A polyalkoxy ether refrigeration oil composition and its preparation method and application

Abstract

The present invention belongs to the technical field of industrial lubricating oils such as refrigeration oils, and specifically relates to a polyalkoxy ether refrigeration oil composition, a preparation method and an application thereof. The present invention also discloses a preparation method and an application of the composition. The polyalkoxy ether refrigeration oil composition of the present invention adopts a composition of a polypropylene oxide polymer and a polypropylene oxide and a polybutylene oxide block polymer. By changing the polymerization degree and the ratio of the above two components, the two-phase separation temperature of the polyalkoxy ether refrigeration oil composition and R290 refrigerant can be regulated, thereby significantly improving its compatibility with R290 refrigerant.

Description

Technical Field

[0001] The invention belongs to the technical field of industrial lubricating oils such as refrigeration oils, and specifically relates to a polyalkoxy ether refrigeration oil composition and a preparation method and application thereof. Background Art

[0002] In recent years, the refrigerant used in refrigeration oil has been increasingly inclined to use hydrofluorocarbon (HFC) refrigerants with zero ozone depletion potential (ODP) and lower global warming potential (GWP). In household air conditioning refrigeration compressors, R410A, R32, etc. are currently used in large quantities. Although HFC refrigerants do not damage the ozone layer, they bring a greater greenhouse effect. Compared with HFC refrigerants, low-level hydrocarbons with carbon numbers of about 2 to 4 do not damage the ozone layer and have a very low impact on global warming, so they have received more and more attention recently. For example, isobutane (R600a) has been used as a refrigerant for refrigerators, and in particular, propane with a carbon number of 3 (R290) has begun to be used as a refrigerant for household air conditioners.

[0003] As the refrigerator oil used for low-level hydrocarbon refrigerants, the mineral oil, alkylbenzene oil, ester oil, and polyether oil used in existing reports are mostly cycloalkane or paraffin series. But, on the one hand, when using existing mineral oil, alkylbenzene oil, and ester oil as lubricating oil, because the above-mentioned lubricating oil and R290 refrigerant are fully compatible, the viscosity of the lubricating oil will be reduced, and the lubrication performance of the oil will decline, thereby causing the wear resistance and sealing of the compressor to decline, and finally causing the compressor performance and life to be greatly reduced. On the other hand, although polyether oil has been widely used in the automobile air-conditioning compressor oil with R134 as refrigerant, for example, prior art CN103089570A also mentions polyether oil, but this type of polyether oil is incompatible with R290, if the refrigerator oil incompatible with refrigerant is adopted in the refrigeration system, the stratification of oil and refrigerant is easily caused on the evaporator in the refrigeration system, and the refrigerator oil is not easy to return to the compressor of the refrigeration system, thereby causing the moving parts of the compressor to be short of oil, affecting the reliability of the compressor. At the same time, the oil retained in the evaporator will affect the heat exchange efficiency of the evaporator, causing the efficiency of the refrigeration system to decrease.

[0004] Therefore, there is a need to further develop refrigeration oils having more suitable compatibility or solubility with refrigerants. Summary of the invention

[0005] In order to improve the above technical problems, the present invention provides a composition comprising a compound A shown in the following formula:

[0006]

[0007] and

[0008] Compound B is shown in the following formula:

[0009]

[0010] Wherein, R1 and R3 are the same or different and are independently selected from hydrogen or C 1-6 alkyl;

[0011] R2 and R4 are selected from hydrogen;

[0012] m is a number between 2.5 and 40;

[0013] n is a number between 0.5 and 40;

[0014] p is a number between 0.5 and 35.

[0015] According to an embodiment of the present invention, the composition is a refrigeration oil composition, for example, a polyalkoxy ether refrigeration oil composition.

[0016] According to an embodiment of the present invention, the compound A is a polyalkoxy ether base oil formed by polymerization of propylene oxide; and the compound B is a polyalkoxy ether base oil formed by block polymerization of propylene oxide and butylene oxide.

[0017] According to an embodiment of the present invention, m, n, and p respectively represent the average number of added moles of the above-mentioned alkylene oxide, which can be independently selected from integers or decimals.

[0018] According to an embodiment of the present invention, m is an integer or decimal between 5 and 20, such as an integer or decimal between 10 and 18.

[0019] According to an embodiment of the present invention, n is an integer or decimal between 1 and 15, for example, an integer or decimal between 5 and 10.

[0020] According to an embodiment of the present invention, p is an integer or decimal between 1 and 15, for example, an integer or decimal between 1 and 5.

[0021] According to an embodiment of the present invention, based on the total weight of the compound A and the compound B, the mass percentage of the compound A is 10-90%, for example, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%;

[0022] According to an embodiment of the present invention, the mass percentage of compound B can be 10-90%, for example 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%, provided that the sum of the mass percentages of compound A and compound B is 100%.

[0023] According to an embodiment of the present invention, the weight ratio of compound A to compound B can vary in the range of 10:90 to 90:10, for example 70:30 to 30:70, examples of which can be 80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50, 45:50, 40:60, 35:65, 30:70, 25:75 or 20:80.

[0024] According to an embodiment of the present invention, the kinematic viscosity of the composition at 40°C is 10 to 160 mm 2 / s, such as 20~85mm 2 / s, preferably 32~80mm 2 / s, an example of which may be 10mm 2 / s, 20mm 2 / s, 30mm 2 / s, 40mm 2 / s, 50mm 2 / s, 60mm 2 / s, 70mm 2 / s, 80mm 2 / s, 90mm 2 / s、100mm 2 / s, 110mm 2 / s, 120mm 2 / s, 130mm 2 / s, 140mm 2 / s, 150mm 2 / s, 160mm 2 / s.

