REFRIGERATION COMPRESSOR LUBRICANT FLUID

专利摘要:
invention patent summary: "refrigeration compressor lubricant". the present invention relates to the described lubricant compositions comprising a mixture of about 1 to 99% by weight of the mixture of one or more ester compounds and about 1 to 99% by weight of the mixture one or more second compounds ester in which r1, r2, r3, r4, r5, r6, r11, and r12 are each h or methyl; a + x, b + y. and c + z are integers from 1 to about 20, and m + n is an integer from 1 to about 10; and r7, r8, r9, r10 and r13 are alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cyclo- substituted or unsubstituted having 1 to about 17 carbon. the lubricant composition can be combined with a refrigerant to form a refrigerant-lubricant composition that can be used as a working fluid in a heat transfer apparatus.
公开号:BR112013033209B1
申请号:R112013033209-3
申请日:2012-06-20
公开日:2020-03-31
发明作者:Louis Rebrovic；William Bradford Boggess
申请人:Emerson Climate Technologies, Inc.；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for REFRIGERATING COMPRESSOR LUBRICANT FLUID.
FIELD [0001] This inventive technology is in the field of lubricants, particularly lubricants used in heat transfer equipment, such as refrigeration compressors; compressors and recovery systems including such lubricants; refrigeration methods using such lubricants are used.
BACKGROUND OF THE INVENTION [0002] The specifications in this section provide background information related to this description and cannot constitute the prior art.
[0003] Heat transfer devices operating using a vapor compression refrigeration cycle, including heat pumps, air conditioners (including auto, residential and industrial air conditioners), and refrigerants (including residential and household refrigerants and freezers) industrial), use refrigerants and lubricants during operation. In a typical heat transfer system, a suitable boiling point liquid evaporates at low pressure, absorbing the heat doing so. The steam produced is then compressed and passed to a condenser where it is condensed, generating heat. The liquid condensate is returned through an expansion valve to the evaporator, completing the refrigeration cycle. An important type of refrigeration system is known as small or domestic refrigeration systems, which cover systems that are typically used in residential homes, apartments and the like for consumer use in refrigerants, freezers, and the like. In addition, often included in this group are vending machines and the like. Another important cooling system comprises systems
Petition 870190097018, of 9/27/2019, p. 13/112
2/55 automotive air conditioning but used to provide cooling in motor vehicles.
[0004] Refrigerants are often combined with compatible lubricants to form the coolants used in refrigeration compressors. Lubricants ensure that the moving parts of heat transfer devices are lubricated to facilitate operation and prevent wear. Government regulations have assumed that fluids can be used as refrigerants in these devices. These, in turn, needed to find new lubricants that will work well with the new refrigerants. The devices are generally designed to use lubricants that are miscible with the refrigerant during operation. To function as a satisfactory coolant, the mixture of coolant and lubricant must be compatible and miscible over a wide temperature range.
SUMMARY [0005] The section provides a general summary of the invention, and is not intended as a comprehensive description of the general scope of the invention or all aspects.
[0006] This invention describes lubricants of particular compositions, refrigerant / lubricant combinations, heat transfer systems, such as heat transfer devices including stationary and mobile cooling and air conditioning applications including these combinations, and methods for these. In certain respects, the refrigerant and lubricant combinations are substantially soluble (for example, miscible) during the operation of the refrigeration and air conditioning equipment to facilitate the circulation of suitable compressor lubricant, pass through the condenser, expansion device , and evaporator, and return to the compressor. Insufficient lubricant circulation can
Petition 870190097018, of 9/27/2019, p. 14/112
3/55 to potentially affect compressor safety. Low temperature solubility is particularly important to ensure that the lubricant p flows through a cold evaporator. The lubricants described provide unexpectedly wide temperature ranges of miscibility and unexpectedly low minimum miscibility temperatures with various refrigerants, including various refrigerants for such lubricant compositions with suitable miscibility temperature ranges were previously unknown, such as refrigerants R410a, R32, and HFO like ΗΤΟΙ 234yf (2,3,3,3, -tetrafluoroprop-1-ene) and HFO-1234ze (trans-1,3,3,3, tetrafluoroprop-1-ene).
[0007] In certain respects, the lubricant compositions described comprise (a) one or more first ester compounds having a representative structure:
The
I [jÇ —lj- OC] l ₂ CI] R ¹ f OC] l ₂ CI] R ² OCR ⁷ o
] IC — í-OCl ^ CHR * - (üClhCnR ⁴ } - OCR ^K o
| [ ₂ C - ^ - OC] I ₂ C1IR ^s ^ OC] l ₂ CI] R ^á --- OCR '(l) [0008] where each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is independently H or methyl; each of a, b, c, x, y, and z is independently an integer and a + x, b + y. and c + z are each independently an integer from 1 to about 20; and R ⁷ , R ⁸ , and R ⁹ are each independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylaryl groups,
Petition 870190097018, of 9/27/2019, p. 1/15
4/55 alkylcycloalkylaryl, alkylarylcycloalkyl, arylcycloalkylalkyl, arylalkylcycloalkyl, cycloalkylalkylaryl, and straight or branched chain cycloalkylalkyl having from 1 to about 17 carbon atoms that can be substituted or unsubstituted; and (b) one or more second ester compounds having a representative structure
[0009] wherein each of R ¹¹ and R ¹² is independently H or methyl; each of men is independently an integer and m + n is an integer from 1 to about 10; and R ¹⁰ and R ¹³ are each independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylalkyl, alkylcycloalkyl, alkylcycloalkyl, cycloalkylalkylalkyl, alkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkyl straight or branched chain having from 1 to about 17 carbon atoms that can be substituted or unsubstituted. Also described are embodiments in which the first ester compound or compounds (a) and the second ester compound or compounds (b) together form at least about 50% by weight of the lubricant composition. Arrangements are also described in which the first ester compound or compounds (a) and the second ester compound or compounds (b) are in a weight ratio of about 1:99 to about 99: 1, or about 1 to about 99% by weight of one or more of the first ester compounds (a) to about 1 to about 99% by weight of the one or more second ester compounds (b), based on a combined weight of the first ester compound or compounds (a) and the second ester compound or compounds (b) being 100%. All strips include the ends.
Petition 870190097018, of 9/27/2019, p. 1/16
5/55 [00010] In certain respects, the lubricant compositions described comprise one or more first ester compounds having a representative structure] IC

OCR ⁷
o | [, C — f-OC] I ₂ C1 IR. ⁵ V- (OC] l ₂ CI] R ^á ) --- OCR ' / c ₍ |) [00011] where each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is independently H or methyl; each of a, b, c, x, y, and z is independently an integer and a + x, b + y. and c + z are each independently an integer from 1 to about 20; and R ^7, R ⁸ and R ⁹ are each independently selected from the group consisting of alkyl groups, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alquilcicloalquila, cycloalkylalkyl, arilcicloalquila, cicloalquilarila, alquilcicloalquilarila, alquilarilcicloalquila, arilcicloalquilalquila, arilalquilcicloalquila, cicloalquilalquilarila , and straight or branched cycloalkylarylalkyl having from 1 to about 17 carbon atoms that can be substituted or unsubstituted; and one or more second ester compounds having a representative structure
R ^id —C
OCI] - CI] R ^L1
OC] I ₂ C] IRJ ²
[00012] wherein each of R ¹¹ and R ¹² is independently H or methyl; each of men is independently an integer and m + n is an integer from 1 to about 10; and R ¹⁰ and R ¹³ are
Petition 870190097018, of 9/27/2019, p. 17/112
6/55 each independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylalkyl, alkylcycloalkyl, alkylcycloalkyl, alkylcycloalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkyl having from 1 to about 17 carbon atoms that can be substituted or unsubstituted, wherein the first compound or compounds of ester of structure (I) and the second compound or compounds of ester of structure (II) are in a ratio of weight from about 1:99 to about 99: 1 and together they form at least about 50 weight percent of the lubricant composition.
[00013] Lubricant compositions can include other additional materials, including additives such as antioxidants, anti-wear additives, and extreme pressure agents in amounts that can be, for example, about 0.1 to about 5% by weight in the composition lubricant, and the lubricant compositions may contain minor amounts of other lubricants, for example, polyol esters and polyalkylene glycols, with the proviso that the percentage by weight of the lubricant composition of all other lubricants together is less than the percentage by weight in the lubricant composition of the mixture consisting of the first ester compound or compounds (a) and the second ester compound or compounds (b).
[00014] The lubricant composition can be combined with a refrigerant to form a combination of lubricant and refrigerant that can be used as a working fluid for a heat transfer device. Lubricant and coolant combinations include a lower weight percentage (less than 50% by weight) of the lubricant composition and a higher weight percentage (more
Petition 870190097018, of 9/27/2019, p. 18/112
7/55 than 50% by weight) of one or more refrigerant compounds. In various embodiments, the lubricant and coolant combinations can be used as working fluids in refrigeration systems, including in automotive air conditioners, domestic or industrial refrigerators, freezers, and air conditioners, heat pumps, vending machines, showcases, and water supply systems. Stationary and mobile air conditioning and refrigeration equipment including such automotive air conditioners, domestic or industrial refrigerators, freezers, and air conditioners, heat pumps, vending machines, showcases, and water supply systems containing water are also described. the refrigerant / lubricant combinations described and methods of operating such equipment including the refrigerant / lubricant combinations described.
[00015] In certain respects, the lubricant compositions described have excellent miscibility with most refrigerants, including refrigerants R410a, R32, and HFO (or combinations of these refrigerants), even at very low temperatures, while providing excellent viscosity and lubricity indexes.
[00016] One, one, an, at least one and one or more are used interchangeably to indicate that at least one of the items is present; a plurality of such items may be present. The terms comprises, comprising, including and having, are inclusive and therefore specify the presence of characteristics, integers, operations, elements, and / or components, but do not exclude the presence or addition of one or more other aspects, steps, elements, components, and / or groups thereof. It should also be understood that additional or alternative method steps can be employed. Throughout this invention, the values
Petition 870190097018, of 9/27/2019, p. 1/1912
8/55 numeric represent approximate measures or limits for the ranges to cover minor deviations from the values provided and modalities around the mentioned value as well as those having exactly the mentioned value. Except for the working examples provided at the end of the detailed description, all numerical values of parameters (for example, quantities or conditions) in this specification, including the appended claims, are to be understood as being modified in all cases by the term about whether or not it actually appears before the numerical value. It indicates that the numerical value established allows some slight inaccuracy (with some approximation of the accuracy in the value; approximately or reasonably close to the value; almost). If the inaccuracy provided by about is not otherwise understood in the art with this usual meaning, then about how used here, indicates at least variations that may arise from usual methods and use such parameters. In addition, the range description includes a description of all values and other ranges divided within the entire range, including ends determined for the ranges. All bands include specific ends.
[00017] Other areas of applicability will become evident from the description provided here. It should be understood that the specific description and examples are intended for purposes of illustration only and are not intended to limit the scope of the present invention. DRAWINGS [00018] The drawings described here are for illustrative purposes of selected modalities only and not all possible implementations, and are not intended to limit the scope of the present invention or claimed invention.
[00019] Figure 1 is a graph of kinematic viscosities of certain lubricant compositions as described, measured according to
Petition 870190097018, of 9/27/2019, p. 1/20
9/55 with ASTM D445;
figure 2 is a graph of kinematic viscosities of certain lubricant compositions of the invention as described, measured according to ASTM D445;
figure 3 is a lubrication graph (or lubricity) of certain lubricant compositions as described, measured according to ASTM D2670;
Figure 4 is a graph of miscibility of certain lubricant compositions as described in R410a;
Figure 5 is a graph of miscibility of certain lubricant compositions as described in R32.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [00020] The details, examples and preferences provided above with respect to any one or more of the particular aspects of the present invention, and described and exemplified below in relation to any one or more of the particular aspects of the present invention , apply to all aspects of the present invention.
[00021] The lubricant compositions described comprise a mixture of one or more first ester compounds (a) and one or more second ester compounds (b). In certain variations, such a mixture comprises about 1 to about 99% by weight of one or more first ester compounds (a) and about 1 to about 99% by weight of one or more second ester compounds (b) . In certain aspects, the first ester compound or compounds (a) and the second ester compound or compounds (b) together form at least about 50% by weight of the lubricant composition. In certain other variations, such a mixture comprises about 20 to about 80% by weight of one or more first ester compounds (a) and about 20 to about 80% by weight of one or more second ester compounds (b) ).
Petition 870190097018, of 9/27/2019, p. 21/112
10/55
In still other variations, such a mixture optionally essentially consists of about 1 to about 99% by weight of one or more first ester compounds (a) and about 1 to about 99% by weight of one or more second compounds of ester (b). In certain variations, a lubricant composition comprises a mixture consisting of about 1 to about 99% by weight of one or more ester compounds (a) and about 1 to about 99% by weight of one or more second ester compounds (b).
[00022] One or more first ester compounds (a) has or has a representative structure (I) o
I [jÇ —OC] l ₂ CI 1R ¹ (OC] l ₂ CI] R ² OCR
O, li] IC — i-OC] l ₂ C] IR H — foClhCUR ^ -íOCR / bo
| [ ₂ C - (^ OC] I ₂ C1IR ^s V-í OC] l ₂ CI] R ^á ) OCR ' z [00023] where each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is independently hydrogen (H) or methyl (CH3); each of a, b, c, x, y, and z is independently an integer and a + x, b + y, and c + z are each independently an integer from 1 to about 20; and R ^7, R ⁸ and R ⁹ are each independently selected from the group consisting of alkyl groups, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alquilcicloalquila, cycloalkylalkyl, arilcicloalquila, cicloalquilarila, alquilcicloalquilarila, alquilarilcicloalquila, arilcicloalquilalquila, arilalquilcicloalquila, cicloalquilalquilarila , and straight or branched chain cycloalkylarylalkyl having 1 to about 17 carbon atoms and which can be substituted or unsubstituted.
[00024] In various modalities, each of R ⁷ , R ⁸ , and R ⁹ can
Petition 870190097018, of 9/27/2019, p. 22/112
11/55 independently being straight or branched chain or branched alkyl or alkenyl groups or substituted or unsubstituted cycloalkyl groups, each of which may contain heteroatoms such as O, F, N, S, or Si or may be hydrocarbonyl groups. In various embodiments, each of R ⁷ , R ⁸ , and R ⁹ independently has about 3 to about 8 carbon atoms or R ⁷ , R ⁸ , and R ⁹ together have an average of about 5 to about 7 carbon atoms on a weight basis or both each of R ⁷ , R ⁸ , and R ⁹ independently have about 3 to about 8 carbon atoms as R ⁷ , R ⁸ , and R ⁹ together have an average of about from 5 to about 7 carbon atoms on a weight basis.
[00025] In various embodiments, a + x, b + y, and c + z are each independently an integer from 1 to about 10, or a + x, b + y, and c + z are each independently an integer from 2 to about 8, or a + x, b + y, and c + z are each independently an integer from 2 to 4.
[00026] In certain embodiments, each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is hydrogen (H), so that the first compound (a) or at least one or more of that a first ester compound (a), if the lubricant composition includes more than one first ester compound (a), has or has a representative structure (III)

