Abstract:
The invention relates to compositions including esters of polyvalent alcohols that are esterified with fatty acids, partially unsaturated, from plant oils, and to the use thereof as cooling and insulating fluids for transformers.

Description:
PRIORITY CLAIM 
       [0001]    This patent application is the U.S National stage under U.S.C. 371 of PCT/DE2013/000222 filed Apr. 26, 2013, and designating the United States and claims priority to German Patent Application No.: DE 10 2012 103 701.9 filed Apr. 26, 2012. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The present invention relates to compositions comprising esters of polyvalent alcohols that are esterified with fatty acids, partially unsaturated, made of plant oils, and to their use as cooling and insulating fluids for transformers. 
       BACKGROUND 
       [0003]    A reliable operation of transformers requires sufficient electrical insulation as well as the dissipation of the heat released during the conversion of electrical voltages. It is known that certain fluids have insulating and heat-dissipating properties. Conventionally, mineral oils or silicones are used. However, they have very poor biodegradability and thus represent a hazard for humans and the environment in the case of leaks, defects in liquid tightness or another discharge from the transformer. Mineral oils in addition have a very low flash point below 150° C., i.e., a high fire hazard potential. 
         [0004]    Therefore, readily biodegradable plant oils have been proposed for use as insulation fluid in transformers. It is obvious to use plant oils as insulation fluid, since they are readily and completely biodegradable and generally not hazardous for water (according to the German “Administrative Regulation on Substances Hazardous to Waters”—VwVwS) and they have flash and fire points above 300° C. (according to the method by Pensky-Martens), all this at advantageous raw material costs. In addition, these plant oils have a higher water absorption capacity than mineral oil, which reduces the degradation of the cellulose of the transformer board and increases the useful life of the transformer. 
         [0005]    Plant oils have already been used as insulation oils approximately since the end of the 19th century. However, their use was soon discontinued, since they resinify relatively rapidly by oxidation when air enters the transformers in which they are used. As a result of the use of hermetically sealed transformers, which largely exclude the entry of air, the requirement profile has changed in recent years. 
         [0006]    The oxidation sensitivity continues to be important, but not to the extent it was in the transformers of the past, and it is manageable in hermetically sealed transformers. On the other hand, awareness about the environment has increased considerably worldwide. Accordingly, plant oils such as castor bean oil, sunflower oil, rapeseed oil, soybean oil and other oils have been proposed a number of times as transformer fluid, see also WO 97/22977 A1 and U.S. Pat. No. 6,340,658 B1. 
         [0007]    In addition to oxidation stability, other required properties of a transformer fluid have become increasingly important, including high flash and fire points, low viscosity (for improved heat convection), and in particular also a low pour point, low acid number, good dielectric stability and low sludge formation in the stability test according to DIN EN 61099 “Specifications for unused synthetic organic esters for electrical purposes” (see Table 1). In addition, good corrosion properties and seal compatibility are absolutely required. Unfortunately, natural plant oils do not satisfy all these necessary or desired properties simultaneously, and they have weaknesses in terms of one or more of the properties, in particular with regard to viscosity and cold properties as well as oxidation stability. The oxidation stability is generally increased to a minimum level by adding antioxidants. However, the cold properties in particular can only be improved marginally by means of additives. Lowering the viscosity by simply mixing plant oils with portions of other clearly thinner base oils is not possible because of required high flash and fire points. 
         [0008]    GB 1602092 discloses the use of trimethylolpropane esters of linear saturated fatty acids with 7 to 10 C atoms and their use as dielectric insulation fluid for transformers. From the examples, trimethylolpropane esters having a viscosity of 25 or 30 mm 2 /s in each case at 30° C. and a fire point of 277° C. or 293° C. are known. WO 2005/118756 A1 has a similar disclosure content. However, it discloses more broadly linear or branched carboxylic acids with 6 to 12 C atoms. However, branched carboxylic acids are not natural fatty acids. 
       SUMMARY OF THE INVENTION 
       [0009]    The present invention relates to esters in the form of mixed esters and/or ester mixtures 
         [0000]    
       
                 
         
             
             
         
       
     
         [0010]    with R, R 1  and R 2  or R, R 1  to R 4  independently of one another and next to another: 
         [0011]    R=methyl, ethyl, propyl, isopropyl or mixtures thereof, 
         [0012]    R 1 =at least 30%, preferably at least 50%, linear saturated acid groups with 6 to 12 C atoms, preferably with 8 to 10 C atoms, and 
         [0013]    R 2 =at least 30%, preferably at least 20%, acid groups with 14 to 22 C atoms, preferably 18 C atoms, comprising one or more double bonds, preferably with cis-configured double bond(s), 
         [0014]    optionally characterized furthermore as follows: 
         [0015]    R 3  0 to at most 20%, preferably 1 to at most 10%, linear saturated acid groups with 14 to 22 C atoms, 
         [0016]    R 4  0 to at most 20%, preferably at most 10%, other acid groups apart from R′, R 2  and optionally R 3 . 
         [0017]    The ester consists of the acid groups R 1  to R 4  and of the alcohol group 
         [0000]    
       