[0025] According to a preferred embodiment of the present invention, the kinematic viscosity of compound A and compound B at 40°C differs within ±20%, more preferably within ±10%, and further preferably within ±5%. The kinematic viscosity difference ratio of compound A to compound B is calculated by formula (1):

[0026] Phase difference ratio=(kinematic viscosity of compound A-kinematic viscosity of compound B) / kinematic viscosity of compound B x 100%.

[0027] According to an embodiment of the present invention, the acid value of the composition is not greater than 0.01 mgKOH / g.

[0028] According to an embodiment of the present invention, when the composition is mixed with propane (such as R290) refrigerant with an oil content of 20 wt%, the low-temperature second layer separation temperature is between -45 and 20°C, such as between -25 and 18°C, preferably between -25 and 15°C.

[0029] According to an embodiment of the present invention, the composition may further contain at least one of an acid scavenger, an anti-wear agent and an antioxidant.

[0030] According to an embodiment of the present invention, the composition may also contain an acid capture agent. The acid capture agent includes, but is not limited to, carbodiimide compounds, such as at least one selected from the following: dialkylcarbodiimide, diphenylcarbodiimide, bis(alkylphenyl)carbodiimide, diisopropylcarbodiimide, dicyclohexylcarbodiimide, etc., xylylcarbodiimide, bis(isopropylphenyl)carbodiimide, bis(diisopropylphenyl)carbodiimide, bis(triisopropylphenyl)carbodiimide, bis(butylphenyl)carbodiimide, bis(dibutylphenyl)carbodiimide or bis(nonylphenyl)carbodiimide, etc.

[0031] According to an embodiment of the present invention, the composition may further contain an anti-wear agent. For example, the anti-wear agent includes but is not limited to at least one selected from the following: phosphate, thiophosphate, thioether compound, zinc dialkyl dithiophosphate, triphenyl phosphate (TPP), tricresyl phosphate (TCP) or triphenyl thiophosphate (TPPT) etc.

[0032] According to an embodiment of the present invention, the polyalkoxy ether refrigeration oil composition may further contain an antioxidant, and the antioxidant includes but is not limited to di-tert-butyl-p-cresol and / or alkyl diphenylamine.

[0033] The present invention also provides a fluid composition comprising the composition described above and a refrigerant. Preferably, the composition is used as a refrigeration oil.

[0034] According to an embodiment of the present invention, the refrigerant is selected from alkane refrigerants, such as R290 refrigerant (propane refrigerant).

[0035] The present invention also provides application of the above composition or fluid composition in compression refrigeration, air conditioning or heat pump system.

[0036] The present invention also provides a method for preparing the above composition, which comprises mixing compound A with compound B.

[0037] Preferably, the preparation method further comprises testing the kinematic viscosity of compound A and compound B before mixing, for example, the kinematic viscosity at 40°C; more preferably, compound A and compound B are selected so that the kinematic viscosity at 40°C differs within ±20%, more preferably within ±10%, and further preferably within ±5%.

[0038] Preferably, the preparation method further comprises selecting compound A, compound B and / or their ratio so that the kinematic viscosity of the composition, for example, the kinematic viscosity at 40° C. is 10 to 160 mm 2 / s, preferably 20~85mm2 / s, for example, 32 to 80 mm 2 / s.

[0039] Alternatively, the preparation method may further include a method for preparing compound A and / or compound B.

[0040] According to an embodiment of the present invention, the method for preparing compound A comprises subjecting propylene oxide to a polymerization reaction in the presence of an initiator and a catalyst to obtain compound A.

[0041] According to an embodiment of the present invention, the method for preparing compound B includes polymerizing propylene oxide and butylene oxide in the presence of an initiator and a catalyst to obtain compound B.

[0042] Preferably, in the method for preparing compound A or B, the polymerization reaction is carried out in an atmosphere inert to the reaction, such as a nitrogen atmosphere.

[0043] Preferably, in the method for preparing compound A or B, the reaction temperature is above 80°C, for example, 100-150°C, such as 110-120°C.

[0044] Preferably, in the preparation method of compound A or B, the initiator can be selected from at least one of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, n-butanol, etc. As an example, in the preparation method of compound A, the initiator can be selected from at least one of ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; in the preparation method of compound B, the initiator can be selected from at least one of ethylene glycol, propylene glycol, and n-butanol.

[0045] Preferably, in the preparation method of compound A, the catalyst can be selected from at least one of alkali metal hydroxides or compounds in which the hydrogen of the alcoholic hydroxyl group is substituted by an alkali metal, such as at least one of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.

[0046] According to an embodiment of the present invention, the preparation method of compound A or B further comprises purifying the crude product obtained from the polymerization reaction to obtain compound A or B. Preferably, the purification comprises adding water, phosphoric acid and magnesium silicate polyether refining agent, as well as dehydration and filtration steps.

[0047] As an example, 1-5 wt% of deionized water, 0.15-0.45 wt% of phosphoric acid, and 0.03-0.1 wt% of magnesium silicate polyether refining agent are added to the crude product.

[0048] Preferably, after adding water, phosphoric acid and magnesium silicate polyether refining agent, the obtained mixture is stirred at 75-95° C. for 1-2 hours, then vacuum dehydrated until the water content reaches below 0.01%, and then circulated and filtered to finally obtain compound A or B.

