CN102746927A - Refrigerator oil composition and method for improving extreme pressure abrasion resistance of refrigerator oil - Google Patents

Refrigerator oil composition and method for improving extreme pressure abrasion resistance of refrigerator oil Download PDF

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CN102746927A
CN102746927A CN2011101003840A CN201110100384A CN102746927A CN 102746927 A CN102746927 A CN 102746927A CN 2011101003840 A CN2011101003840 A CN 2011101003840A CN 201110100384 A CN201110100384 A CN 201110100384A CN 102746927 A CN102746927 A CN 102746927A
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oil composition
machine oil
refrigerated machine
base oil
alkyl
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陈永华
陈晓伟
阎欢
梁宇翔
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention provides a refrigerator oil composition, which includes: A) base oil; and B) an ionic liquid, wherein the component B accounts for 0.01%-0.5% of the component A. Other unnecessary additives, such as an antioxidant, a metal deactivator, a defoaming agent and the like can be added into the composition. The composition of the invention has good extreme pressure abrasion resistance, can maintain the lubricating performance for a long time, and can be used for air-conditioners, refrigerators and other refrigeration equipment. The invention also provides a method for improving the extreme pressure abrasion resistance of refrigerator oil. The method is characterized in that the ionic liquid is added into the base oil, with the ionic liquid accounting for 0.01%-1% of the mass of the base oil.

Description

The method of a kind of refrigerated machine oil composition and raising refrigerator oil extreme pressure and antiwear behavior
Technical field
The present invention relates to a kind of refrigerated machine oil composition, particularly can the long term maintenance lubricity and have a refrigerated machine oil composition of good abrasion resistance.
The invention still further relates to a kind of method that improves the refrigerator oil extreme pressure and antiwear behavior.
Background technology
Main in the past fluorochlorohydrocarbon or the hydrogen fluorochlorohydrocarbon class refrigeration agent of using of compression refrigerating machine; But fluorochlorohydrocarbon or hydrogen fluorochlorohydrocarbon class refrigeration agent destroy and are present in stratospheric ozonosphere; Cause environmental pollution; Therefore its use receives strict restriction in the whole world, uses hydrogen fluorohydrocarbon or hydrocarbon polymer etc. as alternative refrigerant at present.
Because present refrigeration compressor load is increasing; Rotating speed is more and more faster; Novel refrigeration agents such as hydrogen fluorohydrocarbon or hydrocarbon polymer do not contain the chlorine atom; Only depend on the extreme pressure anti-wear of refrigerator oil base oil can satisfy the lubricating requirement of compressor, so in refrigerator oil, must add extreme-pressure anti-friction additive.Traditional with trimethylphenyl SULPHOSUCCINIC ACID ESTER (TCP) be the Phosphorus extreme pressure anti-wear additives of representative owing to thermolysis, hydrolysis or friction chemical reaction takes place on friction surface go bad, exist form sludge, deadlocked, the wear problems of generating heat, can not the long term maintenance lubricity.
Patent 200580030797.9 and 200480043998.8 has been introduced in the refrigerator oil base oil and have been added a certain amount of sulphur content when being the organosulfur compound 35% below, and can obtain can the long term maintenance lubricity and can not stop up the interior capillaceous novel refrigerated machine oil composition of freeze cycle.
Ionic liquid be by certain cationic and negatively charged ion constitute in room temperature or be bordering on the material that is in a liquid state under the room temperature.Ionic liquid has lower fusing point, good electrical conductivity and negligible vp, play an important role at aspects such as chemical separation, catalysis, electrochemistry, but ionic liquid is as the rarely seen report of refrigerator oil additive.
Summary of the invention
The object of the present invention is to provide excellent and the refrigerated machine oil composition that can the long term maintenance lubricity of a kind of extreme pressure and antiwear behavior.
The present invention also provides a kind of method that improves the refrigerator oil extreme pressure and antiwear behavior.
The present invention adds ionic liquid and forms refrigerated machine oil composition in polyvinyl ether (PVE), polyethers or polyol ester class base oil, when refrigeration agents such as use hydrogen fluorohydrocarbon, hydrocarbon polymer, carbonic acid gas, ammonia, hydrocarbon, and can the long term maintenance lubricity.
Specifically, the present invention provides a kind of refrigerated machine oil composition, and this refrigerated machine oil composition comprises: A＞base oil; B＞ionic liquid, wherein B component accounts for 0.01%～0.5% of component A quality.This compsn can also add other non-essential additive, like oxidation inhibitor, metal passivator, skimmer etc.This compsn can use refrigeration agent commonly used, comprises materials such as hydrogen fluorohydrocarbon, hydrocarbon polymer, carbonic acid gas, ammonia, hydrocarbon.
