WO2009043218A1

WO2009043218A1 - Refrigerating machine oil composition and its preparation method

Info

Publication number: WO2009043218A1
Application number: PCT/CN2007/071009
Authority: WO
Inventors: Mengyan Wang
Original assignee: Beijing Friendlink Petrochemical T & D Co.; Ltd
Priority date: 2007-09-29
Filing date: 2007-11-02
Publication date: 2009-04-09
Also published as: CN101177643A; CN101177643B

Abstract

The present invention relates to a refrigerator oil composition, it comprises the mixed α-olefin polymer oil as base oil and the additive, the viscosity of the mixed α-olefin polymer oil is less than 6 mm2/s at 40°C and no less than 3 mm2/s at 40°C. The mixed α-olefin polymer oil is C15-C22 mixed isoolefine, C15-C22 mixed isoparaffin, or the mixture of C15-C22 mixed isoolefine and C15-C22 mixed isoparaffin. The refrigerator oil composition provided by this invention has the following merits: (1) the refrigerator oil composition can finely dissolve R600A refrigerant, its flocculation point may reach lower than -70°C; (2) the refrigerator oil composition has fine cold flow property, its pour point may reach lower than -70°C, its kinematic viscosity is less than 500 mm2/s at -40°C; (3) it has obvious energy saving performance, compared with the refrigerator oil which viscosity is 22 mm2/s at 40°C, it can economize on energy 14%, compared with the refrigerator which viscosity is 10 mm2/s at 40°C, it can economize on energy 4%.

Description

[Technical Field]

The present invention relates to a refrigerating machine oil composition and a method of preparing the same. 【Background technique】

The compression refrigeration system consists of a refrigeration compressor, a condenser, an expansion valve, an evaporator, etc. The working principle is to absorb the heat of the surrounding medium when the refrigerant is vaporized and volatilized, to lower the temperature for cooling, and then to pass the refrigerant through the compressor. Revert to liquid, re-gasify, and so on. This type of refrigeration system is widely used in household appliances such as refrigerators and air conditioners, industrial equipment such as cold storage and cold storage rooms, and commercial equipment such as display cases, beverages, and ice cream machines. The compressor is the heart of this refrigeration system, and the refrigeration oil that acts as lubrication, heat dissipation, sealing and anti-corrosion in the compressor has a very important impact on the performance and life of the compressor and refrigeration system, especially for compression. The energy saving of the refrigeration system is closely related. Therefore, it is very important to select the refrigerating machine oil with excellent performance for the compression refrigeration system.

In the past, compression refrigeration systems generally used Freon, including dichlorodifluoromethane (R12), fluorotrichloromethane (Rll), and difluorochloromethane (R22) as refrigerants. However, the chlorine atoms in the Freon substances react in a chain reaction with ozone, causing severe damage to the ozone layer on the Earth's surface, causing ozone holes in the Arctic and the Arctic. It is well known that there is no ozone layer, and the sun's ultraviolet rays will directly hit the earth, causing environmental problems such as increased risk of skin cancer and beneficial microbial death. In order to protect the atmospheric ozone layer closely related to human life, the governments of the world signed the Montreal Protocol in 1987 and the Rio Declaration in 1992, which jointly formulated restrictions and bans on Freon. Timetable for the production and use of materials. China has completely banned R12 refrigerant since 2005.

In order to comply with the regulations on the restriction and ban of Freon substances, since the 1990s, the world has conducted extensive research on new chlorine-free refrigerants and their associated refrigeration oils. DuPont Company of the United States pioneered the development of a chlorine-free refrigerant, tetrafluoroethylene (R134A), which does not destroy the ozone layer, and its main performance is very close to that of R12, so it has been widely used. However, it was later discovered that the greenhouse effect index of R134A is too high; in addition, the refrigerant is very demanding on the refrigeration system, which limits its use surface. Low molecular hydrocarbon refrigerants such as R600A are favored because they have the advantages of not destroying the ozone layer, small greenhouse effect index, high energy efficiency ratio and no environmental problems. They have been widely promoted recently and have become the mainstream of alternative refrigerants. . Different refrigerants have different solubility and stability than refrigerator oils. Therefore, it is necessary to choose a refrigerating machine oil that has good solubility and stability with R600A refrigerant.

Refrigeration oils generally include base oils and various additives to improve other properties of the refrigeration oil, such as lubricants, friction reducers, antioxidants, corrosion inhibitors, antifoaming agents. The main properties of the refrigerating machine oil such as rheology, viscosity-temperature properties, low-temperature fluidity, flash point, pour point and miscibility with refrigerant are determined by the nature of the base oil. Therefore, the choice of refrigeration oil is mainly focused on the selection of base oil. R600A is a light hydrocarbon. According to the principle of similar compatibility, hydrocarbon oil has good mutual solubility with R600A. As a refrigerating machine oil for R600A refrigerant, Japanese Patent Laid-Open No. 10-130685 proposes the use of anthraquinone mineral oil and deep dewaxed paraffinic mineral oil, branched mercaptobenzene, polyether, ester oil and fluorine oil. Synthetic oil is used as the base oil. However, synthetic oils such as polyethers, ester oils and fluoro oils are expensive and not sufficiently soluble in R600A; deep dewaxed paraffinic mineral oils have poor low-temperature fluidity; deep dewaxing or hydroisomerization Although the waxy base oil and the branched mercaptobenzene have excellent low-temperature properties and good solubility with R600A, their viscosity index and flash point are low, and the lubricating performance is poor. It is not conducive to the reduction of friction and energy saving of low viscosity oil products.