[0049] The present invention also provides a method for preparing the fluid composition, comprising mixing the composition described above with a refrigerant.

[0050] Definition and explanation of terms

[0051] Unless otherwise defined, all technical terms herein have the same meaning as those commonly understood by those skilled in the art to which the subject matter of the claims belongs. Unless otherwise indicated, all patents, patent applications, and public materials cited in the entirety of this article are incorporated herein by reference in their entirety.

[0052] It should be understood that the above brief description and the following detailed description are exemplary and are only used for explanation, and do not limit the subject matter of the present application in any way. In the present application, unless otherwise specifically stated, the use of the singular also includes the plural. It should also be noted that, unless otherwise stated, the use of "or" or "or" means "and / or". In addition, the use of the term "including" and other forms, such as "including", "containing" and "containing" are not intended to be restrictive.

[0053] When the numerical range described in the specification and claims of this application is defined as "a number" or "selected from an integer or a decimal", it should be understood that the two endpoints of the range, each integer within the range and each decimal within the range are recorded. For example, "a number between 0.5 and 40" should be understood as recording not only the endpoint values ​​0.5 and 40, but also each integer of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 ... 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 between the endpoint values, and the sum of any of the above values ​​and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, provided that the sum does not exceed the range of 0.5-40; "a number between 0.5 and 35" should be understood as recording not only the endpoint values ​​0.5 and 35, but also each integer of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 ... 30 between the endpoint values. , 31, 32, 33, 34, 35, and the sum of any of the above values ​​and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, provided that the sum does not exceed the range of 0.5-35; "numbers between 2.5 and 40" should be understood as not only recording the endpoint values ​​2.5 and 40, but also recording each integer of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15...30, 31, 32, 33, 34, 35, and the sum of any of the above values ​​and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, provided that the sum does not exceed the range of 2.5-40.

[0054] The term "alkyl" is understood to preferably mean a linear or branched saturated monovalent hydrocarbon radical. 1-6 “Alkyl” is to be understood as meaning preferably a linear or branched, saturated, monovalent hydrocarbon radical having 1, 2, 3, 4, 5 or 6 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl (2-methylpropyl), sec-butyl (1-methylpropyl), tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2-dimethylbutyl.

[0055] It should be understood that, unless otherwise defined, when the prefix "n-" is omitted when describing, alkyl groups such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, etc. should be understood as n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl.

[0056] Beneficial effects:

[0057] The inventors unexpectedly found that different ratios of oxypropylene groups and oxybutylene groups can change the compatibility of the refrigeration oil with R290, and increasing the ratio of oxybutylene groups in the composition can improve the compatibility of the refrigeration oil with R290. The polyalkoxy ether refrigeration oil composition of the present invention uses a composition of a polypropylene oxide polymer and a polypropylene oxide and a polybutylene oxide block polymer. By changing the polymerization degree and ratio of the above two components, the two-phase separation temperature of the polyalkoxy ether refrigeration oil composition and the R290 refrigerant can be controlled, thereby significantly improving its compatibility with the R290 refrigerant. DETAILED DESCRIPTION

[0058] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technical schemes implemented, modified or adjusted based on the above content of the present invention are included in the scope of protection of the present invention.

[0059] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0060] Example 1

[0061] Preparation method of polyalkoxy ether base oil A:

[0062] First, 35g of propylene glycol and 2g of potassium hydroxide catalyst are added to the reactor in sequence, and the reaction is replaced with nitrogen for 2 to 3 times. The reaction is vacuumed to 0.07Mpa, the temperature is raised to 110°C, and 965g of propylene oxide is continuously introduced. The reaction temperature is controlled not to exceed 120°C. After the feeding is completed, the reaction is aged and absorbed for 0.5h, vacuumed for 10min, and the material is cooled and discharged to obtain crude ether. Subsequently, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent are added to the crude ether, and the mixture is stirred at 75°C for 1h, and then vacuum dehydrated until the moisture content reaches less than 0.01%, and then cyclic filtration is performed to finally obtain polyalkoxy ether base oil A.

[0063] The average molar addition number m of propylene oxide in the prepared polyalkoxy ether base oil A was 33.

[0064] Preparation method of polyalkoxy ether base oil B:

[0065] First, 36g of propylene glycol and 2g of potassium methoxide catalyst are added to the reactor in sequence, and nitrogen is replaced 2 to 3 times. The reaction kettle is evacuated to 0.07Mpa, the temperature is raised to 110°C, and 725g of propylene oxide is continuously introduced to control the reaction temperature not to exceed 120°C. After the feeding is completed, the reaction kettle is aged and absorbed for 0.5h, and the reaction temperature is maintained at 120°C. Then, 245g of butylene oxide is introduced to continue the reaction, and the reaction is evacuated for 5min. The material is cooled and discharged to obtain crude ether. Then, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent are added to the crude ether, and the mixture is stirred at 75°C for 1h, and then vacuum dehydrated until the moisture content reaches less than 0.01%, and then cyclic filtration is performed to finally obtain polyalkoxy ether base oil B.

[0066] The average molar addition number n of propylene oxide of the prepared polyalkoxy ether base oil B is 26.5, and the average molar addition number p of butylene oxide is 6.