As being used for base oil A of the present invention, can select in glymes, polyethers and the polyol ester class base oil one or more for use.
The structure of glymes base oil is formula as follows:
Figure BSA00000478470700021
R in the above-mentioned formula 1, R 2And R 3Represent that respectively Wasserstoffatoms or carbonatoms are 1～8 alkyl, be preferably 2～4 alkyl, can be identical or different between them; R 4The expression carbonatoms is 1～10 alkano groups, is preferably 2～8 alkano groups, and k representes R 4The repeat number of O, its value are the integer between 0～10, the integer between preferred 0～5; R 5The expression carbonatoms is 1～20 alkyl, is preferably 2～10 alkyl.R 1～R 5In each structural unit, can be the same or different.M is the integer between 1～20 in the formula.
The preferred structure of glymes base oil is formula as follows:
Figure BSA00000478470700022
M in the formula 1Be the integer between 1～20, m 2Be the integer between 1～20, m 1With m 2Sum is the integer between 1～30.
The structure of polyethers base oil is formula as follows:
R in the above-mentioned general formula 6Expression Wasserstoffatoms, carbonatoms are the residue that 1～8 alkyl, alkylidene group, acyl group or polyvalent alcohol are removed hydroxyl; R 7Be that carbonatoms is 2～4 alkylidene group; R 8Be that hydrogen, carbonatoms are 1～10 alkyl or acyl group; n 1Be the integer between 2～20, n 2It is 1～6 integer.
Polyol ester class base oil is meant the carboxylicesters of the multi-hydroxy compound that contains 2 hydroxyls at least, and its structure is shown below:
R 9[OCOR 10] q
R in the above-mentioned formula 9For carbonatoms is 2～12 alkyl, R 10For Wasserstoffatoms or carbonatoms are 1～22 alkyl, q is 2～10 integer, a plurality of [OCOR 10] can be identical, also can be different.Polyol ester in the above-mentioned formula can be R through structure 9(OH) qPolyvalent alcohol and structure be R 10The carboxylic acid of COOH carries out esterification and obtains.
The kinematic viscosity of component A base oil under 40 ℃ that is fit to is 3mm 2/ s～1000mm 2/ s.When viscosity is lower than this scope, the oil film attenuation, lack of lubrication, and when viscosity was higher than this scope, rate of heat exchange descended.Consider that from above-mentioned aspect the kinematic viscosity of base oil under 40 ℃ is preferably 5mm 2/ s～500mm 2The scope of/s is preferably 10mm 2/ s～150mm 2The scope of/s.
As being used for B component ions liquid of the present invention, belong to imidazoles, pyridine, pyrrolidines ionic liquid, its structural formula is (Z +Y -), Z wherein +The expression positively charged ion, Y -The expression negatively charged ion.
Ion liquid positively charged ion Z +Can select structure for use:
Figure BSA00000478470700031
R wherein a, R b, R c, R d, R e, R fGroup can be the same or different; Be selected from Wasserstoffatoms or carbonatoms and be 1～18 alkyl; For example methyl, ethyl, propyl group, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octadecane thiazolinyl, preferred carbonatoms are 4～12 alkyl.