                 
         
             
             
         
       
     
         [0018]    The above percentages relate to the relative number of the acid groups R 1 , R 2 , and so on, to the extent that they are bound to the polyvalent alcohol(s) of general formula 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    regardless of whether they are in the form of a mixture of esters (ester mixture) with in each case uniform structure, such as, for example 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    or in the form of mixed esters, in which the acid groups R 1  and R 2  or R 1  to R 4  of an alcohol residue are present in any distribution. The percentages add up to a total of 100. 
         [0019]    The fatty acids in accordance with acid group R 1  or R 2  and R 3  can preferably be obtained from natural fats in the form of a mixture, for example, from natural sources such as sunflower oil or rapeseed oil, preferably from their variants with high oleic acid content. 
         [0020]    The acid groups R 2  are made of fatty acids having a chain length of 6 to 12 C atoms, in particular 8 or 10 C atoms, which can be obtained, for example, as distillation cuts from plant oils such as, for example, coconut oil, palm kernel oil, and others. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0021]    It was found surprisingly that the above-mentioned mixed esters or ester mixtures satisfy and even exceed the requirements of DIN EN 61099 (see Table 1), i.e., in particular that they have simultaneously a low viscosity, a low pour point (DIN ISO 3016), a high flash point according to Pensky-Martens—(DIN ES ISO 2719, &gt;250° C.) and a high fire point (DIN EN ISO 2592—) as well as a high oxidation stability. In addition, they have a satisfactory biodegradability. Moreover, the dielectric insulation fluid according to the invention is produced, in particular largely, for example, more than 80% by weight thereof (relative to the starting material used for the synthesis), on the basis of renewable raw materials. 
         [0022]    Surprisingly, it was discovered that esters of polyvalent alcohols 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    such as particularly trimethylolpropane (R=ethyl) esterified to one another and then mixed or esterified together with two or more different fatty acids excellently satisfy the above-described requirements. 
         [0023]    Therefore, a first subject matter of the present invention relates to compositions comprising the above esters of polyvalent alcohols according to formula V with three hydroxy groups, such as trimethylolpropane esters with a) linear acid groups with 6 to 12 C atoms, and b) fatty acids comprising 14 to 22 C atoms, particularly predominantly 18 C atoms, and one or more double bonds, preferably cis-configured, or of the above definition, in transformers or as transformer oil. 
         [0024]    The acid residue b) can be obtained from natural plant oils such as sunflower oil, rapeseed oil, and others, preferably from their variants with high oleic acid content. In particular, a high oleic acid content of proportion of b) guarantees good cold properties and simultaneously a high aging stability. 
         [0025]    The fatty acid residues a) with a chain length of 6 to 12 C atoms, in particular 8 or 10 C atoms, can be obtained either from plant oils such as, for example, coconut oil (for example, as a distillation cut) or also entirely or partially from synthetic sources. The residues R 2  are linear and they preferably comprise 8 and/or 10 C atoms. 
         [0026]    In a triester, all the residues R can be identical, or only two residues can be identical, or all the residues can be different. It is preferable to use a distribution of the residues R 1  and R 2  such that the flash point or the fire point is higher than, preferably as much as possible higher than 250° C., and the viscosity has a value of &lt;= or &lt;35 mm 2 /s at 40° C. and the pour point has a value &lt;−45° C. The low viscosity and in particular the low pour point can be achieved by selected acid components in the ester. 
         [0027]    For a mixed ester 1 of trimethylolpropane (TMP) with R 2 =oleic residue with 18 C atoms (purity above 95 wt %) and with more than 80 wt % of R 2  with cis-configured double bond and with a residue R 1  with 8 and/or 10 C atoms, the following mixed esters 1 can be obtained 
         [0000]    
       
         
               
             
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Properties of different mixed esters 1 
               
             
          
           
               
                   
                 Ester 1: [R 1 ]:[R 2 ] 
               
             
          
           
               
                   
                   
                   
                   
                 DIN EN 
               
               
                   
                 1:1 
                 2:1 
                 3:1 
                 6199 
               
               
                   
                   
               
             
          
           
               
                 Appearance 
                 Clear 
                 clear 
                 clear 
                 Clear 
               
               
                 Color 
                 1.0 
                 1.0 
                 1.0 
               
               
                 Density 20° C. [g/mL] 
                 0.929 
                 0.930 
                 0.933 
                 &lt;1 
               
