CA2137257A1 - Polyol ester heavy duty compressor lubricants - Google Patents

Abstract

A high quality heavy duty lubricant for refrigerating compressors, especially those using chlorine free hydrofluorocarbon refrigerant working fluids, is provided by mixed esters of hindered polyols, most desirably pentaerythritol with a mixture of car-boxylic acids including at least some iso-pentanoic acid along with at least 13 % of dibasic acids such as adipic.

Description

~ W093/25628 2 1 ~ 7 2 5 7 PCT/US93/04885 POLYOL E8TER ~EAVY D~TY COMPRES~OR L~BRIC~N$~

CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of copend-ing International Application No. PCT/US92/04438 designat-ing the United States and filed June 3, 1992, the entire 5 disclosure of which, except to the extent contrary to any explicit statement herein, is hereby incorporated herein by reference.
BACKGROUND OF THE INVENTION
Field of the Invention 10 This invention relates to lubricant base stocks, which can also serve as complete lubricants in some cases;
compounded lubricants, which include at least one additive for such purposes as improving high pressure resistance and/or wear resistance, corrosion inhibition, and the like 15 along with the lubricant base stocks which contribute the primary lubricity to the compounded lubricants; refriger-ant working fluids including lubricants according to the in~ention along with primary heat transfer fluids; and methods for using these materials. The lubricants and 20 lu~ricant base stocks are generally suitable for use with most or all halocarbon refrigerants and are particularly suitable for use with substantially chlorine-free, fluoro-group-containing organic refrigerating heat transfer flu-ids such as pentafluoroethane, 1,1-difluoroethane, 1,1,1-25 trifluroethane, and tetrafluoroethanes, most particularly1,1,1,2-tetrafluoroethane. The lubricants and base stoc~s, in combination with these heat transfer fluids, are particularly suitable for lubricating compressors that require ISO grades from about 320 to about 1000 because of 30 their heavy duty cycles.
Statement of Related Art . . Chlorine-free heat transfer fluids are desirable for use in refrigerant systems, because their escape into the W093/25628 ~ 2 1 3 7 2 PCT/US93/0 ~S

atmosphere causes less damage to the environment than the currently most commonly used chlorofluorocarbon heat trans-fer fluids such as trichloro~luoromethane and dichlorodi-fluoromethane. The widespread commercial use of chlorine-s free refrigerant heat transfer fluids has been hindered, however, by the lack of commercially adequate lubricants.
This is particularly true for one of the most desirable working fluids, 1,1,1,2-tetrafluoroethane, commonly known in the art as "Refrigerant 134a" or simply "R134a". Other fluoro-substituted ethanes are also desirable working flu-ids.
Esters of hindered polyols, which are defined for this purpose as organic molecules containing at least five carbon atoms, at least 2 -OH groups, and no hydrogen atoms directly bonded to any carbon atom that is directly bonded to a carbon atom bearing an -OH group, have already been recognized in the art as high quality lubricant basestocks for almost any type of refrigeration machinery employing a fluorocarbon refrigerant, particularly one free from chlorine. The following patents and published patent ap-plications teach many general classes and specific exam-ples of polyol esters useful as refrigerant lubricants with chlorine-free fluoro group cont~;n;ng heat transfer fluids: US 4,851,144; UK 2 216 541; US 5,021,179; US 5, zs 096,606; WO 90/12849 (Lubrizol); EP O 406 479 (Kyodo Oil);
EP O 430 6S7 (Asahi Denka KK); EP O 435 2S3 (Nippon Oil);
EP O 445 610 and 0 445 611 (Hoechst AG); EP 0449 406; EP O
458 584 (Unichema Chemie BV); and EP O 485 979 (Hitachi).
PESCRIPTION OF THE INV~N~ION
Except in the claims and the operating examples, or where otherwise expressly indicated, all numerical quant-ities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the term "about" in defining the broadest scope of the invention. Practice of the invention within the boundaries corresponding to the exact quantities stat-ed is usually preferable, however.