Ion liquid negatively charged ion Y -Can select bisulfate ion HSO for use 3 -, nitrate radical NO 3 -, dihydrogen phosphate H 2PO 4 -, alkyl phosphate root (C nH (2n+1)O) 2PO 2 -, tetrafluoroborate BF 4 -, hexafluoro-phosphate radical PF 6 -, acetate moiety CH 3COO -, methylsulphonic acid root CH 3SO 3 -, Phenylsulfonic acid root C 6H 5SO 3 -, toluene sulfonic acide root CH 3(C 6H 4) SO 3 -, trifluoromethanesulfonic acid root CF 3SO 3 -, two (trifluoromethyl sulfonyl) imines negatively charged ion ((CF 3SO 2) 2N -), two (perfluorination ethylsulfonyl) imines negatively charged ion ((CF 3CF 2SO 2) 2N -) and three (perfluoro-methyl alkylsulfonyl) methane negatively charged ion ((CF 3SO 2) 3C -) in one or more, preferably phosphoric acid dihydro root H 2PO 4 -, alkyl phosphate root (C nH (2n+1)O) 2PO 2 -, tetrafluoroborate BF 4 -, hexafluoro-phosphate radical PF 6 -, acetate moiety CH 3COO -, methylsulphonic acid root CH 3SO 3 -, Phenylsulfonic acid root C 6H 5SO 3 -, toluene sulfonic acide root CH 3(C 6H 4) SO 3 -, trifluoromethanesulfonic acid root CF 3SO 3 -, dihydrogen phosphate H preferably 2PO 4 -, alkyl phosphate root (C nH (2n+1)O) 2PO 2 -, tetrafluoroborate BF 4 -, hexafluoro-phosphate radical PF 6 -, acetate moiety CH 3COO -, methylsulphonic acid root CH 3SO 3 -, Phenylsulfonic acid root C 6H 5SO 3 -, toluene sulfonic acide root CH 3(C 6H 4) SO 3 -
The preferred ionic liquid of the present invention comprises 1-propyl group-3-Methylimidazole mesylate, 1-butyl-3-Methylimidazole dibutyl phosphate, 1-butyl-2; 3-methylimidazole mesylate, 1-hexyl-3-Methylimidazole mesylate, 1-hexyl-3-Methylimidazole dihydrogen phosphate, N-hexyl-3-picoline mesylate, N-hexyl-4-picoline hexafluorophosphate, N-methyl; Butyl pyrrolidine mesylate and N-methyl, one or more in the butyl pyrrolidine a tetrafluoro borate.
B component accounts for 0.01%～1% of component A quality, and is preferred 0.05%～0.8%, and preferably 0.1%～0.4%.
In lubricating oil composition of the present invention, can also cooperate employed additive in refrigerated machine oil composition usually, particularly preferably add oxidation inhibitor, acid scavenger, skimmer and metal passivator.As oxidation inhibitor, do not limit especially, for example can use phenolic antioxidant, amine antioxidants etc.Acid scavenger is in refrigerated machine oil composition, to be the additive that purpose is used with the stability to hydrolysis, for example epoxy compoundss such as phenylglycidyl ether, alkyl glycidyl base ether, aklylene glycol glycidyl ether, cyclohexene oxide, oxidation terminal olefin, epoxidised soybean oil.Consider from the consistency aspect, be preferably phenylglycidyl ether, alkyl glycidyl base ether, aklylene glycol glycidyl ether, cyclohexene oxide, oxidation terminal olefin.As skimmer, can select silicone oil, silicon fluoride wet goods for use.As metal passivator, can select the benzotriazole or derivatives thereof for use.These additives account for 0.005%～5% of refrigerated machine oil composition total mass usually.
The preparation method of refrigerated machine oil composition of the present invention joins heating mixing among the component A with B component, and mixing temperature is between 40 ℃-90 ℃, and mixing time is between 1 hour-6 hours.
A kind of method that improves the refrigerator oil extreme pressure and antiwear behavior is characterized in that, in base oil, adds ionic liquid, and wherein ionic liquid accounts for 0.01%～1% of base oil quality.Said base oil can be selected one or more in glymes, polyethers and the polyol ester class base oil for use, and concrete kind is ditto said.Said ionic liquid belongs to imidazoles, pyridine, pyrrolidines ionic liquid, and concrete kind is ditto said.
Refrigerated machine oil composition of the present invention has good extreme pressure and antiwear behavior, can the long term maintenance lubricity, can be used for refrigeration equipments such as air-conditioning, refrigerator.
Embodiment
Embodiment 1～22 and Comparative Examples 1～22
Preparation contains component A base oil shown in table 1, table 2 and the table 3 and the ion liquid refrigerator oil of B component, and heating mixes the preparation method among the component A in order B component is joined, and mixing temperature is 50 ℃, and mixing time is 2 hours.Estimate the frictional behaviour and the rotten performance of copper of each embodiment and Comparative Examples with SRV frictional testing machines and copper strip test.
The SRV test conditions is: frequency 50Hz, and stroke 1mm, 20 ℃ of temperature, load 200N is referring to the standard NB/SH/T 0847-2010 of National Energy Board.
The copper strip test method is: be immersed in the copper sheet that has polished in a certain amount of refrigerated machine oil composition, be heated to 100 ℃ and keep 4h.When treating off-test, take out copper sheet, after washing, compare, confirm corrosion level with the corrosion Standard colour board.
The prescription composition of each embodiment and Comparative Examples and test-results are shown in table 1, table 2 and table 3.