[00027] where x, y, and z are each independently one
Petition 870190097018, of 9/27/2019, p. 23/112
12/55 integer from 1 to about 20, or from 1 to about 10, or from 2 to about 8 or from 2 to about 4, and R ⁷ , R ⁸ , and R ⁹ are as previously defined.
[00028] In various embodiments, each of R ⁷ , R ⁸ , and R ⁹ in structure (III) may be straight or branched chain alkyl or alkenyl groups or substituted or unsubstituted cycloalkyl groups, each of which may contain such hetero atoms such as O, F, N, S, or Si or can be hydrocarbonyl groups. In various embodiments, each of R ⁷ , R ⁸ , and R ⁹ in structure (III) independently has about 3 to about 8 carbon atoms or R ⁷ , R ⁸ , and R ⁹ together have an average of about 5 to about 7 carbon atoms on a weight basis or both each of R ⁷ , R ⁸ , and R ⁹ independently have about 3 to about 8 carbon atoms as R ⁷ , R ⁸ , and R ⁹ together have an average of about 5 to about 7 carbon atoms on a weight basis.
[00029] The first compounds (a) can be prepared by esterification of a glycerol alkoxylate, which alone can be prepared by reacting a glycerol initiator compound with ethylene oxide, propylene oxide, or both ethylene oxide and propylene oxide to provide polyether segments of a, x, b, y. c, and z. The alkoxylation reaction is usually carried out in the presence of a catalyst. Any substance capable of accelerating ring opening, adding the alkylene oxide monomer (s) to the glycerol initiator compound, can be used, including acidic catalyst, basic catalyst, and coordination catalyst. Specific examples of catalysts include alkali or alkaline earth hydroxides such as potassium hydroxide catalysts, double metal cyanide (DMC), mineral acids such as sulfuric acids and phosphoric acids, Lewis acids and Friedel-Crafts catalysts, boron trifluoride and their complexes with, for example, methanol, ethanol, isopropanol, butanols,
Petition 870190097018, of 9/27/2019, p. 24/112
13/55 ethyl ether, butyl ether, and phenyl ether, as well as organic acids such as acetic acid, propionic acid, phenol, organic amines such as monomethylamine, monoethylamine, dimethylamine, triethylamine or piperidine, and tin chlorides and antimony chlorides. Alkali or alkaline earth hydroxides are often used. The reaction can be carried out, for example, at temperatures of about 20 to about 180 ° C, in some embodiments about 80 to about 160 ° C. Ethylene oxide and propylene oxide can be used in the alkoxylation reaction alone, to produce homopoly- or oligoalkylene oxide segments, or in sequence to produce block copolymer polyether segments (poly- or oligo segments (ethylene oxide ) co-poly- or oligo (propylene oxide)). Block copolymer segments can be prepared in any order: that is, either of the poly- or oligo (ethylene oxide) and poly- or oligo (propylene oxide) blocks can be added first in the glycerol. It should be appreciated that segments a, b, and c will all typically be formed from ethylene oxide or propylene oxide, and also for the segments of x, y, and z. The number of monomer joints (a, b, c, x, y, z of the structure) of the ether segments can be controlled by quantity or quantities of ethylene oxide and / or propylene oxide with respect to glycerol.
[00030] Glycerol alkoxylate or a mixture of such glycerol alkoxylates is or is then esterified with one or more monocarboxylic acids having 2 to about 18 carbon atoms. The acid or monocarboxylic acids can be represented by the structural formulas
HOC (= O) R7, HOC (= O) R ⁸ , and HOC (= O) R9, [00031] where R7, R ⁸ , and R9 are as previously defined, or
Petition 870190097018, of 9/27/2019, p. 25/112
14/55 esterifiable derivatives of such acids, including anhydrides, lower alkyl esters of such acids (for example, methyl esters, which produce the relatively easy to remove methanol by-product), and the carboxylic acid halides (for example, chlorides of carboxylic acid and carboxylic acid bromides). One of R7, R8, and R9 can be different from the others, or all of R7, R8, and R9 can be different from the others, and esterification can produce one or a mixture of the first compounds (a).
[00032] The esterification can be carried out with one or a mixture of monocarboxylic esters or esterifiable derivatives thereof. Carboxylic acids including heteroatoms or atoms other than carbon and hydrogen, for example, O, F, N, S, Si can be used. Non-limiting examples of suitable esterified carboxylic acids or derivatives include, for example, acetic acid, acetic anhydride, propanoic acid, butyric acid, isobutanoic acid, pivalic acid, pentanoic acid, isopentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2 -ethylhexanoic acid, 3,3,5-trimethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, stearic acid, stearic acid, palmitoleic acid, citronellic acid, undecenoic acid, lauric acid, undecylenic acid, myristic acid, linolenic acid, arachidic acid, behenic acid, tetrahydrobenzoic acid, hydrogenated or non-hydrogenated abietic acid, 2-ethylhexanoic acid, furonic acid, benzoic acid, 4acetyl acid 2-oxo acid propanoic (pyruvic), 4-tert-butylbenzoic acid, cyclopentane carboxylic acid, naphthenic acid, cyclohexane carboxylic acid, 2,4-dimethyl benzoic acid, 2-methyl benzoic acid, salicylic acid, isomers thereof, methyl esters of themselves, and mixtures thereof.
Petition 870190097018, of 9/27/2019, p. 26/112
15/55 [00033] The esterification is preferably carried out with acid or base catalysts; Suitable catalysts for use in transesterification include, but are not limited to, base catalysts, sodium methoxide, acid catalysts including inorganic acids such as sulfuric acid and acidified clays, organic acids such as methane sulfonic acid, substituted and unsubstituted benzenesulfonic acids , and para-toluenesulfonic acid, and acidic resins such as Amberlyst 15. Metals such as sodium and magnesium, and metal hydrides are also useful catalysts. The esterification temperature can generally be 80 to 250 ° C. In certain cases, the esterification reaction can preferably occur with the continuous removal of the water or alcohol by-product (for example, methanol). This is done, for example, at atmospheric pressure and / or removal with nitrogen or reduced pressure or using a entraining agent, such as, for example, toluene, in the case of water as the by-product.
[00034] In various embodiments, glycerol alkoxylate is esterified with one or more monocarboxylic acids having about 4 to about 9 carbon atoms or having an average of about 6 to about 8 carbon atoms on a weight basis . In several embodiments, glycerol alkoxylate is esterified with one or more monocarboxylic acids selected from the group consisting of n-pentanoic acid, 2-methylbutanoic acid, n-hexanoic acid, n-heptanoic acid,
3,3,5-trimethylhexanoic acid, 2-ethylhexanoic acid, n-octanoic acid, n-nonanoic acid, and isononanoic acid. In several embodiments, it is particularly advantageous to esterify glycerol alkoxylate with one or more monocarboxylic acids selected from the group consisting of n-butyric acid, isobutyric acid, n-pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, n-hexanoic acid, nheptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, 3,3,5
Petition 870190097018, of 9/27/2019, p. 27/112
16/55 trimethylhexanoic, n-nonanoic acid, decanoic acid, undecanoic acid, undecellenic acid, lauric acid, stearic acid, isostearic acids, and combinations thereof.
[00035] The second ester compound or compounds (b) have or have a representative structure (II)
[00036] wherein each of R ¹¹ and R ¹² is independently hydrogen (H) or methyl (CH3); each of men is independently an integer and m + n is an integer from 1 to about 10; and R ¹⁰ and R ¹³ are each independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylalkyl, alkylcycloalkyl, alkylcycloalkyl, cycloalkylalkylalkyl, alkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkyl straight or branched chain having from 1 to about 17 carbon atoms and which can be substituted or unsubstituted.
[00037] In various embodiments, each of R ¹⁰ and R ¹³ can independently be straight or branched chain alkyl or alkenyl groups or substituted or unsubstituted cycloalkyl groups, each of which may contain hetero atoms such as O, F, N, S , or Si or can be hydrocarbonyl groups. In various embodiments, each of R ¹⁰ and R ¹³ independently has about 3 to about 8 carbon atoms or R ¹⁰ and R ¹³ together have an average of about 5 to about 7 carbon atoms on a weight basis or both each of R ¹⁰ and R ¹³ independently have about 3 to about 8 carbon atoms and R ¹⁰ and R ¹³ together have an average of about 5 to about 7 carbon atoms on a weight basis.
Petition 870190097018, of 9/27/2019, p. 28/112
17/55 [00038] In various embodiments, each of R ¹¹ and R ¹² is hydrogen (H) and / or m + n is an integer from about 2 to about 8 or from about 4 to about 10 or from about 2 to about 5 or from about 3 to about 5 or 2 or 3 or 4. In certain embodiments, the second ester compound or at least one of a plurality of second ester compounds is a diethylester of triethylene glycol or a tetraethylene glycol diester, particularly a triethylene glycol diethylester or tetraethylene glycol diester of one or two monocarboxylic acids having about 4 to about 9 carbon atoms. Tetraethylene glycol diesters in particular provide an unexpected advantage in terms of excellent miscibility in both R410a and R32 refrigerants. Tetraethylene glycol diesters of branched monocarboxylic acids also unexpectedly provide high viscosity indices.
[00039] In various embodiments, each of R ¹¹ and R ¹² is hydrogen (H), so that the second ester compound (b) or at least one or a plurality of second ester compounds (b) has or has representative structure (IV) oo
[00040] where m is an integer from 1 to about 10; or from 2 to about 8; or from about 4 to about 10; or from about 2 to about 5; or from about 3 to about 5; or 2 or 3 or 4; and R ¹⁰ and R ¹³ are as previously defined, in some embodiments having about 3 to about 8 carbon atoms.
[00041] Second ester compounds (b) can be prepared by esterification of ethylene glycol, propylene glycol, or an oligo- or polyalkylene glycol, which can be an oligo- or polyethylene glycol, oligo- or polypropylene glycol, or a copolymer of ethylene glycol-propylene glycol of
Petition 870190097018, of 9/27/2019, p. 1/29
18/55 block, with one or two monocarboxylic acids having from 2 to about 18 carbon atoms. Both the etherification reactions can be carried out by the methods already described for the preparation of the first compound or compounds of ester (a). Suitable non-limiting examples of monocarboxylic acids or derivatives that can be used in the preparation of the second ester compounds (b) are those already mentioned in conjunction with the preparation of the first compounds (a).
[00042] In various embodiments, ethylene glycol, propylene glycol, or oligo- or polyalkylene glycol is esterified with one or two monocarboxylic acids having about 4 to about 9 carbon atoms or having an average of about 6 to about 8 carbon atoms on a weight basis. In several embodiments, polyalkylene glycol is esterified with one or two monocarboxylic acids selected from the group consisting of n-pentanoic acid, 2-methylbutanoic acid, n-hexanoic acid, n-heptanoic acid, 3,3,5-trimethylhexanoic acid, 2-ethylhexanoic acid, n-octanoic acid, n-nonanoic acid, and isononanoic acid. In various embodiments, polyalkylene glycol is esterified with one or two monocarboxylic acids selected from the group consisting of n-butyric acid, isobutyric acid, n-pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid,
3,3,5-trimethylhexanoic, n-nonanoic acid, decanoic acid, undecanoic acid, undecellenic acid, lauric acid, stearic acid, isostearic acid, and combinations thereof. In various embodiments, the ether or ethers esterified with these monocarboxylic acids to produce the second ester compound or compounds is or is selected from diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol , and decaethylene glycol.
Petition 870190097018, of 9/27/2019, p. 1/30
19/55 [00043] The first ester compound or compounds (a) and the second ester compound or compounds (b) can be purified, for example, with cation or anion exchange, charcoal, molecular sieves, aluminum oxide , or by distillation (including vacuum distillation), or by a combination of such methods, to remove residual carboxylic acid.
[00044] In various embodiments, the first and second ester compounds are included in a weight ratio of about 20 to about 80% by weight of one or more first ester compounds and about 80 to about 20% in weight of one or more second ester compounds, or about 30 to about 70% by weight of one or more first ester compounds and about 70 to about 30% by weight of one or more second ester compounds, or about 40 to about 60% by weight of one or more first ester compounds and about 60 to about 40% by weight of one or more second ester compounds, in each case the combined weight of the first and second esters together being 100%. In various embodiments, the first compounds form a major portion of the mixture of the first and second esters by weight.
[00045] In embodiments in which the same carboxylic acid or the same combination of monocarboxylic acids is used in the preparation of both the first and second ester compounds, then these ester compounds can be prepared together, and the amounts of alkoxylate of glycerol and ethylene glycol, propylene glycol, or oligo- or polyalkylene glycol used can be selected so that the reaction product has a desired weight ratio of the first and second ester compounds.
[00046] In various embodiments, the first ester compound or compounds (a) and the second ester compound or compounds (b) together form at least about 50% by weight of the composition of
Petition 870190097018, of 9/27/2019, p. 1/31
20/55 lubricant. The lubricant composition may include a minor portion of a lubricant compound that is not a first or second ester compound, such as a lubricant compound selected from polyol ester (POE) compounds other than the first and second ester or polyalkylene compounds glycols (PAG). A smaller portion means less than 50% by weight. Non-limiting examples of other lubricants that can optionally be included in certain modalities of the lubricant composition are those prepared by the condensation of certain polyols such as pentaerythritol, neopentyl glycol and trimethylpropanol, and linear or branched monocarboxylic acids containing about 4 to 10 carbon atoms and those polyol ester (POE) and polyalkylene glycol (PAG) lubricants described in Sorensen et al., United States Patent 6,290,869, Corr, United States Patent 6,245,254; Duncan et al., United States Patent 5,750,750, Salomon et al, United States Patent 5,366,648, Fukuda et al, United States Patent 5185092, Corr et al., United States Patent Application Publication 2002/0013233, Schlossberg et al., United States Patent Application Publication 2003/0201420, among others (the relevant relevant portions of which are incorporated herein by reference). Polyvinyl ether (PVE) lubricants can also be used.
[00047] In various embodiments, the lubricant composition includes as lubricants only the mixture of one or more first ester compounds (a) and one or more second ester compounds (b).
[00048] One or more additives can be included in any combination in the lubricant composition. Non-limiting examples of suitabella additives include antioxidants, anti-wear agents, extreme pressure agents, friction reducing agents, based on silicone and other types of anti-foaming agents, inactive agents
Petition 870190097018, of 9/27/2019, p. 32/112
21/55 tion of metals such as benzotriazoles, viscosity index improvers, spill point depressants, detergent dispersants, stabilizers, corrosion inhibitors, flammability suppressants, acid recoverers and the like. Such additives can be used alone or in any combination of two or more. There is no restriction on the inclusion of such additives. Generally, additives such as these may be present in mono than or equal to about 10% by weight of the lubricant composition. Various embodiments of the lubricant composition can include about 0.1 to about 5% by weight of an additive or combination of additives or about 0.2 to about 2% by weight of an additive or combination of additives.
[00049] Non-limiting examples of antioxidants that can be used include phenolic antioxidants such as 2,6-di-t-butyl-4methylphenol and 4,4'-methylenebis (2,6-di-t-butylphenol), and bisphenol A , amine and thiazine antioxidants such as p, p-dioctylphenylamine, monooctyldiphenylamine, phenothiazine, 3,7-dioctylphenothiazine, N, N-di (2-naphthyl) -phenylenediamine, phenyl-1-naphthylamine, phenyl-2-naphthylamine, alkyl -1naphthylamines, and alkylphenyl-2-naphthylamines; sulfur-containing antioxidants such as alkyl disulfide, thiodipropionic acid esters and benzothiazole; and zinc compounds such as zinc dialkyl dithiophosphates and zinc diaryl dithiophosphates. The lubricant composition can comprise up to about 5.0% by weight of antioxidants, about 0.1 to about 5% by weight, about 0.1 to about 2.0% by weight, or about from 0.2 to about 0.8% by weight of antioxidants. Lubricant compositions can include one or a combination of two or more antioxidant compounds.
[00050] In certain embodiments, lubricant compositions may include one or more additives, such as extreme pressure / anti-wear additives, metal inactivating agents (also called
Petition 870190097018, of 9/27/2019, p. 33/112
22/55 metal deactivators or passivators), corrosion inhibitors, antioxidants, and so on. Non-limiting examples of corrosion inhibitors and metal inactivating agents include diaryl sulfides, arylalkyl sulfides, dialkyl sulfides, diaryl disulfides, dialkyl disulfides, diaryl disulfides, diaryl polysulfides, and dialkyl polysulfides , such as dibenzyl disulfide and dioctyl sulfide, dithiocarbamates such as methylene-bis-dibutyldithiocarbamate, 2-mercaptobenzothiazole derivatives such as 1- [N, N-bis (2-ethylhexyl) aminomethyl] -2-mercapto-1 H- 1,3-benzothiazole, 2,5-dimercapto-1,3,4-thiadiazole derivatives such as 2,5-bis (tercnonildithio) -1,3,4-thiadiazole and 2,5-bis (n-octyltio) -1,3,4-thiadiazole, which can be used alone or in any combination. Non-limiting examples of extreme pressure / anti-wear additives include phosphoric acid esters, acidic phosphoric acid esters, branched alkyl amine phosphates containing 5 to 20 carbon atoms, thiophosphoric acid esters, acidic amine salts of phosphoric acid ester, chlorinated phosphoric acid esters and phosphoric acid esters which are phosphoric acid esters or phosphoric acid with alkanols or polyether alcohols, zinc salts of thiophosphoric acid esters, or derivatives thereof. Specific non-limiting examples of phosphoric acid esters include tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tridodecyl phosphate, tridodecyl phosphate tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresildyrene phosphate and cresildifenate phosphate Specific non-limiting examples of acidic phosphoric acid esters can be mentioned monobutyl acid phosphate, monobutyl acid phosphate, monohexyl acid phosphate, monoepti acid phosphate
Petition 870190097018, of 9/27/2019, p. 34/112
23/55 la, monooctyl acid phosphate, monomonyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, acid phosphate monopentadecyl acid, monoexadecyl acid phosphate, monoeptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid phosphate, dihexyl acid phosphate, dihexyl acid phosphate , dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid phosphate, phosphate of dihexadecyl acid, diheptadecyl acid phosphate, dioctadecyl acid phosphate and dioleyl acid phosphate. Specific non-limiting examples of thiophosphoric acid esters include tributyl phosphorothionate, tripentyl phosphorothionate, trihexyl phosphorothionate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinecyl phosphorothionate, tridecyl phosphorylate phosphorothionate, trorecyl phosphorylate phosphate tritetradecyl phosphorothionate, tripentadecyl phosphorothionate, trihexadecyl phosphorothionate, triheptadecyl phosphorothionate, trioctadecyl phosphorothionate, trioleyl phosphorothionate, tricresyl phosphorethyl phosphorylate, triphylethyl phosphorylate and trisilenyl phosphorylate. Specific non-limiting examples of amine salts of acidic phosphoric acid esters include salts of acidic phosphoric acid esters with amines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptilamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptilamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptilamine and trioctilamine. Examples not
Petition 870190097018, of 9/27/2019, p. 35/112
Specific limiting of chlorinated phosphoric acid esters include tris (dichloropropyl) phosphate, tris (chloroethyl) phosphate, tris (chlorophenyl) phosphate, and polyoxyalkylene bis [di (chloroalkyl)] phosphate. Phosphoric acid esters that may be mentioned include dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, diphylite phosphite diphenyl, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite, trifodilite phosphite, trifodilite phosphite, phosphite and tricresil phosphite. Zinc salts of thiophosphoric acid esters that may be mentioned include zinc dialkyl dithiophosphate and zinc diaryl dithiophosphate. These additives can be used individually or in any combination, in any desired amount. In various embodiments, the lubricant composition may include about 0.01% by weight to about 5.0% by weight, about 0.01% by weight to about 4.0% by weight, about 0.02% by weight to about 3.0% by weight, or 0.1% by weight to about 5.0% by weight of each of the additives. These additives can be used alone or in any combination with each other or with other additives such as antioxidants, oil agents, defoaming agents, best viscosity index, spill point depressants, detergent dispersants, stabilizers, flammability suppressants , and acid recoverers.
[00051] To enhance thermal and chemical stability, the lubricant compositions described may include an acid recover. Non-limiting examples of suitable acid recoverers include epoxide compounds selected from phenylglycidyl ether epoxy compounds, alkylglycidyl ether epoxy compounds, with
Petition 870190097018, of 9/27/2019, p. 36/112