~ W093/25628 i' 2 1 3 7 2 5 7 PCT/US93/04885 More specifically, ester mixtures according to this invention should have a viscosity of not more than 1300, more preferably not more than llO0, still more preferably not more than 990, centistokes at 40 C. Independently, 5 ester mixtures according to this invention should have a viscosity of at least 300, or with increasing preference in the order given, at least 450, 600, or 810, centistokes at 40 C.
It has now been found that selected polyol esters pro-vide high quality lubrication for this kind of service.
Specifically effective are esters or mixtures of esters made by reacting (i) a mixture of alcohol molecules se-lected from the group consisting of 2,2-dimethylol-1-buta-nol (also known as "trimethylolpropane" and often abbrevi-1'5 ated hereinafter as "TMP"); di-trimethylolpropane (often abbreviated hereinafter as "DTMP"), a molecule with four hydroxyl groups and one ether linkage, formally derived from two molecules of TMP by removing one hydroxyl group from one of the TMP molecules and one hydrogen atom from a 20 hydroxyl group of the other TMP molecule to form water and join the two remainders of the original TMP molecules with an ether bond; 2,2-dimethylol-1,3-propanediol (also known as "pentaerythritol" and often abbreviated hereinafter as "PE"~; and di-pentaerythritol (often abbreviated herein-25 after as "DPE"), a molecule with six hydroxyl groups andone ether bond, formally derived from two PE molecules by the same elimination of the elements of water as described above for DTMP, tri-pentaerythritol (often abbreviated hereinafter as "TPE"), a molecule with eight hydroxyl 30 groups and two ether bonds, formally derived from three PE
molecules by an analogous elimination of the elements of two molecules of water as described above (for elimination of a single water molecule) for DTMP and DPE; and tri-tri-methylolpropane (hereinafter often abbreviated as "TTMP"), 35 a molecule with five hydroxyl groups and two ether bonds, formally derived from three TMP molecules by the same . elimination of the elements of two molecules of water as W093/25628 2~1 3:7 2~ ~ PCT~US93/0 ~ 5 described above for TPE, with (ii) a mixture of acid mol-ecules selected from the group consisting of all the straight and branched chain monobasic and dibasic carbox-ylic acids with from four to twelve carbon atoms each, s with the alcohol moieties and acyl groups in the mixture of esters selected subject to the constraints that (a) a total of at least 15 %, or, with increasing preference in the order gi~en, at least 27, 36, 45, 51, 56, or 62 %, of the acyl groups in the mixture are 2-methylbutanoyl or 3-methylbutanoyl groups, which are jointly abbreviated here-inafter as "acyl groups from tor of] i-C5 acid"; (b) the ratio of the % of acyl groups in the mixture that contain 8 or more carbon atoms and are unbranched to the % of acyl groups in the mixture that are both branched and contain not more than six, preferably not more than five, carbon atoms is not greater than 1.56, more preferably not great-er than 1.21, or still more preferably not greater than 1.00; (c) the % of acyl groups in the ester mixture that contain at least nine carbon atoms, whether branched or zo not, is not greater than 81, or increasingly more prefer-ably, not greater than 67 or 49; and (d) not more than 2, more preferably not more than 1, or still more preferably not more than 0.4, % of the acyl groups in the ester mix-ture are from acid molecules with more than two carboxyl groups each; and (e) at least 13.8, or with increasing preference in the order given, at least 15.3, 16.2, 17.0, 17.6, 18.2, or 18.9 %, of the acyl groups in the ester mix-ture are dibasic; and a total of at least 82, or with in-creasing preference in the order given, at least 85, 89, 93, 96, or 99 % of the monobasic acyl groups in the acid mixture have either five or six, or more preferably exact-ly five, carbon atoms each. In all these percentages, acyl qroups are counted as a single group, irrespective of the number of valences they have. For example, each mole-cule of adipic acid yields a single, dibasic, acyl group when completely esterified.
(Of course, for all the types of esters described ~ W093/25628 ` 2~1 3 7 2 ~ 7 PCT/US93/04885 herein as part of the invention, it is possible to obtain the same esters or mixture of esters by reacting acid de-rivatives such as acid anhydrides, acyl chlorides, and esters of the acids with lower molecular weight alcohols than those desired in the ester products according to this invention, instead of reacting the acids themselves. The acids are generally preferred for economy and are normally specified herein, but it is to be understood that the es-ters defined herein by reaction with acids can be equally well obtained by reaction of alcohols with the correspond-ing acid derivatives, or even by other reactions. The only critical feature is the mixture of acyl groups and alcohol moieties in the final mixture of esters formed.) Preferably, with increasing preference in the order given, a total of at least 60, 75, 85, 90, 95, or 98 ~ of the hydroxyl groups in the mixture of alcohols that could be reacted to make the mixture of esters according to this invention are PE, DPE, and/or TPE molecules, and independ-ently, with increasing preference in the order given, at least 60, 75, 85, 90, 95, or 98 % of the hydroxyl groups in the mixture of alcohols that could be reacted to make esters according to this invention are PE molecules. In-dependently, in the mixtures of acids that could be react-ed with alcohols to make the esters according to this in-Z5 vention, with increasing preference in the order given, at least 60, 75, 85, 90, 95, or 98 % of the monobasic acid molecules in the acid mixture consist of molecules having no more than ten carbon atoms each and, with increasing preference in the order given, at least 60, 75, 85, 90, 95, or 98 % of the dibasic acid molecules in the acid mix-ture consist of molecules having no more than ten carbon atoms each, or more preferably from five to seven carbon atoms each. Most preferably, with increasing preference in the order given, a total of at least 60, 75, 85, 90, 95, or 98 % of the monobasic acid molecules in the acid mixture consist of molecules having either five or nine carbon atoms each.