Employed component A and B component are explained as follows:
Component A
A-1: gather ethyl vinyl ether and gather the IVE multipolymer (gather ethyl vinyl ether: the mol ratio of gathering IVE is 9: 1, and the viscosity under 40 ℃ is 68mm 2/ s, synthetic according to patent 94194373.9 methods)
A-2: repeating unit is a propylene oxide, (viscosity under 40 ℃ is 100mm to two ends for the polyethers of methyl 2/ s, available from Nanjing WeiEr chemical engineering Co., Ltd, trade names are SDDM-68)
A-3: (viscosity under 40 ℃ is 32mm to four esters that tetramethylolmethane and 2 ethyl hexanoic acid generation esterification obtain 2/ s, synthetic according to document " the synthetic and performance of polyol ester class used for refrigerator base oil " method, the document is recorded in 2009 " lubricating oil " the 24th the 4th phase of volume, and the author is Fei Jianqi, Zhao Wei)
B-1:1-butyl-3-Methylimidazole dibutyl phosphate, the Cas registration number is 663199-28-8
Figure BSA00000478470700051
B-2:1-hexyl-3-Methylimidazole mesylate, the Cas registration number is 852509-35-4
Figure BSA00000478470700052
B-3:N-hexyl-3-picoline mesylate, the Cas registration number is 929602-04-0
Figure BSA00000478470700053
The B-4:N-methyl, the butyl pyrrolidine mesylate, the Cas registration number is 501943-05-1
Figure BSA00000478470700054
Above B-1～B-4 ionic liquid is all available from the prompt chemical ltd of last marine origin.
Comparative additive D-1:TCP, Tritolyl Phosphate, the 3rd chemical plant, Beijing
Figure BSA00000478470700055
Comparative additive D-2:TPPT, triphenyl-thiophosphate, Ciba ltd
Figure BSA00000478470700056
Table 1
Figure BSA00000478470700061
What add in the table 1 is the glymes base oil, through the comparison of embodiment and Comparative Examples, can find that the present composition has excellent extreme pressure and antiwear behavior and the performance of copper corruption preferably.
Table 2
Figure BSA00000478470700062
What add in the table 2 is the polyethers base oil, through the comparison of embodiment and Comparative Examples, can find that the present composition has excellent extreme pressure and antiwear behavior and the performance of copper corruption preferably.
Table 3
What add in the table 3 is polyol ester class base oil, through the comparison of embodiment and Comparative Examples, can find that the present composition has excellent extreme pressure and antiwear behavior and the performance of copper corruption preferably.

Claims (15)

1. refrigerated machine oil composition comprises following component:
A＞base oil;
B＞ionic liquid accounts for 0.01%～1% of component A quality.
2. according to the described refrigerated machine oil composition of claim 1, it is characterized in that said ionic liquid is selected from one or more in imidazoles, pyridines and the pyrrolidines ionic liquid.
3. according to the described refrigerated machine oil composition of claim 2, it is characterized in that said ion liquid positively charged ion is selected from one or more of structure:
Figure FSA00000478470600011
R wherein a, R b, R c, R d, R e, R fIt is 1～18 alkyl that group is selected from Wasserstoffatoms or carbonatoms.
4. according to the described refrigerated machine oil composition of claim 3, it is characterized in that described R a, R b, R c, R d, R e, R fIt is 4～12 alkyl that group is selected from carbonatoms.
5. according to the described refrigerated machine oil composition of claim 2; It is characterized in that said ion liquid negatively charged ion is selected from one or more in bisulfate ion, nitrate radical, dihydrogen phosphate, alkyl phosphate root, tetrafluoroborate, hexafluoro-phosphate radical, acetate moiety, methylsulphonic acid root, Phenylsulfonic acid root, toluene sulfonic acide root, trifluoromethanesulfonic acid root, bis trifluoromethyl alkylsulfonyl imines negatively charged ion, the fluorinated ethyl of enjoying a double blessing alkylsulfonyl imines negatively charged ion and the three perfluoro-methyl alkylsulfonyl methane negatively charged ion.
6. according to the described refrigerated machine oil composition of claim 2; It is characterized in that said ion liquid negatively charged ion is selected from one or more in dihydrogen phosphate, alkyl phosphate root, tetrafluoroborate, hexafluoro-phosphate radical, acetate moiety, methylsulphonic acid root, Phenylsulfonic acid root, toluene sulfonic acide root and the trifluoromethanesulfonic acid root.
7. according to the described refrigerated machine oil composition of claim 2; It is characterized in that; Said ionic liquid is selected from 1-propyl group-3-Methylimidazole mesylate, 1-butyl-3-Methylimidazole dibutyl phosphate, 1-butyl-2; 3-methylimidazole mesylate, 1-hexyl-3-Methylimidazole mesylate, 1-hexyl-3-Methylimidazole dihydrogen phosphate, N-hexyl-3-picoline mesylate, N-hexyl-4-picoline hexafluorophosphate, N-methyl; Butyl pyrrolidine mesylate and N-methyl, one or more in the butyl pyrrolidine a tetrafluoro borate.