CN 1470626A discloses a refrigerating machine oil composition which utilizes a distillation experiment method by gas chromatography to determine a fraction having a boiling point below 300 ° C and a fraction of 5 to 35 wt %, and a fraction having a boiling point of 500 ° C or more. 5-35 wt%, and using the same method, 20% of the distillation temperature above 250 °〇 is measured, the %〇 of the ndM ring analysis is above 35%, the nitrogen content is below 10 ppm, and the flow point is -20. Below °C, the viscosity at 40 ° C is 7-150 mm 2 / sec. Although the oil has good anti-wear properties and suppresses the advantage of generating sludge at the compressor exhaust valve, those skilled in the art know that the fraction below 300 ° C is actually a diesel fraction, so the method actually passes Diesel fuel is added to reduce the viscosity of the refrigerating machine oil composition, and the addition of diesel fuel undoubtedly results in a low flash point and poor safety of the refrigerating machine oil composition. Moreover, when the diesel is volatilized or the content is lowered, the remaining fraction, especially the fraction having a boiling point above 500 °C, has a very high viscosity, resulting in high energy consumption. Further, such a refrigerating machine oil composition has a disadvantage of poor compatibility with R600A and poor low-temperature fluidity.

CN 1054154 A discloses a refrigerating machine oil composition comprising 0.1 to 5% by weight of an epoxide stabilizer, 0.1 to 5% by weight of a phosphate-based lubricant, 0.1 based on the total amount of the composition. -3% by weight of the phenolic antioxidant and the balance of viscosity of 30-100 mm / sec mixing soft wax cracking of C ₅ -C ₁₈ α-olefin polymerized oil. A soft wax-cracked C ₅ -C ₁₈ mixed alpha olefin prepared mixed alpha olefin polymer oil enables the refrigerating machine oil composition containing the polymer oil to have excellent compatibility with R600A and thermochemical stability, and a high viscosity index. , higher flash point, and low raw material cost. However, the energy saving rate is only 3% or less. For today's world of energy shortages, it is clear that products with higher energy savings are more competitive.

CN 1099454 A discloses a hydrocarbon-containing refrigerator oil composition comprising a hydrocarbon oil as a base oil, the hydrocarbon oil being at least selected from the group consisting of mineral oil, olefin polymer, naphthalene compound and mercaptobenzene. One. The olefin polymer comprises a C ₁₆ -C _2Q a olefin oligomer, which uses a Ziegler catalyst method, a radical polymerization method, an aluminum chloride method, or a boron fluoride by using ethylene as a raw material. A known polymerization method such as a method is obtained by oligomerization. The α-olefin polymer obtained by this method generally has a viscosity at 40 ° C of more than 6 mm 2 /sec, and is 6.5 to 8.0 mm 2 /sec, making it difficult to obtain a lower viscosity oil.

In general, the lower the viscosity of the refrigerating machine oil, the better the low-temperature fluidity, and the better the energy saving effect. Therefore, in order to achieve energy saving, attempts have been made to produce a low-viscosity refrigeration oil by cutting a suitable fraction with cycloaliphatic mineral oil. Although the viscosity of this oil can reach a low viscosity of 5 mm 2 / sec at 40 ° C, the flash point and ignition point of this oil are too low and the safety is poor. It is difficult to reach the minimum flash point of the refrigeration compressor to the refrigerating machine oil ( The requirement of more than 130 ° C), combined with the wide fraction and high volatility of this oil, is easy to carry oil in the compressor. In addition, the oil has a low viscosity index and a slightly poor lubricity, which cannot be satisfied. Requirements for the use of conventional compression refrigeration systems.

In short, there is currently no low-viscosity refrigeration oil that is truly energy efficient and has good compatibility with R600A. Therefore, there is an urgent need to develop a low viscosity refrigerator oil composition product which can further improve the energy saving rate and has good compatibility with R600A.

[Summary of the Invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a refrigerating machine oil composition which is excellent in energy saving effect and good in compatibility with R600A, in order to overcome the disadvantages of the prior art refrigerating machine oil composition having low energy saving effect or poor compatibility with R600A.

The inventors of the present invention have unexpectedly discovered that a C ₁₅ -C ₂₂ mixed olefin polymerization oil obtained by polymerization of a C ₅ -C ₇ mixed alpha olefin or by arylation of a C ₁₀ -C ₁₄ mixed olefin or The arylation product of C ₁₆ -C ₂₂ has a viscosity of 3 to less than 6 mm 2 /sec at 40 ° C, and has a high flash point, good low-temperature fluidity, and good compatibility with R600A, which can satisfy energy saving. The requirements meet the requirements of refrigeration oil for safety, low temperature fluidity and compatibility with R600A.

The refrigerator oil composition provided by the present invention contains a mixed alpha olefin polymer oil and an additive as a base oil, wherein the mixed alpha olefin polymer oil has a viscosity at 40 ° C of 3 to less than 6 mm 2 /sec. The olefin polymer oil is a C ₁₅ -C ₂₂ mixed isoolefin, a C ₁₅ -C ₂₂ mixed isomeric hydrocarbon or a mixture of a C ₁₅ -C ₂₂ mixed isoolefin and a C ₁₅ -C ₂₂ mixed isomeric hydrocarbon.