               
                 Refractive index [—] 
                 1.466 
                 1.462 
                 1.461 
                 ±0.01 
               
               
                 Viscosity −20° C. 
                 993 
                 860 
                 767 
                 &lt;3000 
               
               
                 [mm 2 /s]* 
               
               
                 Viscosity 40° C. 
                 35.0 
                 30.8 
                 28.4 
                 &lt;35 
               
               
                 [mm 2 /s]** 
               
               
                 Pour point [° C.] 
                 −50 
                 −55 
                 −60 
                 &lt;−45 
               
               
                 Flash point, PM [° C.] 
                 &gt;250 
                 &gt;250 
                 &gt;250 
                 &gt;250 
               
               
                   
               
               
                 *calculated 
               
               
                 **kinematic viscosity 
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
               
                   
               
               
                 Physical properties of ester 2 (TMP plus oleic acid) and ester 3 (TMP plus n-C8/C10 acid) 
               
               
                 and properties of the ester mixtures of ester 2 and ester 3 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Ester 2:Ester 3 
                 Ester 2 
                 Ester 3 
                 1:1 
                 1:2 
                 1:3 
                 DIN EN 
               
               
                   
                   
                   
                   
                   
                   
                 6199 
               
               
                 Appearance 
                 clear 
                 Clear 
                 clear 
                 clear 
                 clear 
                 Clear 
               
               
                 Density [g/cm 3 ] 20° C. 
                 0.92 
                 0.945 
                 0.929 
                 0.933 
                 0.936 
               
               
                 Viscosity −20° C. 
                 1400 
                 1000 
                 993 
                 860 
                 767 
                 &lt;3000 
               
               
                 [mm 2 /s]* 
               
               
                 Viscosity 40° C. 
                 48 
                 20 
                 34.0 
                 29.7 
                 27.5 
                 &lt;35 
               
               
                 [mm 2 /s]** 
               
               
                 Pour point [° C.] 
                 &lt;−60 
                 −51 
                 −58 
                 −58 
                 −60 
                 &lt;−45 
               
               
                 Flash point PM [° C.] 
                 &gt;250 
                 230 
                 &gt;250 
                 250 
                 230 
                 &gt;250 
               
               
                 Flash point CoC [° C.] 
                 300 
                 250 
                 288 
                 276 
                 278 
                 — 
               
               
                   
               
               
                 *calculated 
               
               
                 **kinematic viscosity 
               
             
          
         
       
     
         [0028]    By means of the physical mixtures of the trimethylolpropane esters 2 and 3, all the intermediate viscosities can be adjusted, and the pour point is lowered. In particular, however, it was found surprisingly and unpredictably that with the physical mixture of ester 2 and 3 at the ratio of 1:1 to 1:2, the flash point exceeds the limit value of 250° C. required by DIN EN 61099. 
         [0029]    It is important that, by using different ratios of [R 1 ]:[R 2 ] according to Table 1 or of ester 2:ester 3, the viscosity and pour point as well as the flash point can be adjusted. It is also important that the viscosity of the mixed esters or ester mixture according to the invention is clearly lower than that of the pure trimethylolpropane ester 2 (TMP plus R 2 =oleic acid residue), and that the pour point is lower than that of the trimethylolpropane ester 3, which has already been proposed as insulation fluid. Thus, in terms of performance, the ester mixture or the mixture of esters according to the invention is superior to ester 3 (compare Table 1 and Table 2). 
         [0030]    Thus, it must be retained that each one of the “pure type” esters 2 and 3 by itself does not satisfy the requirements in terms of all of the target parameters of viscosity, cold behavior and flash point, in contrast to the special intra- (Table 1) or intermolecular (Table 2) mixtures. 
         [0031]    The mixed esters or mixtures of esters according to the invention thus have advantages in comparison to the prior art and represent progress in the direction toward the desired properties of a transformer oil. 
         [0032]    The class of mixed trimethylolpropane triesters satisfies DIN EN 61099 and it was classified, in accordance with the Administrative Regulation on Substances Hazardous to Waters (VwVwS) of the Commission for the Evaluation of Substances Hazardous to Waters (KBwS) as not hazardous to water (NWG). 
         [0033]    Their natural degradability, which is clearly more than 60% after 28 days, is thus in the range of “readily biodegradable” according to the final degradability test OECD 301. The compositions according to the invention have good thermal properties and excellent dielectric properties. 
         [0034]    In order to further improve the properties of the insulation fluid, it is possible and preferable to use antioxidants and/or metal deactivators and/or pour point depressants. 
         [0035]    In an additional embodiment, the composition according to the invention comprises in addition:
       between 0.01 and 3% by weight %, in particular 0.1 and 2.5% by weight %, particularly preferably 1.0 and 2.0% by weight % of at least one antioxidant and/or   0.01 and 1.0% by weight, preferably 0.02 and 0.08% by weight, of at least one metal deactivator and/or   0.1 to 5% by weight, in particular 0.1 and 3% by weight and particularly preferably 1.5 to 2.5% by weight, of at least one pour point depressant and/or   0.01 to 2% by weight in particular 0.01 and 0.5% by weight, and particularly preferably 0.01% by weight to 0.08% by weight of at least one defoamer in each case relative to the weight of the ester.       
 