25/55 glycidyl ester epoxy stations, allyloxyran compounds, alkyloxyran compounds, alicyclic epoxy compounds, epoxidated fatty acid monoesters and epoxidized vegetable oils. Specific non-limiting examples of epoxy compounds of the phenylglycidyl ether type include phenyl glycidyl ethers and alkylphenyl glycidyl ethers. Alkylphenyl glycidyl ethers can have one to three C1-C13 alkyl groups, preferred examples of which include those with a C4-C10 alkyl group such as n-butylphenyl glycidyl ether, iso-butylphenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert- butylphenyl glycidyl ether, pentylphenyl glycidyl ether, hexylphenyl glycidyl ether, heptylphenyl glycidyl ether, octylphenyl glycidyl ether, nonylphenyl glycidyl ether and decylphenyl glycidyl ether. Specific non-limiting examples of epoxy compounds of the alkyl glycidyl ether type include decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether glycidyl ether glyceryl ether, trimethyl glyceryl ether; , 1,6-hexanediol diglycidyl ether, sorbitolpoliglycidyl ether, polyalkylene glycol monoglycidyl ether and polyalkylene glycol diglycidyl ether. Specific non-limiting examples of epoxy compounds of the glycidyl ester type include phenylglycidyl esters, alkylglycidyl esters and alkenylglycidyl esters such as glycidyl-2,2-dimethyl octanoate, glycidyl benzoate, glycidyl acrylate and glycidyl methacrylate. Specific non-limiting examples of allyloxane compounds include 1,2-epoxystyrene and alkyl-1,2-epoxystyrenes. Specific non-limiting examples of alkyloxyrane compounds include
1.2- epoxybutane, 1,2-epoxipentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxinonane, 1,2-epoxidecane,
1.2- epoxyundecane, 1,2-epoxidodecane, 1,2-epoxytridecane, 1,2epoxitetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2epoxyheptadecane, 1,2-epoxyoctadecane, 1,2-epoxinonadecane and 1, 2epoxyieicosan. Specific non-limiting examples of alicyclic epoxy compounds include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane,
Petition 870190097018, of 9/27/2019, p. 37/112
26/55 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane, bis (3,4epoxycyclohexylmethyl) adipate, exo-2,3-epoxynorbornane, bis (3,4-epoxy-6methylcyclohexylmethyl) adipate, 2- (7- oxyabicyclo [4.1.0] hept-3-yl) -spiro (1,3dioxane-5,3 '- [7] oxyabicyclo [4.1 - .0] heptane, 4- (1'-methylpileethyl) -1,2eppoxy-2 -methylcyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane Specific non-limiting examples of epoxidated fatty acid monoesters include epoxy esters of C12-C20 fatty acids and C1-C8 alcohols or phenols or alkylphenols such as butyl, hexyl, benzyl, cyclohexyl , methoxyethyl, octyl, phenyl and butylphenyl esters of epoxysearic acid Specific non-limiting examples of epoxy vegetable oils include vegetable oil epoxy compounds such as soybean oil, flax seed oil and cottonseed oil. of acid is not particularly restricted, but it can be from 0.1 to 5.0% by weight or 0.2 to 2.0% by weight based on the total weight of the composition. the lubricant. An acid recovery can be used alone, or two or more may be used in combination.
[00052] In certain respects a heat transfer device through which the lubricant and coolant mixture composition passes may include a filter. A filter can include molecular sieves, aluminum oxide charcoal, or other absorbent (s) through which the lubricant and coolant mixture composition passes to remove impurities such as low molecular weight acids and moisture.
[00053] Non-limiting examples of antifoam agents that can be used include silicone oils such as dimethylpolysiloxane and organosilicates such as diethyl silicate. Non-limiting examples of metal inactivating agents that can be used include benzotriazole, tolyltriazole, alizarin, quinizarin and mercaptobenzothiazole. Non-limiting examples of moisture recovery units include trialkylortoformates such as trimethylortoformiate and triethylortoform
Petition 870190097018, of 9/27/2019, p. 38/112
27/55 act, ketals such as 1,3-dioxacyclopentane, and amino ketones such as
2,2-dialkyloxazolidines.
[00054] In various embodiments, the lubricant composition may include one or more corrosion inhibitors, such as those selected from isomeric mixtures of N, N-bis (2-ethylhexyl) -4-methyl-1H-benzotriazole-1methylamine and N , N-bis (2-ethylhexyl) -5-methyl-1H-benzotriazole-1-methylamine. The lubricant composition can include about 0.01 to about 1.0% by weight of one or more corrosion inhibitors, about 0.01 to about 0.5% by weight of one or more corrosion inhibitors, or about 0.05 to about 0.15% by weight of one or more corrosion inhibitors.
[00055] Non-limiting examples of suitable viscosity enhancers that can be included in the lubricant composition are polyolefins, such as ethylene-propylene copolymers, or polybutylene rubbers, including hydrogenated rubbers, such as styrene-butadiene or styrene-isoprene rubbers ; or polyacrylates, including polymethacrylates and those described in Huang et al., United States Patent Publication No. 2010/0292114, the relevant portions of which are incorporated herein by reference.
[00056] Non-limiting examples of spill point depressants include polyalkyl methacrylates, polyalkyl acrylates, polyvinyl acetate, polyalkylstilenes, polybutene, chlorinated paraffin and naphthalene condensates, chlorinated paraffin condensates and phenol [00057] Detergent dispersants can be broadly classified into metal based detergents that contain a metal, and ashless dispersants that do not contain metal. Non-limiting examples of the initiator include colloids prepared by dispersing a metal hydroxide or carbonate in a neutral or basic sulfonate, overbased sulfonate, overbased phenate, overbased salicylate, overbased phosphonate, overbased carboxylate or the like. Non-imitators of the metal include calcium, magnesium, barium or similar
Petition 870190097018, of 9/27/2019, p. 39/112
28/55 res. Examples of ashless dispersants include monosuccinimides, bis-succinimides or the like.
[00058] Non-limiting examples of flammability suppressants include trifluorochloromethane, trifluoroiodomethane, phosphate esters and other phosphorus compounds, and hydrocarbon containing iodine or bromine, hiroflorocarbons, or fluorocarbons.
[00059] The mixture of first and second ester compounds in the lubricant composition can be adjusted to provide an ideal viscosity for the heat transfer device, compressor, and refrigerant or refrigerants with which the lubricant composition is employed. In general, the viscosity of the lubricant composition increases when the mixture is changed to increase the weight percentage of the first ester compound or compounds (a) or when the first and second ester compounds are changed (referring to representative structures I -IV) to increase the values of a, b, c, m, n, x, y, and / or z (that is, to increase the length of the ether segments) or to increase the number of portions R ⁷ , R ⁸ , and R ⁹ , R ¹⁰ and R ¹³ non-linear (i.e., to increase the branching of the ester moieties), or by a combination thereof. Viscosity is generally expressed as kinematic viscosity, which is measured according to ASTM D445. Lubricity, which can be determined according to ASTM D2670, can be increased by decreasing the number of non-linear R ⁷ , R ⁸ , and R ⁹ , R ¹⁰ and R ¹³ portions (ie, increasing the number of groups straight chain ester). Lubricant compositions in various embodiments can have a viscosity index of at least about 150, and typically lubricant compositions can have a viscosity index of at least about 200, particularly when the lubricants in the lubricant composition consist of or essentially consist of mixing the first and second esters. The viscosity index can be determined
Petition 870190097018, of 9/27/2019, p. 40/112
29/55 according to ASTM D2270.
[00060] In certain embodiments, about 20% by weight of the lubricant composition added to about 80% by weight of a refrigerant maintains a liquid phase at markedly low temperatures, particularly when the lubricants in the lubricant composition consist of or essentially they consist of the mixture of the first and second ester compounds, and particularly when the refrigerant is selected from refrigerants R410a, R32, and HFO or combinations of these refrigerants or combinations including these refrigerants. The miscibility temperature range of a lubricant composition in a refrigerant is determined by combining the lubricant composition (20% by weight) and the refrigerant (80% by weight) gravimetrically for a thick-walled glass test tube. The tube is sealed, and the mixture of lubricant and refrigerant in the sealed tube is visually observed while being cooled or heated. The temperature at which the phase separation is visually observed is referred to as the miscibility limit. The maximum miscibility temperature is the highest temperature before phase separation is observed; minimum miscibility temperature is the lowest temperature before phase separation is observed. In various embodiments, the lubricant and coolant combinations with the lubricant composition have a minimum miscibility temperature of about -40 ° C or less or about -55 ° C or less or about -70 ° C or less . In various embodiments, the minimum miscibility temperature can be for lubricant and refrigerant combinations where the refrigerant is selected from refrigerants R410a, R32, and HFO or combinations of these refrigerants or combinations including these refrigerants.
[00061] The moisture content of the lubricant composition is not
Petition 870190097018, of 9/27/2019, p. 41/112
30/55 particularly restricted, but in certain cases it is no greater than about 500 ppm, or no greater than about 300 ppm, or no greater than about 200 ppm, based on the total amount of the lubricant composition. A lower moisture content is desired from the point of view of the effect of thermal and chemical stability and electrical insulating properties of the lubricant composition, especially for use in hermetic type refrigeration machines. The moisture content can be measured using the Karl Fisher method (ASTM D4928-83).
[00062] The acid value of the lubricant composition is also not particularly restricted, but in order to prevent corrosion of metals used in the refrigeration machine or parts, and in order to prevent the decomposition of esters in the lubricant composition, it can be maintained at no more than about 0.1 mg KOH / g, particularly at no more than about 0.05 mg KOH / g. The acid value can be measured by titrating a known amount of lubricating composition with 0.01 to 0.1N NaOH.
[00063] The lubricant compositions described can be combined with one or more refrigerant compounds to form a lubricant-refrigerant combination, or working fluid, for use in a heat transfer device. Working cooling fluids generally include a smaller amount of the lubricant composition. In this way, the lubricant and coolant are combined in quantities so that it is relatively more lubricant than coolant in the lubricant coolant compositions. Based on the combined weight of lubricant and coolant, the refrigerant is greater than 50% by weight and the lubricant is less than 50% by weight of the combined weight. In various embodiments, the lubricant is about 1 to about 30% by weight of the combined weight of lubricant and coolant or 5 to about
Petition 870190097018, of 9/27/2019, p. 42/112
31/55 20% by weight of the combined weight of lubricant and coolant. Typically, working fluids include between about 5 to about 20 or optionally about 5 to about 15% by weight of lubricant with a balance being the refrigerant. The lubricant composition can be adjusted for optimal compatibility with the refrigerant with which it will be used in a refrigeration compressor or heat transfer device.
[00064] A simple refrigerant or mixture of refrigerants can be used. In particular embodiments, the refrigerant can be a simple compound or it can be a mixture of compounds. The mixture can be an azeotrope, zeotrope, or intimate boiling point mixture.
[00065] The lubricant compositions described have unexpected benefits used with refrigerants R410a, R32, and HFO, but can also be used with other refrigerants. Non-limiting examples of refrigerants that can be used with the described lubricant compositions include hydrocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, fluorocarbons, and hydrofluorocarbons, Particular non-limiting examples of useful refrigerants include propane, n-butane, isobutene, 2-methylbutane, npentane refrigerants , trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC12), difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,2,2 tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane ( HFC-134a), difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3heptafluorpropane (HFC-227ea), 1,1,1,2,3,3- hexafluorpropane (HFC236ea), 1,1,1,3,3,3-hexafluorpropane (HFC-236fa), 1,1,1,3,3pentafluorpropane (HFC-245fa), 1,1,1,3,3-pentafluorbutane (HFC365mfc), and HFO.
[00066] HFO refrigerants include C2 to C fluoroalkenes, especially straight or branched chain ethylene having 1 to 3
Petition 870190097018, of 9/27/2019, p. 43/112
32/55 fluorine atoms, propenes having 1 to 5 fluorine atoms, butenes having 1 to 7 fluorine atoms, pentenes having 1 to 9 fluorine atoms, hexenes having 1 to 11 fluorine atoms, cyclobutenes having to 1 to 5 fluorine atoms, cyclopentenes having 1 to 7 fluorine atoms, and cyclohexenes having 1 to 9 fluorine atoms. Suitable non-limiting examples of specific refrigerants of this species include 3,3,3, -trifluoropropene (HFO-1234zf), HFO1234 refrigerants type 2,3,3,3, -tetrafluoropropene (HFO-1234yf), 1,2,3, 3, tetrafluoropropene (HFO-1234yf), cis- and trans-1,3,3,3, tetrafluoropropene (HFO-1234ye), pentafluoropropenes (HFO-1225) such as 1,1,3,3,3, pentafluoropropene (HFO-1225) -1225zc) or those having a hydrogen at the terminal unsaturated carbon such as 1,2,3,3,3, pentafluoropropene (HFO-1225yez), fluorochloropropenes such as trifluoro, monochloropropenes (HFO-1233) type CF3CCl = CH2 (HFO-1233xf ) and CF3CH = CHCl (HFO-1233zd), most of which are described in Smutny, United States Patent 4,788,352 and Singh et al., United States Patent Application Publication 2008/0099190, descriptions of both documents incorporated herein by reference. Refrigerants can be used in combination, including combinations of fluoroalkene refrigerants with saturated hydrofluorocarbon refrigerants, C3-C8 hydrocarbon, dimethyl ether, carbon dioxide, bis (trifluoromethyl) sulfide, and trifluoroiodomethane.
[00067] In certain respects, the lubricant compositions described have unexpected benefits when used with R410a refrigerants (an almost azeotropic mixture of difluoromethane (R32) and pentafluoroethane (R125)) or difluoromethane (R32) or HFO or any combinations of R410a, R32 , and HFOs; however, the lubricant compositions of the present teachings can also be used with other refrigerants. As described above, suitable exemplary HFO refrigerants include 1,1,1,2-tetrafluoropropene (HFO
Petition 870190097018, of 9/27/2019, p. 44/112
33/55
1234yf), both cis- and trans-1,1,1,3-tetrafluoropropene (HFO1234ze), 1,1,1, trifluoro-2, chloro-propene (HFCO-1233xf), and both cis and trans-1,1, 1-trifluoro-3, chlororopropene (HFCO-1233zd), by way of non-limiting example.
[00068] The lubricant and coolant combinations described can be used in compression type heat transfer devices. Non-limiting examples of compression-type heat transfer devices are compressor systems for refrigerators, heat pumps, and air conditioning equipment, including auto, residential, commercial, and industrial air conditioners. The lubricant composition is used in sufficient quantity to provide lubrication for the compressor. In these devices, the refrigerant typically evaporates at low pressure consuming the heat from the surrounding area. The resulting steam is then compressed and passed to a condenser where it is condensed and supplies heat to a second zone. The condensate is then returned via an expansion valve to the evaporator, thereby completing the cycle. The mechanical energy required to compress the steam and pump the fluid is supplied, for example, by an electric motor or an internal combustion machine.
[00069] Types of compressors useful for the above applications can be classified into broad categories; dynamic and positive displacement compressors. Positive displacement compressors increase the vapor pressure of the refrigerant by reducing the volume of the compression chamber through the work applied to the compressor mechanism. Positive displacement compressors include many styles of compressors currently in use, such as reciprocating, rotary (rolling piston, rotating vane, single screw, twin screw), and orbital (scrolling or trochoidal). Dynamic compressors increase refrigerant vapor pressure by transfer
Petition 870190097018, of 9/27/2019, p. 45/112
34/55 continuous rotation of the rotating member to the steam, followed by conversion of this energy into a pressure increase. Centrifugal compressors work on these principles. Details of the design and function of these compressors for refrigeration applications can be found in the 2010 ASHRAE Handbook, HVAC systems and Equipment, chapter 37, incorporated here by reference.
[00070] Working fluids comprising the composition of lubricant and a refrigerant or refrigerants can be used in a wide variety of refrigeration and heat energy transfer applications, in some cases particularly industrial or commercial air conditioning units, for example , for stores, commercial buildings, apartment buildings, warehouses, ice skating rinks, or for retail sales.
[00071] It is generally desirable for the lubricant composition to be soluble in the refrigerant (or combination of refrigerants) in concentrations of about 5 to 20% by weight over a temperature range of about -40 ° C, or less than about 40 ° C. or greater, depending on the application. In addition to the lubricant and coolant miscibility, the coolant-lubricant combination must have viscosity characteristics suitable for particular application and equipment.
Examples [00072] In the following examples, properties are determined by the following methods.
[00073] Kinematic viscosity is measured according to ASTM D445.
[00074] Lubricity is measured according to ASTM D2670.
[00075] The viscosity index is determined according to
ASTM D2270.
[00076] The miscibility temperature range of a
Petition 870190097018, of 9/27/2019, p. 46/112
35/55 lubricant composition in a refrigerant is determined as follows: The lubricant composition (20% by weight) and the refrigerant (80% by weight) are added gravimetrically to a thick-walled glass test tube. The tube is then sealed. The mixture of lubricant and coolant in the sealed tube is visually observed while being cooled (usually to no less than -40 ° C.) And heated (usually to no more than 78 ° C.). The temperature at which the phase separation is visually observed has been designated as the miscibility limit. The maximum miscibility temperature is the highest temperature before phase separation is observed; minimum miscibility temperature is the lowest temperature before phase separation is observed.
[00077] Preparation A of Ethoxylated Glycerol Ester (by procedures A-1 and A-2) and Preparations B and C of Triethylene Glycol Ester represent the generalized procedures for synthesizing all the use of esters in the examples. These generalized preparation procedures will refer to the preparations of the other esters used in the examples, together with the reagent weights and any deviation from the generalized procedures used to prepare each ester.
Preparation A. Preparation of Ethoxylated Glycerol (Mn ~ 1000)
Esterified with a mixture of carboxylic acids [00078] This ester is prepared by either of two procedures, A-1 or A-2.
A-1 Procedure without solvent [00079] To a 2 liter reactor equipped with a mechanical stirrer, water collector, nitrogen source, thermo coupled, and reflux condenser are added 500 grams of ethoxylated glycerol (Mn ~ 1000) and 210 grams a mixture of carboxylic acid (34% by weight)
Petition 870190097018, of 9/27/2019, p. 47/112
36/55 are n-pentanoic acid, 44% by weight n-heptanoic acid, and 22% by weight 3,3,5-trimethylhexanoic acid) all at once. This is followed by the addition of 0.25 grams of tin (II) oxylate. The mixture is stirred under a blanket of nitrogen and slowly heated to 230 ° C for approximately 4 hours. During this heating period, the reaction water is collected in the water collector; any distilled carboxylic acid is returned to the reactor. After 3 hours at 230 ° C, the reaction mixture is cooled to approximately 80 ° C and filtered through Whatman # 1 paper filter. The resulting oil is then subjected to distillation in the linear direction between 0.2 and 0.4 Torr to remove residual volatile carboxylic acids. Later, the residual oil is passed through a column of charcoal and aluminum oxide to provide 458 grams of esterified ethoxylated glycerol.
A-2. Azeotropic Distillation of Water Procedure [00080] To a 1-liter, single-neck, round-bottom flask equipped with a magnetic stirrer, Dean-Stark water collector, and reflux condenser are added 200 grams of ethoxylated glycerol (Mn ~ 1000) and 84.8 grams of a mixture of carboxylic acid (34% by weight n-pentanoic acid, 44% by weight n-heptanoic acid, and 22% by weight 3,3,5-trimethylhexanoic acid) all at once . This is followed by the addition of 1.90 grams of p-toluenesulfonic acid and 400 ml of toluene. The reaction mixture is stirred and heated under reflux until 11 ml of water is collected. After cooling to room temperature, the reaction mixture is washed four times with 250 ml of 5% aqueous NaOH, twice with 250 ml of water, and once with 250 ml of saturated aqueous NaCl. The solution is dried with anhydrous Na2SO4 and filtered. Later, the solution is subjected to rotoevaporation to provide 197 grams of esterified ethoxylated glycerol.
Preparation B. Preparation of Triethylene Glycol Esterified with
Petition 870190097018, of 9/27/2019, p. 48/112
37/55 a mixture of carboxylic acids (without solvent) [00081] To a 2 liter reactor equipped with a mechanical stirrer, water collector, nitrogen source, thermo coupled, and reflux condenser are added 270 grams of triethylene glycol, 451 grams of a mixture of carboxylic acid (34% by weight n-pentanoic acid, 44% by weight n-heptanoic acid, and 22% by weight acid
3,3,5-trimethylhexanoic) followed by 0.20 grams of tin (II) oxalate all at once. Under a blanket of nitrogen, the mixture is slowly heated to 220 ° C in about 6 hours. During this heating period, the reaction water is collected in the water collector and any distilled carboxylic acids are returned to the reactor. This reaction mixture is maintained at 220 ° C for a little over an hour, then increased to 230 ° C momentarily, and then cooled to room temperature. Later, the reaction product is subjected to fractional vacuum distillation through a Vigreux column 2 cm in diameter and 18 cm in length. The material distilled between 192 and 232 ° C at 0.3 Torr is collected to supply 532 grams of esterified triethylene glycol.
