A refrigeration oil composition for hydrofluorocarbon and preparation method thereof

Abstract

The present invention relates to the technical field of lubricating oils, and in particular to a refrigeration oil composition for hydrofluorocarbons and a preparation method thereof. The composition comprises the following components by weight: 90-180 parts of base oil, 1-2 parts of anti-wear agent, 0.5-1 parts of stabilizer, 0.1-0.5 parts of anti-foam agent, 0.05-0.1 parts of acid trap and 0.01-0.02 parts of corrosion inhibitor; the base oil comprises the following components by weight: 80-100 parts of linear alkylbenzene and 10-80 parts of fluorinated benzoate. The refrigeration oil provided by the invention has excellent compatibility with hydrofluorocarbon refrigerants and has broad application prospects in the field of refrigeration oils.

Description

Technical Field

[0001] The invention relates to the technical field of lubricating oils, and in particular to a refrigeration oil composition for hydrofluorocarbons and a preparation method thereof. Background Art

[0002] Refrigeration oil is a lubricating oil used in refrigeration systems, which plays an important role in lubrication, sealing and cooling in the refrigeration cycle. However, traditional refrigeration oil has some problems when it comes into contact with hydrofluorocarbons.

[0003] Conventional refrigeration oils usually use alkylbenzenes as base oil components. However, alkylbenzenes have poor compatibility with hydrofluorocarbons, which can easily cause phase separation or precipitation problems, resulting in reduced performance of the refrigeration oil. Secondly, refrigeration oils need to have good lubrication, anti-wear, anti-oxidation and anti-foaming properties to ensure efficient operation and long-term stability of the refrigeration system. However, under low temperature conditions, conventional refrigeration oils may not meet these requirements.

[0004] Patent document CN112048355B discloses a refrigeration oil and a working fluid composition for a refrigeration machine, wherein the refrigeration oil uses alkylbenzene as a base oil, and the alkylbenzene has a 5% distillation temperature of more than 250° C. and a 95% distillation temperature of less than 460° C. Although the invention uses a specific alkylbenzene as a base oil to improve its compatibility with hydrofluorocarbons, due to the properties of the alkylbenzene itself, it still has poor compatibility with hydrofluorocarbons.

[0005] Therefore, it is very necessary to develop a refrigeration oil with alkylbenzene as the base oil and suitable for hydrofluorocarbons. Summary of the invention

[0006] In view of this, the object of the present invention is to provide a refrigeration oil composition for hydrofluorocarbon and a preparation method thereof, so as to solve the problem that alkylbenzene as a base oil has poor compatibility with hydrofluorocarbon.

[0007] Based on the above purpose, the present invention provides a refrigeration oil composition for hydrofluorocarbons, which comprises the following components by weight: 90-180 parts of base oil, 1-2 parts of anti-wear agent, 0.5-1 parts of stabilizer, 0.1-0.5 parts of anti-foaming agent, 0.05-0.1 parts of acid trap and 0.01-0.02 parts of corrosion inhibitor;

[0008] Wherein, the base oil comprises the following components by weight: 80-100 parts of linear alkylbenzene, 10-80 parts of fluorinated benzoate;

[0009] Wherein, the structural formula of the fluorinated benzoate is as follows:

[0010] or ,

[0011] Wherein, R is selected from one of C8-C14 straight chain alkyl groups.

[0012] Preferably, the linear alkylbenzene is a C9-C14 linear alkylbenzene.

[0013] Preferably, the antiwear agent is a phosphate antiwear agent.

[0014] Preferably, the stabilizer is a phenolic or amine antioxidant.

[0015] Preferably, the anti-foaming agent is a mixture of fluorinated silicone oil and dimethyl silicone oil.

[0016] Preferably, the weight ratio of the fluorine-containing silicone oil to the dimethyl silicone oil is 1:4.

