Synthetic ester refrigeration equipment lubricant

Abstract

The invention belongs to the field of synthetic ester refrigerating machine oils, and relates to a synthetic ester refrigerating equipment lubricant which is base oil containing an ABC type molecular structure, and the specific molecular structural formula of the synthetic ester refrigerating equipment lubricant is base oil # imgabs0 #. Due to the special molecular structure, the synthetic ester type refrigerating equipment lubricant is suitable for a chlorofluorocarbon-free refrigerant, does not generate gas capable of destroying the ozone layer in the aspect of environmental protection, and solves the problem that part of the ozone layer is destroyed. The compatibility with a green and environment-friendly novel refrigerant is good. The hydrolysis is difficult, and the thermal stability is good.

Description

Technical Field

[0001] The invention belongs to the field of synthetic ester refrigeration oil and relates to a synthetic ester refrigeration equipment lubricant. Background Art

[0002] In order to prevent the destruction of the ozone layer and the deterioration of the earth's climate, people have done a lot of work. In refrigeration equipment, such as refrigerators, air conditioners, freezers, industrial refrigeration machinery, cars, ships and airplanes, people have gradually eliminated chlorofluorocarbon refrigerants. As a result, new relatively environmentally friendly refrigerants have been developed. The emergence of new refrigerants requires new refrigeration equipment lubricants to match them.

[0003] Globally, the refrigeration equipment lubricants with the largest usage are: Patented product with publication number CN108699470A, NOF Corporation invented refrigeration oil based on citric acid ester. Patented product with publication number CN1205321C, Nippon Oil & Gas Mitsubishi Corporation invented refrigerator fluid composition with pentaerythritol organic acid ester as base oil, used in chlorofluorocarbon-free refrigeration system. Patented product with publication number CN104220415B, KH Shinka Corporation invented refrigeration oil composition with dipentaerythritol and organic acid ester as base oil.

[0004] The polyol organic acid ester lubricants (i.e. base oils) synthesized from the above polyol esters and organic acids are required to have 1. good lubricity, 2. excellent chemical stability, 3. low hydrolysis, 4. good thermal conductivity, 5. excellent electrical insulation, 6. environmental performance, 7. compatibility with the internal structural materials of the compressor, and 8. ability to dissolve refrigerant gas. The polyol organic acid ester lubricants synthesized from polyols and organic acids have poor compatibility with refrigerant gas because the organic acid (-R group) -R refers to the alkane chain composed of C and H atoms, which has been an unresolved problem in the industry. Summary of the invention

[0005] Purpose of the Invention

[0006] In order to solve the problem of poor compatibility between the prior art refrigeration equipment lubricant and the refrigerant gas, the present invention provides a synthetic ester refrigeration equipment lubricant, which has an ABC type molecular structure and contains multiple -CH2-O-CH2- groups. The O atom in the ether chemical bond in the group has good compatibility with the refrigerant, thereby increasing the solubility of the refrigerant. In addition, the ABC type ester lubricant also has the other 7 advantages of the polyol organic acid ester lubricant.

[0007] Technical Solution

[0008] A synthetic ester refrigeration equipment lubricant, the synthetic ester refrigeration equipment lubricant is a base oil containing an ABC type molecular structure, and the specific molecular structure is Base oil;

[0009] The molecular structure of the synthetic ester refrigeration equipment lubricant is middle, The segment has the following molecular structure groups:

[0010]

[0011] n is 2, 3 or 4;

[0012] The molecular structure of the synthetic ester refrigeration equipment lubricant is In the A-segment, there are the following molecular structural groups:

[0013]

[0014] m is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, R is C1~C 10 A normal, isomeric or cycloalkane group, y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3;

[0015] The molecular structure of the synthetic ester refrigeration equipment lubricant In the -C segment, there are the following molecular structural groups:

[0016]

[0017] Where R3 is j1 is 2, 3, 4, 5, 6, 7, 8, 9 or 10;

[0018] y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3;

