CN1047192C - Compression Refrigerator - Google Patents

Abstract

Disclosed is a lubricating oil for compression type refrigerators, which comprises the following components

The polyoxyalkylene glycol derivative represented by the formula wherein each symbol is as defined in the specification. The lubricating oil has good compatibility with refrigerants and excellent lubricity, and is suitable for lubricating a compression refrigerator.

Description

Compression Refrigerator

This invention relates to compression refrigerators. More specifically, the present invention relates to a refrigerator (compression refrigerator) having a compressor in which a lubricating oil composed of high lubricity and 1,1,1,2-tetrafluoroethane (hereinafter referred to as Flon134a) is used A class of hydrogen-containing fluorine compounds with good miscibility as the main component - polyoxyalkylene glycol (polyoxyalkyleneglycol) derivatives, and the tetrafluoroethane can replace dichlorodifluoromethane (hereinafter referred to as Flon12 ) A class of fluorine compounds as refrigerants.

Generally speaking, a compression refrigerator consists of a compressor, a condenser, an expansion ball and an evaporator, and its working mechanism is that a mixture of refrigerant and lubricating oil circulates in a closed system. In this type of refrigerator, although it depends on the kind of equipment, usually the temperature of the compressor rises to 40°C or above, and the temperature can be lowered to below -40°C in the cooler. Therefore, refrigerant and lubricating oil must circulate in the system without phase separation in most cases (-40°C-40°C).

If a refrigerator is operating with phase separation, it can have a very detrimental effect on the life and efficiency of the equipment. For example, if the refrigerant and lubricating oil phase separate in a compressor, the moving parts will lose their lubrication, causing seizing or other problems that greatly reduce the life of the equipment. If phase separation occurs in the evaporator, a highly viscous lubricating oil will reduce the efficiency of heat exchange.

Since the lubricating oil of the refrigerator is used to lubricate the moving parts of the refrigerator, its lubricity is naturally regarded as important. Especially in compressors, temperatures can become very high, so it is important that the viscosity of the oil film is sufficient to maintain the required lubrication. The desired viscosity varies depending on the type of compressor and operating conditions, but the viscosity of the lubricating oil before mixing with the refrigerant is preferably 2 to 250 cst at 100°C. If the viscosity is lower than this range, the oil film will become thinner, thereby losing the lubricating effect, and the sealing performance will be deteriorated. Conversely, if the viscosity is higher than this range, the efficiency of heat exchange will decrease. Since the lubricating oil used in the refrigerator is used in a cycle process where the temperature varies widely, the viscosity index is preferably higher, and the viscosity index is usually required to be 40 or above. In addition to the above-mentioned properties, low hygroscopicity and other properties are required in order to prevent ball blocking due to ice formation at the expanding ball.

In the past, Flon12 was often used as a refrigerant for compression refrigerators, and various mineral oils and synthetic oils meeting the aforementioned requirements were used as lubricating oils. However, in recent years, the use of Flon12 has been increasingly restricted worldwide, because it is easy to pollute the environment, including the destruction of the ozone layer.

Under these circumstances, hydrogen-containing flon compounds (including Flon134a) have attracted increasing attention as new refrigerants. Among the hydrogen-containing flon compounds, especially Flon134a has the least possibility of damaging the ozone layer, can replace Flon12, and has little effect on the structure of commonly used refrigerants, so it is a popular refrigerant for compression refrigerators.

When using hydrogen-containing flon compounds (including the Flon134a) as the refrigerant for compression refrigerators instead of Flon12, the required lubricating oil and hydrogen-containing flon compounds (including Flon134a) have high compatibility, and the lubrication High resistance, enough to meet the above characteristics.

However, since the compatibility of conventional lubricating oils using Flon 12 with hydrogen-containing flon compounds (including Flon 134a) is still not satisfactory, there is still a need for new lubricating oils suitable for these compounds. However, in this case, especially in automobile air conditioners, it is required to replace Flon 12 without changing the mechanical structure. Significant changes in mechanical configuration due to lubricating oil are ideal. Therefore, there is a need for a lubricity that is compatible with hydrogen-containing flon compounds (including Flon134a).