[0017] Preferably, the fluorine-containing silicone oil is methyl fluorosilicone oil, the viscosity of the methyl fluorosilicone oil differs from that of the dimethyl silicone oil by less than 50 cs, and the viscosity of the methyl fluorosilicone oil is 100-200 cs.

[0018] Preferably, the acid capture agent is one of neopentyl glycol diglycidyl ether and octyl glycidyl ether; and the corrosion inhibitor is benzotriazole.

[0019] Preferably, the preparation method of the fluorinated benzoic acid ester is as follows: under a nitrogen atmosphere, C8-C14 straight-chain alkyl alcohol and triethylamine are added to dichloromethane, stirred at 0-20°C for 5-10 minutes, and then fluorinated benzoyl chloride is added, reacted at 0-20°C for 2-4 hours, extracted, washed, and purified to obtain the fluorinated benzoic acid ester.

[0020] Preferably, the molar ratio of the C8-C14 straight-chain alkyl alcohol, fluorinated benzoyl chloride, triethylamine and dichloromethane is 1:0.8-0.9:1:5-10.

[0021] Preferably, the fluorinated benzoyl chloride is one of 4-fluorobenzoyl chloride and 3-fluorobenzoyl chloride.

[0022] Furthermore, the present invention also provides a method for preparing the above-mentioned hydrofluorocarbon refrigeration oil composition, comprising the following steps:

[0023] (1) In a nitrogen atmosphere, linear alkylbenzene and fluorinated benzoate are mixed, and stirred at room temperature and 150-300 rpm for 10-20 min to obtain a base oil;

[0024] (2) Under a nitrogen atmosphere, fluorinated silicone oil and dimethyl silicone oil were mixed, and stirred at room temperature and 100-150 rpm for 5-10 minutes to obtain an anti-foaming agent;

[0025] (3) Under a nitrogen atmosphere, an anti-wear agent, a stabilizer, an anti-foaming agent, an acid scavenger and a corrosion inhibitor are added to the base oil, and stirred at 50-80° C. and 300-450 rpm for 10-20 min to obtain a refrigeration oil composition for hydrofluorocarbons.

[0026] Beneficial effects of the present invention:

[0027] Improve the compatibility between alkylbenzene and hydrofluorocarbons: Traditional base oil alkylbenzene has poor compatibility with hydrofluorocarbons and is prone to precipitation or phase separation problems. In the present invention, linear alkylbenzene and fluorinated benzoate are used as base oils, which are more compatible with hydrofluorocarbons and can effectively improve the compatibility.

[0028] Improve lubrication performance: The addition of anti-wear agents can reduce the wear of friction surfaces and increase the service life of mechanical parts. The addition of stabilizers can inhibit the oxidative decomposition of oil under high temperature conditions and prevent oil deterioration. The use of anti-foaming agents can prevent the formation of bubbles and maintain the lubrication performance of oil. The combined effect of these additives can improve the lubrication performance of refrigeration oil.

[0029] Corrosion resistance: The addition of acid capture agents can neutralize the acidic substances in the oil, prevent acid corrosion and the generation of corrosive gases, and the use of corrosion inhibitors can form a protective film to reduce corrosion and wear on the surface of mechanical parts.

[0030] In general, the refrigeration oil composition for hydrofluorocarbons provided by the present invention has significant advantages in improving the compatibility of alkylbenzene and hydrofluorocarbons, enhancing lubrication performance, corrosion resistance and acid neutralization ability. These characteristics make the composition and preparation method have broad application prospects in the field of refrigeration oils. DETAILED DESCRIPTION

[0031] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0032] The sources or properties of the raw materials used in the present invention are as follows:

[0033] Linear alkylbenzene was purchased from the Alkylbenzene Plant of Sinopec Jinling Petrochemical Co., Ltd., with an average molecular weight of 241.6 and a density of 0.8562 g / cm 3 , including C9-C14 linear alkylbenzene, the product batch number is WJB20220612-301-2-02; methyl fluorosilicone oil was purchased from Zhejiang Huanxin Fluoro Materials Co., Ltd. with a viscosity of 120 cs; dimethyl silicone oil was purchased from Guangzhou Changhong Chemical Co., Ltd. with a viscosity of 100 cs.