[0019] Where R4 is j2 is 2, 3, 4, 5, 6, 7, 8, 9 or 10;

[0020] y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3;

[0021] Where R5 is j3 is 2, 3, 4, 5, 6, 7, 8, 9 or 10;

[0022] y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3;

[0023] The molecular structure of the synthetic ester refrigeration equipment lubricant is The specific expression is:

[0024]

[0025] Furthermore, The molecular structure groups are composed of:

[0026]

[0027] It is provided by the diester compound with molecular structure B1 through esterification or transesterification chemical reaction. In the molecular structure, the molecular structure of B1 is

[0028]

[0029] Wherein X is H, -CH3, -CH2CH3, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, or the like normal or isomeric alkyl groups;

[0030] B1 is produced from nylon acid, a byproduct of a production line for producing adipic acid by oxidation of cyclohexanone and cyclohexanol. Nylon acid contains a mixture of succinic acid: glutaric acid: adipic acid = (10-25): (40-65): (10-25). In addition to the three main dibasic acids of succinic acid, glutaric acid and adipic acid, it also contains industrial catalyst copper vanadium oxide and other trace impurities.

[0031] Nylon acid and X-OH unit alcohol undergo esterification and distillation to obtain a dibasic acid ester mixture with a B1 molecular structure. After distillation, the product is refined and the impurity removal process is completed. Molecular structure needs.

[0032] Furthermore, the molecular structure groups of the A-segment are composed of:

[0033]

[0034] The molecular structure compound having the molecular structure A1 is provided by transesterification reaction or esterification reaction In the molecular structure, the molecular structure of A1 is:

[0035]

[0036] Furthermore, the molecular structure groups of the -C segment are composed of:

[0037]

[0038] It is provided by a molecular structure compound having a molecular structure C1 through esterification or exchange reaction. In the molecular structure, the molecular structure of C1 is:

[0039]

[0040] Furthermore, the molar ratio of A1, B1 and C1 is (0.8-1.2):(0.8-1.2):(0.8-1.2), and 300,000 to 10,000 parts of an esterification or transesterification catalyst is added to a stirred transesterification reactor. The reaction temperature is 180-260° C. under N2 gas protection. The reaction process is carried out under vacuum conditions. The vacuum degree gradually increases as the reaction proceeds, and the vacuum residual pressure is 1-20 mmHg. The reaction is carried out for 2-5 hours, and the reaction by-products, small molecule alcohols and trace amounts of water, are evaporated. The material is cooled to room temperature to obtain a synthetic ester refrigeration equipment lubricant with a molecular structure of The lubricant content is ≥99%.

[0041] Furthermore, the esterification or transesterification catalyst is, for example, tetrabutyl titanate, isopropyl titanate, stannous oxide, stannous oxalate, stannous glutarate or stannous adipate.

[0042] Furthermore, the specific parameters of the gradual increase in the vacuum degree as the reaction proceeds are: the residual pressure in the ester exchange reactor gradually decreases from the normal pressure of 101325Pa to 90000Pa, then gradually decreases to 50000Pa, then gradually decreases to 20*133Pa, and finally decreases to 133Pa, with a reduction rate of 28000 to 32000Pa per hour.

[0043] An application of the synthetic ester refrigeration equipment lubricant, wherein the synthetic ester refrigeration equipment lubricant is added with various required additives to prepare an industrial fluid mixture for civil refrigerators, air conditioners and various refrigeration equipment.

[0044] Furthermore, the various required additives are 0.15-0.25% by weight of RHY501 antioxidant, 0.5 to 1 ten thousandths of T921 antifoaming agent, 0.25-0.5% of RHY306 triphenol phosphate, and 0.1-0.2% of cardura E109 acid scavenger added to a certain amount of the synthetic ester refrigeration equipment lubricant.