It is known that Ulcon LB-165 or Ulcon LB-525 (trademark, all produced by Union Carbide Co., Ltd.) composed of polyalkylene glycol is a lubricant compatible with Flon134a, and it is reported that at -50-50 At low temperatures at or below these lubricating oils are soluble or compatible with Flon 134a in all parts ("Research Disclosure" 17463, October 1978). Furthermore, a high-viscosity refrigerator oil composition using polyoxypropylene glycol-butyl ether as a base oil is known (Japanese Patent Publication No. 42119/1982).

These lubricating oils are polyalkylene glycol derivatives with propylene glycol bearing a hydroxyl group at one end and an n-butyl ether linkage (n-butoxyl) at the other end. They have good compatibility with Flon134a at low temperature, but not enough compatibility at high temperature. For example, it has been known that the above-mentioned Ulcon LB-525 will phase-separate with Flon134a at room temperature (US patent specification 4,755,316).

On the other hand, it has been proposed that polyethylene glycol having at least two hydroxyl groups in one molecule is a substance having relatively satisfactory compatibility with Flon134a (US Specification No. 4,755,316).

However, in the above-mentioned polyethylene glycol, the compatibility is still not sufficient.

At the same time, it is known that polyethylene glycol generally shows temperature dependence, that is, when the mixture mixed with Flon is heated from low temperature to high temperature, the phase-separated mixture will phase-separate once dissolved.

On the other hand, Flon134a and compounds in which it can be dissolved have been proposed for absorption type refrigerators (Japanese Laid-Open Patent No. 79175/1989). However, the absorption refrigerator is completely different from the above-mentioned compression refrigerator in terms of its working principle. The tetraethylene glycol dimethyl ether introduced in the patent example is not suitable for compression refrigeration because of its particularly low viscosity. lubricating oil for the appliance.

As described above, no lubricating oil for compression refrigerators having excellent compatibility with Flon 134a and high wettability has been found so far, and further development thereof is particularly desired.

For this reason, the present inventor has developed a kind of lubricating oil that is suitable for the compression refrigerator through long-term meticulous research, and described refrigerator uses the flon compound (comprising Flon134a) containing hydrogen as refrigerant, can replace Flon12 to avoid Environmental pollution problems and alternatives to other flon compounds that are difficult to decompose.

The object of the present invention is to provide a lubricating oil for compression refrigerators which has good compatibility with hydrogen-containing flon compounds (including Flon134a) as refrigerants.

Another object of the present invention is to provide a lubricating oil for compression refrigerators which has good compatibility with the above-mentioned hydrogen-containing flon compounds over the entire range of temperatures used.

Still another object of the present invention is to provide a lubricating oil for a compression refrigerator, which lubricating oil has satisfactory compatibility and also has the above-mentioned lubricating properties.

It is a further object of the present invention to provide a compressive lubricating oil which, in addition to the above characteristics, is also resistant to tearing.

The present invention includes the following lubricating oils 1-VI.

Lubricating oil Ⅰ

其中R¹表示C_1-10烷基、C_1-10酰基或2-6价脂肪烃基，R²是C_2-4亚烷基，R³是C_1-10烷基或C_1-10酰基，n表示1-6中的一个整数，m为1-80中的一个整数。Lubricating oil for compression refrigerators, the main component of which is composed of at least one polyoxyalkylene glycol derivative represented by the following general formula:

Where R ¹ represents C _1-10 alkyl, C _1-10 acyl or 2-6 valent aliphatic hydrocarbon group, R ² is C _2-4 alkylene, R ³ is C _1-10 alkyl or C _1-10 acyl , n represents an integer in 1-6, m is an integer in 1-80.

Lubricant II

Lubricating oil for compression refrigerators, the main component of which is composed of polyoxyalkylene glycol derivatives represented by the following general formula:

R ⁴ (OR ⁵ ) _k OH...(II) wherein R ⁴ represents a C _1-3 alkyl group, R ⁵ represents a C _2-4 alkylene group, and K represents a number from 6-80.