W093/25628 ~ '` PCT/US93/0 ~ ~3~t2~ ~5 These preferences for the acyl groups and alcohol moi-eties in esters according to this invention are based on empirically determined generali2ations. In order to achieve the desired range of viscosity, it is advantageous to have a substantial fraction of dibasic acids and of al-cohols with at least four hydroxyl grou~s. Among the com-mercially available hindered alcohols that satisfy this criterion, PE is less expensive than DTMP and is free from the ether linkage in DTMP, which increases the hygroscop-icity of the esters formed and thereby may promote unde-sirable corrosion of the metal surfaces lubricated.
When the number of carbon atoms per molecule is nine or more, not even branching is sufficient to produce ade-quate solubility ~y itself, so that an upper limit on the fraction of such acids is independently required. In gen-eral, a minimum amount of the particularly advantageous i-Cs acid is specified to aid in solubilizing the parts of the esters in the mixture that contain dibasic acids or those with eight or more carbon atoms.
For both performance and economic reasons, it has been found that ~ive carbon monobasic acids and six carbon dibasic acids are the most preferred constituents.
It is to be understood that only the desired alcohols and acids are explicitly specified, but some amount of the sort of impurities normally present in commercial or in-dustrial grade products can be tolerated in most cases.
For example, "commercial pentaerythritol" normally con-tains only a~out 85 - 90 mole % of pure pentaerythritol, along with 10 - 15 mole % of di-pentaerythritol, and com-mercial pentaerythritol is satisfactory for use in making lubricant esters according to this invention in many cas-es. In general, however, it is preferred, with increasing preference in the order given, that not more than 25, 21, 17, 12, 8, 5, 3, 2, 1, 0.5, or 0.2 ~ of either the hydrox-yl groups in the alcohol mixtures specified herein or of the carboxyl groups in the acid mixtures specified herein should be part of any molecules other than those exp}icit-~ W093/25628 2 1 3 7 2 5 7 PCT/US93/04885 ly specified for each type of lubricant base stock. Per-centages of specific chemical molecules or moieties speci-fied herein, such as the percentages of carboxyl and hy-droxyl groups stated in the preceding sentence, are to be 5 understood as number percentages, which will be mathemat-ically identical to percentages by chemical equivalents, with Avogadro's number of each specified chemical moiety regarded as a single chemical equivalent.
The above descriptions for each of the acid and al-cohol mixtures reacted to produce lubricànt esters accord-ing to this invention refers only to the mixture of acids or alcohols that actually reacts to form esters and does not necessarily imply that the mixtures of acids or alco-hols contacted with each other for the purpose of reaction 15 will have the same composition as the mixture that actu-ally reacts. In fact, it has been found that reaction be-tween the alcohol(s) and the acid(s) used proceeds more effectively if the quantity of acid charged to the reac-tion mixture initially is enough to provide an excess of 20 10 - 2S % of equivalents of acid over the equivalents of alcohol reacted with the acid. (An equivalent of acid is defined for the purposes of this specification as the - amount containing one gram equivalent weight of carboxyl groups, while an equivalent of alcohol is the amount con-Z5 taining one gram equivalent weight of hydroxyl groups.) The composition of the mixture of acids that actually re-acted can be determined by analysis of the product ester mixture for its acyl group content.
In making most or all of the esters and mixtures of 30 esters preferred accordinq to this invention, the acid(s) reacted will be lower boiling than the alcohol(s) reacted and the product ester(s). When this condition obtains, it is preferred to remove the bulk of any excess acid remain-ing at the end of the esterification reaction by distilla-35 tion, most preferably at a low pressure such as 1 - 5 torr.
After such vacuum distillation, the product is often W093~25628 X ~ 3 7 2 ~ 7 PCT/US93/0 ~5 ready for use as a lubricant or lubricant base stock ac-cording to this invention. If further refinement of the product is desired, the content of free acid in the prod-uct after the first vacuum distillation may be further 5 reduced by treatment with epoxy esters as taught in U. S.
Patent 3,485,754 or by neutralization with any suitable alkaline material such as lime, alkali metal hydroxide, or alkali metal carbonates. If treatment with epoxy esters is used, excess epoxy ester may be removed by a second 10 distillation under very low pressure, while the products of reaction between the epoxy ester and residual acid may be left behind in the product without harm. If neutrali-zation with alkali is used as the refinement method, sub-sequent washing with water, to remove any unreacted excess ~s alkali and the small amount of soap formed from the excess fatty acid neutralized by the alkali, is strongly pre-ferred before using the product as a lubricant and/or base stoc~ according to this invention.
Under some conditions of use, the ester(s) as de-20 scribed herein will function satisfactorily as completelubricants. It is generally preferable, however, for a complete lubricant to contain other materials generally denoted in the art as additives, such as oxidation resist-ance and thermal stability improvers, corrosion inhibi-Z5 tors, metal deactivators, lubricity additives, viscosityindex improvers, pour and/or floc point depressants, de-tergents, dispersants, antifoaming agents, anti-wear agents, and extreme pressure resistant additives. Many additives are multifunctional. For example, certain ad-30 ditives may impart both anti-wear and extreme pressure resistance properties, or function both as a metal de-activator and a corrosion inhibitor. Cumulatively, all additives prefera~ly do not exceed 8 % by weight, or more preferably do not exceed 5 % by weight, of the total com-35 pounded lubricant formulation.
An effective amount of the foregoing additive typesis generally in the range from 0.01 to 5 % for the anti-~ W093/25628 ~ 2 1 3 ~ 2 5 7 PCT/US93/04885 oxidant component, 0.01 to 5 % for the corrosion inhibitorcomponent, from 0.001 to 0.5 % for the metal deactivator component, from 0.5 to 5 % for the lubricity additives, from 0.01 to 2 % for each of the viscosity index improvers s and pour and/or floc point depressants, from 0.1 to 5 %
for each of the detergents and dispersants, from 0.001 to 0.1 % for anti-foam agents, and from 0.1 - 2 ~ for each of the anti-wear and extreme pressure resistance components.
All these percentages are by weight and are based on the total lubricant composition. It is to be understood that more or less than the stated amounts of additives may be more suitable to particular circumstances, and that a single molecular type or a mixture of types may be used for each type of additive component. Also, the examples 15 listed below are intended to be merely illustrative and not limiting, except as described in the appended claims.
Examples of suitable oxidation resistance and thermal stability improvers are diphenyl-, dinaphthyl-, and phenyl-naphthyl-amines, in which the phenyl and naphthyl groups zo can be substituted, e.g., N,N'-diphenyl phenylenediamine, p-octyldiphenylamine, p,p-dioctyldiphenylamine, N-phenyl-1-naphthyl amine, N-phenyl-2-naphthyl amine, N-(p-dodecyl)-phenyl-2-naphthyl amine, di-1-naphthylamine, and di-2-naphthylamine; phenothazines such as N-alkylphenothia-25 zines; imino(bisbenzyl); and hindered phenols such as 6-(t-butyl) phenol, 2,6-di-(t-butyl) phenol, 4-methyl-2,6-di-(t-butyl) phenol, 4,4'-methylenebis(-2,6-di-{t-butyl}
phenol), and the like.
Examples of suitable cuprous metal deactivators are 30 imidazole, benzamidazole, 2-mercaptobenzthiazole, 2,5-di-mercaptothiadiazole, salicylidine-propylenediamine, pyr-azole, benzotriazole, tolutriazole, 2-methylbenzamidazole, 3,5-dimethyl pyrazole, and methylene bis-benzotriazole.
Benzotriazole derivatives are preferred. Other examples 35 of more general metal deactivators and/or corrosion inhib-itors include organic acids and their esters, metal salts, and anhydride~, e.g., N-oleyl-sarcosine, sorbitan monoole-~ 2 1 3 72 5 7 PCT/US93/0 ~S