[0045] Advantages and effects

[0046] The synthetic ester refrigeration equipment lubricant of the present invention is suitable for chlorofluorocarbon-free refrigerants due to its special molecular structure, does not produce ozone-destroying gases in terms of environmental protection, and solves the problem of partial ozone layer destruction. It has good compatibility with green and environmentally friendly new refrigerants R410a, R134a, R32, R40a and other environmentally friendly refrigerants, and is an excellent green and environmentally friendly refrigeration equipment lubricant. The lubricant is not easy to hydrolyze due to its special molecular structure and has good thermal stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] The present invention is further described below in conjunction with the accompanying drawings and specific implementation methods. The protection scope of the present invention is not limited to the following description.

[0048] Figure 1 It is an ester exchange reaction device.

[0049] Explanation of the reference numerals: 1. ester exchange reactor, 2. agitator, 3. distillation tower, 4. condenser, 51. reaction by-product receiving device a, 52. reaction by-product receiving device b. DETAILED DESCRIPTION

[0050] like Figure 1 The ester exchange reaction device shown includes an ester exchange reactor 1, a fractionating tower 3, a condenser 4 and a reaction by-product receiving device. A jacket layer is provided on the periphery of the ester exchange reactor 1, and heat transfer oil is circulated and heated in the jacket layer. An agitator 2 is provided in the ester exchange reactor 1. The ester exchange reactor 1 is connected in series with the fractionating tower 3, the condenser 4 and the reaction by-product receiving device. There are two reaction by-product receiving devices, namely, a reaction by-product receiving device a 51 and a reaction by-product receiving device b 52 connected in parallel.

[0051] A synthetic ester refrigeration equipment lubricant, the synthetic ester refrigeration equipment lubricant is a base oil containing an ABC type molecular structure, and the specific molecular structure is Base oil;

[0052] Molecular structure of synthetic ester refrigeration equipment lubricant middle, The segment has the following molecular structure groups:

[0053]

[0054] n is 2, 3 or 4;

[0055] Molecular structure of synthetic ester refrigeration equipment lubricant In the A-segment, there are the following molecular structural groups:

[0056]

[0057] m is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, R is C1~C 10 A normal, isomeric or cycloalkane group, y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3;

[0058] Molecular structure of synthetic ester refrigeration equipment lubricant In the -C segment, there are the following molecular structural groups:

[0059]

[0060] Where R3 is j1 is 2, 3, 4, 5, 6, 7, 8, 9 or 10;

[0061] y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3;

[0062] Where R4 is j2 is 2, 3, 4, 5, 6, 7, 8, 9 or 10;

[0063] y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3;

[0064] Where R5 is j3 is 2, 3, 4, 5, 6, 7, 8, 9 or 10;

[0065] y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3;

[0066] The molecular structure of synthetic ester refrigeration equipment lubricant is The specific expression is:

[0067]

[0068] The molecular structure groups are composed of:

[0069]

[0070] It is provided by the diester compound with molecular structure B1 through esterification or transesterification chemical reaction. In the molecular structure, the molecular structure of B1 is

[0071]

[0072] Wherein X is H, -CH3, -CH2CH3, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, or the like normal or isomeric alkyl groups;

[0073] B1 is produced from nylon acid, a byproduct of a production line for producing adipic acid by oxidation of cyclohexanone and cyclohexanol. Nylon acid contains a mixture of succinic acid: glutaric acid: adipic acid = (10-25): (40-65): (10-25). In addition to the three main dibasic acids of succinic acid, glutaric acid and adipic acid, it also contains industrial catalyst copper vanadium oxide and other trace impurities.

[0074] Nylon acid and X-OH unit alcohol undergo esterification and distillation to obtain a dibasic acid ester mixture with a B1 molecular structure. After distillation, the product is refined and the impurity removal process is completed. Molecular structure needs.

