Abstract:
Refrigerating oils useful in refrigerating devices to produce temperatures lower than -86° C. and as low as -130° C. and free from salts, alcohols, halogenated hydrocarbons and halocarbons and having a viscosity below 10 mm 2  /s at -40° C., consisting essentially of mixtures of at least two members selected from the group consisting of hexamethyl disiloxane, octamethyl trisiloxane, linear decamethyl tetrasiloxane, octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane.

Description:
This application is a continuation of application Ser. No. 07/689,161, filed Apr. 22, 1991, now abandoned. 
    
    
     This application is a continuation-in-part of the applicant&#39;s co-pending patent application Ser. No. 07/434,189, filed Nov. 13, 1989 now abandoned. 
     This invention relates to a refrigerating oil which consists of siloxanes and which is suitable for use at low temperatures down to -140° C. 
     BACKGROUND OF THE INVENTION 
     It is known that silicone oils can be used for refrigerating mixtures providing oils having a viscosity in the range from 5 to 20 mm 2  /s, as measured at 20° C., are used (W. Simmler, &#34;G-I-T Fachzeitschrift fur das Laboratorium,&#34; 6, 101, 189, 278 -1962-). Since the application in question is static by nature, it is immaterial if the viscosity is relatively high at low temperatures. 
     On the one hand, the refrigerants of the refrigerating machine circuit itself (halocarbon and halogenated hydrocarbon compounds, such as for example R 11 , R 12 , R 22  and R 502 ) have hitherto been used as low-viscosity refrigerants at low temperatures; on the other hand, aqueous solutions of alcohols (methanol, ethylene and propylene glycol) and of salts (calcium chloride, soda, etc.) are used, depending on the temperature range. The disadvantages of these refrigerants are well known. On account of their low flashpoint, lower alcohols require elaborate safety precautions and, in some cases, are toxic. Aqueous salt solutions are highly corrosive and have an excessive viscosity at low temperatures. Finally, the halocarbon and halogenated hydrocarbon compounds are partly responsible for the photochemical degradation of the ozone layer and, in some cases, are also toxic. Accordingly, mixtures of silicone oils with halocarbon and halogenated hydrocarbon compounds, as described for example in Japanese patent application 50/453500, are poor compromises. 
     BRIEF DESCRIPTION OF THE INVENTION 
     The disadvantages mentioned above are obviated in refrigerants according to the present invention. The refrigerants according to the invention are refrigerating oils which are free from salts, alcohols, halogenated hydrocarbons and halocarbons and which have a low viscosity at low temperatures, characterized in that they consist of mixtures of hexamethyl disiloxane and/or octamethyl trisiloxane and/or linear decamethylene tetrasiloxane and/or octamethyl cyclotetrasiloxane and/or decamethyl cyclopentasiloxane. These refrigerating oils may be used at temperatures as low as -130° C., or in some cases as low as -140° C., without danger of solidification. The refrigerating oils of the present invention have a viscosity below 10 mm 2  /s at -40° C. and contain octamethyl trisiloxane in an amount of between 0.1 to 99% by weight, preferably 5 to 95% by weight and particularly preferred 10 to 90% by weight and decamethyl tetrasiloxane in an amount of between 99 to 0.1% by weight, preferably 95 to 5% by weight and particularly preferred 90 to 10% by weight, the weight percentages based on the weight of the oil. The octamethyl trisiloxane and/or decamethyl tetrasiloxane may be substituted for by equal amounts of at least one member selected from the group consisting of 0 to 23% by weight hexamethyl disiloxane, 0 to 15% by weight octamethyl cyclotetrasiloxane and 0 to 20% by weight decamethyl cyclopentasiloxane. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The nomenclature for silicones as described, for example, in W. Noll, Chemie und Technologie der Silicone (Chemistry and Technology of the Silicones), 2nd Edition, pages 3 et seq (1968), is used in the following in the interests of simplicity. Accordingly, the linear siloxanes, octamethyl trisiloxane and decamethyl tetrasiloxane, are respectively abbreviated to M 2  D and M 2  D 2  while the correspondingly higher homologs are generally abbreviated to M 2  D n . The cyclic siloxanes, octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane, are abbreviated to the D 4  and D 5 , respectively, while the higher homologs are abbreviated to D 6 , D 7  etc. 
     These short-chain and cyclic siloxanes are obtained, for example, in an acidic equilibration reaction of M 2  (hexamethyl disiloxane) with silicone oil, which is formed by hydrolysis of dimethyl dichlorosilane (A-oil), in a ratio by weight of 1:1, and acidic ion exchanger, such as acid-activated bleaching earth for example, generally being used. If a reaction product of this type is heated after removal of the catalyst by filtration, a low viscosity siloxane mixture, such as, for example, Baysilone-O1 M 3  (a product of Bayer Ag, Leverkusen), is obtained. A characterization by GC analysis and a list of the corresponding boiling points is provided in Table 1. If a product mixture of this type is subjected to fractional distillation, the individual siloxanes can be separated from one another or the claimed siloxane mixture desired in accordance with the invention can be obtained by a corresponding distillation cut. 