The method for producing a refrigerating machine oil composition provided by the present invention comprises uniformly mixing a mixed α-olefin polymerization oil as a base oil and an additive, wherein the mixed α-olefin polymerization oil has a viscosity at 40 ° C of 3 to less than 6 mm 2 / Second, the mixed a-olefin polymerization oil is a C ₁₅ -C ₂₂ mixed isomer, a C ₁₅ -C ₂₂ mixed isomer or a C ₁₅ -C ₂₂ mixed isomer and a C ₁₅ -C ₂₂ mixed isomer Mixing of Hydrocarbons The refrigerating machine oil composition provided by the invention has the following advantages: (1) excellent solubility with R600A refrigerant, flocculation point as low as -70 ° C or less; (2) high flash point and ignition point a flash point of up to 160 ° C, flash point up to 170 ° _C; (3) having excellent low temperature fluidity, low pour point -70 ° C, -40 ° C kinematic viscosity is less than 500 mm2 / s (4) With a significant energy saving effect, the refrigerating machine oil composition provided by the present invention is 12% more energy efficient than a refrigerating machine oil having a viscosity of 22 mm 2 /sec at 40 ° C, and a viscosity of 10 mm 2 at 40 ° C. / sec refrigerating machine oil energy saving 4%; (5) has a higher viscosity index, than the ring垸-based freezer oil is 20-40 high; (6) has a lower friction coefficient in the elastic fluid lubrication zone (EHL), which is 0.02-0.03 lower than that of the ring-based chiller oil; (7) has good thermochemical stability Sex. The refrigerating machine oil provided by the invention is particularly suitable for use as a refrigerating machine oil with R600A as a refrigerant, and can also be used for multi-component mixed working fluids and hydrochlorofluorocarbons. Refrigerator for refrigerant

【detailed description】

According to the present invention, the content of the base oil and the additive in the refrigerating machine oil composition may be a conventional content in the art. For example, the base oil may be contained in an amount of 70 to 99.5% by weight based on the total amount of the composition. It is from 75 to 97% by weight; the content of the additive may be from 0.5 to 30% by weight, preferably from 3 to 25% by weight.

According to the present invention, the object of the present invention can be attained as long as the viscosity of the mixed alpha olefin polymerized oil obtained by polymerization of an olefin is from 3 to less than 6 mm 2 /sec, for example, a viscosity of 40 ° C of the mixed alpha olefin polymerization oil. It may be 3-5.9 square millimeters per second, preferably 4-5.9 square millimeters per second.

Although any mixed alpha olefin polymer oil satisfying the above conditions can achieve the object of the present invention, preferably, the distillation range of the mixed alpha olefin polymerization oil is 250-310 ° C measured by a gas chromatographic distillation range method. It is preferably 270 to less than 300 °C. More preferably, the fraction having a distillation range of from 250 to 290 ° C accounts for 60 to 100% by weight, and the fraction having a distillation range of more than 290 ° C to 300 ° C accounts for 0 to 40% by weight. Further, it is preferable that the fraction having a temperature of 270-290 ° C accounts for 60-100% by weight, and the fraction having a distillation range of more than 290 ° C to less than 300 ° C accounts for 0-40% by weight.

The inventors of the present invention have found that when the mixed alpha olefin polymerization oil is a mixture of a C ₁₅ -C ₂₂ mixed isomer and a C ₁₅ -C ₂₂ mixed isomerized amidine, the mixture is used as a base oil to obtain a refrigerating machine oil. It is better than the mixed alpha olefin polymerized oil C ₁₅ -C ₂₂ mixed olefin or C ₁₅ -C ₂₂ mixed isomeric terpene hydrocarbon as a base oil in terms of low temperature fluidity, lubricity and extreme pressure, therefore, Preferably, the mixed alpha olefin polymer oil is a mixture of a C ₁₅ -C ₂₂ mixed isoolefin and a C ₁₅ -C ₂₂ mixed isomeric terpene. Despite the mixing of the C ₁₅ -C ₂₂ mixed olefin with a C ₁₅ -C ₂₂ mixed isomeric terpene hydrocarbon The c ₁₅ -c ₂₂ mixed olefin and the c ₁₅ -c ₂₂ mixed isomeric hydrocarbon may be in any ratio, but preferably, the C ₁₅ -C ₂₂ mixed olefin is mixed with C ₁₅ -C ₂₂ . The weight ratio of isomeric terpene hydrocarbons is from 2:8 to 3:7. This may be because the mixed olefin can increase the asymmetry of the molecule and improve the low temperature performance of the oil; it can also increase the polarity of the molecule and increase the extreme pressure performance of the oil. When the C ₁₅ -C ₂₂ mixed olefin is mixed with the C ₁₅ -C ₂₂ mixed isomerized hydrocarbon in a weight ratio of 2:8 to 3:7, the "coordination effect" is exhibited, and the best effect is obtained.

The inventors of the present invention have found that although the C ₁₅ -C ₂₂ mixed olefin can be obtained in various ways, for example, in addition to the following trimerization of a C ₅ -C ₇ ci olefin, it can also be obtained by oligomerization of the aforementioned ethylene, or by The C ₈ -C ₁₂ ci olefin is dimerized, or obtained by pentapolymerization of a C ₃ -C ₅ ci olefin, but the mixed a olefin polymerized oil obtained by dimerization of a C ₈ -C ₁₂ ci olefin generally has a viscosity at 40 ° C. More than 6 square millimeters per second. The use of C ₃ -C ₅ mixed pentapolymers of olefins, the viscosity index is too small, the flash point is low, the safety is too poor, and it is not suitable as a base oil for low viscosity refrigeration oil. The C ₁₅ -C ₂₂ mixed olefin obtained by the trimerization reaction of C ₅ -C ₇ a olefin is mostly a trimer of C ₅ -C ₇ ci olefin, and this trimer has moderate asymmetry. High flash point, excellent low temperature fluidity and a suitable low viscosity (generally in the range of 3 to less than 6 mm 2 /sec).