ate, lead naphthenate, dodecenyl-succinic acid and its par-tial esters and amides, and 4-nonylphenoxy acetic acid;
primary, secondary, and tertiary aliphatic and cycloali-phatic amines and amine salts of organic and inorganic ac-ids, e.g., oil-soluble alkylammonium carboxylates; hetero-cyclic nitrogen containing compounds, e.g., thiadiazoles, substituted imidazolines, and oxazolines; quinolines, qui-nones, and anthraquinones; propyl gallate; barium dinonyl naphthalene sulfonate; ester and amide derivatives of al-kenyl succinic anhydrides or acids, dithiocarbamates, di-thiophosphates; amine salts of alkyl acid phosphates and their derivatives.
Examples of suitable lubricity additives include long chain derivatives of fatty acids and natural oils, such as esters, amines, amides, imidazolines, and borates.
Examples of suita~le viscosity index improvers in-clude polymethacrylates, copolymers of vinyl pyrrolidone and methacrylates, polybutenes, and styrene-acrylate co-polymers.
Examples of suitable pour point and/or floc point de-pressants include polymethacrylates such as methacrylate-ethylene-vinyl acetate terpolymers; alkylated naphthalene derivatives; and products of Friedel-Crafts catalyzed con-densation of urea with naphthalene or phenols.
Examples of suitable detergents and/or dispersants in-clude polybutenylsuccinic acid amides; polybutenyl phos-phonic acid derivatives; long chain alkyl substituted aro-matic sulfonic acids and their salts; and metal salts of alkyl sulfides, of alkyl phenols, and of condensation prod-ucts of alkyl phenols and aldehydes.
Examples of suitable anti-foam agents include sili-cone polymers and some acrylates.
Examples of suitable anti-wear and extreme pressure resistance agents include sulfurized fatty acids and fatty acid esters, such as sulfurized octyl tallate; sulfurized terpenes; sulfurized olefins; organopolysulfides; organo phosphorus derivatives including amine phosphates ! alkyl ~ W093/25628 ~ 2 1 3 ~ 2 S 7 PCT/US93/0~85 acid phosphates, dialkyl phosphates, aminedithiophos-phates, trialkyl and triaryl phosphorothionates, trialkyl and triaryl phosphines, and dialkylphosphites, e.g., amine salts of phosphoric acid monohexyl ester, amine salts of dinonylnaphthalene sulfonate, triphenyl phosphate, tri-naphthyl phosphate, diphenyl cresyl and dicresyl phenyl phosphates, naphthyl diphenyl phosphate, triphenylphos-phorothionate; dithiocarbamates, such as an antimony di-alkyl dithiocarbamate; chlorinated and/or fluorinated hy-o drocarbons, and xanthates.
Under some conditions of operation, it is believed that the presence in lubricants of the types of polyether polyols that have been prominent constituents of most pri-or art lubricant base stocks taught as useful with fluoro-carbon refrigerant working fluids are less than optimally stable and/or inadequately compatible with some of the most useful lubricant additives. Thus, in one embodiment of this invention, it is preferred that the lubricant base stocks and lubricants be substantially free of such poly-ether polyols. By "substantially free", it is meant that the compositions contain no more than about 10 % by weight, preferably no more than about 2.6 % by weight, and more preferably no more than about 1.2 % by weight of the materials noted.
One major embodiment of the present invention is a refrigerant working fluid comprising both a suitable heat transfer fluid such as a fluorocarbon and a lubricant ac-cording to this invention. Preferably, the refrigerant working fluid and the lubricant should have chemical char-acteristics and be present in such a proportion to each other that the working fluid remains homogeneous, i.e., free from visually detectable phase separations or turbid-ity, over the entire range of working temperatures to which the working fluid is exposed during operation of a refrigeration system in which the working fluid is used.
This working range may vary from -600 C to as much as +175 C. It is often adequate if the working fluid re-W093J25628 ~ ~3~ æ~ PC~/US93/0 mains single phase up to +300 C, although it is increas-ingly more preferable if the single phase behavior is maintained up to 40, 56, 71, 88, or 100 C. Similarly, it is often adequate if the wor~ing fluid compositions 5 remains a single phase when chilled to oo C, although it is increasingly more preferable if the single phase behav-ior persists to -10, -20, -30, -40, or -55 C. Single phase mixtures with chlorine free hydrofluorocarbon re-frigerant working fluids are usually obtained with the suitable and preferred types of esters described above.