     Among these discrete siloxanes, M 2  D 2  appears at first to be the product with the best characteristic data for a refrigerating oil because it has a low viscosity at -40° C. and a flash point above 55° C. This flash point is the reason why M 2  D 2  is no longer classified as &#34;inflammable&#34; under the relevant legislation, so that no elaborate safety precautions have to be taken. However, pure M 2  D 2  has a crystallization point of -76° C. (see Table 2) which would seriously restrict its use as a refrigerating medium. 
     It has now surprisingly been found that additions of M 2  D and/or D 4  and/or D 5  greatly reduce the pour point or the solidification point of M 2  D 2 . In a proportion of up to 20% by weight, a mixture of M 2  D 2  /M 2  D gives a system which has a low viscosity at -40° C. and a flash point above 55° C. If more M 2  D or M 2  is added, the viscosity and the solidification/pour point are reduced, as is the flash point, although this might be of interest for special industrial applications of deep cooling. The solidification point (according to DIN 51 556) is generally 3 to 5° C. below the associated pour point (according to DIN ISO 3016). 
     If either M 2  and/or the cyclic siloxanes D 4  and/or D 5  are added to M 2  D 2  or to a mixture of M 2  D 2  and M 2  D, the addition should not exceed 30% by weight in the case of the D 4  and 50% by weight in the case of D 5  to avoid separation and crystallization clouding at low temperatures. D 4  is preferably added in a quantity of 5 to 15% by weight and D 5  in a quantity of 5 to 20% by weight, D 5  being superior to D 4  in its greater effectiveness in depressing the pour point and solidification point. As shown in the Examples of Tables 2 and 3, the siloxanes may be mixed in accordance with the invention in such a way that the viscosity at -40° C. is below 10 mm 2  /second and preferably as low as possible while the flash point is above 43° C. and preferably above 55° C. 
     If corresponding statistical mixtures of M 2  and higher M 2  D n  types (Examples of Table 4) are used instead of the claimed discrete siloxanes, the viscosity is increased and the flash point reduced, so that a refrigerating oil such as this is generally of poorer quality. However, in special applications where the low flash point is not a key factor, statistical mixtures having a very narrow distribution, as shown in Examples 17 to 19, may also be of interest. In that case, M 2  may be added to a mixture of the siloxanes M 2  D and M 2  D 2  and D 4  and/or D 5  in a concentration of up to 23% by weight without the flash point falling below 21° C. A mixture such as this would be classified as &#34;inflammable,&#34; although it would not necessitate the same safety precautions as &#34;readily inflammable&#34; substances or mixtures (flash point below 21° C). 
     The refrigerating oils thus produced may be used for refrigeration at temperatures of down to -130° C. or even in some cases -140° C. Acccordingly, the refrigerating oils are preferably used for cold stores, deep-freeze equipment freezers, but also for earth probes and other heating/refrigerating liquids which are associated with heat pumps and which, as already known, can cool down considerably after removal of the heat on the evaporator side of the heat pump. So-called brine systems such as these, which have hitherto been produced from mixtures of water and ethylene glycol, do not reach the low temperatures. 
     The refrigerating oils according to the invention have the advantage for this application that they are non-corrosive and toxicologically safe. Since, on the one hand, a mixture of M 2  D 2  and D 5 , as in Example 5, only changes into the solid aggregate state beyond -130° C., but since on the other hand its individual components have high boiling points of 194° C. and 210° C. under normal conditions, applications involving extreme temperature stressing may also be considered, including for example automotive cooling fluids or transformer fillings in climates subject to wide variations in temperature. 
     The siloxane mixtures according to the invention may be colored to show up possible leakages. For example, quantities of 0.01% by weight of the following anthraquinone dyes may be stirred in at room temperature: anthraquinone, 1-aminoanthraquinone, 1,4-bis-isobutylaminoanthraquinone, 1-(3-dimethylaminopropylamino)-4-methylaminoanthraquinone, 1-(4-methylphenylamino)-anthraquinone, 1,4-bis-(2,6-diethyl-4-methylphenylamino)-anthraquinone, 1,4-bis-(4-tert.-butylphenylamino)-anthraquinone, 1-methylamino-4-(3-methylphenylamino)-anthraquinone, 1-methyamino-4-(4-methylphenylamino)-anthraquinone,1-(3-dimethylaminopropylamino)-4-(4-methylphenylamino)-anthraquinone. 
     In addition, quantities of up to about 0.002% by weight of the following natural dyes may be used for coloring: Ceresrot 7 B, Ceresgelb CRN, cochineal, Ceresblau GN. 
     The Examples of Tables 2 and 3 are intended to illustrate the invention. In addition, Table 2 shows the characteristic data of the associated pure substances. The siloxanes of Table 4 are mixtures of statistical siloxanes and show either a higher viscosity at low temperatures or a lower flash point than the corresponding mixtures of discrete siloxanes claimed in accordance with the invention. 
     