Therefore, according to the present invention, the C ₁₅ -C ₂₂ mixed olefin is obtained by a trimerization reaction of a C ₅ -C ₇ ci olefin, specifically, the preparation method of the C ₁₅ -C ₂₂ mixed olefin includes under olefin polymerization conditions, The C ₅ -C ₇ mixed a olefin is contacted with an olefin polymerization catalyst at a temperature of 130-160 ° C, a contact pressure of 0.1-0.2 MPa, and an olefin polymerization catalyst of a C ₅ -C ₇ mixed a olefin weight. 0.2-3% by weight, the olefin polymerization catalyst is a super acid catalyst, a heteropoly acid catalyst or a Lewis acid complex catalyst. The type, composition and preparation method of the catalyst have been reported in detail in various patents and non-patent documents. Wherein, the super acid catalyst may be a solid super acid catalyst or a liquid super acid catalyst, and the solid super acid catalyst may be selected, for example, from S0 ₄ ² —, CK or N0 ₃ — a solid superacid supported on a metal oxide selected from the group consisting of oxides of metal elements of Groups IV, IVB, VB, VIB, VIIB, VII, VIII and IIIA of the Periodic Table of the Elements, preferably said oxidation The material is an oxide of zinc, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, aluminum or gallium, more preferably an oxide of zirconium. Wherein the ratio of S0 ₄ ² —, CK , N0 ₃ — to the metal oxide is a conventional ratio in the art, for example, the content of N0 ₃ — is 0.1 to 10% by weight based on the total amount of the solid super acid. The weight of the metal oxide is from 90 to 99.9% by weight. The preparation method of the super acid is well known to those skilled in the art and will not be described herein. The heteropolyacid may be phosphotungstic heteropoly acid, molybdenum vanadium heteropoly acid, tungsten silicopoly acid, phosphomolybdic heteropoly acid, tungsten phosphopolyacid. The Lewis acid complex catalyst may be BF ₃ 'ROH, AlCl ₃ -NaCK AlCl ₃ 'Eto, A1C1 ₃ 'R0H, A1C1 ₃ -RC=0, and R is preferably a fluorenyl group having 1 to 6 carbon atoms. The olefin polymerization may be continuous or batch, and the continuous form may be, for example, in the form of a fixed bed. For general laboratory testing, olefin polymerization is usually carried out in a batch process; for industrial production, a continuous process is generally employed for olefin polymerization. When the olefin polymerization is carried out by a batch method, the contact time may be from 1 to 4 hours.

According to the present invention, the preparation method of the C ₁₅ -C ₂₂ mixed olefin further comprises adding a basic substance and a filter aid after the C ₅ -C ₇ mixed α olefin is contacted with the olefin polymerization catalyst, at 70-80 ° C The lower reaction is distilled after 0.5 to 2 hours, and a fraction having a viscosity of 3 to less than 6 mm 2 /sec is cut out, i.e., a C ₁₅ -C ₂₂ mixed olefin which is a mixed alpha olefin polymerization oil required for the present invention. Wherein, the alkaline substance may be an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkali metal oxide or an alkali metal hydroxide, such as CaO, Ca(OH) ₂ , magnesium oxide, sodium hydroxide, preferably Ca (OH) ₂ . The filter aid may be, for example, activated clay, alumina, preferably activated clay. The basic substance such as Ca(OH) ₂ and a filter aid such as activated clay may be added in an amount of 1-5 wt%, preferably 2-3 wt%, of the total amount of the C ₅ -C ₇ mixed a olefin and the catalyst, respectively. %. The c ₁₅ -c ₂₁ mixed isomeric hydrocarbon may be a hydrogenated product of the c ₁₅ -c ₂₁ mixed olefin or

The arylation product of C _{1 (r} C ₁₄ mixed ci olefin. The hydrogenated product of the C ₁₅ -C ₂₂ mixed olefin can be obtained by various methods well known in the art, preferably the C ₁₅ -C ₂₂ mixed olefin The preparation method of the hydrogenation product comprises: contacting the c ₁₅ -c ₂₂ mixed olefin with hydrogen under hydrogenation conditions and in the presence of a hydrogenation catalyst; the hydrogenation conditions include a temperature of 260-280 ° C, hydrogen partial pressure The volume ratio of 3-7 MPa, hydrogen to C ₁₅ -C ₂₂ mixed olefin is 8-16; the hydrogenation catalyst is Ni-W-Mo-F, Pt- a A1 ₂ 0 ₃ Rayleigh (Raney Ni One or more of nickel and amorphous nickel. The hydrogenation is preferably a two-stage hydrogenation, wherein one stage of hydrogenation is preferably at a temperature of 270-280 ° C and a hydrogen partial pressure of 3-7 MPa, The volume ratio of hydrogen to oil is 8-16, and the catalyst is carried out under the condition of Ni-W-Mo-F; the second stage hydrogenation is preferably at a temperature of 260-270 ° C, a hydrogen partial pressure of 3-7 MPa, hydrogen and The oil has a volume ratio of 8 to 16 and the catalyst is Pt-a A1 ₂ 0 ₃ . The hydrogenation operation is well known to those skilled in the art and will not be described herein. The C ₁₅ -C ₂₂ mixture The side of the olefin in contact with hydrogen The formula may be continuous or batch, and the continuous type may be carried out using a fixed bed. When the olefin hydrogenation is carried out by a batch method, the contact time may be 2-12 hours; when the olefin polymerization is carried out by a batch method When the volume airspeed can be 5-24 hours - ¹ .

When the above hydrogenation is combined with the preparation of a C ₁₅ -C ₂₂ mixed olefin, the hydrogenation may be carried out before the above-mentioned distillation with the basic substance and the filter aid, or after the distillation.