Lubricant Ⅲ

Lubricating oil for compression refrigerators, its main components are as follows:

表示的环氧乙烷-环氧丙烷共聚物的聚亚氧烷基乙二醇衍生物构成，其中R⁶,R⁷,R⁸,R⁹和R¹⁶分别代表氢或C_1-3烷基，A是环氧乙烷和环氧丙烷的聚合链，由p倍环氧乙烷单元和q倍环氧丙烷单元构成，且p和q是满足以下条件的数：R ⁶ -OAR ⁷ …(Ⅲ) and/or the following general formula

Represented by polyoxyalkylene glycol derivatives of ethylene oxide-propylene oxide copolymer, wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁶ represent hydrogen or C _1-3 alkyl , A is a polymer chain of ethylene oxide and propylene oxide, consisting of p times ethylene oxide units and q times propylene oxide units, and p and q are numbers satisfying the following conditions:

0.1≤p/q=10,5≤p+q≤100.

Lubricant Ⅳ

(其中R¹⁶表示氢或C_1-3烷基，r表示整数1或2。若r为2，则R¹⁶可相同或不同。但(R¹⁶)r的总碳数不高于3)与含有以下通式Lubricating oil for compression refrigerators characterized by a phosphate represented by the general formula

(wherein R ¹⁶ represents hydrogen or C _1-3 alkyl, r represents an integer 1 or 2. If r is 2, then R ¹⁶ can be the same or different. But (R ¹⁶ ) r has a total carbon number not higher than 3) and Contains the general formula

R ¹¹ -OA ¹ -R ¹² ...(Ⅵ) and/or general formula

CH ₂ -OA ¹ -R ¹³

CH-OA ² -R ¹⁴ ...(VII)

The polyoxyalkylene glycol derivative represented by CH ₂ -OA ³ -R ¹³ is compounded as the base oil of the main component. In the formulas (IV) and (VII), R ¹¹ -R ¹⁸ represent hydrogen or C respectively _1-3 alkyl groups, A ¹ -A ³ respectively represent polymer chains composed of 3-100 one or more alkylene oxides (containing 2-4 carbon atoms).

Lubricating oil Ⅴ

(其中R¹⁷,R¹⁸和R¹⁹分别表示C_2-4亚烷基，s,t和u分别表示1-30中的一个整数)且其粘度在40℃下为50-250cst。Lubricating oil for compression refrigerators, the main component of which is composed of polyhydroalkylene glycol derivatives represented by the following general formula:

(wherein R ¹⁷ , R ¹⁸ and R ¹⁹ respectively represent C _2-4 alkylene, s, t and u represent an integer from 1-30 respectively) and its viscosity is 50-250cst at 40°C.

Lubricating oil Ⅵ

Lubricating oil for compression refrigerators, characterized in that it contains (a) polyoxyalkylene glycol and derivatives and (b) selected from (i) dibasic acid esters, (ii) cyanated oils, (iii) polyhydric At least one compound selected from alcohol esters and (iv) siloxane fluorides.

First, the lubricating oil I will be described. The lubricating oil I contains a polyoxyalkylene glycol derivative represented by the aforementioned general formula (I) as a main component.

In the general formula, R ¹ is a C _1-10 alkyl group, a C _1-10 acyl group or an aliphatic hydrocarbon group with a valence of 2-6, R ² is a C _2-4 alkylene group, and R ³ is a C _1-10 alkane group group or C _1-10 acyl group, n is an integer of 1-6, m is a number, and the average value of m×n is 6-80.

The alkyl group can be a straight chain, a branched chain, or a cyclic alkyl group. Specific examples of the alkyl group are methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups , various decyl, cyclopentyl, cyclohexyl, etc. If the carbon number of the alkyl group exceeds 10, the compatibility with Flon134a will decrease, causing phase separation. The number of carbon atoms of the alkyl group is preferably 1-6.

