Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
  • C10M105/18—Ethers, e.g. epoxides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
  • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
  • C10M107/34—Polyoxyalkylenes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

• the present invention relates to lubricating base oils, lubricating oil compositions, and cooling systems.
• the present invention provides a lubricating base oil that improves the chemical stability of refrigerants blended with the lubricating base oil when used over an extended period of time, and a lubricating oil composition containing the lubricating base oil.
• a lubricating base oil that is mixed with a refrigerant,
• the refrigerant contains a hydrocarbon compound having 1 to 8 carbon atoms
• the lubricating base oil contains at least one selected from the group consisting of polyoxyalkylene monools and polyoxyalkylene polyols,
• the chemical stability of refrigerants blended with lubricating base oils is improved when used over long periods of time.
• FIG. 1 is a diagram illustrating a schematic configuration of a cooling system according to an embodiment.
• the lubricating base oil of the present invention can impart lubricity to the sliding parts of a compressor in a compression-type refrigerator, for example, by mixing with a refrigerant.
• the refrigerant to be mixed with the lubricating base oil of the present invention contains a hydrocarbon compound having 1 to 8 carbon atoms.
• the hydrocarbon compound of the refrigerant preferably has 1 to 5 carbon atoms, more preferably 3 to 5 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
• hydrocarbon compounds for the refrigerant examples include methane, ethane, ethylene, propane, cyclopropane, propylene, n-butane, isobutane, n-pentane, and isopentane. Of these, propane and propylene are preferred.
• the hydrocarbon compounds of the refrigerant may be used singly or in combination of two or more kinds.
• the lubricating base oil of the present invention contains at least one member selected from the group consisting of polyoxyalkylene monools and polyoxyalkylene polyols (also referred to as "polyether polyols").
• the polyoxyalkylene polyol may be a polyoxyalkylene diol having two hydroxyl groups, a polyoxyalkylene triol having three hydroxyl groups, or a polyoxyalkylene tetraol having four or more hydroxyl groups.
• polyoxyalkylene monools and polyoxyalkylene polyols will be collectively referred to as polyoxyalkylene alcohols.
• polyoxyalkylene alcohol is not particularly limited.
• polyoxyalkylene alcohol can be synthesized by addition polymerization of an alkylene oxide to an initiator having an active hydrogen-containing group in the presence of a catalyst.
• the initiator is not particularly limited as long as it is a compound having an active hydrogen-containing group.
• the initiator may have one or more active hydrogen-containing groups.
• Examples of initiators include aliphatic monoalcohols, aliphatic diols, aliphatic alcohols having 3 to 8 hydroxyl groups, amines, phenols, salts thereof, and alkylene oxide adducts thereof.
• the initiator is not limited to these examples.
• the initiators may be used alone or in combination of two or more.
• aliphatic diols examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, and 1,6-hexanediol. However, aliphatic diols are not limited to these examples.
• the catalyst examples include alkali metal catalysts and double metal cyanide complex catalysts (hereinafter referred to as "DMC catalysts"), but the catalyst is not limited to these examples.
• the catalyst may be used alone or in combination of two or more kinds.
• the DMC catalyst is believed to have at least a metal element and an organic ligand.
• metal elements of the DMC catalyst include Zn, Fe, Co, Ni, Al, Sr, Mn, Cr, Cu, Sn, Pb, Mo, W, and V.
• the metal elements of the DMC catalyst are not limited to these examples.
• the DMC catalyst may contain one or more metal elements.
• the polyoxyalkylene alcohol is preferably a compound represented by the following formula 1: R 1 ⁇ (R 2 O) m H ⁇ n ...Formula 1
• R1 is a residue of an initiator. Details and preferred embodiments of the initiator are as described above.
• Each R2 is independently a hydrocarbon group having 2 to 4 carbon atoms.
• the hydrocarbon group preferably has 2 or 3 carbon atoms, and more preferably has 3 carbon atoms. Therefore, it is preferable that at least one R2 is a hydrocarbon group having 3 carbon atoms, and it is more preferable that all R2 are hydrocarbon groups having 3 carbon atoms.
• the number average molecular weight of the polyoxyalkylene alcohol is preferably 300 to 5,000, more preferably 500 to 3,000, and even more preferably 700 to 2,000.
• the number average molecular weight is equal to or greater than the lower limit of the above numerical range, it is easy to achieve adequate compatibility with the refrigerant.
• the number average molecular weight is equal to or less than the upper limit of the above numerical range, it is easy to obtain a lubricating base oil with good kinematic viscosity.