The arylation product of the C _1Q -C ₁₄ mixed a olefin can be carried out by various methods known in the art, and the method for preparing the aryl thiolated product of the _{1 ()} - ₁₄ mixed olefin is preferably included in the present invention. The C _1Q -C ₁₄ mixed a olefin is contacted with a C ₆ -C ₈ aromatic hydrocarbon in the presence of a thiolation catalyst; the thiolation condition includes a catalyst added in an amount of C _1Q -C ₁₄ mixing 0.2-2 weight olefins and C ₆ -C ₈ aromatics total weight%, C _1Q -C ₁₄ olefins mixture and a C ₆ -C ₈ aromatics weight ratio 1 : 1-1 : 1.2, the contact temperature is 60-90 ° C; the thiolation catalyst is one or more of HF, BF ₃ , A1C1 ₃ , solid super acid catalyst and heteropoly acid catalyst. The C _1Q -C ₁₄ mixed a olefin may be contacted with a C ₆ -C ₈ aromatic hydrocarbon in a continuous or batch manner, and the continuous process may be carried out using a fixed bed. When the arylation is carried out by a batch method, the contact time may be 1-3 hours. The C _1Q -C ₁₄ mixed olefin is one or more of a C _1Q -C ₁₄ alpha olefin, a C _1Q -C ₁₄ wax cracking olefin, and a C _1Q -C ₁₄ normal terpene hydrocarbon dehydro olefin; The C ₆ -C ₈ arene is one or more of benzene, toluene, xylene, and ethylbenzene.

According to the refrigerating machine oil composition provided by the present invention, the additive and its content may be various conventional additives for the refrigerating machine oil composition and their conventional contents. For example, the additive may be a lubricant for improving the lubricating properties of the refrigerating machine oil, an antifriction agent for improving the antifriction property, and an antioxidant, an anticorrosive agent, an antifoaming agent and the like for improving the thermal oxidation stability.

The lubricant may be a phosphate ester lubricant commonly used in the art, such as tricresyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, benzyl diphenyl phosphate, phenyl thiophosphoric acid. One or more of the esters. The lubricant may be included in an amount of from 0 to 6.0% by weight, based on the total amount of the composition, preferably from 1.0 to 3.5% by weight.

The friction reducing agent may be one or more of long-chain fatty acids, long-chain fatty alcohols, long-chain fatty esters, amides, phosphonates, and commercially available energy-saving antifriction agents commonly used in the art, and specifically may be Oleic acid, dimerized linoleic acid, decadiol, butyl stearate, ethylene oleate, oleic acid amide, benzotriazole dodecylamine, etc., diisooctylphosphonate and eutectic roll One or several of the balls. The antifriction agent may be included in an amount of 0 to 0.8% by weight, preferably 0.02 to 0.6% by weight based on the total amount of the composition.

The antioxidant may be various phenolic antioxidants commonly used in the art, such as 2,6-di-tert-butyl-p-cresol, 2,3-di-tert-butyl-4-methylphenol, 2,6- Di-tert-butylphenol, 4,4'-tetramethylbis(2,6-di-tert-butylphenol), One or more of hydroquinone and β-naphthol. The antioxidant may be included in an amount of from 0 to 3% by weight, preferably from 0.2 to 0.8% by weight, based on the total amount of the composition.

The anticorrosive agent may be a benzotriazole derivative and a thiadiazole derivative anticorrosive agent commonly used in the art, such as anthracene, fluorenyl-dimercaptoaminomethylene benzotriazole, 2,5-dimercapto-1. One or more of a 3,4-thiadiazole derivative, a dimercapto-benzothiadiazole, or a dimercaptothiadiazole sodium. The anticorrosive agent may be included in an amount of 0 to 0.1% by weight, preferably 0.02 to 0.05% by weight based on the total amount of the composition.

The antifoaming agent may be an antifoaming agent commonly used in the art, such as one or more of a dimethicone, a homopolymer or a copolymer of acrylate. The antifoaming agent may be included in an amount of 0 to 0.01% by weight, preferably 0.001 to 0.005% by weight based on the total amount of the composition.

Unless otherwise stated, the starting materials and reagents of the present invention are all commercially available.

Since the present invention relates only to the improvement of the components of the refrigerating machine oil composition, the preparation method of the refrigerating machine oil composition is not particularly limited, and a conventional operation method may be employed, for example, including mixing the base oil and various additives uniformly. Wherein, the base oil can be prepared by the above method of the invention.

In the present invention, the distillation range is measured by the ASTM D 2887 standard method, which is a petroleum product fraction distribution measurement method by gas chromatography; the viscosity is measured by the GB/T 265 method.

The invention will now be further illustrated by way of examples. Example 1

This embodiment is for explaining the refrigerating machine oil composition provided by the present invention and a preparation method thereof.

1000 parts by weight of C ₅ -C ₇ mixed a olefin (provided by Lanzhou Petrochemical General Plant) and 10 parts by weight of phosphotungstic heteropoly acid were reacted at 140 ° C, 0.1 MPa for 1.5 hours, cooled and settled to remove sediment, after product 20 parts by weight of Ca(OH) ₂ and 30 parts by weight of activated clay were added thereto, and reacted at 75 ° C for 0.5 hour. The clay was removed by filtration, and cut under reduced pressure to obtain 600 parts by weight of an ISO VG5 fraction, and the viscosity of the fraction was measured to be 4 mm 2 /sec, wherein the distillation range was 272-288 ° C, 80% by weight, and the distillation range was greater than 288. 20% by weight from °C to 300 °C. 100 parts by weight of the above fraction and 0.5 parts by weight of 2,6-di-tert-butyl-p-cresol, 3 parts by weight of tricresyl phosphate, 0.2 parts by weight of ethylene oleate and 0.03 parts by weight of ruthenium, ruthenium-II were taken out therefrom. The mercaptoaminomethylene benzotriazole was uniformly mixed and formulated into a refrigerating machine oil composition Sl, and its physical and chemical properties are shown in Table 1. Example 2