Inasmuch as it is often difficult to predict exactly how much lubricant will be mixed with the heat transfer fluid to form a working fluid, it is most preferable if the lubricant composition forms a single phase in all 15 proportions with the heat transfer fluid over the temper-ature ranges noted above. This however, is a very strin-gent re~uirement, and it is often sufficient if there is single phase behavior over the entire temperature range for a working fluid mixture containing up to 1 % by weight 20 of lubricant according to this invention. Single phase ~ehavior over a temperature range for mixtures containing up to 2, 4, 10, and 15 % ~y weight of lubricant is suc-cessively more preferable.
In some cases, single phase behavior is not required.
25 The term "miscible" is used in the refrigeration lubrica-tion art and hereinafter, except when part of the phrase "miscible in all proportions", when two phases are formed but are readily capable of being mixed into a uniform dis-persion that r~m~jn~ stable as long as it is at least mod-30 erately agitated mechani~ally. Some refrigeration (andother) compressors are designed to operate satisfactorily with such miscible mixtures of refrigerant working fluid and lubricant. In contrast, mixtures that lead to coagu-lation or significant thicken; ng and form two or more 35 phases are unacceptable commercially and are designated herein as "immiscible". Any such mixture described below is a comparative example and not an embodiment of the ~ W093/25628 ` 21~7~5~ PCT/US93/04885 present invention.
Another major embodiment of the invention is the use of a lubricant according to the invention, either as total lubricant or lubricant base stock, in a process of operat-s ing refrigerating machinery in such a manner that the lub-ricant is in contact with the refrigerant working fluid.
The practice of the invention may be further under-stood and appreciated by consideration of the following examples and comparative examples.
General Ester SYnthesis Procedure The alcohol(s) and acid(s) to be reacted, together with a suitable catalyst such as dibutyltin diacetate, tin oxalate, phosphoric acid, and/or tetrabutyl titanate, were charged into a round bottomed flask equipped with a stir-rer, thermometer, nitrogen sparging means, condenser, and a recycle trap. Acid(s) were charged in about a 15 % mol-ar excess over the alcohol(sj. The amount of catalyst was from 0.02 to 0.1 % by weight of the weight of the total acid~s) and alcohol(s) reacted.
The reaction mixture was heated to a temperature be-tween about 220 and 230 C, and water from the resulting reaction was collected in the trap while refluxing acids were returned to the reaction mixture. Partial vacuum was maintained above the reaction mixture as necessary to achieve a reflux rate of between 8 and 12 % of the orig-inal reaction mixture volume per hour.
The reaction mixture was sampled occasionally for de-termination of hydroxyl number, and after the hydroxyl num-ber had fallen below 5.0 mg of KOH per gram of mixture, the majority of the excess acid was removed by distilla-tion after applying the highest vacuum obtainable with the apparatus used, corresponding to a residual pressure of about 0.05 torr, while maintaining the reaction temper-ature. The reaction mixture was then cooled, and any re-sidual acidity was removed, if desired, by treatment with lime, sodium hydroxide, or epoxy esters. The resulting lubricant or lubricant base stock was dried and filtered WO 93/2~628 2 ~.3 7 2 ~ PCr/US93/0~5 before phase compatibility testing.
General Procedure for Phase Com~atibilitY Testin~
One milliliter ("ml"~ of the lubricant to be tested is placed into a thermal shock resistant, volumetrically graduated glass test tube 17 millimeters ("mm") in diam-eter and 145 mm long. The test tube is then stoppered and placed into a cooling bath regulated to -29 + 0.2 C. Af-ter the tube and contents have equilibrated in the cooling bath for 5 minutes ("min"), sufficient refrigerant working fluid is added to give a total volume of 10 ml.
At least 15 min after the working fluid has been add-ed, during which time the tube and contents have been e~uilibrating in the cooling bath and the contents may have ~een agitated if desired, the tube contents are visu-ally ~m j ~ed for evidence of phase separation. If there is any such phase separation, the tube is shaken to deter-mine whether the combination can ~e rated as miscible or is totally unacceptable.
If there is no evidence of phase separation at -29 C, the temperature of the cooling bath is usually lowered at a rate of 0.3 per min until phase separation is ob-served. The temperature of first observation of phase separation, if within the ran~e of the cooling e~uipment used, is then noted as the insolubility onset temperature.
Com~osition of Specific Example A suitable ester mixture as described above was pre-pared by reacting a mixture of alcohol molecules in which 99.9 % were P~ molecules, with most of the remainder being DPE molecules, with a mixture of acid molecules that in-cluded 80 % of 3-methyl~utanoic acid and 19 % of adipic acid, with the remainder predominantly other five car~on monobasic acids. This ester mixture had a viscosity at 40 C of about 900 centistokes.

