C.sub.3
alkylene group; m is from 5 to 80, especially from 7 to 65; and
R.sup.3 is a hydrogen atom or, preferably, a C.sub.1-4 alkyl group,
especially a methyl group.
[0030] The compounds of the formula (I) are disclosed in EP
1257623. They may be prepared by any suitable method known in the
art, including the methods described or referenced in EP
1257623.
[0031] Preferably the acid from which the ester component (B) is
derived is an alkanoic or alkandioic acid, and preferably the
alcohol is a mono-, di- or poly-hydroxyl alkanol. The ester may be
a mixed ester derived from one or more alcohols and/or one or more
acids. Preferably the ester is an ester of neopentyl glycol,
monopentaerythritol, dipentaerythritol and/or trimethylolpropane
with a C.sub.2-18 mono or di-alkanoic acid, more preferably an
ester of neopentyl glycol and/or monopentaerythritol with a
C.sub.2-10 mono alkanoic acid or a C.sub.6 dialkanoic acid, or a
dipentaerythritol ester of a C.sub.2-10 mono alkanoic acid or a
C.sub.8-9 dialkanoic acid, most preferably an ester of
monopentaerythritol with a C.sub.5-9 mono alkanoic or a C.sub.6
dialkanoic acid. Esters of mixed acids are commonly used.
[0032] Suitable esters for use in the invention are well known, and
many are commercially available. They may be prepared by methods
known in the art.
[0033] In addition to the compound of the formula I and the ester,
the composition according to the invention may also contain one or
more additives, such as extreme pressure, antiwear, anticorrosion,
antioxidants, and viscosity improver additives. Other additives
include acidity regulators, reactive water-eliminating additives,
antifoams, and demulsifiers. Typical additive packages include
those available under the Trade Marks Irgalube 349, TBPP (tributyl
phenyl phosphate), TCP (tricresyl phosphate) and Cardura E-10
(glycidyl neodecanoate).
[0034] Preferably the composition contains from 5 to 95% wt ester
and from 5 to 95% of the compound of the general formula I.
[0035] Preferably the composition is formulated to have a viscosity
in the range of from 2 to 220, more preferably 5 to 100, especially
5 to 68, cSt at 40.degree. C.
[0036] The lubricant composition according to the invention may be
used with a wide range of refrigerants. Accordingly, the invention
also provides a refrigerant composition for refrigeration apparatus
which comprises a lubricant composition according to the invention
together with a refrigerant. Preferably the refrigerant is 30
selected from fluorocarbons, hydrofluorocarbons (for example
1,1,1,2-tetrafluoroethane (R134a), difluoromethane (R32,
pentafluoroethane (R125) and 1,1,1-trifluoroethane (R143a)),
hydrocarbons (for example iso-butane), ammonia, and carbon dioxide.
Preferably the refrigerant is a hydrofluorocarbon, for example
1,1,1,2-tetrafluoroethane (R134a), or carbon dioxide. Mixtures of
different refrigerants may be used.
[0037] Compositions of the invention find particular application in
compressors used in refrigeration and air-conditioning systems, for
example domestic and industrial refrigeration and air-conditioning
systems, and also automotive air-conditioning systems. Throughout
this specification and claims, references to refrigeration systems
and apparatus should be understood to include all refrigeration and
air-conditioning systems, and also heat-pump systems and apparatus:
these are refrigeration systems with a reverse heat flow compared
with cooling systems. The invention further provides a
refrigeration apparatus which includes a refrigerant composition
according to the invention.
[0038] The lubricant compositions of the present invention provide
a number of advantages. In particular, they provide advantageous
lubricity, hygroscopicity and electrical properties.
[0039] The following Examples illustrate the invention.
EXAMPLES 1 to 5
[0040] The following lubricant compositions were tested: [0041]
Example 1 (comparative). BREOX RFL (1250 g/mol mol.wt). [0042]
Example 2 (comparative). MPE (monopentaerythritol) ester of
iso-C.sub.8 (2-ethyhexanoic) (46.8 wt. %) and iso-C.sub.9
(iso-nonanoic acid) (53.2 wt %). [0043] Example 3. BREOX RFL (1250
g/mol) (50 wt %) blended with MPE (monopentaerythritol) ester (50
wt %) of iso-C.sub.8 (2-ethyhexanoic) (46.8 wt %) and iso-C.sub.9
(iso-nonanoic acid) (53.2 wt %). [0044] Example 4. BREOX RFL (1750
g/mol) (70 wt %) blended with MPE ester (30 wt %) of iso-C.sub.5
(57 wt %) and iso-C.sub.9 acid (43 wt %).
[0045] Example 5 (comparative). BREOX MAC (1550 g/mol) (67 wt %)
blended with 33% MPE ester (33 wt %) of iso-C.sub.5 (isopentanoic)
acid (57 wt %) and iso-C.sub.9 (iso-nonanoic) acid (43 wt %).
[0046] The BREOX RFL products are commercial refrigerator
lubricants available from Cognis, and contain a compound of the
formula I in which R is a tetrahydrofurfuryl group, x and z are
both 0, and R.sup.d is a methyl group. The BREOX MAC product is a
commercial refrigerator lubricant available from Cognis, and
contains a polypropylene glycol initiated with an n-butyl group and
terminated with a hydroxy group.