[0067] Preparation of polyalkoxy ether refrigeration oil composition:

[0068] The polyalkoxy ether base oils A and B were mixed in weight percentages of 70:30, 65:35, 60:40, 50:50, 40:60 and 30:70, respectively, and stirred evenly to obtain a polyalkoxy ether refrigeration oil composition.

[0069] Example 2

[0070] Preparation method of polyalkoxy ether base oil A:

[0071] First, 50g of propylene glycol and 2g of potassium hydroxide catalyst were added to the reactor in sequence, and the reaction was replaced with nitrogen for 3 times. The reaction was evacuated to 0.08Mpa, the temperature was raised to 120°C, and 950g of propylene oxide was continuously introduced. The reaction temperature was controlled at 120°C. After the feeding was completed, the reaction was aged and absorbed for 1h, and the reaction was evacuated for 10min. The crude ether was then cooled and discharged to obtain a crude ether. Subsequently, 10g of deionized water, 3g of phosphoric acid, and 1g of a magnesium silicate polyether refining agent were added to the crude ether. The mixture was stirred at 85°C for 1.5h, and then vacuum dehydrated until the moisture content was less than 0.01%, and then cyclic filtration was performed to finally obtain a polyalkoxy ether base oil A.

[0072] The average molar addition number m of propylene oxide of the prepared polyalkoxy ether base oil A was 25.5.

[0073] Preparation method of polyalkoxy ether base oil B:

[0074] First, 50g of propylene glycol and 2g of potassium methoxide catalyst were added to the reactor in sequence, and the reaction was replaced with nitrogen for 3 times. The reaction was evacuated to 0.08Mpa, and the temperature was raised to 120°C. 690g of propylene oxide was continuously introduced, and the reaction temperature was controlled at 120°C. After the feeding was completed, the reaction was aged and absorbed for 1h, and the reaction temperature was maintained at 120°C. Then, 270g of butylene oxide was introduced, and the reaction was continued. The reaction was evacuated for 15min, and the material was cooled and discharged to obtain crude ether. Then, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent were added to the crude ether, and the mixture was stirred at 90°C for 1.5h, and then vacuum dehydrated until the moisture content reached less than 0.01%, and then cyclic filtration was performed to finally obtain polyalkoxy ether base oil B.

[0075] The average molar addition number n of propylene oxide of the prepared polyalkoxy ether base oil B is 19, and the average molar addition number p of butylene oxide is 6.

[0076] Preparation of polyalkoxy ether refrigeration oil composition:

[0077] The polyalkyl polyether base oils A and B were mixed in weight percentages of 70:30, 65:35, 60:40, 50:50, 40:60 and 30:70, respectively, and stirred evenly to obtain a polyalkoxy ether refrigeration oil composition.

[0078] Example 3

[0079] Preparation method of polyalkoxy ether base oil A:

[0080] First, 76g of propylene glycol and 2g of potassium hydroxide catalyst were added to the reactor in sequence, and the reaction was replaced with nitrogen for 3 times. The reaction was evacuated to 0.06Mpa, the temperature was raised to 110°C, and 950g of propylene oxide was continuously introduced. The reaction temperature was controlled not to exceed 120°C. After the feeding was completed, the reaction was aged and absorbed for 0.5h, and the reaction was evacuated for 10min. The crude ether was then cooled and discharged to obtain a crude ether. Subsequently, 10g of deionized water, 3g of phosphoric acid, and 1g of a magnesium silicate polyether refining agent were added to the crude ether. The reaction was stirred at 90°C for 1h, and then vacuum dehydrated until the moisture content was less than 0.01%, and then cyclic filtration was performed to finally obtain a polyalkoxy ether base oil A.

[0081] The average molar addition number m of propylene oxide of the prepared polyalkoxy ether base oil A was 17.1.

[0082] Preparation method of polyalkoxy ether base oil B:

[0083] First, 65g of propylene glycol and 2g of potassium methoxide catalyst were added to the reactor in sequence, and the reaction was replaced with nitrogen twice. The reaction was evacuated to 0.07Mpa, and the temperature was raised to 115°C. 700g of propylene oxide was continuously introduced, and the reaction temperature was controlled at 115°C. After the feeding was completed, the aging absorption was performed for 0.5h, and the reaction temperature was maintained at 120°C. Then, 250g of butylene oxide was introduced, and the reaction was continued. The reaction was evacuated for 10min, and the material was cooled and discharged to obtain crude ether. Then, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent were added to the crude ether, and the mixture was stirred at 80°C for 1h, and then vacuum dehydrated until the moisture content reached less than 0.01%, and then cyclic filtration was performed to finally obtain polyalkoxy ether base oil B.

[0084] The average molar addition number n of propylene oxide of the prepared polyalkoxy ether base oil B is 14, and the average molar addition number p of butylene oxide is 4.

[0085] Preparation of polyalkoxy ether refrigeration oil composition:

[0086] The polyalkoxy ether base oils A and B were mixed in weight percentages of 70:30, 65:35, 60:40, 50:50, 40:60 and 30:70, respectively, and stirred evenly to obtain a polyalkoxy ether refrigeration oil composition.

[0087] Example 4

[0088] Preparation method of polyalkoxy ether base oil A:

[0089] First, 76g of propylene glycol and 2g of potassium hydroxide catalyst were added to the reactor in sequence, and the reaction was replaced with nitrogen for 3 times. The reaction was evacuated to 0.08Mpa, the temperature was raised to 120°C, and 680g of propylene oxide was continuously introduced. The reaction temperature was controlled at 120°C. After the feeding was completed, the reaction was aged and absorbed for 1h, and the reaction was evacuated for 10min. The crude ether was then cooled and discharged to obtain a crude ether. Subsequently, 10g of deionized water, 3g of phosphoric acid, and 1g of a magnesium silicate polyether refining agent were added to the crude ether. The mixture was stirred at 85°C for 1.5h, and then vacuum dehydrated until the moisture content was less than 0.01%, and then cyclically filtered to finally obtain a polyalkoxy ether base oil A.