         [0040]    The antioxidants here are selected preferably from the following substances and mixtures of the listed substances:
       from the group of the phenolic antioxidants such as, for example, alkylated monophenols (for example, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-phenol, 2-tert-butyl-4,6-dimethylphenol and/or 2,6-di-tert-butyl-4-ethylphenol) and/or alkylated hydroquinones (for example, 2,5-di-tert-butyl-hydroquinone and/or 2,6-di-tert-butyl-4-methoxyphenol) and/or hydroxylated thiodiphenyl ethers (for example, 2,2′-thio-bis-(4-octylphenol)) and/or alkylidene bisphenols (for example, 2,2′-methylene-bis-(6-tert-butyl-4-methylphenol)) and/or benzyl compounds (for example, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-tri-methylbenzene) and/or acylaminophenols (for example, N-(3,5-di-tert-butyl-4-hydroxyphenol)-carbamic acid octyl ester)®   and from the group of the aminic antioxidants: di-phenylamine, octylized di-phenylamine and/or N-phenyl-1-naphthylamine® tocopherols and gallates.       
 
         [0043]    The metal deactivators are preferably selected from the following substances and mixtures of the listed substances: benzotriazoles and their derivatives, salicylaminoguanidine, toluenetriazoles and their derivatives, 2-mercaptobenzothiazole, 2-mercaptobenzotriaozole and/or salicylidene-propylenediamine and their derivatives. 
         [0044]    The pour point depressants are preferably organic compounds such as diethyl hexyl adipates, methacrylate polymers, polyvinyl acetates and their derivatives and/or mixtures of the listed substances. 
         [0045]    The antifoaming additives are preferably compounds such as polyethylene glycol ethers, amino alcohols and/or additives based on esters. 
         [0046]    According to another embodiment, compositions according to the various embodiments described herein, comprising the esters of general formula I according to the above definition(s) can be used as dielectric insulation fluid in electrical power engineering units such as transformers. 
         [0047]    The transformers are power transformers, distribution transformers, pole transformers, on-load tap changers or changeover switches. 
         [0048]    The embodiments are explained in the following test examples without being limited to them. 
       TEST EXAMPLES 
     Test Example 1 
     Mixed Esters, Acid Catalyzed Esterification of Trimethylolpropane with the Fatty Acid Mixture 
       [0049]    1.03 mol fatty acid mixture (0.26 mol oleic acid, 0.46 mol caprylic acid and 0.31 mol capric acid), 5 g p-toluenesulfonic acid and 0.33 mol (40.7 g) trimethylolpropane were boiled with 150 mL o-xylene in the Dean-Stark apparatus at reflux (3 h, 145° C.) until water stopped being removed. Subsequently, the preparation was washed in the separation funnel with deionized water until the aqueous phase was neutral. The o-xylene was separated using a rotary evaporator. Residues of the solvents and of the fatty acids were removed by short-path distillation at 168° C. and 2×10 −2  mbar. The yield was 80%. 
       Test Example 2 
     Mixed Esters, Alkaline Transesterification of TMP Trioleyl Esters and C8/C10 TMP Triesters 
       [0050]    300 g dried mixture of trimethylolpropane trioleyl esters and C8/C10 trimethylolpropane triesters at a ratio of 1:2 were repeatedly frozen and thawed under oxygen-free nitrogen and after heating to 60° C., 2 g sodium methoxide were added. After a reaction time of 2 hours, the preparation was taken up in 500 mL tert-butyl methyl ether. 
         [0051]    After the addition of diluted HCl for the neutralization of the sodium methoxide, the preparation was washed with deionized water until the aqueous phase was neutral. 
         [0052]    The tert-butyl methyl ester was separated by means of the rotary evaporator. Residues of the solvent and free acids were removed by short-path distillation at 168° C. and 2*10-2 mbar. The yield was            
         [0053]    The present disclosure includes that contained in the appended claims, as well as that of the foregoing description. Although this invention has been described in its preferred form with a certain degree of particularity, it is understood that the present disclosure of the preferred form has been made only by way of example and that numerous changes in the details of the structures and the combination of the individual elements may be resorted to without departing from the spirit and scope of the invention.