1000 parts by weight of ash cracked C ₆ -C ₇ mixed a olefin (supplied by Fushun Petroleum Plant No. 1) and 5 parts by weight of AlCl ₃ .NaCl were reacted at 150 ° C, 0.2 MPa for 1.5 hours, and after cooling and sedimentation, the sediment was separated. 30 parts by weight of Ca OH; i ₂ and 20 parts by weight of activated clay were added to the product, and the mixture was reacted at 75 ° C for 0.5 hour, and the clay was removed by filtration, and cut under reduced pressure to obtain 700 parts by weight of an ISO VG5 fraction, and the fraction was measured. The viscosity was 5 mm 2 /s, the distillation range was 271-290 ° C, which was 68% by weight, and the distillation range was 290 ° C or more to 300 ° C, which was 32% by weight. 100 parts by weight of the above fraction and 0.3 parts by weight of 4,4'-tetramethylbis(2,6-di-tert-butylphenol), 2 parts by weight of phenylphosphorothioate, 1 part by weight of eutectic balls, 0.03 parts by weight of the dimercapto-benzothiadiazole was uniformly mixed and formulated into a refrigerating machine oil composition S2, and its physical and chemical properties are shown in Table 1. Example 3

1000 parts by weight of soap-cracked C ₅ -C ₇ mixed a olefin (provided by Fushun Petroleum No. 1 Plant) and 12 parts by weight of BF ₃ .CH ₃ C3⁄4OH was reacted at 140 ° C, 0.15 MPa for 1.5 hours, and after cooling and sedimentation, 30 parts by weight of Ca OH; i ₂ and 20 parts by weight of activated clay were added to the product. The reaction was carried out at ° C for 0.5 hour, and the clay was removed by filtration, and cut under reduced pressure to obtain 500 parts by weight of an ISO VG5 fraction. The viscosity of the fraction was 3.6 mm 2 /sec, and the distillation range was 262-280 ° C. %, the distillation range is 280-300 ° C, accounting for 19% by weight. 100 parts by weight of the above fraction and 0.3 parts by weight of 4,4'-tetramethylbis(2,6-di-tert-butylphenol), 2 parts by weight of phenylphosphorothioate, 1 part by weight of eutectic balls, 0.03 parts by weight of dimercaptobenzothiadiazole was uniformly mixed and formulated into a refrigerating machine oil composition S3, and its physical and chemical properties are shown in Table 1. Example 4

1000 parts by weight of soft wax (oil content 20%) cracked C ₅ -C ₆ mixed alpha olefin (provided by Fushun Petroleum Plant No. 1) and 10 parts by weight of S0 ₄ ² 7Zr0 ₂ catalyst were reacted at 135 ° C, 0.11 MPa 1.0. After cooling and sedimentation, the product was added with 30 parts by weight of Ca OH; i ₂ and 20 parts by weight of activated clay, and reacted at 75 ° C for 0.5 hours. The clay was removed by filtration and cut under reduced pressure to obtain 680 weight. The fraction of ISO VG5 was measured to have a viscosity of 4.5 mm 2 /s, a distillation range of 270-290 ° C of 63% by weight, and a distillation range of 290 ° C or more to 310 ° C of 37 % by weight. 100 parts by weight of the above fraction and 0.3 parts by weight of 4,4'-tetramethylbis(2,6-di-tert-butylphenol), 2 parts by weight of phenylphosphorothioate, 1 part by weight of eutectic balls, 0.05 parts by weight of benzotriazole dodecylamine salt and 0.03 parts by weight of 2,5-dimercapto-1,3,4-thiadiazole were uniformly mixed and formulated into a refrigerating machine oil composition S4, and the physical and chemical properties thereof are shown in Table 1. Example 5

200 parts by weight of white wax cracked C _1Q -C ₁₄ mixed a olefin (provided by Fushun Petroleum Plant No. 1) and 100 parts by weight of benzene were reacted in 3 parts by weight of C10 ₄ 7Zr0 ₂ catalyst at 65 ° C, 0.1 MPa for 3 hours, and cooled. After sedimentation and sedimentation, 10 parts by weight of Ca OH; i ₂ and 10 parts by weight of activated clay were added to the product, and reacted at 75 ° C for 0.5 hour. The clay was removed by filtration and cut under reduced pressure to obtain 560 parts by weight of ISO VG5. The fraction was found to have a viscosity of 4.6 mm 2 /sec, a distillation range of 272 to 290 ° C of 88% by weight, and a distillation range of 290 to 300 ° C of 12% by weight. 100 parts by weight of the above fraction and 0.3 parts by weight of 4,4'-tetramethylbis(2,6-di-tert-butylphenol), 2 parts by weight of phenylphosphorothioate, 1 part by weight of eutectic balls, 0.05 parts by weight of benzotriazole dodecylamine salt and 0.03 parts by weight of 2,5-dimercapto-1,3,4-thiadiazole were uniformly mixed and formulated into a refrigerating machine oil composition S5, and the physical and chemical properties thereof are shown in Table 1. Example 6

1000 parts by weight of C ₅ -C ₇ mixed a olefin (provided by Lanzhou Petrochemical General Plant) and 10 parts by weight of phosphotungstic heteropoly acid were reacted at 140 ° C, 0.12 MPa for 1.5 hours, cooled and settled to remove sediment, after product 20 parts by weight of Ca OH; i ₂ and 30 parts by weight of activated clay were added, and reacted at 75 ° C for 0.5 hour, and the clay was removed by filtration, and cut under reduced pressure to obtain 600 parts by weight of an ISO VG5 fraction, and the viscosity of the fraction was measured. It is 4.8 mm 2 /sec, in which the distillation range is 272-288 ° C, which accounts for 80% by weight, and the distillation range is more than 288 ° C to 300 ° C, which is 20% by weight.