[0090] The average molar addition number m of propylene oxide of the prepared polyalkoxy ether base oil A was 11.5.

[0091] Preparation method of polyalkoxy ether base oil B:

[0092] First, 95g of propylene glycol and 2g of potassium methoxide catalyst were added to the reactor in sequence, and the reaction was replaced with nitrogen for 3 times. The reaction was evacuated to 0.08Mpa, and the temperature was raised to 120°C. 655g of propylene oxide was continuously introduced, and the reaction temperature was controlled at 120°C. After the feeding was completed, the reaction was aged and absorbed for 1h, and the reaction temperature was maintained at 120°C. Then, 255g of butylene oxide was introduced, and the reaction was continued. The reaction was evacuated for 15min, and the material was cooled and discharged to obtain crude ether. Then, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent were added to the crude ether, and the mixture was stirred at 90°C for 1.5h, and then vacuum dehydrated until the moisture content reached less than 0.01%, and then cyclic filtration was performed to finally obtain polyalkoxy ether base oil B.

[0093] The average molar addition number n of propylene oxide of the prepared polyalkoxy ether base oil B is 9, and the average molar addition number p of butylene oxide is 2.8.

[0094] Preparation of polyalkoxy ether refrigeration oil composition:

[0095] The polyalkyl polyether base oils A and B were mixed in weight percentages of 70:30, 65:35, 60:40, 50:50, 40:60 and 30:70, respectively, and stirred evenly to obtain a polyalkoxy ether refrigeration oil composition.

[0096] Example 5

[0097] Preparation method of polyalkoxy ether base oil A:

[0098] First, 140g of propylene glycol and 2g of potassium hydroxide catalyst were added to the reactor in sequence, and the reaction was replaced with nitrogen twice. The reaction was evacuated to 0.07Mpa, the temperature was raised to 115°C, and 860g of propylene oxide was continuously introduced. The reaction temperature was controlled not to exceed 120°C. After the feeding was completed, the reaction was aged and absorbed for 0.5h, and the reaction was evacuated for 10min. The crude ether was then added with 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent, and the mixture was stirred at 90°C for 1h. The mixture was then vacuum dehydrated until the moisture content was less than 0.01%, and then cyclic filtration was performed to finally obtain polyalkoxy ether base oil A.

[0099] The average molar addition number m of propylene oxide of the prepared polyalkoxy ether base oil A was 8.1.

[0100] Preparation method of polyalkoxy ether base oil B:

[0101] First, 135g of propylene glycol and 2g of potassium methoxide catalyst were added to the reactor in sequence, and the reaction was replaced with nitrogen for 3 times. The reaction was evacuated to 0.08Mpa, and the temperature was raised to 120°C. 650g of propylene oxide was continuously introduced, and the reaction temperature was controlled at 120°C. After the feeding was completed, the reaction was aged and absorbed for 1h, and the reaction temperature was maintained at 120°C. Then, 220g of butylene oxide was introduced, and the reaction was continued. The reaction was evacuated for 10min, and the material was cooled and discharged to obtain crude ether. Then, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent were added to the crude ether, and the mixture was stirred at 85°C for 2h, and then vacuum dehydrated until the moisture content reached less than 0.01%, and then cyclic filtration was performed to finally obtain polyalkoxy ether base oil B.

[0102] The average molar addition number n of propylene oxide of the prepared polyalkoxy ether base oil B is 6.3, and the average molar addition number p of butylene oxide is 1.7.

[0103] Preparation of polyalkoxy ether refrigeration oil composition:

[0104] The polyalkyl polyether base oils A and B were mixed in weight percentages of 70:30, 65:35, 60:40, 50:50, 40:60 and 30:70, respectively, and stirred evenly to obtain a polyalkoxy ether refrigeration oil composition.

[0105] Example 6

[0106] Preparation method of polyalkoxy ether base oil A:

[0107] First, 200g of propylene glycol and 2g of potassium hydroxide catalyst are added to the reactor in sequence, and nitrogen is replaced for 2 to 3 times. The reaction kettle is evacuated to no more than 0.09Mpa, and the temperature is raised to 120°C. 800g of propylene oxide is continuously introduced, and the reaction temperature is controlled not to exceed 120°C. After the feeding is completed, the reaction kettle is aged and absorbed for 0.5h, and the reaction kettle is evacuated for 10min. The reaction kettle is cooled and discharged to obtain crude ether. Then, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent are added to the crude ether, and the mixture is stirred at 90°C for 1h, and then vacuum dehydrated until the moisture content reaches less than 0.01%, and then cyclic filtration is performed to finally obtain polyalkoxy ether base oil A.

[0108] The average molar addition number m of propylene oxide of the prepared polyalkoxy ether base oil A was 5.5.