Preparation C. Preparation of 3,3,5-trimethylhexanoic acid esterified triethylene glycol (azeotropic water distillation) [00082] To a 1-liter, single-necked, round-bottom flask equipped with a magnetic stirrer, Dean water collector -Stark, and reflux condenser are added 75 grams of triethylene glycol, 166 grams of 3,3,5-trimethylhexanoic acid, 0.95 grams of ptoluenesulfonic acid, and 200 ml of toluene all at once. The reaction mixture is stirred and heated under reflux until ~ 19 ml of water is collected. Later, the reaction product is cooled to room temperature and washed three times with 250 ml of 5% aqueous NaOH, twice with 250 ml of water, and dried over MgSO4. The mixture is then filtered and subjected to rotoevaporation. The resulting oil is
Petition 870190097018, of 9/27/2019, p. 49/112
38/55 then distilled through a column of 2 cm in diameter and 18 cm in length Vigreux, and the material distilled between 201 to 218 ° C at 0.1 to 0.2 Torr is collected. This material is 176 grams of esterified triethylene glycol.
Preparation D. Preparation of Ethoxylated Glycerol (Mn ~ 1000)
Esterified with 3,3,5-trimethylhexanoic acid (Without solvent) [00083] The ester of preparation D is made as in preparation A, using 500 grams of ethoxylated glycerol (Mn ~ 1000), and 249 grams of 3.3 acid, 5-trimethylhexanoic to provide 567 grams of product.
Preparation E. Preparation Ethoxylated Glycerol (Mn ~ 1240)
Esterified with a mixture of carboxylic acids (without solvent) [00084] The ester of preparation E is made as in preparation A, using 620 grams of ethoxylated glycerol (Mn ~ 1240) and 195 grams of a mixture of carboxylic acid (34% in weight of npentanoic acid, 44% by weight of n-heptanoic acid, and 22% by weight of 3,3,5-trimethylhexanoic acid) to provide 730 grams of product. The product is subjected to linear distillation vacuum distillation (0.35 Torr, 41-47 ^o C) to remove residual volatile material.
Preparation F. Preparation of Ethoxylated Glycerol (Mn ~ 1240) with 3,3,5-trimethylhexanoic acid (Without solvent) [00085] The ester of preparation F is made as in preparation A starting with 620 grams of ethoxylated glycerol (Mn ~ 1240 ) and 248 grams of 3,3,5-trimethylhexanoic acid to provide 534 grams of product.
Examples 1-11. Lubricants according to Inventive Technology [00086] The 78% linear esters of Preparation A and Preparation C were combined in the weight ratios indicated in Examples 1 to 8 and tested for the properties shown. In a way
Petition 870190097018, of 9/27/2019, p. 50/112
39/55 similarly, the 100% branched esters of Preparation D and Preparation C were combined at the weight ratios indicated in Examples 9 to 11 and tested for the properties shown.
TABLE 1
Lubricant composition,% by weight properties Example Preparation Preparation Preparation Preparation Viscosity Index Miscibility Miscibilityto the B D o C o kinematics (cSt) in is on and in R32at 40 ° C / 100 ° C viscosi R410a (° C) (° C) dade Example 1 - 100 - - 6.97 / 2.28 154 72 to -70 *Example 2 30 70 - - 39 to -70 * 56 to -40 * Example 3 40 60 - - 41 to -70 *Example 4 50 50 - - 21.3 / 5.48 214 18 ** to -57 *Example 5 60 40 - - 29 / 6.8 204 32 to -60 25 to -60 Example 6 68 32 - - 35.6 / 7.40 181 18 ** to -57 *Example 7 85 15 - - 45.0 / 9.79 211 Example 8 100 - - - 62.6 / 12.7 208 -7.8 to -57 *Example 9 - - - 100 13.4 / 3.46 141 72 to -70 *Example - - 25 75 22.2 / 5.08 16756 to -40 * 10 Example - - 30 70 39 to -70 *11
* Temperature limit tested ** The maximum miscibility temperature limit has not been determined.
[00087] Conventionally, it was understood that esters more
Petition 870190097018, of 9/27/2019, p. 51/112
Highly branched 40/55 are significantly more miscible in soft drinks than linear chain analogs. In the composition of glycerol ethoxylated ester lubricants and polyalkylene glycol esters according to the inventive technology; however, both highly branched and highly linear compositions surprisingly have almost the same miscibilities in both R410a and R32. This is demonstrated in Figures 1-5, where the abbreviation% iC9 refers to a percentage by weight of isononoate ester (3,3,5-trimethylhexanoate) in the lubricant composition, with 100% iC9 meaning that both are ethoxylated glycerol and polyalkylene glycol esters were prepared using only 3,3,5-trimethylhexanoic acid as the esterifying acid and 22% iC9 meaning that both ethoxylated glycerol and polyalkylene glycol esters were prepared using a mixture of 22% by weight of isononanoic acid (3.3 , 5-trimethylhexanoic), 34% by weight of normal pentanoic acid, and 44% by weight of normal heptanoic acid as the esterifying acids. The esters of Preparations C, D, and F are prepared using only 3,3,5-trimethylhexanoic acid as the esterifying acid, and lubricant compositions made from these preparations are designated as 100% iC9 in the Figures. Preparations A, B, and E are prepared using a mixture of 22% by weight of isononanoic acid (3,3,5-trimethylhexanoic), 34% by weight of normal pentanoic acid, and 44% by weight of normal heptanoic acid, and composition of lubricants made from these preparations are designated as 22% iC9 in the figures.
[00088] In figure 1, the kinematic viscosities at 40 ° C (determined in accordance with ASTM D445) of the lubricant composition containing combinations of Preparations A and B as shown in Table 2 are graphed as a 22% iC9 curve, and 40 ° C kinematic viscosities of lubricating compositions
Petition 870190097018, of 9/27/2019, p. 52/112
41/55 containing combinations of preparations D and C as shown in Table 3 are represented as a 100% iC9 curve. Figure 1 compares the kinematic viscosities at 40 ° C of composition of 100% iC9 curve lubricants, combinations of highly branched ethoxylated glycerol esters (Mn ~ 1000) and triethylene glycol, to the kinematic viscosities at 40 ° C of lubricant composition curve of 22% iC9, combinations of highly linear ethoxylated glycerol esters (Mn ~ 1000) and triethylene glycol. The 100% iC9 curve lubricant compositions having a higher degree of branching exhibit higher viscosities compared to the 22% iC9 curve. TABLE 2
22% curve iC9 - Ethoxylated Glycerol (Mn ~ 1000) Esterified with Mixed Acids (Preparation A) Mixed with Triethylene Glycol Esterified with Mixed Acids (Preparation B)
Preparation A (% by weight) Preparation B (% by weight) Viscosity at 40 ° C(cSt.) 0 100 6.97 50 50 21.3 60 40 29 68 32 35.6 85 15 45 100 0 62.6
TABLE 3
Curve 100% iC9 - Ethoxylated Glycerol (Mn ~ 1000) Esterified with 3,3,5-trimethylhexanoic acid (Preparation D) Mixed with Triethylene Glycol Esterified with 3,3,5-trimethylhexanoic acid (Preparation C)
Preparation D (% by weight) Preparation C (% by weight) Viscosity at 40 ° C (cSt.) 0 100 13.4 25 75 22.2 38 62 28.2
Petition 870190097018, of 9/27/2019, p. 53/112
42/55
50 50 36.2 100 0 92.2
[00089] Figure 2 is similar to figure 1 in that it compares the viscosities at 40 ° C (determined according to ASTM D445) of highly branched lubricating esters, curve of 100% iC9, with highly linear lubricating esters, curve of 22 % iC9. However, the starting ethoxylated glycerol in figure 2 was of a higher molecular weight (Mn ~ 1240) than in figure 1. In figure 2, the 100% iC9 curve represents the composition of lubricants made by combining preparations F and C as mentioned in Table 5, while the 22% iC9 curve represents lubricant composition made by combining preparations E and B, as mentioned in Table 4. In figure 2, the 100% iC9 curve lubricant compositions they are more highly branched and exhibit higher viscosities than the 22% iC9 curve. Those lubricating esters with higher degrees of branching that exhibit correspondingly higher viscosities are typical. In fact, on a molecular and individual ester basis, ester lubricants exhibit typical viscosity behavior.
TABLE 4
22% curve iC9 - Ethoxylated Glycerol (Mn ~ 1240) Esterified with Mixed Acids (Preparation E) Mixed with Triethylene Glycol Esterified with Mixed Acids (Preparation B)
Preparation E (% by weight) Preparation B (% by weight) Viscosity at 40 ° C (cSt.) 0 100 6.97 25 75 14.01 50 50 27.46 75 25 49.05 100 0 90.1
TABLE 5
Curve of 100% iC9 - Ethoxylated Glycerol (Mn ~ 1240) Esterified with 3,3,5-trimethylhexanoic acid (Preparation F) Mixed
Petition 870190097018, of 9/27/2019, p. 54/112
43/55 with Triethylene Glycol Esterified with 3,3,5-trimethylhexanoic acid (Preparation C)
Preparation F (% by weight) Preparation C (% by weight) Viscosity at 40 ° C (cSt,) 0 100 13.4 10 90 16.95 20 80 21.09 30 70 26.5 40 60 32.75 100 0 117.7
[00090] It is well documented that lubricity is better with straight chain esters rather than branched chains. Figure 3 compares the lubricity (FALEX test, determined according to ASTM D2670) of lubricating compositions prepared from branched versus partially branched esters. All lubricant compositions were formulated to have kinematic viscosities between 25 and 29 cSt. at 40 ° C. The measured lubricity for each lubricating composition is mentioned in Table 6.
TABLE 6 [00091] Comparison of Lubricity (FALEX, ASTM D2670) of Mixtures of Etoxylated Glycerol Ester and Branched Versus Branched Triethylene Glycol. (All mixtures have kinematic viscosities between 25 and 29 cSt. At 40 ^o C).
Glycerol EsterEthoxylated,% by weight of preparation Triethylene glycol ester,% by weight of preparation Falex(Pounds for breakdown) Viscosity at 40 ° C (cSt.) 33% by weight of preparation D 67% by weight of preparation C 794 26 60% by weight of preparation A 40% by weight of preparation B 1085 29 27% by weight of preparation F 73% by weight of preparation C 824 24 47% by weight of preparation E 53% by weight of preparation B 854 24
[00092] In spite of following the expected, the viscosity and lubricity trends, the inventive technology lubricants just described presented unexpected degrees of miscibility with
Petition 870190097018, of 9/27/2019, p. 55/112
44/55 soft drinks. The literature reports that branching increases the miscibility of ester lubricants in refrigerants. However, the lubricants of the inventive technology now described were surprisingly unresponsive to branching, with lubricants having relatively straight chain esters working as well as those having relatively branched esters. Figure 4 shows the miscibility of the lubricant composition in R410a where the lubricant compositions contained combinations of preparations A and B as shown in table 7 (shown in a graph as a 22% iC9 curve). Figure 4 also shows the miscibility of the lubricant composition in R410a where the lubricant compositions contained combinations of preparations D and C as shown in table 8 (graphed as a 100% iC9 curve). Figure 4 compares the miscibility of R410a and lubricant composition with highly branched ether glycerol esters (Mn ~ 1000) and highly branched triethylene glycol (100% iC9 curve) to the miscibility of R410a and lubricant composition with combinations of ethoxylated glycerol esters ( Mn ~ 1000) and highly linear triethylene glycol (curve 22% iC9).
TABLE 7
22% Branched Curve - Ethoxylated Glycerol (Mn ~ 1000) Esterified with Mixed Acids (Preparation A) Mixed with Triethylene Glycol Esterified with Mixed Acids (Preparation B)
Preparation A (% by weight) Preparation B(% by weight) Maximum Miscibility Temperature of R410a in the Composition oflubricant, ° C 0 100 72 30 70 39 40 60 41 60 40 32 68 32 18 100 0 -7.8
Petition 870190097018, of 9/27/2019, p. 56/112
45/55
TABLE 8
100% Branched Curve - Ethoxylated Glycerol (Mn ~ 1000)
Esterified with 3,3,5-trimethylhexanoic acid (Preparation D) Mixed with Triethylene Glycol Esterified with 3,3,5-trimethylhexanoic acid (Preparation C)
Preparation D(% by weight) Preparation C (% by weight) Maximum Miscibility temperature of R410a in Lubricant composition, ° C 0 100 72 30 70 39 40 60 42 60 40 32
[00093] Figure 5 similarly shows the miscibility of R32 with lubricant composition containing combinations of preparations A and B as shown in table 9 (shown in graph as curve 22% iC9) and with lubricant composition containing combinations of preparations D and C as shown in table 10 (graphed as a 100% iC9 curve). Figure 5 compares the miscibility of R32 with lubricant composition with ethoxylated glycerol esters (Mn ~ 1000) and highly branched triethylene glycol (100% iC9 curve) to the miscibility of R32 with lubricant composition with etherylated glycerol ester combinations (Mn ~ 1000) and highly linear triethylene glycol (curve 22% iC9).
TABLE 9
Curve 22iC9 - Ethoxylated glycerol (Mn ~ 1000) Esterified with mixed acids (Preparation A) Mixed with Triethylene Glycol Esterified with mixed acids (Preparation B)
Preparation A (% by weight) Preparation B(% by weight) Maximum Miscibility temperature of R32 in Lubricant composition, ° C 30 70 56 60 40 25
TABLE 10
Curve 100iC9 - Esterified Glycerol (Mn ~ 1000)
Petition 870190097018, of 9/27/2019, p. 57/112
46/55 with 3,3,5-trimethylhexanoic acid (Preparation D) Mixed with Triethylene Glycol Esterified with 3,3,5-trimethylhexanoic acid (Preparation C)
Preparation D (% by weight) Preparation C (% by weight) Maximum Miscibility temperature of R32 in Lubricant composition, ° C 25 75 56 33 67 47 38 62 45 50 50 33
[00094] Thus, the lubricants of the inventive technology now described unexpectedly provide a certain miscibility in a refrigerant at a lower viscosity than can be expected before lubricant compositions. The fact that the miscibility in refrigerants is by branching the carboxylate group, can be used as an advantage in the preparation of lubricant compositions described as having the desired viscosity and lubricity.
[00095] In all miscibility studies, the low temperature miscibility of esters with soft drinks was less than 40 ° C, than the lowest temperature tested. The minimum miscibility temperature was not reached in the test. Thus, comparing the composition of straight versus branched chain lubricants also showed the same unexpected insensitivity in miscibility at the low end temperature of the study.
Example 12. Preparation of a lubricant pot according to the inventive technology: Combination of 25% by weight of Etoxylated Glycerol Ester (Glycerol Etoxilado Mn ~ 1000) and 75% by weight of Tetraethylene Glycol Acid 3.3.5 -trimethylhexanoic (Without solvent) [00096] To a 2 liter reactor equipped with a mechanical stirrer, water collector, nitrogen source, thermo coupled, and reflux condenser were added 176 grams of ethoxylated glycerol (Mn ~ 1000) at once , 307 grams of tetraethylene glycol, and 611 grams
Petition 870190097018, of 9/27/2019, p. 58/112
47/55 3,3,5-trimethylhexanoic acid. This addition was followed by an addition of 0.25 grams of tin (II) oxylate. The mixture was stirred under a blanket of nitrogen and slowly heated to 230 ° C. The temperature was maintained at 230 ° C for about 6.5 hours. During the heating period, the reaction water was collected in the water collector and any distilled carboxylic acid was returned to the reactor. At the end of the reaction (as measured by the collected water), the excess carboxylic acid was distilled, collected, and did not return again to the reactor. The reaction mixture was allowed to cool to room temperature and was passed through a heated aluminum oxide column, filtered, and purged with a stream of nitrogen. This resulted in 830 grams of combined esters.
[00097] The properties of the Example 12 lubricant were determined as follows,
Example 12 Kinematic viscosity (cSt) at 40 ° C / 100 ° C 25.5 / 5.82 Viscosity index 183 FALEX (0.1% BHT added) 860 pounds for loss Miscibility at R410a (° C) (20% by weight of lubricant load) 50 ° C to -60 ° C * Miscibility at R32 (° C) (20% by weight of lubricant load) 51 ° C to -60 ° C *
* Lower test limit [00098] This description of the inventive technology is merely exemplary in nature and, therefore, variations that do not depart from the heart of the subject of the present invention are intended to be within the scope of the inventive technology. Such variations should not be considered a departure from the spirit and scope of the inventive technology.
[00099] Lubricant composition modalities comprising a mixture of about 1 to 99% by weight of the mixture of one or more ester compounds are specifically described
Petition 870190097018, of 9/27/2019, p. 59/112
48/55 ο
I [jC - £ OC] l ₂ CI 1R ¹ -j— (OC] l ₂ CI i R. ² OCR
O] IC — j-OC] I ₂ C1IR '^ OC] I ₂ CI] R' ¹ ^ —OCR *
O | ( ₂ C — ÉOC] I ₂ C1IR. ^S 4— (oC] I ₂ CHR ⁶ } OCR ' / c Z (I) [000100] and about 1- 99% by weight of the mixture of one or more second ίι ° ester compounds
R_ ^lü —C — í-OCI] nCI] R ^L1 -j — foC] l ₂ C] IR. ¹² J — QCR ^r '''η (μ) [000101] where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , and R ¹² are each H or methyl; a + x, b + y. and c + z are integers from 1 to about 20, and m + n is an integer from 1 to about 10; and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹³ are alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylalkyl, alkylcycloalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkylalkyl linear and branched, substituted or unsubstituted having 1-17 carbons which optionally have any or any combination of more than one of the following characteristics: (1) each of a + x, b + y, and c + z is independently an integer from 1 to about 10; or m + n is an integer from about 2 to about 8; or each of a + x, b + y. and c + z is independently an integer from 1 to about 10 and m + n is an integer from about 2 to about 8; (2) each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is H; or each of R ¹¹ and R ¹² is H; or each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , eR ¹² is H; (3) each of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹³ is independently selected from straight chain and chain alkyl and alkenyl groups
Petition 870190097018, of 9/27/2019, p. 60/112
49/55 branched and substituted or unsubstituted cycloalkyl groups that may optionally contain one or more heteroatoms selected from the group consisting of O, F, N, S, and Si or where each of R7, R ⁸ , R ⁹ , R ¹⁰ and R13 is independently selected from straight chain alkyl and alkyl groups that may optionally contain one or more heteroatoms selected from the group consisting of O, F, N, S, and Si; (4) each of R7, R8, R ⁹ , R ¹⁰ and R13 independently has about 3 to about 8 carbon atoms or one or both of R ⁷ , R ⁸ , and R ⁹ together have an average of about 5 to about 7 carbon atoms on a weight basis and R10 and R13 together have an average of about 5 to about 7 carbon atoms on a weight basis;
(5) the mixture has about 20 to about 80% by weight of one or more of the first ester compounds and about 80 to about 20% by weight of the one or more second ester compounds or the mixture has a portion greater in weight of one or more first ester compounds; (6) at least one of the first and second ester compounds is an ester of n-pentanoic acid, 2-methylbutanoic acid, nhexanoic acid, n-heptanoic acid, 3,3,5-trimethylhexanoic acid, 2ethylhexanoic acid, n- octanoic, n-nonanoic acid, and isononanoic acid, or combinations thereof or at least one of the first and second ester compounds is an ester of n-butyric acid, isobutyric acid, n-pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid , n-hexanoic acid, n-heptanoic acid, noctanoic acid, 2-ethylhexanoic acid, 3,3,5-trimethylhexanoic acid, n-nonanoic acid, decanoic acid, undecanoic acid, undecellic acid, lauric acid, stearic acid, isosearic acid , or combinations thereof; (7) the second ester compound or compounds (b) comprise a diethylester of triethylene glycol; (8) the lubricant composition is free of lubricant compounds other than the mixture of first and second ester compounds or the
Petition 870190097018, of 9/27/2019, p. 61/112
Brisker 50/55 includes a different lubricant or lubricants than the first and second ester compounds of the mixture with the proviso that the percentage by weight in the lubricant composition of the other lubricant or lubricants is less than the percentage by weight in the composition lubricant mixture consisting of the first and second ester compounds, the other lubricant or lubricants of which may be selected from the group consisting of polyol ester (POE) lubricants, poyalkylene glycol (PAG) lubricants, polyvinyl ether (PVE) lubricants, and combinations of the same; (9) the lubricant composition includes an additive or additives selected from the group consisting of antioxidants, anti-wear agents, extreme pressure agents, oil agents, anti-foaming agents, metal inactivating agents, better viscosity index, spot depressants spill dispersants, detergent dispersants, stabilizers, metal passivators, corrosion inhibitors, flammability suppressants, acid recoverers, and combinations thereof, which can be from about 0.1 to about 5% by weight of the additive or additives; (10) the lubricant composition has a viscosity index of at least about 150, where these characteristics include all values and ends of numerical ranges and combinations thereof and all materials and material combinations described above that can be included in the compositions mentioned for these characteristics. As mentioned, all possible combinations of the listed optional features of these methods are specifically described as modalities. Also specifically described are all combinations of lubricant and coolant including this lubricant composition optionally with any or any combination of more than one of the listed features (1) - (10), where each combination of lubricant and coolant can optionally have any one or more
Petition 870190097018, of 9/27/2019, p. 62/112
51/55 of these characteristics: (11) a minimum miscibility temperature of -40 ° C or less of the lubricant in the refrigerant; (12) in which the refrigerant is selected from the group consisting of refrigerants R410a, R32, and HFO or combinations of these refrigerants or combinations including these refrigerants; (13) where the refrigerant is greater than about 50% by weight of the lubricant and refrigerant combination or where the lubricant is from about 5 to about 20% by weight of the lubricant and refrigerant combination. also specifically described are all compression type heat transfer devices comprising any of these described lubricant and refrigerant combinations, which may optionally be a positive displacement compressor or selected from stationary and mobile air conditioning and refrigeration equipment. Also described is a method of lubricating compression refrigeration equipment, comprising the circulation of any of the described lubricant compositions.
[000102] Lubricant composition modalities comprising a mixture of about 1 - 99% by weight of the mixture of one or more ester compounds are also specifically described
] IC
OC] l ₂ CU