1000 parts by weight of C ₅ -C ₇ mixed a olefin (provided by Lanzhou Petrochemical General Plant) and 10 parts by weight of phosphotungstic heteropoly acid were reacted at 140 ° C, 0.2 MPa for 1.5 hours, cooled and settled to separate the residue, after the product 20 parts by weight of Ca(OH) ₂ and 30 parts by weight of activated clay were added, and reacted at 75 ° C for 0.5 hours, and then the obtained product was subjected to two-stage hydrogenation, wherein a hydrogenation temperature was 270-280 ° C, hydrogen The partial pressure is 3-7 MPa, the volume ratio of hydrogen to oil is 8-16, the catalyst is Ni-W-Mo-F; the temperature of the second stage hydrogenation is 260-270 ° C, and the hydrogen partial pressure is 3-7 MPa, the volume ratio of hydrogen to oil is 8-16, and the catalyst is Pt-α A1 ₂ 0 ₃ . After hydrogenation, the clay is removed by filtration and cut under reduced pressure to obtain 600 parts by weight of ISO VG5 fraction. The viscosity of the fraction was 4.3 mm 2 /sec, wherein 70% by weight of the distillation range was 272-288 ° C and 30 wt % of the distillation range was more than 288 ° C to 300 ° C.

50 parts by weight and 0.5 part by weight of 2,6-di-tert-butyl-p-cresol, 3 parts by weight of tricresyl phosphate, 0.2 parts by weight of ethylene oleate and 0.03 parts by weight of hydrazine were taken out from each of the above two fractions. The hydrazine-dimercaptoaminomethylene benzotriazole was uniformly mixed and formulated into a refrigerating machine oil composition S6, and its physical and chemical properties are shown in Table 1. Comparative example 1

1000 parts by weight of C _1Q ci olefin obtained by ethylene oligomerization (supplied by Jilin Petrochemical Co., Ltd.) and 10 parts by weight of phosphotungstic heteropoly acid were reacted at 140 ° C for 1.5 hours, and after cooling and sedimentation, the product was added to 20 Parts by weight of Ca OH; i ₂ and 30 parts by weight of activated clay were reacted at 75 ° C for 0.5 hour, and the clay was removed by filtration and cut under reduced pressure to obtain 200 parts by weight of ISO VG7 fraction, and the viscosity of the fraction was determined to be 6.5 square. Mm/sec, wherein 20% by weight of the distillation range is 270-288 ° C and 80 wt% of the distillation range is greater than 288 ° C to 300 ° C. 100 parts by weight of the above fraction and 0.5 parts by weight of 2,6-di-tert-butyl-p-cresol, 3 parts by weight of tricresyl phosphate, 0.2 parts by weight of ethylene oleate and 0.03 parts by weight of ruthenium, ruthenium-II were taken out therefrom. The mercaptoaminomethylene benzotriazole was uniformly mixed and formulated into a reference refrigeration oil composition CS1, and its physical and chemical properties are shown in Table 1. Comparative example 2

1000 parts by weight of C ₈ -C ₁₂ mixed a olefin (provided by Lanzhou Petrochemical General Plant) and 10 parts by weight of phosphotungstic heteropoly acid were reacted at 140 ° C for 1.5 hours, and after cooling and sedimentation, the weight was added to the product, and 20 weight was added to the product. Ca OH; i ₂ , 30 parts by weight of activated clay, reacted at 75 ° C for 0.5 hour, the clay was removed by filtration, and cut under reduced pressure to obtain 300 parts by weight of ISO VG7 fraction, and the viscosity of the fraction was measured to be 7.5 mm 2 . / sec, wherein 20% by weight of the distillation range is 270-290 ° C, and 80% by weight of the distillation range is greater than 290 ° C to 340 ° C. 100 parts by weight of the above fraction and 0.5 parts by weight of 2,6-di-tert-butyl-p-cresol, 3 parts by weight of tricresyl phosphate, 0.2 parts by weight of ethylene oleate and 0.03 parts by weight of ruthenium, ruthenium-II were taken out therefrom. The mercaptoaminomethylene benzotriazole was uniformly mixed and formulated into a reference refrigeration oil composition CS2, and its physical and chemical properties are shown in Table 1. Comparative example 3

1000 parts by weight of C ₃ -C ₅ mixed a olefin (provided by Lanzhou Petrochemical General Plant) and 10 parts by weight of phosphotungstic heteropoly acid were reacted at 40 ° C for 1.5 hours, and after cooling and sedimentation, the weight was added to the product, and 20 weight was added to the product. Ca OH; i ₂ , 30 parts by weight of activated clay, reacted at 75 ° C for 0.5 hour, the clay was removed by filtration, and cut under reduced pressure to obtain 200 parts by weight of ISO VG10 fraction, and the viscosity of the fraction was measured to be 9.5 mm 2 . / sec, wherein the distillation range is 275-288 ° C, accounting for 15% by weight, and the distillation range is greater than 288 ° C to 360 ° C, accounting for 85% by weight. 100 parts by weight of the above fraction and 0.5 parts by weight of 2,6-di-tert-butyl-p-cresol, 3 parts by weight of tricresyl phosphate, 0.2 parts by weight of ethylene oleate and 0.03 parts by weight of ruthenium, ruthenium-II were taken out therefrom. The mercaptoaminomethylene benzotriazole was uniformly mixed and formulated into a reference refrigeration oil composition CS3, and its physical and chemical properties are shown in Table 1. Comparative example 4

The same physicochemical properties were evaluated for the most widely used hydrocarbon-based refrigerating machine oil CS4 (produced by sunisolGS Aj sun oil Co.) with R600A as the refrigerant. The results are shown in Table 1.

Comparative Example 5 The same physical and chemical properties were evaluated. The results are shown in Table 1. Table 1

Note 1: The SRV friction and wear tester measures the test conditions: room temperature, 1500 y / min, 50 N, 60 min.