Claims (20)

1. A composition of matter suitable for serving as a lub-ricant or lubricant base stock, said composition being a liquid with a viscosity between about 300 and about 1300 centistokes at 40° C and consisting essentially of a mix-ture of polyol ester molecules in which at least about 92 % of the alcohol moieties are selected from the group con-sisting of the alcohol moieties derived from TMP, DTMP, PE, DPE, TPE, and TTMP and at least about 92 % of the acyl groups are selected from the group consisting of the acyl groups of all the straight and branched chain monobasic and dibasic carboxylic acids with from four to twelve carbon atoms each, said alcohol moieties and acyl groups being further selected subject to the constraints that (a) a total of at least about 15 % of the acyl groups in the mixture are acyl groups of i-C5 acid; (b) the ratio of the % of acyl groups in the mixture that contain 8 or more carbon atoms and are unbranched to the % of acyl groups in the mixture that are both branched and contain not more than six carbon atoms is not greater than about 1.56; (c) the % of acyl groups in the mixture that contain at least nine carbon atoms, whether branched or not, is not greater than about 81; (d) not more than about 2 % of the acyl groups in the ester mixture contain more than two carboxyl groups each; and (e) at least about 13.8 % of the acyl groups in the ester mixture are dibasic; and a total of at least about 82 % of the monobasic acyl groups in the acid mixture have either five or six carbon atoms each.