The alkyl group in the acyl group may be linear, branched or cyclic. Specific examples of the alkyl group in the acyl group are methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various Nonyl, cyclopentyl, cyclohexyl, etc.

If the number of carbon atoms in the acyl group exceeds 10, the compatibility with Flon134a will decrease, resulting in phase separation. The number of carbon atoms of the acyl group is preferably 2-6.

When said R ¹ and R ³ are each an alkyl group or an acyl group, R ¹ and R ³ may be the same or different from each other.

Also, when n is 2 or higher, a plurality of Rs in one molecule may be the same or different.

When R ¹ is an aliphatic hydrocarbon group having 1-10 carbon atoms and a valence of 2-6, the aliphatic hydrocarbon group may be chain or globular. Examples of divalent aliphatic groups are ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, cyclopentenyl and cyclohexenyl . Examples of 3-6 valent aliphatic hydrocarbon groups are polyhydric groups from trimethylolpropane, glycerol, pentaerythritol, sorbitol, 1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane The group obtained after removing the hydroxyl group from the alcohol.

If the aliphatic hydrocarbon group has more than 10 carbon atoms. Compatibility with Flon134a will decrease, causing phase separation. The preferred number of carbon atoms is 2-6.

In the aforementioned general formula (I), R ² is a C _2-4 alkylene group, and oxyethylene, oxypropylene and oxybutenyl are specified as oxyalkylene repeating units. The oxyalkylene groups in one molecule may be the same or varied in two or more kinds, but it is preferable to include at least one oxypropylene unit in one molecule.

In the general formula (I), n is an integer of 1-6 and is defined by the valence of R ¹ . For example, n is 1 if R ¹ is alkyl or acyl. If R ¹ is a 2, 3, 4, 5 or 6-valent aliphatic hydrocarbon group, n is 2, 3, 4, 5 or 6, respectively. m is an integer from 1 to 80, if m exceeds this range, the object of the present invention cannot be fully achieved.

The general formula (I) refers not only to one polyoxyalkylene glycol, but also includes a mixture of two or more derivatives.

The polyoxyalkylene glycol derivative represented by the general formula I for the lubricating oil I can be prepared by various methods as shown below.

Method (A):

其中R和R¹分别为C_1-10烷基或酰基，它们相互可相同或不同R²和a定义如上。Polymerize C _2-4 alkylene oxides including ethylene oxide and propylene oxide with water or alkali metal hydroxide initiators to obtain polyoxyethylenes with hydroxyl groups at both ends represented by the following general formula: Oxyalkylene Glycols: where a is a number with an average value of 6-80, and ^R2 is as defined above. Subsequently, the two hydroxyl groups of the polyoxyalkylene glycol are etherified or esterified, or one hydroxyl group is etherified and the other hydroxyl group is esterified to obtain a polyoxyalkylene glycol represented by the following general formula derivative:

Wherein R and R ¹ are C _1-10 alkyl or acyl, and they may be the same or different from each other. R ² and a are as defined above.

method (B)

(其中R¹¹是C_1-10烷基，R²和a定义如上)，此化合物在其一端具有一个醚键，在其另一端具有一羟基。之后，将聚亚氧烷基乙二醇一烷基醚的羟基醚化或酯化，得到下列通式表示的聚亚氧烷基乙二醇衍生物：

(其中R²、R、R¹¹和a定义如上)。Make C _2-4 alkylene oxide and C _1-10 monohydric alcohol or its alkali metal salt carry out polymerization as initiator, obtain the polyoxyalkylene glycol one alkyl ether represented by following general formula:

(wherein R ¹¹ is C _1-10 alkyl, R ² and a are as defined above), this compound has an ether bond at its one end and a hydroxyl group at its other end. Afterwards, the hydroxyl groups of polyoxyalkylene glycol monoalkyl ethers are etherified or esterified to obtain polyoxyalkylene glycol derivatives represented by the following general formula:

(wherein R ² , R, R ¹¹ and a are as defined above).

method (C)

Polymerize C _2-4 alkylene oxide with 2-6 valence, C _1-10 polyhydric alcohol or its alkali metal salt initiator to obtain the following polyoxyalkylene ethylene represented by , having a hydroxyl group at one end Diol derivatives:

Wherein R ^11' is an aliphatic hydrocarbon group with C _1-10 and 2-6 valence, c is an integer of 2-6, b is a number, and the average value of b×c is 6-80, and R ² is defined as above. Afterwards, the hydroxyl groups of the obtained polyoxyalkylene glycol derivatives are etherified or esterified to obtain polyoxyalkylene glycol derivatives represented by the following general formula: (wherein R ² , R, R ^11' , b and c are as defined above).