[0034] Example 1: A refrigeration oil composition for hydrofluorocarbons, the specific preparation steps are as follows:

[0035] (1) Under a nitrogen atmosphere, 13 g of C8 straight-chain alkyl alcohol and 10.1 g of triethylamine were added to 60 g of dichloromethane, stirred at 10°C for 5 min, then 12.7 g of 4-fluorobenzoyl chloride was added, reacted at 10°C for 2 h, extracted, washed, and purified by chromatography column (1:9, ethyl acetate / hexane) to obtain a fluorinated benzoate;

[0036] (2) Under a nitrogen atmosphere, 80 g of linear alkylbenzene and 10 g of fluorinated benzoate were mixed and stirred at room temperature and 200 rpm for 15 min to obtain a base oil;

[0037] (3) Under a nitrogen atmosphere, 0.02 g of methyl fluorosilicone oil and 0.08 g of dimethyl silicone oil were mixed and stirred at room temperature and 120 rpm for 8 min to obtain an antifoaming agent;

[0038] (4) Under a nitrogen atmosphere, 1 g of tricresyl phosphate, 0.5 g of 2,6-di-tert-butyl-p-methylphenol, 0.1 g of an antifoaming agent, 0.05 g of neopentyl glycol diglycidyl ether and 0.01 g of benzotriazole were added to 90 g of a base oil, and the mixture was stirred at 50° C. and 300 rpm for 10 min to obtain a refrigeration oil composition for hydrofluorocarbons.

[0039] Example 2: A refrigeration oil composition for hydrofluorocarbons, the specific preparation steps are as follows:

[0040] (1) Under a nitrogen atmosphere, 21.6 g of C9 straight-chain alkyl alcohol and 15.2 g of triethylamine were added to 90 g of dichloromethane, stirred at 10°C for 8 min, then 19.1 g of 4-fluorobenzoyl chloride was added, reacted at 10°C for 3 h, extracted, washed, and purified by chromatography column (1:9, ethyl acetate / hexane) to obtain a fluorinated benzoate;

[0041] (2) Under a nitrogen atmosphere, 90 g of linear alkylbenzene and 20 g of fluorinated benzoate were mixed and stirred at room temperature and 200 rpm for 15 min to obtain a base oil;

[0042] (3) Under a nitrogen atmosphere, 0.05 g of methyl fluorosilicone oil and 0.2 g of dimethyl silicone oil were mixed and stirred at room temperature and 120 rpm for 8 min to obtain an antifoaming agent;

[0043] (4) Under a nitrogen atmosphere, 1.5 g of tricresyl phosphate, 0.7 g of 2,6-di-tert-butyl-p-methylphenol, 0.25 g of an antifoaming agent, 0.07 g of neopentyl glycol diglycidyl ether and 0.015 g of benzotriazole were added to 110 g of a base oil, and the mixture was stirred at 60° C. and 350 rpm for 15 min to obtain a refrigeration oil composition for hydrofluorocarbons.

[0044] Example 3: A refrigeration oil composition for hydrofluorocarbons, the specific preparation steps are as follows:

[0045] (1) Under a nitrogen atmosphere, 47.4 g of C14 straight-chain alkyl alcohol and 30.3 g of triethylamine were added to 180 g of dichloromethane, stirred at 10°C for 10 min, then 38.1 g of 4-fluorobenzoyl chloride was added, reacted at 10°C for 4 h, extracted, washed, and purified by chromatography column (1:9, ethyl acetate / hexane) to obtain a fluorinated benzoate;