2. A composition according to claim 1, with a viscosity between about 450 and about 1100 centistokes at 40° C and consisting essentially of a mixture of polyol ester mole-cules in which the alcohol moieties and acyl groups are selected subject to the constraints that (a) a total of at least about 27 % of the acyl groups in the mixture are acyl groups of i-C5 acid; (b) the ratio of the % of acyl groups in the mixture that contain 8 or more carbon atoms and are unbranched to the % of acyl groups in the mixture that are both branched and contain not more than six car-bon atoms is not greater than about 1.21; (c) the % of acyl groups in the mixture that contain at least nine car-bon atoms, whether branched or not, is not greater than about 67; and (e) at least about 15.3 % of the acyl groups in the ester mixture are dibasic and a total of at least about 85 % of the monobasic acyl groups in the ester mix-ture have either five or six carbon atoms each.

3. A composition according to claim 2 consisting essen-tially of a mixture of polyol ester molecules in which at least about 95 % of the alcohol moieties are selected from the group consisting of the alcohol moieties derived from TMP, DTMP, TTMP, PE, DPE, and TPE and at least about 95 %
of the acyl groups are selected from the group consisting of the acyl groups of all the straight and branched chain monobasic and dibasic carboxylic acids with from four to twelve carbon atoms each, said alcohol moieties and acyl groups being further selected subject to the constraints that (a) a total of at least about 36 % of the acyl groups in the mixture are acyl groups of i-C5 acid; (b) the ratio of the % of acyl groups in the mixture that contain 8 or more carbon atoms and are unbranched to the % of acyl groups in the mixture that are both branched and contain not more than six carbon atoms is not greater than about 1.00; (c) the % of acyl groups in the mixture that contain at least nine carbon atoms, whether branched or not, is not greater than about 49; (d) not more than 1 % of the acyl groups in the esters contain more than two carboxyl groups each; and (e) at least about 16.2 % of the acyl groups in the ester mixture are dibasic; and a total of at least about 93 % of the monobasic acyl groups in the acid mixture have five carbon atoms each.

4. A composition according to claim 3 consisting essen-tially of a mixture of polyol ester molecules in which the alcohol moieties and acyl groups are selected subject to the constraints that (a) a total of at least about 45 % of the acyl groups in the mixture are acyl groups of i-C5 acid; (d) not more than 0.4 % of the acyl groups in the ester mixture contain more than two carboxyl groups each;
and (e) at least about 17.0 % of the acyl groups in the ester mixture are dibasic and contain from five to seven carbon atoms each and a total of at least about 96 % of the monobasic acyl groups in the acid mixture have five carbon atoms each.

5. A composition according to claim 4 with a viscosity between about 810 and about 990 centistokes at 40° C and consisting essentially of a mixture of polyol ester mole-cules in which a total of at least about 95 % of the acyl groups are selected from the group consisting of the acyl groups of all the straight and branched chain monobasic and dibasic carboxylic acids with from four to twelve car-bon atoms each and the alcohol moieties and acyl groups are selected subject to the constraints that (a) a total of at least 51 % of the acyl groups in the ester mixture are acyl groups of i-C5 acid; (d) at least about 95 % of the alcohol moieties in the esters are those of PE; and (e) at least 17.6 % of the acyl groups in the ester mix-ture are dibasic.

6. A compounded lubricant consisting essentially of at least about 95 % by weight of a composition according to claim 5 and a balance of one or more additives selected from the group consisting of oxidation resistance and thermal stability improvers, corrosion inhibitors, metal deactivators, lubricity additives, viscosity index im-provers, pour and floc point depressants, detergents, dis-persants, antifoaming agents, anti-wear agents, and ex-treme pressure resistant additives.