In these production methods, in order to esterify the hydroxyl group of polyoxyalkylene glycol or its salt having a hydroxyl group at one end thereof, the substance is usually derivatized with a C _1-10 aliphatic carboxylic acid or reactive substances (such as acid anhydrides, acid halides and their esters), or convert the hydroxyl group of the polyoxyalkylene glycol or its derivatives into sulfonates or halides, and then react with the carboxylic acid or its salt reaction.

Examples of the carboxylic acid are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, capric acid cyclohexanecarboxylic acid and the like.

When carrying out the esterification reaction with the acid or its anhydride, or the transesterification with the ester of the carboxylic acid, an acid catalyst such as sulfuric acid and p-toluenesulfonic acid is generally used. When esterification is carried out with acid halides, amines are generally used as dehydrohalogenation reagents.

On the other hand, in order to etherify the hydroxyl group of polyoxyalkylene glycol or derivatives thereof having a hydroxyl group at one end thereof, it is generally combined with a carbon metal (such as metal sodium) or a carbon metal salt (methanol) of a lower alcohol. Sodium) reaction to obtain the alkali metal salt of the polyoxyalkylene glycol or its derivatives, and then react with C _1-10 alkyl halide or sulfonate, or make the polyoxyalkylene The hydroxyl groups of ethylene glycol or its derivatives are converted into sulfonates or halides, and then reacted with C _1-10 fatty alcohols or their metal salts.

In the polyoxyalkylene glycol derivatives thus obtained, the linkage of the oxyalkylene units is generally head-to-tail in the case of propylene oxide or butylene oxide units, but may also include head-to-tail linkages in some cases. - Head-to-head or tail-to-tail connections.

The lubricating oil I of the present invention contains the polyoxyalkylene glycol derivative represented by the general formula (I) and obtained in this way as a main component, and the polyoxyalkylene glycol can be used alone Derivatives can also be used in combination of two or more. The lubricating oil can be satisfactorily used even if the lubricating oil contains a polyoxyalkylene glycol derivative having a hydroxyl group at its terminal in addition to the aforementioned polyoxyalkylene glycol derivative represented by the aforementioned general formula (I). Oxyalkyl glycol derivatives, as long as said hydroxyl group content does not exceed 30 mole percent of the total terminal groups.

The object of the present invention cannot be achieved with the polyoxyalkylene glycol derivatives in which R ^{and R} are aryl in the aforementioned general formula (I), although the mechanism is unclear.

In the general formula (I), n is 1, and R ¹ and R ³ are methyl polyoxyalkylene glycol derivatives are preferred.

It is recommended that the viscosity of lubricating oil 1 of the present invention at 100°C is 2-50cst, preferably 5-30cst, more preferably 6cst (n=1, m=12 in the general formula (I))-30cst, preferably 7cst (n=1·m=14)-30cst is best to be 9cst(n=1,m=19)-30cst, in order to maintain the oil film thickness required for lubrication and maintain sufficient sealing. If necessary, various additives used in conventional lubricating oils can be added to the lubricating oil I of the present invention, such as anti-carrying agent, chlorine capture agent, antioxidant, metal deactivation, defoaming agent, cleaning and dispersing agent, viscosity index improvement agent, oily agent, antiwear agent, extreme pressure agent, rust inhibitor, corrosion inhibitor, pour point depressant, etc.