[0046] (2) Under a nitrogen atmosphere, 100 g of linear alkylbenzene and 80 g of fluorinated benzoate were mixed and stirred at room temperature and 300 rpm for 20 min to obtain a base oil;

[0047] (3) Under a nitrogen atmosphere, 0.1 g of methyl fluorosilicone oil and 0.4 g of dimethyl silicone oil were mixed and stirred at room temperature and 150 rpm for 10 min to obtain an antifoaming agent;

[0048] (4) Under a nitrogen atmosphere, 2 g of tricresyl phosphate, 1 g of 2,6-di-tert-butyl-p-methylphenol, 0.5 g of an antifoaming agent, 0.1 g of neopentyl glycol diglycidyl ether and 0.02 g of benzotriazole were added to 180 g of a base oil, and the mixture was stirred at 80° C. and 450 rpm for 20 min to obtain a refrigeration oil composition for hydrofluorocarbons.

[0049] Comparative Example 1:

[0050] The difference between Comparative Example 1 and Example 2 is that the base oil in Comparative Example 1 is 110 g of linear alkylbenzene.

[0051] Comparative Example 2:

[0052] The difference between Comparative Example 2 and Example 2 is that the antifoaming agent in Comparative Example 2 is 0.25 g of dimethyl silicone oil.

[0053] Comparative Example 3:

[0054] The difference between Comparative Example 3 and Example 2 is that in Comparative Example 3, the base oil is 110 g of linear alkylbenzene and the antifoaming agent is 0.25 g of dimethyl silicone oil.

[0055] Comparative Example 4:

[0056] The difference between Comparative Example 4 and Example 2 is that the fluorinated benzoate in Comparative Example 4 is ethyl 4-fluorobenzoate.

[0057] Comparative Example 5

[0058] The difference between Comparative Example 5 and Example 2 is that the base oil in Comparative Example 4 is 90 g of linear alkylbenzene and 20 g of nonyl benzoate.

[0059] Performance test: The above embodiments and comparative examples were subjected to application performance tests, and the results are shown in Tables 1 and 2.

[0060] Table 1 Performance test results of refrigeration oil compositions prepared in Examples and Comparative Examples

[0061]

[0062] Table 2 Performance test results of refrigeration oil compositions prepared in Examples and Comparative Examples

[0063]

[0064] Among them, the compatibility with the refrigerant refers to "SH / T 0699-2000 Refrigeration Oil and Refrigerant Miscibility Test Method", the specific test process is: a certain mass of test oil and refrigerant is filled into a test tube, heated at room temperature or in a water bath to make the test oil and refrigerant become a uniform, transparent solution, and then the test tube is cooled in a cold bath, and the test mixture of refrigeration oil and refrigerant with an oil content of 5%-50% is slowly cooled from 25°C to -40°C, and the temperature at which the mixture produces phase separation or white turbidity is used as the two-phase separation temperature under the measured oil content. The two-phase separation curve is drawn for the two-phase separation temperatures corresponding to different oil contents. The highest measured temperature on the curve is the two-phase separation temperature of the test oil and refrigerant. The lower the two-phase separation temperature, the better the miscibility of the refrigeration oil and the refrigerant. Below and equal to -40°C, it is judged as good compatibility, and above -40°C, it is judged as poor compatibility.

[0065] It can be seen from Examples 1-3 in Table 1 that the 40°C kinematic viscosity range of the refrigeration oil prepared by the present invention is wide, and it has excellent compatibility with both new hydrofluorocarbon refrigerants and traditional alkyl refrigerants; it can be seen from Example 2 and Comparative Examples 1-3 that the fluorinated benzoic acid ester and methyl fluorosilicone oil in the present invention jointly adjust the 40°C kinematic viscosity of the refrigeration oil, so that it has a wider application range, and the fluorinated benzoic acid ester greatly improves the compatibility of the refrigeration oil with hydrofluorocarbon refrigerants; it can be seen from Example 2 and Comparative Examples 4 and 5 that the length of the fluorine and carbon chains in the fluorinated benzoic acid ester has a crucial influence on the compatibility of the refrigeration oil with hydrofluorocarbon refrigerants.