OCR ⁷
OC] l ₂ CU
[000103] where x, y, and z are each independently an integer from 1 to about 20 and R ⁷ , R ⁸ , and R ⁹ are each independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylcycloal
Petition 870190097018, of 9/27/2019, p. 63/112
52/55 kyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyl, arylcycloalkylalkyl, arylalkylcycloalkyl, cycloalkylalkylalkyl, and cycloalkylalkyl, which may be substituted for a linear or branched chain; and (b) about 1 to about 99% by weight of the mixture of one or more second ester compounds
R. ¹⁰ - _c
OCIhCI]
[000104] where m is an integer from 1 to about 10 and R ¹⁰ and R ¹³ are each independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl groups , arylcycloalkyl, cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyl, arylcycloalkylalkyl, arylalkylcycloalkyl, cycloalkylalkylaryl, and straight or branched chain cycloalkylalkylalkyl having 1 to about 17 compounds which are substituted for or which are substituted or which are compounds of which are substituted or consisting of 17 carbon atoms (a) and the second ester compound or compounds (b) together form at least about 50% by weight of the lubricant composition, which optionally have any or any combination of more than one of the following characteristics: (1) in that x, y, and z are each independently an integer 1 to about 10, m is an integer 2 to about 8 and each one of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹³ independently have 3 to about 8 carbon atoms or where x, y, and z are each independently an integer 1 to about 10, m is an integer 2 to about 8, R ⁷ , R ⁸ , and R ⁹ together have an average of about 5 to about 7 carbon atoms on a weight basis, and R ^{10 and} R ¹³ together have an average from about 5 to about 7 carbon atoms on a weight basis; (2) where each
Petition 870190097018, of 9/27/2019, p. 64/112
53/55 one of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹³ is independently selected from straight and branched chain alkyl and alkenyl groups and substituted or unsubstituted cycloalkyl groups that can optionally contain one or more selected heteroatoms from the group consisting of O, F, N, S, and Si or where each of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹³ is independently selected from straight chain alkyl and alkyl groups that can optionally contain one or more heteroatoms selected from the group consisting of O, F, N, S, and Si; (3) each of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹³ independently has about 3 to about 8 carbon atoms or one or both of R ⁷ , R ⁸ , and R ⁹ together have an average from about 5 to about 7 carbon atoms on a weight basis and R ¹⁰ and R ¹³ together have an average of about 5 to about 7 carbon atoms on a weight basis; (4) the mixture has about 20 to about 80% by weight of one or more of the first ester compounds and about 80 to about 20% by weight of the one or more second ester compounds; (5) the mixture has a larger portion by weight of one or more first ester compounds; (6) at least one of the first and second ester compounds is an ester of n-pentanoic acid, 2-methylbutanoic acid, nhexanoic acid, n-heptanoic acid, 3,3,5-trimethylhexanoic acid, 2ethylhexanoic acid, n- octanoic, n-nonanoic acid, and isononanoic acid, or combinations thereof or at least one of the first and second ester compounds is an ester of n-butyric acid, isobutyric acid, n-pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid , n-hexanoic acid, n-heptanoic acid, noctanoic acid, 2-ethylhexanoic acid, 3,3,5-trimethylhexanoic acid, n-nonanoic acid, decanoic acid, undecanoic acid, undecellic acid, lauric acid, stearic acid, isosearic acid , or combinations thereof; (7) the second ester compound or compounds (b) comprise a diethylester of triethylene glycol; (8) the composition of
Petition 870190097018, of 9/27/2019, p. 65/112
54/55 lubricant is free of lubricant compounds other than the first and second ester compounds or the lubricant composition includes another lubricant or lubricants other than the first and second ester compounds of the mixture with the proviso that the percentage by total weight in the lubricant composition of the other lubricant or lubricants is less than the weight percentage in the lubricant composition of the mixture of the first and second ester compounds, whose other lubricant or lubricants can be selected from the group consisting of polyol ester lubricants (POE ), polyalkylene glycol (PAG) lubricants, polyvinyl ether (PVE) lubricants, and combinations thereof; (9) the lubricant composition includes an additive or additives selected from the group consisting of antioxidants, anti-wear agents, extreme pressure agents, oil agents, anti-foaming agents, metal inactivating agents, better viscosity index, spot depressants spillages, detergent dispersants, stabilizers, metal passivators, corrosion inhibitors, flammability suppressants, acid recoverers, and combinations thereof, which may be about 0.1 to about 5% by weight of the additive or additives; (10) the lubricant composition has a viscosity index of at least about 150, where these characteristics include all values and ends of numerical ranges and combinations thereof and all materials and material combinations described above that can be included in the compositions mentioned for these characteristics. As mentioned, all possible combinations of the listed optional features of these methods are specifically described as modalities. Also specifically described are all combinations of lubricant and coolant including this lubricant composition optionally with any or any combination of more than one of the
Petition 870190097018, of 9/27/2019, p. 66/112
55/55 listed characteristics (1) - (10), in which each combination of lubricant and refrigerant can optionally have any one or more of these characteristics: (11) a minimum miscibility temperature of -40 ° C or less of the lubricant in the refrigerant ; (12) in which the refrigerant is selected from the group consisting of refrigerants R410a, R32, and HFO or combinations of these refrigerants or combinations including these refrigerants; (13) where the refrigerant is greater than about 50% by weight of the lubricant and refrigerant combination or where the lubricant is about 5 to about 20% by weight of the lubricant and refrigerant combination. Also specifically described are all compression-type heat transfer devices comprising any or these described lubricant and refrigerant combinations, which can optionally be a positive displacement compressor or selected from stationary and mobile air conditioning and refrigeration equipment. Also described is a method of lubricating compression refrigeration equipment, comprising the circulation of any of the described lubricant compositions.
[000105] The previous description of the modalities has been provided for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention. Individual elements or characteristics of a particular modality are not generally limited by that particular modality, but where applicable, they are interchangeable and can be used in a selected modality, even if not shown or described specifically. It can also be varied in many ways. Such variations should not be considered a departure from the invention, and all such modifications are intended to be included in the scope of the invention.