[0075] A-segment molecular structure group composition:

[0076]

[0077] The molecular structure compound having the molecular structure A1 is provided by transesterification reaction or esterification reaction In the molecular structure, the molecular structure of A1 is:

[0078]

[0079] -C segment molecular structure group composition:

[0080]

[0081] It is provided by a molecular structure compound having a molecular structure C1 through esterification or exchange reaction. In the molecular structure, the molecular structure of C1 is:

[0082]

[0083] A1, B1 and C1 are in a molar ratio of (0.8-1.2):(0.8-1.2):(0.8-1.2). In an ester exchange reactor with stirring, 300,000 to 10,000 parts of esterification or ester exchange catalyst are added. Under N2 gas protection, the reaction temperature is 180-260°C. The reaction process is carried out under vacuum conditions. The vacuum degree is gradually increased as the reaction proceeds. The vacuum residual pressure is 1-20 mmHg. The reaction is carried out for 2-5 hours. The reaction by-products, small molecule alcohol and trace water, are evaporated. The material is cooled to room temperature to obtain a synthetic ester refrigeration equipment lubricant with a molecular structure of The lubricant content is ≥99%.

[0084] The esterification or transesterification catalyst is, for example, tetrabutyl titanate, isopropyl titanate, stannous oxide, stannous oxalate, stannous glutarate or stannous adipate.

[0085] The specific parameters of the vacuum degree gradually increasing with the progress of the reaction are: the residual pressure in the ester exchange reactor gradually decreases from the normal pressure of 101325Pa to 90000Pa, then gradually decreases to 50000Pa, then gradually decreases to 20*133Pa, and finally decreases to 133Pa, with a reduction rate of 28000-32000Pa per hour.

[0086] Application of synthetic ester refrigeration equipment lubricant: Synthetic ester refrigeration equipment lubricant can be added with various required additives to make industrial fluid mixture for civil refrigerators, air conditioners and various refrigeration equipment. The synthesized industrial fluid mixture is also called ABC type synthetic ester lubricant. Various required additives are 0.15-0.25% RHY501 antioxidant, 0.5-10,000% T921 antifoaming agent, 0.25-0.5% RHY306 triphenol phosphate, 0.1-0.2% cardura E109 acid scavenger added to a certain amount of synthetic ester refrigeration equipment lubricant. Other types of required additives can also be used.

[0087] Example 1

[0088] Synthetic ester refrigeration equipment lubricants are used in Figure 1 During the reaction, the transesterification reactor 1 is heated by external circulating heat transfer oil, the stirrer 2 is a stirring paddle stirrer, the stirring speed is 175-200 rpm, and the effective volume of the transesterification reactor 1 is 20L.

[0089] Before the reaction, the ester exchange reaction device was replaced with N2 gas three times, and 2656g of mixed dibasic acid dimethyl ester was added to the ester exchange reactor 1, which contained 1600g of dimethyl glutarate (equivalent to 10mol, equivalent to 60.24% by mass), 574.2g of dimethyl adipate (equivalent to 3.3mol, equivalent to 21.62% by mass), and 481.8g of dimethyl succinate (equivalent to 3.3mol, mass percentage 18.14%). The total number of moles of the mixed dibasic acid dimethyl ester is 10+3.3+3.3=16.6mol. 16.6mol of triethylene glycol monobutyl ether was added to the ester exchange reactor 1, 16.6mol*206 (molecular weight of triethylene glycol monobutyl ether 206)=3419.6g.

[0090] Triethylene glycol monobutyl ether molecular formula:

[0091]

[0092] Add 16.6 mol of monoalcohol compound of pentaerythritol mixed ester with molecular structure C1: 16.6 mol*464=7702.4 g

[0093] The molecular structure of C1 is:

[0094]

[0095] Where -R3 is -(CH2)3CH3

[0096] -R4 is -(CH2)5CH3

[0097] -R5 is -(CH2)8CH3

[0098] The mol molecular weight of C1 is 464.

[0099] 3.817 g of tetrabutyl titanate catalyst, which accounts for 3 ten-thousandths of the total mass, was added into the transesterification reactor 1 .

[0100] After loading the materials, N2 gas was purged 3 times.