[0109] Preparation method of polyalkoxy ether base oil B:

[0110] First, 185g of propylene glycol and 2g of potassium methoxide catalyst are added to the reactor in sequence, and nitrogen is replaced for 2 to 3 times. The reaction kettle is evacuated to no more than 0.09Mpa, and the temperature is raised to 115°C. 610g of propylene oxide is continuously introduced, and the reaction temperature is controlled not to exceed 120°C. After the feeding is completed, the reaction kettle is aged and absorbed for 1h, and the reaction temperature is maintained at 120°C. Then, 210g of butylene oxide is introduced, and the reaction is continued. The reaction is evacuated for 10min, and the material is cooled and discharged to obtain crude ether. Then, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent are added to the crude ether, and the mixture is stirred at 90°C for 2h, and then vacuum dehydrated until the moisture content reaches less than 0.01%, and then cyclic filtration is performed to finally obtain polyalkoxy ether base oil B.

[0111] The average molar addition number n of propylene oxide of the prepared polyalkoxy ether base oil B is 4.3, and the average molar addition number p of butylene oxide is 1.3.

[0112] Preparation of polyalkoxy ether refrigeration oil composition:

[0113] The polyalkyl polyether base oils A and B were mixed in weight percentages of 70:30, 65:35, 60:40, 50:50, 40:60 and 30:70, respectively, and stirred evenly to obtain a polyalkoxy ether refrigeration oil composition.

[0114] Comparative Example 1: Polyether base oil A of Example 1

[0115] Comparative Example 2: Polyether base oil B of Example 1

[0116] Comparative Example 3: Polyether base oil A of Example 2

[0117] Comparative Example 4: Polyether base oil B of Example 2

[0118] Comparative Example 5: Polyether base oil A of Example 3

[0119] Comparative Example 6: Polyether base oil B of Example 3

[0120] Comparative Example 7: Polyether base oil A of Example 4

[0121] Comparative Example 8: Polyether base oil B of Example 4

[0122] Comparative Example 9: Polyether base oil A of Example 5

[0123] Comparative Example 10: Polyether base oil B of Example 5

[0124] Comparative Example 11: Polyether base oil A of Example 6

[0125] Comparative Example 12: Polyether base oil B of Example 6

[0126] Comparative Example 13:

[0127] Preparation method of polyalkoxy ether base oil A:

[0128] First, 580g of propylene glycol and 2g of potassium hydroxide catalyst are added to the reactor in sequence, and the reaction is replaced with nitrogen for 2 to 3 times. The reaction is vacuumed to 0.07Mpa, the temperature is raised to 110°C, and 420g of propylene oxide is continuously introduced. The reaction temperature is controlled not to exceed 120°C. After the feeding is completed, the reaction is aged and absorbed for 0.5h, vacuumed for 10min, and the material is cooled and discharged to obtain crude ether. Subsequently, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent are added to the crude ether, and the mixture is stirred at 75°C for 1h, and then vacuum dehydrated until the moisture content reaches less than 0.01%, and then cyclic filtration is performed to finally obtain polyalkoxy ether base oil A.

[0129] The average molar addition number m of propylene oxide of the prepared polyalkoxy ether base oil A was 1.0.

[0130] Preparation method of polyalkoxy ether base oil B:

[0131] First, 580g of propylene glycol and 2g of potassium methoxide catalyst are added to the reactor in sequence, and the reaction is replaced with nitrogen for 2 to 3 times. The reaction is vacuumed to 0.07Mpa, the temperature is raised to 110°C, and 310g of propylene oxide is continuously introduced to control the reaction temperature not to exceed 120°C. After the feeding is completed, the reaction is aged and absorbed for 0.5h, and the reaction temperature is maintained at 120°C. Then, 110g of butylene oxide is introduced to continue the reaction, and the reaction is vacuumed for 5min. The material is cooled and discharged to obtain crude ether. Then, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent are added to the crude ether, and the mixture is stirred at 75°C for 1h, and then vacuum dehydrated until the moisture content reaches less than 0.01%, and then cyclic filtration is performed to finally obtain polyalkoxy ether base oil B.

[0132] The average molar addition number n of propylene oxide of the prepared polyalkoxy ether base oil B is 0.7, and the average molar addition number p of butylene oxide is 0.2.

[0133] Preparation of polyalkoxy ether refrigeration oil composition:

[0134] The polyalkoxy ether base oils A and B are mixed in a weight percentage of 50:50 and stirred evenly to finally obtain a polyalkoxy ether refrigeration oil composition.

[0135] Comparative Example 14:

[0136] Preparation method of polyalkoxy ether base oil A:

[0137] First, 30g of propylene glycol and 2g of potassium hydroxide catalyst are added to the reactor in sequence, and nitrogen is replaced for 2 to 3 times. The reaction kettle is evacuated to 0.07Mpa, the temperature is raised to 110°C, and 970g of propylene oxide is continuously introduced. The reaction temperature is controlled not to exceed 120°C. After the feeding is completed, the reaction kettle is aged and absorbed for 0.5h, and the reaction kettle is evacuated for 10min. The reaction kettle is cooled and discharged to obtain crude ether. Subsequently, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent are added to the crude ether. The reaction kettle is stirred at 75°C for 1h, and then vacuum dehydrated until the moisture content is less than 0.01%, and then cyclic filtration is performed to finally obtain polyalkoxy ether base oil A.

[0138] The average molar addition number m of propylene oxide of the prepared polyalkoxy ether base oil A was 42.