权利要求:
Claims (14)
[1]
1. Working fluid for a refrigeration system comprising a compressor, characterized by the fact that it comprises:
an ester-based lubricant comprising a mixture of 20 to 80% by weight of one or more first ester compounds and 20 to 80% by weight of one or more second ester compounds, wherein one or more first ester compounds has a structure represented by:
The
IfiC - ^ - OCII ^ CUR ¹ - (oC] l ₂ CHR ² ) ^ - OCR

[2]
2/6 one or more second ester compounds having a structure represented by:
the o
R_ ^lü —C - Í-OCI] -. CI] R ^L1 J — foci l, CJ IR ^I2 -1 — OCRi '''mã> n where each of R ¹¹ and R ¹² is independently H or methyl ;
each of m and n is independently an integer and m + n is an integer 1 to 10; and
R ¹⁰ and R ¹³ are each independently selected from the group consisting of: alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylalkyl, alkylcycloalkyl, cycloalkylalkyl, alkylalkylalkyl, alkylalkylalkyl, alkylalkyl, alkyl straight or branched chain having 1 to 17 carbon atoms that can be substituted or unsubstituted;
one or more additives selected from the group consisting of: diaryl sulfides, arylalkyl sulfides, dialkyl sulfides, diaryl disulfides, dialkyl disulfides, diaryl polysulfides, arylalkyl polysulphides, dialkyl polysulphides, ditiocarbamates, derivatives 2-mercaptoben-zothiazole, and 2,5-dimercapto-1,3,4-thiadiazole derivatives; and one or more refrigerants selected from the group consisting of: difluoromethane (HFC-32), R410A (an almost azeotropic mixture of difluoromethane (HFC-32) and pentafluoroethane (HFC-125)), and hydrofluoroolefins, in which the lubricant and one or more refrigerants in the working fluid has a minimum miscibility temperature of -40 ° C or less.
2. Working fluid according to claim 1,
Petition 870190097018, of 9/27/2019, p. 69/112
[3]
3/6 characterized by the fact that the one or more first ester compounds or the first or second ether compounds are formed from a carboxylic acid selected from the group consisting of: npentanoic acid, 2-methylbutanoic acid, n-hexanoic acid, nheptanoic acid, 3,3,5-trimethylhexanoic acid, 2-ethylhexanoic acid, n-octanoic acid, n-nonanoic acid, and isononanoic acid.
Working fluid according to claim 1, characterized in that the one or more first ester compounds comprising an ethoxylated glycerol triester and the one or more second ester compounds comprising at least one triethylene glycol diester and a tetraethylene glycol diester.
[4]
4. Working fluid according to claim 1, characterized by the fact that the mixture comprises:
(a) 40 to 60% by weight of one or more first ester compounds and (b) 40 to 60% by weight of one or more second ester compounds, wherein the combined weight of one or more first and second ester compounds together is 100%.
[5]
5. Working fluid according to claim 1, characterized by the fact that the one or more refrigerants comprise a hydrofluoroolefin which is a C2 to C8 fluoroalkene selected from the group consisting of: 3,3,3, -trifluoropropene (HFO- 1234zf), 2,3,3,3, tetrafluoropropene (HFO-1234yf), 1,2,3,3, -tetrafluoropropene (HFO1234ze), cis- and trans-1,3,3,3, -tetrafluoropropene (HFO- 1234ye), 1,1,3,3,3, pentafluoropropene (HFO-1225zc), 1,2,3,3,3, -pentafluoropropene (HFO1225yez), and CF3CCl = CH (HFO-1233xf), CF3CH = CHCl ( HFO-1233zd).
[6]
6. Working fluid according to claim 1, characterized by the fact that the one or more refrigerants comprise a refrigerant selected from the group consisting of:
Petition 870190097018, of 9/27/2019, p. 70/112
4/6 difluoromethane (HFC-32),
3.3.3, -trifluoropropene (HFO-1234zf),
2.3.3.3, -tetrafluoropropene (HFO-1234yf), and
1.2.3.3, -tetrafluoropropene (HFO-1234ze).
[7]
7. Working fluid according to claim 1, characterized by the fact that the ester-based lubricant also includes one or more additional additives selected from the group consisting of: antioxidants, anti-wear agents, extreme pressure agents, oil agents , defoaming agents, metal inactivating agents, better viscosity index, spill point depressants, detergent dispersants, stabilizers, metal passivators, corrosion inhibitors, flammability suppressants and acid recoverers.
[8]
8. Working fluid according to claim 1, characterized by the fact that it has a minimum miscibility temperature of -55 ° C or less.
[9]
9. Working fluid according to claim 1, characterized by the fact that the one or more additives comprise
2.5- dimercapto-1,3,4-thiadiazole or a substituted 2,5-dimercapto-1,3,4-thiadiazole.
[10]
10. Working fluid according to claim 1, characterized by the fact that one or more additives is present in the ester-based lubricant at 0.1 to 5% by weight.
[11]
11. Working fluid according to claim 1, characterized by the fact that the one or more additives is selected from the group consisting of:
2.5- bis (n-octyltin) -1,3,4-thiadiazole, dioctyl disulfide,
2.5- bis (tert-nonildithio) -1,3,4-thiadiazole, and
2.5- bis (n-octyltin) -1,3,4-thiadiazole.
Petition 870190097018, of 9/27/2019, p. 71/112
5 / Q
[12]
12. Working fluid according to claim 1, characterized in that the ester-based lubricant comprises an ester compound formed from a linear or branched carboxylic acid having from 4 to 10 carbon atoms and a polyol selected from the group that consists of:
pentaerythritol, neopentyl glycol, and trimethylpropanol.
[13]
13. Working fluid according to claim 1, characterized by the fact that the one or more first ester compounds represented by the structure:

[14]
14. Working fluid according to claim 1, characterized by the fact that the ester-based lubricant is present in more than or equal to 1% less than or equal to 30% of the working fluid and the refrigerant it is present in more than or equal to 70% less than or equal to 99% by weight.

类似技术:

---

公开号 | 公开日 | 专利标题

---

US9255219B2|2016-02-09|Refrigeration compressor lubricant

---

JP6082704B2|2017-02-15|Refrigerator oil and working fluid composition for refrigerator

---

KR20200101401A|2020-08-27|Refrigeration cycle device

---

US20150307761A1|2015-10-29|Refrigerant-oil composition and cooling-equipment working-fluid composition

---

JP6495318B2|2019-04-03|Refrigerator oil and working fluid composition for refrigerator

---

WO2019123897A1|2019-06-27|Refrigeration cycle device

---

JP5399821B2|2014-01-29|Refrigerator oil and working fluid composition for refrigerator

---

JP5390992B2|2014-01-15|Refrigerator oil and working fluid composition for refrigerator

---

JP5390995B2|2014-01-15|Refrigerator oil and working fluid composition for refrigerator

---

JP5399819B2|2014-01-29|Refrigerator oil and working fluid composition for refrigerator

---

JP5390993B2|2014-01-15|Refrigerator oil and working fluid composition for refrigerator

---

JP2019158233A|2019-09-19|Refrigerating machine, use of refrigerating machine oil, method for suppressing elution of oligomer, refrigerating machine oil, refrigerating machine working fluid composition, and method for manufacturing refrigerating machine oil

---

JP5399820B2|2014-01-29|Refrigerator oil and working fluid composition for refrigerator

---

JP5390994B2|2014-01-15|Refrigerator oil and working fluid composition for refrigerator

---

JP2011207837A|2011-10-20|Ester and refrigerator oil

---

KR20220020930A|2022-02-21|Refrigeration oil and working fluid composition for refrigeration

---

JP2011195726A|2011-10-06|Refrigerating machine oil, and working fluid composition for refrigerating machine

---

JP2011208075A|2011-10-20|Refrigerator oil and working fluid composition for refrigerator

同族专利:

---

公开号 | 公开日

---

RU2571416C2|2015-12-20|

---

WO2012177742A2|2012-12-27|

---

US20130200295A1|2013-08-08|

---

WO2012177742A3|2013-04-25|

---

US20120329689A1|2012-12-27|

---

BR112013033209A2|2017-03-01|

---

EP2723834A2|2014-04-30|

---

RU2013157760A|2015-07-27|

---

US9187682B2|2015-11-17|

---

US9255219B2|2016-02-09|

---

EP2723834A4|2015-03-25|

---

CN103717716B|2017-04-12|

---

CN103717716A|2014-04-09|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2926139A|1952-11-08|1960-02-23|Bayer Ag|Lubricants for refrigerating systems|

---

IT991051B|1973-07-09|1975-07-30|Snam Progetti|ORGANIC ESTERS FOR LUBRICANT COMPOSITIONS|

---

US4234497A|1979-04-30|1980-11-18|Standard Lubricants, Inc.|Iso-palmitate polyol ester lubricants|

---

US4788352A|1986-07-21|1988-11-29|Shell Oil Company|Trifluoroalkenes and a method for their preparation|

---

EP0406433B9|1988-11-11|2007-10-10|Asahi Glass Company Ltd.|Tetrafluoroethane composition for a regrigerator|

---

US6458288B1|1988-12-06|2002-10-01|Idemitsu Kosan Co., Ltd.|Lubricating oil for refrigerator with compressor|

---

EP0377122B1|1988-12-06|1995-06-28|Idemitsu Kosan Company Limited|Use of a specific polyoxyalkylene-glycol derivative as a lubricant for compression-type refrigerators and a method for effecting lubrication and a compression-type refrigerator system comprising it|

---

US4851144A|1989-01-10|1989-07-25|The Dow Chemical Company|Lubricants for refrigeration compressors|

---

US5021180A|1989-01-18|1991-06-04|The Dow Chemical Company|Polyglycol lubricants for refrigeration compressors|

---

JP2624893B2|1989-04-25|1997-06-25|ザルブリゾルコーポレイション|Liquid composition containing carboxylic acid ester|

---

US4971712A|1989-06-02|1990-11-20|E. I. Du Pont De Nemours And Company|Compositions for compression refrigeration and methods of using them|