Such anticarriers include organic sulfide based additives such as monosulfides, polysulfides, sulfones, sulfoxides, thiosulfinates, sulfurized fats and oils, thiocarbonates, thiophenols, thiazoles, methanesulfonates acid esters; phosphate-based additives such as phosphoric-ester, phosphoric diester, and phosphoric acid triester (tricresyl phosphate); phosphite-based additives such as phosphorous-ester, phosphorous diester, and phosphorous triester; sulfur Phosphate-based additives, such as phosphorothioate triester; fatty acid-based additives, such as higher fatty acids, hydroxyaryl fatty acids, carboxylic acid-containing polyol esters, and metal soaps; fatty acid ester-based additives, such as polyol esters and aryl acid esters; organic chlorine-based additives such as chlorinated hydrocarbons and chlorinated carboxylic acid derivatives; organic fluorine-based additives such as fluorinated fatty acids, vinyl fluoride resins, fluoroalkyl polysiloxanes, and fluorinated graphite; alcohol-based additives , such as higher alcohols; and metal compound-based additives such as naphthenates (lead naphthenates), fatty acid salts (lead fatty acids), thiophosphates (such as zinc dialkylthiophosphates), thiocarbamate salts, organomolybdenum compounds, organotin compounds, organogermanium compounds and borate esters.

Chlorine capture agents include compounds with glyceryl ether groups, epoxy fatty acid-esters, epoxy fatty compounds and oils and compounds with epoxy cycloalkyl groups.

Antioxidants include phenol (2,6-di-tert-butyl-p-cresol), aromatic amine (α-naphthylamine), and the like.

Metal deactivators include benzotriazole derivatives.

Antifoaming agents include silicone oils (dimethylpolysiloxane) and polymethacrylates. Detergent and dispersants include sulfonates, benzoates, succinimides, and the like.

Viscosity index improvers include polymethacrylates, polyisobutylenes, ethylene-propylene copolymers, hydrogenated styrene-diene copolymers, and the like.

The lubricating oil I of the present invention, which has high compatibility with refrigerants and excellent lubricity, is used in compression refrigerators, and is particularly suitable for compression refrigerators using Flon134a as a refrigerant, because the lubricating oil is compatible with Flon134a has good compatibility and is different from conventional lubricating oils. Furthermore, Lubricating Oil I may be used in the form of a mixture with another lubricating oil for compression refrigerating machines in order to improve its compatibility with refrigerants.

The above-mentioned lubricating oil II will be described below. This lubricating oil II contains the polyoxyalkylene glycol derivative represented by the aforementioned general formula (II) as a main component. In formula II, R ⁴ is C _1-3 alkyl, R ⁵ is C _2-4 alkylene and k is a number from 6-80, preferably 10-40.

Such an alkyl group is any of methyl, ethyl, propyl or isopropyl. If such an alkyl group has 4 or more carbon atoms, compatibility with hydrogen-containing Flon compounds (such as Flon134a, etc.) decreases and phase separation occurs. Among these alkyl groups, methyl is preferred.

In the aforementioned general formula (II), R ⁵ is the aforementioned C _2-4 alkylene group. Thus, the oxyalkylene having a repeating unit represented by OR ⁵ includes oxyethylene, oxypropylene and oxybutylene. The oxyalkylene groups in one molecule may be the same, or two or more kinds of oxyalkylene groups may be contained in one molecule. However, it is preferred to contain at least one oxypropylene unit in one molecule. The alkylene group in the oxypropylene group may be a straight chain group or a branched chain group.

k in the general formula (II) is a number in the range of 6-80, preferably 10-40, on average. If this average value is too small, the lubricating effect is lowered, and if it is too large, the solubility is lowered, so that the object of the present invention cannot be achieved satisfactorily.