[0101] The reaction temperature gradually rises. When the temperature rises to 190°C, a large amount of by-product methanol begins to distill out. The distilled methanol is measured from the reaction by-product receiving device a51. When the reaction temperature rises to 230°C, the amount of distilled methanol is quantitatively calculated. The esterification reaction is more than 99% complete. The reaction takes 6 hours. At this time, the temperature is gradually raised and the vacuum is gradually drawn. Finally, the reaction temperature reaches 250°C±2°C and the vacuum reaches 10-15mmHg, and the reaction is completed.

[0102] Switch the reaction by-product receiving device a 51 to the reaction by-product receiving device b 52, distill the residual trace by-products, and under the conditions of 2-5 mmHg and 240-250° C., evaporate the by-products to obtain product A in the ester exchange reactor 1, cool product A to 70-80° C., take samples to measure the acid value: the acid value is <1 mgKOH / g sample, wash product A with an equal mass of 18% NaCl aqueous solution to NaOH aqueous solution, and add NaOH in an amount equivalent to the acid value in product A.

[0103] Stir and neutralize at room temperature 30-40°C for 10 minutes, separate the layers to obtain organic product B, and then wash with an equal volume of deionized water 4 times at room temperature 30-40°C, wash with deionized water and stir for 10 minutes to obtain organic product C.

[0104] Detection of Cl in organic products C - The ions are below 0.1ppm, and the organic product C after neutralization and dehydration is dehydrated at 100℃ / 10mmHg and cooled to room temperature to obtain the organic product D.

[0105] Take 1000g of product D, add 3g of RHy501 phenolic antioxidant, 5g of RHy306 tricresyl phosphate (TCP), 2g of Cardure E10P acid scavenger, and 150ppm of T92 antifoaming agent. Stir at 80℃ for 30 minutes to obtain ABC type synthetic lubricant-1. The test results of ABC type synthetic lubricant-1 according to Q / GH1008 test method are listed in Table 1.

[0106] The product number is ABC type synthetic ester lubricant-1. The product is tested for kinematic viscosity, viscosity index, flash point (opening), pour point, density, refractive index, and compatibility according to the national standard: Q / GH1008 implementation standard. The test results are shown in Table 1.

[0107] Example 2

[0108] 16.6 mol of tetraethylene glycol monobutyl ether was added. The other parts of Example 2 were the same as those of Example 1, except that the raw material triethylene glycol monobutyl ether was replaced with 16.6 mol of tetraethylene glycol monobutyl ether.

[0109] Tetraethylene glycol monobutyl ether molecular formula

[0110]

[0111] The molecular weight of tetraethylene glycol monobutyl ether is 250.

[0112] The reaction was completed under the same operating conditions as in Example 1. The product was numbered ABC type synthetic ester lubricant-2. The test results are listed in Table 1.

[0113] Table 1 Test results

[0114]

[0115] It can be seen from the data in Table 1 that the ABC type synthetic ester lubricant synthesized in this patent meets the use requirements of lubricants for domestic refrigerators, air conditioners and industrial refrigeration equipment.

[0116] Obviously, the above-mentioned embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the embodiments of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to list all the embodiments here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A synthetic ester refrigeration equipment lubricant, characterized in that: Synthetic ester refrigeration equipment lubricant is a base oil with an ABC type molecular structure. The specific molecular structure is Base oil; The molecular structure of the synthetic ester refrigeration equipment lubricant middle, The segment has the following molecular structure groups composition: n is 2, 3 or 4; The molecular structure of the synthetic ester refrigeration equipment lubricant In the A-segment, there are the following molecular structural groups: composition: m is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, R is C1~C 10 A normal, isomeric or cycloalkane group, y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3; The molecular structure of the synthetic ester refrigeration equipment lubricant In the -C segment, there are the following molecular structural groups: composition: Where R3 is j1 is 2, 3, 4, 5, 6, 7, 8, 9 or 10; y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3; Where R4 is j2 is 2, 3, 4, 5, 6, 7, 8, 9 or 10; y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3; Where R5 is j3 is 2, 3, 4, 5, 6, 7, 8, 9 or 10; y is H, -CH3, -CH2CH3 or -(CH2)2-O-CH3; The molecular structure of the synthetic ester refrigeration equipment lubricant is The specific expression is:

2. The synthetic ester refrigeration equipment lubricant according to claim 1, characterized in that: Segment molecular structure group composition: It is provided by the diester compound with molecular structure B1 through esterification or transesterification chemical reaction. In the molecular structure, the molecular structure of B1 is Wherein X is H, -CH3, -CH2CH3, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, or the like normal or isomeric alkyl groups; B1 is produced from nylon acid, a byproduct of a production line for producing adipic acid by oxidation of cyclohexanone and cyclohexanol. Nylon acid contains a mixture of succinic acid: glutaric acid: adipic acid = (10-25): (40-65): (10-25). In addition to the three main dibasic acids of succinic acid, glutaric acid and adipic acid, it also contains industrial catalyst copper vanadium oxide and other trace impurities. Nylon acid and X-OH unit alcohol undergo esterification and distillation to obtain a dibasic acid ester mixture with a B1 molecular structure. After distillation, the product is refined and the impurity removal process is completed. Molecular structure needs.

3. The synthetic ester refrigeration equipment lubricant according to claim 2, characterized in that: A-segment molecular structure group composition: The molecular structure compound having the molecular structure A1 is provided by transesterification reaction or esterification reaction In the molecular structure, the molecular structure of A1 is:

4. The synthetic ester refrigeration equipment lubricant according to claim 3, characterized in that: -C segment molecular structure group composition: It is provided by a molecular structure compound having a molecular structure C1 through esterification or exchange reaction. In the molecular structure, the molecular structure of C1 is:

5. The synthetic ester refrigeration equipment lubricant according to claim 4, characterized in that: The molar ratio of A1, B1 and C1 is (0.8-1.2):(0.8-1.2):(0.8-1.2). In an ester exchange reactor with stirring, 300,000 to 10,000 parts of esterification or ester exchange catalyst are added. Under N2 gas protection, the reaction temperature is 180-260°C. The reaction process is carried out under vacuum conditions. The vacuum degree is gradually increased as the reaction proceeds. The vacuum residual pressure is 1-20 mmHg. The reaction is carried out for 2-5 hours. The reaction by-products, small molecule alcohol and trace water, are evaporated. The material is cooled to room temperature to obtain a synthetic ester refrigeration equipment lubricant with a molecular structure of The lubricant content is ≥99%.

6. The synthetic ester refrigeration equipment lubricant according to claim 5, characterized in that: The esterification or transesterification catalyst is, for example, tetrabutyl titanate, isopropyl titanate, stannous oxide, stannous oxalate, stannous glutarate or stannous adipate.

7. The synthetic ester refrigeration equipment lubricant according to claim 5, characterized in that: The specific parameters of the gradual increase in vacuum degree as the reaction proceeds are: the residual pressure in the ester exchange reactor gradually decreases from normal pressure 101325Pa to 90000Pa, then gradually decreases to 50000Pa, then gradually decreases to 20*133Pa, and finally decreases to 133Pa, with a reduction rate of 28000-32000Pa per hour.

8. A use of the synthetic ester refrigeration equipment lubricant as claimed in claim 1, characterized in that: The synthetic ester refrigeration equipment lubricant can be added with various required additives to prepare an industrial fluid mixture for civil refrigerators, air conditioners and various refrigeration equipment.

9. The use of the synthetic ester refrigeration equipment lubricant according to claim 8, characterized in that: The various required additives are: taking a certain amount of the synthetic ester refrigeration equipment lubricant and adding 0.15-0.25% RHY501 antioxidant, 0.5 to 1 ten thousandths of T921 antifoaming agent, 0.25-0.5% RHY306 triphenol phosphate, and 0.1-0.2% cardura E109 acid scavenger.

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