[0139] Preparation method of polyalkoxy ether base oil B:

[0140] First, 580g of propylene glycol and 2g of potassium methoxide catalyst are added to the reactor in sequence, and the reaction is replaced with nitrogen for 2 to 3 times. The reaction is vacuumed to 0.07Mpa, the temperature is raised to 110°C, and 310g of propylene oxide is continuously introduced to control the reaction temperature not to exceed 120°C. After the feeding is completed, the reaction is aged and absorbed for 0.5h, and the reaction temperature is maintained at 120°C. Then, 110g of butylene oxide is introduced to continue the reaction, and the reaction is vacuumed for 5min. The material is cooled and discharged to obtain crude ether. Then, 10g of deionized water, 3g of phosphoric acid, and 1g of magnesium silicate polyether refining agent are added to the crude ether, and the mixture is stirred at 75°C for 1h, and then vacuum dehydrated until the moisture content reaches less than 0.01%, and then cyclic filtration is performed to finally obtain polyalkoxy ether base oil B.

[0141] The average molar addition number n of propylene oxide of the prepared polyalkoxy ether base oil B is 32, and the average molar addition number p of butylene oxide is 10.

[0142] Preparation of polyalkoxy ether refrigeration oil composition:

[0143] The polyalkoxy ether base oils A and B are mixed in a weight percentage of 50:50 and stirred evenly to finally obtain a polyalkoxy ether refrigeration oil composition.

[0144] Test Example 1

[0145] Test method:

[0146] (1) Kinematic viscosity

[0147] The kinematic viscosity of each sample at 40°C was tested according to the determination method described in GB / T 265-1988 "Method for determination of kinematic viscosity and calculation of dynamic viscosity of petroleum products".

[0148] (2) Compatibility

[0149] The test was conducted according to the test method described in SH / T 0699-2000 "Test Method for Compatibility of Refrigerator Oil and Refrigerant", and the compatibility (miscibility) was characterized by the two-phase separation temperature when the polyalkoxy ether refrigeration oil composition sample content was 20 wt%.

[0150] (3) Stability

[0151] Chemical stability: Tested using the SH / T 0698-2000 chemical stability test method for refrigeration oil in refrigeration systems.

[0152] Hydrolysis stability: Referring to SH / T 0698-2000, add steel, copper and aluminum metal test rod materials as catalysts and 2000ppm of water into the beaker containing the polyalkoxy ether refrigeration oil composition sample, then place the beaker in a pressure-resistant stainless steel autoclave, inject a certain amount of R290 refrigerant, and seal the autoclave. Then heat the sealed stainless steel autoclave at 150°C for 14 days, and evaluate the hydrolysis stability of the refrigeration oil and refrigerant based on the appearance and color of the metal test rod material and the acid value of the polyalkoxy ether refrigeration oil after the test. Qualification standard: The acid value of the oil sample after the hydrolysis stability test is not greater than 0.05mgKOH / g.

[0153] Test results:

[0154] The raw material compositions and performance test results of Examples 1-6 and Comparative Examples 1-14 of the present invention are shown in Tables 1 and 2 below, respectively.

[0155] Table 1 Summary of specific composition and performance test results of the embodiments

[0156]

[0157]

[0158] Table 1 (Continued) Summary of specific composition and performance test results of the embodiments

[0159]

[0160]

[0161] Table 2 Summary of specific compositions and performance test results in Comparative Examples 1-14

[0162]

[0163] From the analysis of Table 1, it can be seen that the refrigeration oils in Examples 1-6 have good compatibility and hydrolysis stability with the R290 refrigerant.

[0164] Comparative Examples 1, 3, 5, 7, 9 and 11 are polyalkoxy ethers obtained by polymerization of propylene oxide, which are incompatible with R290 refrigerant, so it is meaningless to continue with other test items.

[0165] Comparative Examples 2, 4, 6, 8, 10 and 12 use block polyalkoxy ethers polymerized from propylene oxide and butylene oxide. Although they all have good compatibility with R290, their two-phase separation temperatures are all below -50°C. When they are combined with the refrigerant, the refrigerant will dilute the viscosity of the refrigeration oil and cause a significant drop in viscosity. The decrease in viscosity will reduce lubricity and cause wear of sliding parts. Therefore, it is meaningless to continue testing other liquid items.

[0166] Comparative Examples 13 and 14 use a composition formed by compounding a polyalkoxy ether polymerized from propylene oxide and a block polyalkoxy ether polymerized from propylene oxide and butylene oxide, but the average molar addition numbers m, n and p of the above-mentioned alkylene oxides do not fully meet the value requirements at the same time. On the one hand, the two-phase separation temperatures of the above-mentioned comparative examples and the R290 refrigerant are both lower than -50°C. On the other hand, the 40°C kinematic viscosities of Comparative Examples 9 and 10 are relatively small and relatively large, respectively, which are two uncommon downstream application viscosity levels. In general, the refrigeration oil of Comparative Example 9 will cause the lubrication performance to fail to meet the application requirements, and the refrigeration oil of Comparative Example 10 has a high energy consumption and cannot meet the application requirements.