[0047] Experiments were carried out and data collected using a
Falex Block on Ring test machine as follows. The procedure was in
accordance with ASTM D3704, with some modification to the procedure
to allow for the correct refrigerant atmosphere. The chamber
containing the test equipment was evacuated of air and recharged
with R410a HFC refrigerant, typically to a pressure of 180-280 psi.
The equipment was computer software controlled to generate the
coefficient of friction and wear data. Tests were run using steel
blocks and rings of compressor grade steel. Tests were run in
periods of 5 minutes at 3001b break-in load followed by 3501b load
for 45 minutes, at 300 rpm. Operating temperature was 120.degree.
C. Surface finish measurements were obtained using a commercially
available standard profilometer. Results are shown in the following
Table.
[0048] Examples 1 and 2 were carried out using a compound of
formula I alone, and using an ester alone. Examples 3 and 4 were
carried out using two different mixtures, and the results show that
the blends in accordance with the invention are better than the
separate components in coefficient of friction and surface finish
(relates to wear) on the test pieces.
[0049] Example 5 is a comparative experiment using an ester of the
same type as in Example 4 with a polyalkylene glycol which does not
have the formula I. The results show a significant reduction in
performance, both with respect to friction and to wear, compared
with the mixtures using a compound of formula I. TABLE-US-00001
TABLE Coefficient of Wear Surface Finish Example No. Friction
(inches) (Delta Ra) 1 0.0868 0.0006 3.2425 (comparative) 2 0.1153
0.0008 6.1171 (comparative) 3 0.0719 0.0006 1.5353 4 0.0765 0.0006
1.7695 5 0.0874 0.0010 4.1156 (comparative)
EXAMPLES 6 to 9
[0050] Further testing was carried using the following
materials:
[0051] (A) BREOX RFL (Trade Mark) (1750 g/mol mol.wt)
[0052] (B) ProExo 32M (Trade Mark): MPE ester of ISO-C.sub.5 (57 wt
%) and ISO-C.sub.9 acid (43 wt %)
[0053] (C) ProEco 100 C: adipate ester of ISO-C.sub.5 (57 wt %) and
iso-C.sub.9 acid (43 wt %)
[0054] (D) A blend of 30% (B) and 70% (C) (which is a blend
conforming to ISO 68).
[0055] All materials were formulated together with an Extreme
Pressure/antiwear t-butylphenyl diphenyl phosphate type, SYN-O-AD
8478 (Trade mark).
[0056] The various materials were tested by a variety of standard
tests. In all cases, the composition according to the invention
gave superior results to comparison compositions.
EXAMPLE 6
[0057] Materials were tested by the Falex 4-ball wear test under
the test procedure of ASTM D4172-94, using steel balls, under the
following conditions: load: 20 kg; speed: 1200 rpm; temp:
107.degree. C.; time: 1 hour. The wear scar was measured, and the
results are given in the following Table: TABLE-US-00002 Test
Material Wear Scar (mm) B (comparison) 0.75 C (comparison) 0.67 A
(comparison) 0.63 D (comparison) 0.68 B + A (30:70) 0.32
EXAMPLE 7
[0058] Materials were tested using the block-on-ring test using M2
vane steel blocks and cast iron rings, using the test procedure
according to ASTM D-2714-94. Conditions were as follows: load: 300
lbs (break-in) and 250 lbs (test); speed: 300 rpm; temp: 120 C;
time: 5 mins (break-in) and 45 mins (test). The results are given
in the following Table: TABLE-US-00003 Test Material Ring Weight
(mg) A (comparison) 3.00 D (comparison) 5.40 A + B 70:30 1.50
EXAMPLE 8
[0059] Materials were tested using the Pin and VBlock test
according to ASTM D-2670-95. Conditions were as follows: aluminium
pins, steel blocks; load: 350 lbs (break-in) and 400 lbs (test);
time: 5 mins (break-in) and 30 mins (test). Pin weight was
recorded. The results are given in the following Table.
TABLE-US-00004 Materials Tested Pin Weight (mg) A (comparison) 13.8
D (comparison) 10.8 A + B 70:30 33.0
EXAMPLE 9
[0060] Materials were tested in a boundary friction test according
to ASTM D-6079 with temperature modification. The equipment was a
high frequency reciprocating rig, and the test conditions were as
follows: stroke length: 1.+-.0.02 mm; frequency: 50.+-.1 Hz; temp:
50.degree. C., 100.degree. C., 120.degree. C.; duration: 75.+-.0.1
min; load: 200.+-.1 g. The results (average film and average
friction at each temperature) are given in the following Table.
TABLE-US-00005 Friction Film Friction Film Friction Test Materials
Film (50.degree. C.) (50.degree. C.) (100.degree. C.) (100.degree.
C.) (120.degree. C.) (120.degree. C.) A + B 70:30 90.8 0.079 68.0
0.106 85.9 0.120 A (comparison) 97.6 0.094 96.2 0.126 97.4
0.126
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