• the metal content of the lubricating base oil of the present invention is 10 ppm or less. Therefore, the chemical stability of a refrigerant blended with the lubricating base oil is improved when used for a long period of time.
• the metal content of the lubricating base oil is preferably 8 ppm or less, more preferably 5 ppm or less, and even more preferably 3 ppm or less. From the viewpoint of production efficiency, the lower limit of the metal content of the lubricating base oil is preferably 0.1 ppm or more.
• the viscosity index of the lubricating base oil is preferably 50 or higher, more preferably 80 or higher, and even more preferably 100 or higher, as this improves viscosity characteristics.
• the volume resistivity of the lubricating base oil is not particularly limited, but may be, for example, 1 ⁇ 10 10 to 1 ⁇ 10 15 ⁇ cm, 6 ⁇ 10 10 to 1 ⁇ 10 14 ⁇ cm, or 1 ⁇ 10 11 to 1 ⁇ 10 14 ⁇ cm.
• the volume resistivity is equal to or greater than the lower limit of the above-mentioned range, electrical insulation properties are improved.
• the volume resistivity is equal to or less than the upper limit of the above-mentioned range, static electricity generation is easily prevented.
• any of Method 1, Method 2, and Method 3 may be performed alone, or two or more of them may be combined as appropriate, or all of Methods 1, 2, and 3 may be performed.
• the order in which they are performed is not particularly limited.
• Methods 1 and 2 are preferred, with Method 1 being more preferred, from the perspective of further reducing the metal content.
• Examples of the neutralizing agent include amines, alkali metal hydroxides, organic acids, inorganic acids, and salts thereof.
• Examples of the inorganic acid include sulfuric acid, phosphoric acid, and hydrochloric acid.
• Examples of the organic acid include lactic acid.
• the neutralizing agents may be used alone or in combination of two or more.
• the lubricating oil composition of the present invention comprises the above-described lubricating base oil and either or both of a refrigerant and an additive.
• the lubricating oil composition may comprise a lubricating base oil and a refrigerant, a lubricating base oil and an additive, or a lubricating base oil, a refrigerant, and an additive.
• the lubricating oil composition of the present invention can, for example, impart lubricity to the sliding parts of a compressor supplied with a refrigerant.
• the refrigerant is as described above.
• additives examples include antioxidants, extreme pressure agents, stabilizers, copper deactivators, antifoaming agents, load-bearing additives, chlorine scavengers, oxygen scavengers, detergent-dispersants, viscosity index improvers, oiliness agents, rust inhibitors, corrosion inhibitors, and pour point depressants, but the additives are not limited to these examples.
• the additives may be used alone or in combination of two or more.
• antioxidants examples include phenol-based antioxidants and amine-based antioxidants.
• examples of phenol-based antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and 2,2'-methylenebis(4-methyl-6-tert-butylphenol).
• examples of the amine antioxidant include phenyl- ⁇ -naphthylamine and N,N'-diphenyl-p-phenylenediamine. The antioxidants may be used alone or in combination of two or more.
• extreme pressure agents include phosphorus-based extreme pressure agents such as phosphate esters, acid phosphate esters, phosphites, acid phosphites, and amine salts of these.
• stabilizers include epoxy compounds such as phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, ⁇ -olefin oxide, and epoxidized soybean oil.
• copper deactivators examples include benzotriazole and its derivatives, such as N-[N,N'-dialkyl (alkyl group having 3 to 12 carbon atoms) aminomethyl]triazole.
• the metal content of the lubricating base oil of the present invention as described above is 10 ppm or less. Therefore, even when the refrigerant is used for a long period of time under severe conditions, deposits are unlikely to occur. Thus, the lubricating base oil of the present invention improves the chemical stability of the refrigerant blended with the lubricating base oil when used for a long period of time.
• the lubricating base oil and the lubricating oil composition can be used in various refrigeration systems such as car air conditioners, indoor air conditioners, refrigerators, freezers, vending machines, hot water supply systems for showcases, refrigeration/heating systems, gas heat pump systems, etc.
• the lubricating base oil and the lubricating oil composition are particularly preferably used in a compression-type refrigeration system equipped with a compressor 1, a condenser 2, an expansion valve 3, and an evaporator 4 as shown in FIG.
• the compression refrigeration system shown in Figure 1 contains a refrigerant containing a hydrocarbon compound having 1 to 8 carbon atoms and a lubricating base oil.
• the lubricating base oil and lubricating oil composition circulate through a compressor 1, a condenser 2, an expansion valve 3, and an evaporator 4.
• the lubricating base oil provides lubricity to the sliding parts of the compressor 1.