                       TABLE 1______________________________________GC Analysis of Baysilon-1 M.sub.3 and Physical Characteristics               Ret. Time   Bp. (mm Hg)*Component  % Area   (mins.)     (°C.)______________________________________M.sub.2    0.4      3.56        110.1 (757)M.sub.2 D  4.0      6.53        151.7 (747)D.sub.4    0.4      8.36        175   (760)M.sub.2 D.sub.2      16.7     9.53        194   (760)D.sub.5    0.5      10.87       210   (760)M.sub.2 D.sub.3      23.2     12.17       229   (760)D.sub.6    0.1      13.41       245   (760)M.sub.2 D.sub.4      18.8     14.49       184.2 (101)M.sub.2 D.sub.5      12.9     16.54       184.5 (40)M.sub.2 D.sub.6      8.4      18.37       202.0 (39.3)______________________________________ *Lit.: W. Noll, Chemie und Technologie der Silicone (Chemistry and Technology of Silicones), 2nd Edition, pages 216 and 238 (1968) 
    
     
                                           TABLE 2__________________________________________________________________________Discrete Siloxane Compounds              Solidification                       Viscosity at                                 Density at                                           Flash Point              Point According                       -40° C. According                                 -40° C. According                                           According to              to DIN 51 556                       to DIN 53 211                                 to DIN 51 757                                           DIN 51 755ExamplesProduct       (°C.)                       (mm.sup.2 /s)                                 (kg/dm.sup.3)                                           (°C.)__________________________________________________________________________1    90% M.sub.2 D + 10% D.sub.4              -110     3.3       0.893     442    90% M.sub.2 D + 10% D.sub.5              -140     3.5       0.894     453    95% M.sub.2 D.sub.2 + 5% D.sub.4               -85*    5.4       0.917     584    90% M.sub.2 D.sub.2 + 10% D.sub.4               -98*    5.5       0.921     645    90% M.sub.2 D.sub.2 + 10% D.sub.5              -130     6.0       0.923     766    81% M.sub.2 D.sub.2 + 19% M.sub.2 D              -138     4.7       0.908     57Characteristic Data of The Pure Substances for Comparison:M.sub.2        - 68    1.67      0.826      0M.sub.2 D      -86*    3.0       0.878     43M.sub.2 D.sub.2               -76*    5.4       0.910     65D.sub.4        -17.5*  at -40° C. solid                                           56D.sub.5        -38*    at -40° C. solid                                           70__________________________________________________________________________ *Crystallization point 
    
     
                                           TABLE 3__________________________________________________________________________Discrete Siloxane Mixtures                               Viscosity at                                         Density at                                                   Flash Point                     Solidification                               -40° C. According                                         -40° C.                                                   According toExam-    Product Mixture       Point According                               to DIN 53 211                                         to DIN 51                                                   DIN 51 755ples    % M.sub.2   % M.sub.2 D        % M.sub.2 D.sub.2             % D.sub.4                 % D.sub.5                     to DIN 51 556 (°C.)                               (mm.sup.2 /s)                                         (kg/dm.sup.3)                                                   (°C.)__________________________________________________________________________ 7  --  31   64.3 4.7 --  -140      4.5       0.909     44 8  --  18.1 77.1 4.8 --  -140      4.8       0.911     57 9  --  19   68.5 12.5                 --   -60*     5.1       0.920     5510  --  19   73.5 7.5 --  -134      4.8       0.908     5611  --  19   78.5 2.5 --  -135      4.7       0.908     5712  --  19   78.5 --  2.5 -135      4.75      0.910     6313  --  19   73.5 --  7.5 -135      5.0       0.915     6414  --  19   68.5 --  12.5                     -136      5.18      0.920     6315  --  19   73.5 2.5 5   -138      4.89      0.915     6316  --  5.6  82.4 11  1   -136      5.1       0.920     5917  22.9   33.3 43.8 --  --  &lt;-140     3.12      0.880     2118  20.6   30.0 39.4 10  --  &lt;-140     3.41      0.894     2319  20.6   30.0 39.4 --  10  &lt;-140     3.46      0.894     22__________________________________________________________________________ *Crystallization point 
    
     
                                           TABLE 4__________________________________________________________________________For Comparison: Statistical Siloxane Mixtures                               Viscosity at                                         Density at                                                   Flash Point                     Solidification                               -40° C. According                                         -40° C.                                                   According toExam-    Product Mixture       Point According                               to DIN 53 211                                         to DIN 51                                                   DIN 51 755ples    % M.sub.2   % M.sub.2 D        % M.sub.2 D.sub.2             % D.sub.4                 % D.sub.5                     to DIN 51 556 (°C.)                               (mm.sup.2 /s)                                         (kg/dm.sup.3)                                                   (°C.)__________________________________________________________________________20  Baysilone-01 M 3      -130      12.4      0.955     7421  80% Baysilone-01      -128      8.85      0.937     62    M 3 + 20% M.sub.2 D22  79.4% Baysilone-01    -134      7.67      0.931     34    M 3 + 9.88% M.sub.2 D    + 10.7% M.sub.2__________________________________________________________________________