[0066] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention (including the claims) is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

[0067] The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A refrigeration oil composition for hydrofluorocarbons, characterized in that: The components include the following by weight: 90-180 parts of base oil, 1-2 parts of anti-wear agent, 0.5-1 parts of stabilizer, 0.1-0.5 parts of anti-foaming agent, 0.05-0.1 parts of acid trap and 0.01-0.02 parts of corrosion inhibitor; The base oil comprises the following components by weight: 80-100 parts of linear alkylbenzene, 10-80 parts of fluorinated benzoate; The structural formula of the fluorinated benzoate is as follows: or , Wherein, R is selected from one of C8-C14 straight chain alkyl groups.

2. The refrigeration oil composition for hydrofluorocarbon according to claim 1, characterized in that The linear alkylbenzene is a C9-C14 linear alkylbenzene.

3. The refrigeration oil composition for hydrofluorocarbon according to claim 1, characterized in that The anti-wear agent is a phosphate anti-wear agent; the stabilizer is a phenol or amine antioxidant.

4. The refrigeration oil composition for hydrofluorocarbon according to claim 1, characterized in that The anti-foaming agent is a mixture of fluorinated silicone oil and dimethyl silicone oil, and the weight ratio of the fluorinated silicone oil to the dimethyl silicone oil is 1:

4.

5. The refrigeration oil composition for hydrofluorocarbon according to claim 4, characterized in that The fluorine-containing silicone oil is methyl fluorosilicone oil, the viscosity of the methyl fluorosilicone oil differs from that of the dimethyl silicone oil by less than 50 cs, and the viscosity of the methyl fluorosilicone oil is 100-200 cs.

6. The refrigeration oil composition for hydrofluorocarbon according to claim 1, characterized in that The acid capture agent is one of neopentyl glycol diglycidyl ether and octyl glycidyl ether; and the corrosion inhibitor is benzotriazole.

7. The refrigeration oil composition for hydrofluorocarbon according to claim 1, characterized in that The preparation method of the fluorinated benzoic acid ester is as follows: under a nitrogen atmosphere, C8-C14 straight-chain alkyl alcohol and triethylamine are added to dichloromethane, stirred at 0-20°C for 5-10 minutes, then fluorinated benzoyl chloride is added, reacted at 0-20°C for 2-4 hours, extracted, washed, and purified to obtain the fluorinated benzoic acid ester.

8. The refrigeration oil composition for hydrofluorocarbon according to claim 7, characterized in that The molar ratio of the C8-C14 straight-chain alkyl alcohol, fluorinated benzoyl chloride, triethylamine and dichloromethane is 1:0.8-0.9:1:5-10.

9. The refrigeration oil composition for hydrofluorocarbon according to claim 7, characterized in that The fluorine-containing benzoyl chloride is one of 4-fluorobenzoyl chloride and 3-fluorobenzoyl chloride.

10. A method for preparing a refrigeration oil composition for hydrofluorocarbon according to any one of claims 1 to 8, characterized in that: The steps include: (1) In a nitrogen atmosphere, linear alkylbenzene and fluorinated benzoate are mixed, and stirred at room temperature and 150-300 rpm for 10-20 min to obtain a base oil; (2) Under a nitrogen atmosphere, fluorinated silicone oil and dimethyl silicone oil were mixed, and stirred at room temperature and 100-150 rpm for 5-10 minutes to obtain an anti-foaming agent; (3) Under a nitrogen atmosphere, an anti-wear agent, a stabilizer, an anti-foaming agent, an acid scavenger and a corrosion inhibitor are added to the base oil, and stirred at 50-80° C. and 300-450 rpm for 10-20 min to obtain a refrigeration oil composition for hydrofluorocarbons.

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