Compositions – Vaporization – or expansion – refrigeration or heat or energy... – With lubricants – or warning – stabilizing or anti-corrosion...
Reexamination Certificate
1996-01-22
2001-02-06
Diamond, Alan (Department: 1111)
Compositions
Vaporization, or expansion, refrigeration or heat or energy...
With lubricants, or warning, stabilizing or anti-corrosion...
C508S579000
Reexamination Certificate
active
06183661
ABSTRACT:
This invention relates to lubricants and more particularly to their use in heat transfer devices.
Heat transfer devices of the mechanical vapour recompression type, including refrigerators, heat pumps and air conditioning systems, are well known. In such devices, a working fluid of suitable boiling point evaporates at low pressure taking heat from the surrounding zone. The resulting vapour is then compressed and passed to a condenser where is condenses and gives off heat to a second zone. The condensate is then returned through an expansion valve to the evaporator, so completing the cycle. The mechanical energy required for compressing the vapour and pumping the fluid is provided by, for example, an electric motor or internal combustion engine.
The working fluid used in these heat transfer devices include chlorofluorocarbons such as dichlorodifluoromethane (Refrigerant R-12) the production of which is likely to be severely limited by international agreement in order to protect the stratospheric ozone layer. As is the case with other mechanical equipment, it is necessary for the moving parts of the heat transfer devices to be adequately lubricated and the devices are generally designed to use lubricants which are miscible with the working fluids, mineral oil commonly being used in conjunction with dichlorodifluoromethane.
Unfortunately, some of the compounds, for example 1, 1, 1, 2-tetrafluoroethane (R-134a), which have been proposed as working fluids to replace dichlorodifluoromethane are insufficiently soluble in mineral oils to allow the latter to be used as lubricants. Polyalkylene glycols have been proposed in U.S. Pat. No. 4,755,316 as alternatives but they are not entirely satisfactory for a number of reasons. Thus whilst they show reverse solubility such that the fluid tends to separate from the lubricant at temperatures above about 40° C., they often attract water to an extent sufficient to cause corrosion in the equipment. Furthermore, they often fail to wet metals sufficiently to provide efficient lubrication and have an adverse effect on aluminium commonly used for the construction of compressors.
The polyalkylene glycols described in U.S. Pat. No. 4,755,316 are at least difunctional with respect to the hydroxyl groups, polypropylene glycols being preferred. It is claimed that these polyether polyols are superior to polyoxypropylene glycol mono-ethers in that the polyols have significantly wider ranges of miscibility with 1, 1, 1, 2-tetrafluoroethane. In view of this claim that polyethers having at least two hydroxyl groups are superior to polyethers having one hydroxyl group, it is extremely surprising that polyethers which are substantially free of hydroxyl groups have now been found to be superior to polyether polyols in respect of their miscibilities with R-134a and related working fluids.
Thus according to the invention there is provided a composition for use in a compression type heat transfer device comprising:
a) a hydrofluoroalkane or hydrochlorofluoroalkane fluid; and
b) a sufficient amount to provide lubrication of a polyether having a molecular weight between about 150 and about 3000, said polyether having the general formula
wherein
A represents the residue remaining after removing the active hydrogens from a compound containing one or more active hydrogen atoms;
R represents hydrogen or an alkyl radical;
Q represents an optionally substituted alkyl, aralkyl, or aryl radical; and
each of n and x, independently, is an integer having a value of at least 1.
Hydrofluoroalkanes and hydrochlorofluoroalkanes which may be present as working fluids in the compositions of the invention typically have boiling points in the range from about −85° C. to about 30° C. Examples of suitable hydrofluoroalkanes and hydrochlorofluoroalkanes are given in the following table:
Refrigerant
Chemical
Boiling Point
No.