• the amounts of lubricating base oil and refrigerant used in this invention can be varied widely within the range of 99/1 to 10/90 in terms of the refrigerant/lubricating base oil mass ratio.
• the mass ratio is preferably within the range of 90/10 to 50/50.
• Examples 1-9 are examples, and Examples 10-12 are comparative examples.
• the test for evaluating chemical stability was conducted in accordance with the sealed tube test described in JIS K2211-2009. More specifically, iron, copper, and aluminum were placed in a test tube as catalysts. Then, 0.7 mL of the lubricating base oil containing the polyoxyalkylene alcohol obtained in each example and 0.7 mL of a refrigerant were placed in the test tube, and the opening of the test tube was sealed. The sealed test tube was heated at 175°C for 14 days, and the presence or absence of precipitates in the solution in the test tube was confirmed. Propane was used as the refrigerant.
• Example 1 74 g of n-butanol and 12 g of sodium hydroxide (purity 95% by mass) as a catalyst were added to a 5 L autoclave. The temperature was then raised to 100°C, and 1,200 g of propylene oxide was introduced into the autoclave over 15 hours. After confirming that the pressure inside the autoclave had stabilized and all of the propylene oxide had reacted, the contents were transferred to a separable flask. 1.0 equivalent of 14 g of sulfuric acid was added to the contents to neutralize them.
• Example 2 400 g of propylene glycol as an initiator and 12 g of potassium hydroxide (purity 95% by mass) as a catalyst were added to a 5 L autoclave. The temperature of the autoclave was then raised to 110 ° C, and 3,600 g of propylene oxide was introduced into the autoclave over 10 hours. After confirming that the pressure inside the autoclave had stabilized and all of the propylene oxide had reacted, the contents were transferred to a 5 L separable flask. 30 g of acidic sodium pyrophosphate and 20 g of water were added to the contents and mixed at 100 ° C for 30 minutes. Subsequently, the catalyst was insolubilized by dehydration under reduced pressure over 2 hours. The catalyst was then thoroughly removed by filtration of insoluble matter, yielding a polyether polyol. The amount of residual metal in the obtained polyether polyol was 5.2 ppm, and the number average molecular weight determined by GPC was 580.
• Example 3 92 g of glycerin and 5 g of potassium hydroxide (purity 95% by mass) as a catalyst were added to a 5 L autoclave. The temperature was then raised to 110°C, and 1,500 g of propylene oxide was introduced into the autoclave over 12 hours. After confirming that the pressure inside the autoclave had stabilized and all of the propylene oxide had reacted, the contents were transferred to a separable flask. 100 g of a synthetic hydrotalcite adsorbent (Kyowado 1000, manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the contents, and the product and adsorbent were mixed at 100°C for 2 hours.
• a synthetic hydrotalcite adsorbent Kelowado 1000, manufactured by Kyowa Chemical Industry Co., Ltd.
• Example 4 550 g of a pentaerythritol PO adduct (EXCENOL 410NE manufactured by AGC) and 6.3 g of potassium hydroxide (purity 95% by mass) as a catalyst were added to a 5 L autoclave. The temperature was then raised to 120 ° C., and the system was subjected to vacuum dehydration for 1 hour to reduce the water content in the system, after which 1500 g of propylene oxide was introduced into the autoclave over 8 hours. After confirming that the pressure inside the autoclave had stabilized and all of the propylene oxide had reacted, the contents were transferred to a separable flask.
• EXCENOL 410NE manufactured by AGC
• Example 5 182 g of sorbitol and 14.8 g of potassium hydroxide (purity 95% by mass) as a catalyst were added to a 5 L autoclave. The temperature was then raised to 110 ° C., and the system was subjected to reduced pressure dehydration for 1 hour to reduce the water content in the system. Then, 4,500 g of propylene oxide was introduced into the autoclave over 10 hours. After the pressure inside the autoclave became constant and it was confirmed that all of the propylene oxide had reacted, the contents were transferred to a separable flask.
• magnesium silicate-based adsorbent (Kyowado 600, manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the contents, and the product and adsorbent were mixed at 100 ° C. for 2 hours. After the catalyst was adsorbed onto the adsorbent, insoluble matter was removed by filtration to obtain a polyether polyol from which the catalyst had been removed. The amount of residual metal in the obtained polyether polyol was 1.1 ppm, and the number average molecular weight determined by GPC was 4,600.
• Example 6 A 5-L autoclave was charged with 342 g of sucrose, 13.6 g of potassium hydroxide (purity 95% by mass) as a catalyst, and 300 g of propylene oxide. The mixture was then heated to 100°C and mixed to dissolve the sucrose and catalyst in the propylene oxide. After confirming that the autoclave pressure had decreased and stabilized due to the reaction of the propylene oxide, an additional 3,700 g of propylene oxide was introduced into the autoclave over 10 hours. After confirming that the pressure inside the autoclave had stabilized and all of the propylene oxide had reacted, the contents were transferred to a separable flask.