---

JP2744470B2|1989-06-09|1998-04-28|出光興産株式会社|Lubricating oil composition|

---

US4959169A|1989-10-20|1990-09-25|The Dow Chemical Company|Esterified polyglycol lubricants for refrigeration compressors|

---

GB8924057D0|1989-10-25|1989-12-13|Ici Plc|Lubricants|

---

DE69125518T2|1990-01-31|1997-11-13|Tonen Corp|Esters as lubricants for haloalkane freezers|

---

US5366648A|1990-02-23|1994-11-22|The Lubrizol Corporation|Functional fluids useful at high temperatures|

---

US5080834A|1990-10-18|1992-01-14|Lce Partnership|Branched ether esters as viscosity index modifiers|

---

US5194621A|1991-05-20|1993-03-16|R. T. Vanderbilt Company, Inc.|Ether derivatives of 2,5-dimercapto-1,3,4-thiadiazoles|

---

DE69232218T2|1991-10-11|2002-06-27|Ici Plc|working fluids|

---

JP3038062B2|1991-10-15|2000-05-08|旭電化工業株式会社|Lubricants for refrigerators|

---

ZA928934B|1991-12-06|1994-05-19|Exxon Chemical Patents Inc|Refrigeration working fluid compositions|

---

DE69333851T2|1992-06-03|2006-01-12|Cognis Ip Management Gmbh|A method of making a polyol ester lubricant for high temperature refrigerator compression|

---

JP2613526B2|1992-07-04|1997-05-28|花王株式会社|Composition for working fluid of refrigerator|

---

US5830833A|1992-08-18|1998-11-03|Rwe-Dea Aktiengesellschaft Fur Mineraloel Und Chemie And Texaco Deutschland Gmbh|Synthetic ester lubricants for refrigerator systems|

---

GB2279998B|1993-07-14|1997-04-09|T & N Technology Ltd|Plain bearing|

---

US5512190A|1994-08-22|1996-04-30|Texaco Inc.|Lubricating oil composition providing anti-wear protection|

---

US5866030A|1994-09-07|1999-02-02|Witco Corporation|Enhanced hydrocarbon lubricants for use with immiscible refrigerants|

---

US5858266A|1994-10-05|1999-01-12|Idemitsu Kosan Co., Ltd.|Refrigerating machine oil composition|

---

TW349119B|1996-04-09|1999-01-01|Mitsubishi Gas Chemical Co|Polyol ester based-lubricant|

---

JP3983328B2|1996-04-26|2007-09-26|出光興産株式会社|Refrigerator oil composition|

---

SE9602465D0|1996-06-24|1996-06-24|Perstorp Ab|A lubricant ester|

---

JP4079469B2|1996-06-25|2008-04-23|出光興産株式会社|Refrigerator oil composition|

---

WO1998023444A1|1996-11-26|1998-06-04|Learonal, Inc.|Lead-free deposits for bearing surfaces|

---

US5750750C1|1997-02-07|2001-03-27|Exxon Chemical Patents Inc|High viscosity complex alcohol esters|

---

GB9713079D0|1997-06-21|1997-08-27|T & N Technology Ltd|Manufacture of plain bearings|

---

US5895778A|1997-08-25|1999-04-20|Hatco Corporation|Poly ester based coolants and improved additive package|

---

GB9817249D0|1998-08-07|1998-10-07|Glacier Vandervell Ltd|Bearing material|

---

JP4564111B2|1998-09-02|2010-10-20|Ｊｘ日鉱日石エネルギー株式会社|Refrigeration oil|

---

GB9901667D0|1999-01-26|1999-03-17|Ici Plc|Lubricant composition|

---

DE29914502U1|1999-08-18|1999-11-25|Fuchs Dea Schmierstoffe Gmbh &|Polyether as a lubricant for CO2 chillers|

---

JP4848576B2|2000-04-19|2011-12-28|ダイキン工業株式会社|Refrigeration equipment|

---

US6436881B1|2001-06-01|2002-08-20|Hatco Corporation|High temperature lubricant composition|

---

DE60310412T8|2002-08-21|2008-11-13|Bp Corporation North America Inc., Warrenville|SYNERGISTIC COMBINATION OF ADDITIVES WITH HIGH LOAD CAPACITY AND CORROSION INHIBITORS FOR LUBRICANT COMPOSITIONS|

---

US9085504B2|2002-10-25|2015-07-21|Honeywell International Inc.|Solvent compositions containing fluorine substituted olefins and methods and systems using same|

---

US20040089839A1|2002-10-25|2004-05-13|Honeywell International, Inc.|Fluorinated alkene refrigerant compositions|

---

US7763574B2|2003-10-10|2010-07-27|R.T. Vanderbilt Company, Inc.|Lubricating compositions containing synthetic ester base oil, molybdenum compounds and thiadiazole-based compounds|

---

WO2005085402A1|2004-03-04|2005-09-15|Nippon Oil Corporation|Refrigerating machine oil composition|

---

CN101018844A|2004-09-14|2007-08-15|出光兴产株式会社|Refrigerator oil composition|

---

US7776804B2|2005-03-16|2010-08-17|The Lubrizol Corporation|Viscosity improver compositions providing improved low temperature characteristics to lubricating oil|

---

JP5390738B2|2005-11-15|2014-01-15|出光興産株式会社|Lubricating oil composition for internal combustion engines|

---

EP2428555A1|2006-07-06|2012-03-14|Nippon Oil Corporation|Metalworking oil composition|

---

JP5211752B2|2007-03-29|2013-06-12|日油株式会社|Lubricating oil composition for refrigerator and working fluid composition for refrigerator using the same|

---

KR101477832B1|2007-06-12|2014-12-30|이데미쓰 고산 가부시키가이샤|Lubricant composition for refrigerator and compressor using the same|

---

JP2008308610A|2007-06-15|2008-12-25|Idemitsu Kosan Co Ltd|Refrigerator oil composition|

---

DE102007033902B3|2007-07-20|2008-12-18|Federal-Mogul Wiesbaden Gmbh|Lead-free sintered sliding bearing material and sintered powder for producing the same|

---

EP2215363B1|2007-10-24|2017-06-28|Emerson Climate Technologies, Inc.|Scroll compressor for carbon dioxide refrigerant|

---

EP2719750A1|2007-10-29|2014-04-16|Nippon Oil Corporation|Refrigerator oil and working fluid composition for refrigerating machine|

---

US20090156441A1|2007-12-12|2009-06-18|Rowland Robert G|Cycloalkyl phenylenediamines as deposit control agents for lubricants|

---

US8563489B2|2007-12-12|2013-10-22|Chemtura Corporation|Alkylated 1,3-benzenediamine compounds and methods for producing same|

---

JP5241261B2|2008-02-15|2013-07-17|出光興産株式会社|Lubricating oil composition for refrigerator|

---

US8585385B2|2008-03-21|2013-11-19|Toshiba Carrier Corporation|Refrigerant compressor and refrigerating cycle device|

---

EP2274408B1|2008-04-28|2012-10-17|Dow Global Technologies LLC|Polyalkylene glycol-based wind turbine lubricant compositions|

---

JP2011528394A|2008-07-16|2011-11-17|ダウグローバルテクノロジーズエルエルシー|Refrigerant composition containing silyl-terminated polyalkylene glycol as lubricant and method for producing the same|

---

US8419968B2|2008-11-13|2013-04-16|Chemtura Corporation|Lubricants for refrigeration systems|

---

ES2673993T3|2008-12-23|2018-06-26|Shrieve Chemical Products, Inc.|Lubricant composition for refrigerants|

---

RU2011134285A|2009-01-16|2013-02-27|Кемтура Корпорейшн|CARBON DIOXIDE WORKING FLUIDS FOR AIR COOLING AND AIR CONDITIONING|

---

US20100210487A1|2009-02-16|2010-08-19|Chemtura Coproration|Fatty sorbitan ester based friction modifiers|

---

AU2010303861B2|2009-10-07|2016-03-03|Chemtura Corporation|Lubricants for refrigeration systems|

---

JP5466556B2|2010-03-25|2014-04-09|出光興産株式会社|Lubricating oil composition for refrigerator|

---

BR112012022734A2|2010-04-06|2018-05-22|Chemtura Corp|working fluid for a heat transfer device and process for preparing a polyol ester lubricant composition|

---

RU2013100175A|2010-06-10|2014-07-20|Федерал-Могул Висбаден Гмбх|METHOD FOR PRODUCING LEAD-FREE SLIDING BEARING|

---

JP2012012532A|2010-07-02|2012-01-19|Panasonic Corp|Compressor and refrigerating cycle equipment|

---

US9187682B2|2011-06-24|2015-11-17|Emerson Climate Technologies, Inc.|Refrigeration compressor lubricant|

---

US20140024563A1|2012-07-23|2014-01-23|Emerson Climate Technologies, Inc.|Anti-wear coatings for compressor wear surfaces|

---

US20150147012A1|2013-11-27|2015-05-28|Emerson Climate Technologies, Inc.|Bearing performance for compressors using high energy refrigerants with sulfur-based oil additives|JP2016513166A|2013-02-25|2016-05-12|ハネウェル・インターナショナル・インコーポレーテッド|Composition comprising difluoromethane and fluorine-substituted olefin|

---

US8980118B2|2009-05-08|2015-03-17|Honeywell International Inc.|Heat transfer compositions and methods|

---

US9187682B2|2011-06-24|2015-11-17|Emerson Climate Technologies, Inc.|Refrigeration compressor lubricant|

---

EP3249230B1|2015-01-13|2019-08-21|Fujitsu General Limited|Rotary compressor|

---

US10253232B2|2015-02-10|2019-04-09|Patech Fine Chemicals Co., Ltd.|Method of lubricating a rotary screw compressor|

---

TWI522456B|2015-03-27|2016-02-21|Novel refrigeration oil|

---

KR20170133340A|2015-03-30|2017-12-05|이데미쓰 고산 가부시키가이샤|Mixing composition for refrigerator lubricating oil and refrigerator|

---

CN107429953A|2015-03-30|2017-12-01|开利公司|Low oily refrigerant and steam compression system|

---

US9683158B2|2015-06-26|2017-06-20|Lanxess Solutions Us, Inc.|Working fluids comprising fluorinated olefins and polyol esters|

---

US20170314825A1|2016-04-29|2017-11-02|Emerson Climate Technologies, Inc.|Co-fluid refrigeration system and method|

---

FR3056222B1|2016-09-19|2020-01-10|Arkema France|COMPOSITION BASED ON 1-CHLORO-3,3,3-TRIFLUOROPROPENE|

---

FR3057272B1|2016-10-10|2020-05-08|Arkema France|AZEOTROPIC COMPOSITIONS BASED ON TETRAFLUOROPROPENE|

---

FR3057271B1|2016-10-10|2020-01-17|Arkema France|USE OF TETRAFLUOROPROPENE COMPOSITIONS|

---

JP6937108B2|2016-11-04|2021-09-22|日立ジョンソンコントロールズ空調株式会社|Electric compressor and freezing air conditioner|

---

EP3556829B1|2016-12-13|2022-02-23|Kao Corporation|Lubricant base oil and lubricant composition including said lubricant base oil|

---

FR3061905B1|2017-01-19|2019-05-17|Arkema France|COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE|

---

FR3061906B1|2017-01-19|2019-03-15|Arkema France|COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE|

---

FR3063733B1|2017-03-10|2020-02-07|Arkema France|QUASI-AZEOTROPIC COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE AND TRANS-1,3,3,3-TETRAFLUOROPROPENE|

---

FR3064264B1|2017-03-21|2019-04-05|Arkema France|COMPOSITION BASED ON TETRAFLUOROPROPENE|

---

CA3062327A1|2017-05-05|2018-11-08|Honeywell International Inc.|Heat transfer compositions, methods and systems|

---

FR3067035B1|2017-06-02|2020-10-30|Arkema France|COMPOSITIONS BASED ON TRIFLUOROETHYLENE, AND THEIR USES|

---

FR3069864B1|2017-08-03|2019-08-16|Total Marketing Services|LUBRICATING COMPOSITION COMPRISING A DIESTER|

---

US10731066B2|2017-11-17|2020-08-04|Honeywell International Inc.|Heat transfer compositions, methods and systems|

---

US20190161662A1|2017-11-30|2019-05-30|Honeywell International Inc.|Heat transfer compositions, methods, and systems|

---

US10883063B2|2018-01-23|2021-01-05|The Chemours Company Fc, Llc|Compositions, system and methods for introducing PAG lubricant or refrigerant into an air-conditioning or system using lower or low GWP refrigerant or refrigerant blends|

---

FR3077822B1|2018-02-15|2020-07-24|Arkema France|REPLACEMENT HEAT TRANSFER COMPOSITIONS FOR R-134A|

---

FR3077773A1|2018-02-15|2019-08-16|Arkema France|METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE|

---

US11214724B1|2020-07-30|2022-01-04|Saudi Arabian Oil Company|Epoxidized alpha olefin based lubricant for water-based drilling fluids|

法律状态:
2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-07-02| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

---

2020-02-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2020-03-31| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |

---

2021-04-20| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 9A ANUIDADE. |

---

2021-08-10| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2624 DE 20-04-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201161500867P| true| 2011-06-24|2011-06-24|

---

US61/500,867|2011-06-24|

---

US13/526,971|2012-06-19|

---

US13/526,971|US9187682B2|2011-06-24|2012-06-19|Refrigeration compressor lubricant|

---

PCT/US2012/043319|WO2012177742A2|2011-06-24|2012-06-20|Refrigeration compressor lubricant|

---