[0167] The above is an exemplary description of the embodiments of the present invention. However, the protection scope of the present invention is not limited to the above embodiments. Any modification, equivalent substitution, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A fluid composition, characterized in that: Containing a polyalkoxy ether refrigeration oil composition and R290 refrigerant; The polyalkoxy ether refrigeration oil composition comprises a compound A shown in the following formula: （A） and Compound B is shown in the following formula: （B） Wherein, R1 and R3 are the same or different and are independently selected from hydrogen or C 1-6 alkyl; R2 and R4 are selected from hydrogen; m, n, and p are the average molar addition numbers; m is an integer or decimal between 2.5 and 40; n is an integer or decimal between 0.5 and 40; p is an integer or decimal between 0.5 and 35; The compound A is a polyalkoxy ether base oil formed by polymerization of propylene oxide; the compound B is a polyalkoxy ether base oil formed by block polymerization of propylene oxide and butylene oxide; The kinematic viscosity of the polyalkoxy ether refrigeration oil composition at 40° C. is 10 to 160 mm 2 / s; When the polyalkoxy ether refrigeration oil composition is mixed with R290 refrigerant at an oil content of 20 wt%, the two-layer separation temperature is between -45 and 20°C.

2. The fluid composition according to claim 1, characterized in that m is an integer or decimal between 5 and 20.

3. The fluid composition according to claim 1, characterized in that m is an integer or decimal between 10 and 18.

4. The fluid composition according to claim 1, characterized in that n is an integer or decimal between 1 and 15.

5. The fluid composition according to claim 1, characterized in that n is an integer or decimal between 5 and 10.

6. The fluid composition according to claim 1, characterized in that p is an integer or decimal between 1 and 15.

7. The fluid composition according to claim 1, characterized in that p is an integer or decimal between 1 and 5.

8. The fluid composition according to claim 1, characterized in that In the polyalkoxy ether refrigeration oil composition, based on the total weight of the compound A and the compound B, the mass percentage of the compound A is 10-90%, and the mass percentage of the compound B is 10-90%.

9. The fluid composition according to claim 8, characterized in that The weight ratio of compound A to compound B is 10:90 to 90:

10.

10. The fluid composition according to claim 8, characterized in that The weight ratio of compound A to compound B is 70:30 to 30:

70.

11. The fluid composition according to claim 1, characterized in that The kinematic viscosity of the polyalkoxy ether refrigeration oil composition at 40° C. is 20 to 85 mm 2 / s.

12. The fluid composition according to claim 1, characterized in that The kinematic viscosity of compound A and compound B in the polyalkoxy ether refrigeration oil composition at 40° C. differs within ±20%; Phase difference ratio = (kinematic viscosity of compound A - kinematic viscosity of compound B) / kinematic viscosity of compound B × 100%.

13. The fluid composition according to claim 12, characterized in that The kinematic viscosity of compound A and compound B in the polyalkoxy ether refrigeration oil composition at 40° C. differs within ±10%.

14. The fluid composition according to claim 1, characterized in that The second layer separation temperature is between -25 and 18°C.

15. The fluid composition according to claim 1, characterized in that The polyalkoxy ether refrigeration oil composition further contains at least one of an acid scavenger, an anti-wear agent and an antioxidant.

16. The fluid composition according to claim 15, characterized in that The acid scavenger is selected from carbodiimide compounds.

17. The fluid composition according to claim 15, characterized in that The acid scavenger is selected from at least one of the following: dialkylcarbodiimide, diphenylcarbodiimide, and bis(alkylphenyl)carbodiimide.

18. The fluid composition according to claim 15, characterized in that The acid scavenger is selected from at least one of the following: diisopropylcarbodiimide, dicyclohexylcarbodiimide, xylylcarbodiimide, bis(isopropylphenyl)carbodiimide, bis(diisopropylphenyl)carbodiimide, bis(triisopropylphenyl)carbodiimide, bis(butylphenyl)carbodiimide, bis(dibutylphenyl)carbodiimide or bis(nonylphenyl)carbodiimide.

19. The fluid composition according to claim 15, characterized in that The anti-wear agent is selected from at least one of the following: phosphate esters, thiophosphate esters, thioether compounds, and zinc dialkyl dithiophosphates.

20. The fluid composition of claim 15, wherein: The anti-wear agent is selected from at least one of the following: triphenyl phosphate, tricresyl phosphate or triphenyl thiophosphate.

21. The fluid composition of claim 15, wherein: The antioxidant is selected from di-tert-butyl-p-cresol and / or alkyl diphenylamine.

22. Use of the fluid composition according to any one of claims 1 to 21 in a compression refrigeration, air conditioning or heat pump system.

23. The method for preparing the fluid composition according to any one of claims 1 to 14, characterized in that: The preparation method comprises mixing compound A and compound B for the first time to obtain the polyalkoxy ether refrigeration oil composition, and then mixing the mixture with R290 refrigerant for the second time.

24. The preparation method according to claim 23, characterized in that: The preparation method further comprises testing the kinematic viscosity of compound A and compound B before the first mixing.

25. The preparation method according to claim 24, characterized in that: The kinematic viscosity is the kinematic viscosity at 40°C.

26. The preparation method according to claim 24, characterized in that: After testing the kinematic viscosities of compound A and compound B before the first mixing, compound A and compound B are selected so that the kinematic viscosities at 40°C differ by within ±20%. Phase difference ratio = (kinematic viscosity of compound A - kinematic viscosity of compound B) / kinematic viscosity of compound B × 100%.

27. The preparation method according to claim 26, characterized in that: The kinematic viscosities differed within ±10%.

28. The preparation method according to claim 25, characterized in that: The preparation method further comprises selecting the ratio of compound A to compound B so that the kinematic viscosity of the composition is 10 to 160 mm 2 / s.

29. The preparation method according to claim 28, characterized in that: The kinematic viscosity is 20 to 85 mm 2 / s.

30. The preparation method according to claim 28, characterized in that The kinematic viscosity is 32 to 80 mm 2 / s.

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