• the contents were neutralized by adding 30 g of sodium acid pyrophosphate as a neutralizing agent. Then, 100 g of an aluminum silicate-based adsorbent (Kyowado 700, manufactured by Kyowa Chemical Industry Co., Ltd.) was added as an adsorbent. The mixture was then mixed while dehydrating under reduced pressure at 100°C for 2 hours, allowing the neutralized catalyst to be adsorbed onto the adsorbent. Thereafter, the catalyst was thoroughly removed by filtering insoluble matter to obtain a polyether polyol. The amount of residual metal in the obtained polyether polyol was 1.7 ppm, and the number average molecular weight determined by GPC was 4,000.
• Example 8 200 g of propylene glycol and 12 g of potassium hydroxide (purity 95% by mass) as a catalyst were added to a 5 L autoclave. The temperature of the autoclave was then raised to 110°C, and a mixture of 2600 g of propylene oxide and 1000 g of ethylene oxide was introduced into the autoclave over 10 hours. After confirming that the pressure inside the autoclave had stabilized and all of the propylene oxide and ethylene oxide had reacted, the contents were transferred to a 5 L separable flask. 6.6 g of 1.0 equivalent of phosphoric acid was added to the contents for neutralization.
• a magnesium silicate adsorbent (Kyowado 600S, manufactured by Kyowa Chemical Industry Co., Ltd.) was added.
• the catalyst was then neutralized at 100°C for 2 hours and adsorbed onto the adsorbent.
• the catalyst was then thoroughly removed by filtration of insoluble matter to obtain a polyether polyol.
• the amount of residual metal in the obtained polyether polyol was 1.8 ppm, and the number average molecular weight determined by GPC was 1,350.
• Example 9 92 g of glycerin and 0.9 g of potassium hydroxide (purity 95% by mass) as a catalyst were added to a 5 L autoclave, which was then heated to 110° C., and a mixture of 700 g of propylene oxide and 300 g of ethylene oxide was introduced into the autoclave over 12 hours. After the pressure inside the autoclave became constant and it was confirmed that all of the propylene oxide and propylene oxide had reacted, the contents were transferred to a separable flask. 20 g of acidic sodium pyrophosphate was added to the contents as a neutralizing agent to neutralize them.
• a synthetic hydrotalcite-based adsorbent (Kyowado 1000, manufactured by Kyowa Chemical Industry Co., Ltd.) was added as an adsorbent.
• the adsorbent was then mixed while dehydrating under reduced pressure at 100°C for 2 hours, allowing the neutralized catalyst to be adsorbed onto the adsorbent.
• the catalyst was then thoroughly removed by filtration of insoluble matter, yielding a polyether polyol.
• the amount of residual metal in the obtained polyether polyol was 0.5 ppm, and the number average molecular weight determined by GPC was 1,000.
• Example 10 A 5L autoclave was charged with 400g of propylene glycol as an initiator and 12g of potassium hydroxide (purity 95% by mass) as a catalyst. The temperature of the autoclave was then raised to 110°C, and 3600g of propylene oxide was introduced into the autoclave over 10 hours. After confirming that the pressure inside the autoclave had stabilized and all of the propylene oxide had reacted, the contents were transferred to a 5L separable flask.
• Example 11 92 g of glycerin and 0.9 g of potassium hydroxide (purity 95% by mass) as a catalyst were added to a 5 L autoclave, which was then heated to 110° C., and 1,500 g of propylene oxide was introduced into the autoclave over 12 hours. After the pressure inside the autoclave became constant and it was confirmed that all of the propylene oxide had reacted, the contents were transferred to a separable flask, to which an equivalent amount of 2.2 g of 2-ethylhexanoic acid was added to neutralize the catalyst. The amount of residual metal in the obtained polyether polyol was 370 ppm, and the number average molecular weight determined by GPC was 1,500.
• the mixture was then heated to 100°C and mixed for 30 minutes, after which it was subjected to a catalyst insolubilization treatment by dehydration under reduced pressure for 2 hours.
• the insolubilized catalyst was then removed by filtration to obtain a polyether polyol.
• the amount of residual metal in the obtained polyether polyol was 50 ppm, and the number average molecular weight determined by GPC was 4,600.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• General Chemical & Material Sciences (AREA)
• Emergency Medicine (AREA)
• Physics & Mathematics (AREA)
• Combustion & Propulsion (AREA)
• Thermal Sciences (AREA)
• Materials Engineering (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Lubricants (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=96699878

Family Applications (1)

Country Status (2)

Citations (3)

Family Cites Families (1)

• 2025
  • 2025-01-30 JP JP2025562959A patent/JPWO2025169830A1/ja active Pending
  • 2025-01-30 WO PCT/JP2025/002975 patent/WO2025169830A1/ja active Pending

Patent Citations (3)

Also Published As

Similar Documents

Legal Events