7. A compounded lubricant consisting essentially of at least about 92 % by weight of a composition according to claim 3 and a balance of one or more additives selected from the group consisting of oxidation resistance and thermal stability improvers, corrosion inhibitors, metal deactivators, lubricity additives, viscosity index im-provers, pour and floc point depressants, detergents, dis-persants, antifoaming agents, anti-wear agents, and ex-treme pressure resistant additives.

8. A compounded lubricant consisting essentially of at least about 92 % by weight of a composition according to claim 2 and a balance of one or more additives selected from the group consisting of oxidation resistance and thermal stability improvers, corrosion inhibitors, metal deactivators, lubricity additives, viscosity index im-provers, pour and floc point depressants, detergents, dis-persants, antifoaming agents, anti-wear agents, and ex-treme pressure resistant additives.

9. A compounded lubricant consisting essentially of at least about 92 % by weight of a composition according to claim 1 and a balance of one or more additives selected from the group consisting of oxidation resistance and thermal stability improvers, corrosion inhibitors, metal deactivators, lubricity additives, viscosity index im-provers, pour and floc point depressants, detergents, dis-persants, antifoaming agents, anti-wear agents, and ex-treme pressure resistant additives.

10. A refrigerant working fluid consisting essentially of at least 85 % by weight of a primary heat transfer fluid selected from the group consisting of pentafluoroethane, 1,1-difluoroethane, 1,1,1-trifluroethane, tetrafluoroeth-anes, and mixtures thereof and a balance of a lubricant according to claim 9.

11. A refrigerant working fluid consisting essentially of at least 85 % by weight of a primary heat transfer fluid selected from the group consisting of pentafluoroethane, 1,1-difluoroethane, 1,1,1-trifluroethane, tetrafluoroeth-anes, and mixtures thereof and a balance of a lubricant according to claim 8.

12. A refrigerant working fluid consisting essentially of at least 85 % by weight of a primary heat transfer fluid selected from the group consisting of pentafluoroethane, 1,1-difluoroethane, 1,1,1-trifluroethane, tetrafluoroeth-anes, and mixtures thereof and a balance of a lubricant according to claim 7.

13. A refrigerant working fluid consisting essentially of at least 85 % by weight of 1,1,1,2-tetrafluoroethane and a balance of a lubricant according to claim 6.

14. A refrigerant working fluid consisting essentially of at least 85 % by weight of a primary heat transfer fluid selected from the group consisting of pentafluoroethane, 1,1-difluoroethane, 1,1,1-trifluroethane, tetrafluoroeth-anes, and mixtures thereof and a balance of a lubricant according to claim 5.

15. A refrigerant working fluid consisting essentially of at least 85 % by weight of a primary heat transfer fluid selected from the group consisting of pentafluoroethane, 1,1-difluoroethane, 1,1,1-trifluroethane, tetrafluoroeth-anes, and mixtures thereof and a balance of a lubricant according to claim 4.

16. A refrigerant working fluid consisting essentially of at least 85 % by weight of a primary heat transfer fluid selected from the group consisting of pentafluoroethane, 1,1-difluoroethane, 1,1,1-trifluroethane, tetrafluoroeth-anes, and mixtures thereof and a balance of a lubricant according to claim 3.

17. A refrigerant working fluid consisting essentially of at least 85 % by weight of a primary heat transfer fluid selected from the group consisting of pentafluoroethane, 1,1-difluoroethane, 1,1,1-trifluroethane, tetrafluoroeth-anes, and mixtures thereof and a balance of a lubricant according to claim 2.

18. A refrigerant working fluid consisting essentially of at least 85 % by weight of a primary heat transfer fluid selected from the group consisting of pentafluoroethane, 1,1-difluoroethane, 1,1,1-trifluroethane, tetrafluoroeth-anes, and mixtures thereof and a balance of a lubricant according to claim 1.

19. A process for operating a refrigerator comprising cyclic compression, liquefaction, expansion, and evapor-ation of a heat transfer fluid, said heat transfer fluid consisting essentially of at least 85 % by weight of 1,1,1,2-tetrafluoroethane and a balance of a lubricant according to claim 6.

20. A process for operating a refrigerator comprising cyclic compression, liquefaction, expansion, and evapor-ation of a heat transfer fluid, said heat transfer fluid consisting essentially of at least 85 % by weight of a primary heat transfer fluid selected from the group con-sisting of pentafluoroethane, 1,1-difluoroethane, 1,1,1-trifluroethane, tetrafluoroethanes, and mixtures thereof and a balance of a lubricant according to claim 1.