Note 2: Determined by micro-tractor (MTM), the test conditions are: 1.25 gigapascals, 40 ° C, 10% rolling ratio. Compressor performance test

The refrigerating machine oil samples prepared in Examples 1-6 and Comparative Examples 1-5 were each taken into a refrigerator compressor, and 30 g of R600A was used as a refrigerant, and performance tests were performed on a compressor performance test stand to determine their COP. Values, and their energy saving effects are derived from the COP values. The results are shown in Table 2.

Table 2

It can be seen from the results of Tables 1 and 2 above that the refrigerating machine oil composition provided by the present invention has excellent compatibility with thermochemical stability with R600A refrigerant, and has a higher viscosity index, a higher flash point, and an excellent The low temperature fluidity and good lubricity and low friction coefficient show obvious energy saving effects.

Claims

Claim

A refrigerating machine oil composition comprising a mixed alpha olefin polymer oil and an additive as a base oil, wherein the mixed alpha olefin polymer oil has a viscosity of from 3 to less than 6 mm 2 at 40 ° C / Second, the mixed alpha olefin polymer oil is a C ₁₅ -C ₂₂ mixed isoolefin, a C ₁₅ -C ₂₂ mixed isomeric hydrocarbon or a C ₁₅ -C ₂₂ mixed isoolefin and a C ₁₅ -C ₂₂ mixed isomer a mixture of hydrocarbons.

The composition according to claim 1, wherein the content of the mixed α-olefin-polymerized oil is 70 to 99.5% by weight, and the content of the additive is 0.5 to 30% by weight based on the total amount of the composition.

The composition according to claim 1 or 2, wherein the mixed alpha olefin polymer oil has a viscosity at 40 ° C of from 4 to 5.9 mm 2 /sec.

4. The composition of claim 1 or claim 2, wherein the α-olefin polymerized oil is mixed C ₁₅ -C ₂₂ mixture was mixed with ₂₂ isoolefin embankment mixed isomers of C ₁₅ -C hydrocarbons, the C a mixture of hydrocarbons ₁₅ -C ₂₂ mixed isomers embankment ₁₅ -C ₂₂ olefins with C mixed isomers, the C ₁₅ -C ₂₂ isoolefin mixed C ₁₅ -C ₂₂ hydrocarbon weight ratio of mixed isomers embankment 2 :8-3:7.

The composition according to claim 1, wherein the C ₁₅ -C ₂₂ mixed isomer is prepared by contacting a C ₅ -C ₇ mixed a olefin with an olefin polymerization catalyst under olefin polymerization conditions. The contact temperature is 130-160 ° C, the contact pressure is 0.1-0.2 MPa, and the olefin polymerization catalyst is used in an amount of 0.2-3% by weight based on the weight of the C ₅ -C ₇ mixed a olefin. The olefin polymerization catalyst is super strong. An acid catalyst, a heteropolyacid catalyst or a Lewis acid complex catalyst.

The composition according to claim 6, wherein the method for producing a hydrogenated product of the C ₁₅ -C ₂₂ mixed isoolefin comprises C ₁₅ - under hydrogenation conditions and in the presence of a hydrogenation catalyst. The C ₂₂ mixed isomerized olefin is contacted with hydrogen; the hydrogenation conditions include a temperature of 260-280 ° C, a hydrogen partial pressure of 3-7 MPa, and a volume ratio of hydrogen to a C ₁₅ -C ₂₂ mixed isomer of olefins of 8 The hydrogenation catalyst is one or more of Ni-W-Mo-F, Pt-α Α1 ₂ 0 ₃ and Raney nickel.

8. The composition according to claim 6, wherein the method for preparing the arylation product of the ₁₍₎ - ₁₄ mixed olefin comprises, under thiolation conditions, in the presence of a thiolation catalyst, a C ₁₀ -C ₁₄ mixed olefin is contacted with a C ₆ -C ₈ aromatic hydrocarbon; the thiolation condition comprises a catalyst in an amount of from C _{2 (r} 2 ₁₄ mixed olefin and from 0.2 to 2% by weight based on the total weight of the C ₆ -C ₈ aromatic hydrocarbon) , the weight ratio of C _1Q -C ₁₄ mixed olefin to C ₆ -C ₈ aromatic hydrocarbon is 1:1-1:1.2, the temperature of contact is 60-90 ° C; the thiolation catalyst is HF, BF ₃ , A1CL _3. One or more of a super acid catalyst and a heteropolyacid catalyst.

The composition according to claim 8, wherein the C _1Q - C ₁₄ mixed olefin is a C _1Q - C ₁₄ alpha olefin, a wax cracking olefin of _{1 ()} - ₁₄ , and a positive C _1Q - C ₁₄ One or more of a hydrocarbon dehydrogenating olefin; the C ₆ -C ₈ arene is one or more of benzene, toluene, xylene, and ethylbenzene. The composition according to claim 1, wherein the c ₁₅ -c ₂₂ mixed isomer, the c ₁₅ -c ₂₂ mixed isomer or the c ₁₅ -c ₂₂ mixed isomer with c ₁₅ - The mixture of c ₂₂ mixed isomeric terpene hydrocarbons has a distillation range of from 270 ° C to less than 300 ° C. The composition according to claim 10, wherein the C ₁₅ -C ₂₂ mixed isomer, the c ₁₅ -c ₂₂ mixed isomer or the c ₁₅ -c ₂₂ mixed isomer with c ₁₅ - The mixture of c ₂₂ mixed isomeric terpene hydrocarbons has a fraction of 270-290 ° C in the range of 60-100% by weight, and a fraction having a distillation range of more than 290 ° C to less than 300 accounts for 0-40% by weight. The composition according to claim 1 or 2, wherein the additive is one or more selected from the group consisting of a lubricant, an antifriction agent, an antioxidant, an anticorrosive agent, and an antifoaming agent.