8. according to the described refrigerated machine oil composition of claim 1, it is characterized in that said ionic liquid accounts for 0.05%～0.8% of base oil quality.
9. according to the described refrigerated machine oil composition of claim 1, it is characterized in that said base oil is selected from one or more in glymes, polyethers and the polyol ester class base oil.
10. according to the described refrigerated machine oil composition of claim 9, it is characterized in that the structure of said glymes base oil is:
R in the formula 1, R 2And R 3Be respectively Wasserstoffatoms or carbonatoms and be 1～8 alkyl, R 4The expression carbonatoms is 1～10 alkano groups, and k is the integer between 0～10, R 5The expression carbonatoms is 1～20 alkyl, and m is the integer between 1～20.
11., it is characterized in that the structure of said polyethers base oil is according to the described refrigerated machine oil composition of claim 9:
Figure FSA00000478470600022
R wherein 6Expression Wasserstoffatoms or carbonatoms are the residue that 1～8 alkyl, alkylidene group, acyl group or polyvalent alcohol are removed hydroxyl, R 7Be that carbonatoms is 2～4 alkylidene group, R 8Be that hydrogen, carbonatoms are 1～10 alkyl or acyl group, n 1Be the integer between 2～20, n 2It is 1～6 integer.
12., it is characterized in that said polyol ester class base oil is meant the carboxylicesters of the multi-hydroxy compound that contains 2 hydroxyls at least according to the described refrigerated machine oil composition of claim 9, its structure is:
R 9[OCOR 10] q
R wherein 9For carbonatoms is 2～12 alkyl, R 10For Wasserstoffatoms or carbonatoms are 1～22 alkyl, q is 2～10 integer.
13., it is characterized in that the kinematic viscosity of said base oil under 40 ℃ is 3mm according to the described refrigerated machine oil composition of claim 1 2/ s～1000mm 2/ s.
14., it is characterized in that the kinematic viscosity of said base oil under 40 ℃ is 5mm according to the described refrigerated machine oil composition of claim 1 2/ s～500mm 2/ s.
15. a method that improves the refrigerator oil extreme pressure and antiwear behavior is characterized in that, in base oil, adds ionic liquid, wherein ionic liquid accounts for 0.01%～1% of base oil quality.
CN2011101003840A 2011-04-21 2011-04-21 Refrigerator oil composition and method for improving extreme pressure abrasion resistance of refrigerator oil Pending CN102746927A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862032A (en) * 2015-06-05 2015-08-26 广西大学 Lubricant combination for universal polyether refrigerator
CN106190483A (en) * 2016-07-15 2016-12-07 山东源根石油化工有限公司 A kind of complete synthesis antiwear hydraulic oil of environmental protection and energy saving and preparation method thereof
CN111690457A (en) * 2020-07-08 2020-09-22 卡松科技股份有限公司 Synthetic environment-friendly refrigerator oil
CN114410282A (en) * 2022-02-14 2022-04-29 四川大学 Low-temperature heat conduction oil based on ionic liquid and preparation method thereof
CN114854473A (en) * 2021-02-05 2022-08-05 中国石油天然气股份有限公司 Centrifugal compressor oil additive composition and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009263666A (en) * 2008-04-04 2009-11-12 Denso Corp Refrigerating machine oil composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009263666A (en) * 2008-04-04 2009-11-12 Denso Corp Refrigerating machine oil composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862032A (en) * 2015-06-05 2015-08-26 广西大学 Lubricant combination for universal polyether refrigerator
CN106190483A (en) * 2016-07-15 2016-12-07 山东源根石油化工有限公司 A kind of complete synthesis antiwear hydraulic oil of environmental protection and energy saving and preparation method thereof
CN111690457A (en) * 2020-07-08 2020-09-22 卡松科技股份有限公司 Synthetic environment-friendly refrigerator oil
CN114854473A (en) * 2021-02-05 2022-08-05 中国石油天然气股份有限公司 Centrifugal compressor oil additive composition and application thereof
CN114854473B (en) * 2021-02-05 2023-04-25 中国石油天然气股份有限公司 Centrifugal compressor oil additive composition and application thereof
CN114410282A (en) * 2022-02-14 2022-04-29 四川大学 Low-temperature heat conduction oil based on ionic liquid and preparation method thereof

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Application publication date: 20121024