Formula
° C. at 1 bar
R-23
CHF
3
−82.1
R-32
CH
2
F
2
−51.7
R-125
CHF
2
CF
3
−48.5
R-22
CHClF
2
−40.8
R-134a
CF
3
CH
2F
−26.5
R-152a
CHF
2
CH
3
−24.7
R-134
CHF
2
CHF
2
−19.7
R-124
CHClFCF
3
−12
R-124a
CHF
2
CClF
2
−10.2
R-142b
CClF
2
CH
3
−9.2
R-143
CHF
2
CH
2
F
5
R-133
CHClFCHF
2
17
R-123
CHCl
2
CF
3
27.2
R-123a
CHClFCClF
2
28.2
A single hydrofluoroalkane or hydrochlorofluoroalkane may be employed as working fluid in the composition of the invention or alternatively, a mixture of hydrofluoroalkanes and/or hydrochlorofluoroalkanes may be used. Any such mixture may be azeotropes, zeotropes, (mixtures of varying boiling points) or close boiling point mixtures.
In the polyether of Formula I, A may represent the residue of any active hydrogen containing compound. Thus, for example, A may be the residue remaining after removing the active hydrogens from water, ammonia or a compound containing one or more hydroxyl, primary amino, secondary amino or mercapto groups.
Alkyl radicals which may be represented by R in the polyethers of Formula I particularly include C
1-4
alkyl radicals, especially methyl. The polyethers may be homopolymers, or alternatively, copolymers wherein, in any given molecule, R can be a mixture of hydrogen atoms and alkyl radicals arranged in a random or ordered manner.
Optionally substituted alkyl radicals which may be represented by Q include optionally substituted, for example halogen substituted, C
1-12
alkyl radicals especially C
1-4
alkyl radicals. Thus, especially suitable alkyl radicals include methyl, ethyl, the various propyl and butyl radicals, —CF
2
CF
2
H and chlorobutyl. Aralkyl radicals which may be represented by Q particularly include benzyl and aryl radicals also include phenyl and alkyl substituted phenyl radicals.
Preferred polyethers for use in the compositions of the invention are polyoxyethylene ethers, polyoxypropylene ethers and random or block poly(oxyethylene-oxypropylene) ethers. In particularly preferred polyethers, at least 33% of the oxyalkylene units on a molar basis are oxyethylene units, any other oxyalkylene units being oxypropylene.
Another preferred class of polyethers for use in the compositions of the invention have the general formula:
wherein
Qrepresents C
1-4
alkyl or —CF
2
CF
2
H;
each of y and z, independently, represents an integer from 0 to 15, the sum of y and z being from 4 to 15; and
the oxyethylene and oxypropylene units being randomly distributed.
Polyethers of Formula (I) may be obtained by etherification, under conventional conditions of a polyether of the formula:
wherein A, R, n and x have the meanings given above.
Polyethers of Formula III have been fully described in the prior art and may be obtained by the oxyalkylation (especially oxyethylation and/or oxypropylation) of an initiator compound of the formula:
AH
x
(IV)
wherein A and x have the meanings given above.
Suitable initiator compounds of Formula IV include water, ammonia, mono- and polyhydric alcohols, for example methanol, ethanol, 1-butanol, 1-hexanol, 1-decanol, benzyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol, glycerol, 1, 2, 6-hexanetriol, trimethylolpropane, triethanolamine, pentaerythritol, dipentaerythritol, sorbitol and sucrose, phenols, for example phenol, cresols, nonylphenol, resorcinol and bisphenol A, amines, for example ethylamine, diethylamine, cyclohexylamine, aniline, ethylene diamine, hexamethylene diamine, tolylene diamine, diaminodiphenylmethane, polymethylene polyphenylene polyamines and amino-alcohols, for example ethanolamine and diethanolamine. Mixtures of initiators may be used.
The weight ratio of hydrofluoroalkane and/or hydrochlorofluoroalkane refrigerant to polyether lubricant in the compositions of the invention is generally within the range 99:1 to 1:99, preferably 99:1 to 70:30.
The compositions of the invention are useful in compression cycle heat transfer devices including refrigerators, air conditioning and heat pump systems and may be used for producing both cooling and heating.
REFERENCES:
patent: 4267064
Makin Pamela Louise
Powell Richard Llewellyn
Diamond Alan
Imperial Chemical Industries plc
Pillsbury Madison & Sutro LLP
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