For example, the polyoxyalkylene glycol derivative represented by the foregoing general formula (II) for the lubricating oil of the present invention is prepared by the following method.

method (D)

Polyoxyalkylene glycol having hydroxyl groups at both ends and represented by the following general formula is prepared as follows:

H(OR ⁵ ) _k OH...(D ₁ ) (wherein R ⁵ and k are as defined above) initiates C _2-4 alkylene oxides (such as ethylene oxide and propylene oxide) and water or alkali metal hydroxides Agents are polymerized, and then a polyoxyalkylene glycol derivative represented by the following general formula is obtained by etherifying a hydroxyl group:

R ⁴ (OR ⁵ ) _k OH...(II) wherein R ⁴ , R ⁵ and k are as defined above.

Etherification can be carried out by various methods, such as reacting polyoxyalkylene glycols with dialkyl sulfates, reacting alkoxides in polyoxyalkylene glycols with alkyl halides or reacting halogenated poly Alkylene glycols (where one terminal hydroxyl group is halogenated) react with alkoxides, etc.

The reaction of polyoxyalkylene glycol and dialkyl sulfate is usually carried out at -10°C to 100°C in the presence of an aqueous alkali metal solution for 5 minutes to 50 hours. When the reaction was carried out at a temperature above 40°C, one of the two alkyl groups in the alkyl sulfate reacted, and when it was above 50°C, all the alkyl groups reacted. If desired, inert liquids can be used as solvents. Dialkyl sulfates include dimethyl sulfate, diethyl sulfate, dipropyl sulfate and diisopropyl sulfate. Aqueous alkali metal solutions include sodium hydroxide, potassium hydroxide, and the like.

The reaction of the alkoxide in the polyoxyalkylene glycol with the halogenated alkyl group is usually carried out at 50-150° C. under atmospheric pressure or under increased pressure for 30 minutes to 30 hours. Solvents such as toluene and tetrahydrofuran are preferably used. Alkyl halides include methyl halide, methyl bromide, methyl iodide, ethyl chloride, propyl chloride, isopropyl chloride, and the like.

The method of reacting a terminal hydroxyl group of polyoxyalkylene glycol with alkoxide after halogenation is a halogenated derivative of the terminal hydroxyl group at 50°C-150°C (through polyoxyalkylene glycol and thionyl dichloride, phosphorus pentachloride, phosphorus pentabromide and other halogenated reagents) react with alkoxide for 30 minutes to 30 hours. Alkoxides include sodium methoxide, potassium methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, and the like.

In the above-mentioned method (D), in addition to polyoxyalkylene glycol derivatives (where one terminal hydroxyl group of the polyoxyalkylene group is an alkyl ether, and the other terminal group is a hydroxyl group), it is also possible to include both ends Both are polyoxyalkylene glycol derivatives and polyoxyalkylene glycol substances of alkyl ethers. A polyoxyalkylene glycol in which one of the terminal groups is an alkyl ether may also be used alone. Also, it can be used in the form of a mixture without separating these components.

Method (E):

The preparation method of the polyoxyalkylene glycol derivative (wherein R ⁴ , R ⁵ and k are as defined above) represented by the following general formula R ⁴ (OR ⁵ ) _k OH (II) is to make C _2-4 alkylene Oxygen is polymerized with a C _1-3 monohydric alcohol or its alkali metal salt initiator.

When alcohol is used as a raw material, an aqueous alkali metal solution of 0.05 to 1.3 equivalents of alcohol is used. Alcohols and alkali metal aqueous solutions of alcohols or alkali metal salts are added to the autoclave and heated to 50-150°C. Under pressure, a specified amount of alkylene oxide is added and stirred for 10 minutes to 50 hours to obtain the desired polyoxyalkylene glycol derivative. Monohydric alcohols include methanol, ethanol, propanol and isopropanol. Alkali metal salts of monoalcohols include sodium methoxide, potassium methoxide, sodium ethoxide, sodium isopropoxide and the like.

In the above method (E), only a polyoxyalkylene glycol derivative having an alkyl ether at one end and a hydroxyl group at the other end is obtained. Therefore, method (E) is preferred over method (D) in this regard.

The polyoxyalkylene glycol derivatives thus obtained may be used either alone or as a mixture of two or more thereof.

In order to maintain a certain oil film thickness enough to lubricate, the viscosity of lubricating oil II at 100°C is preferably between 2-50cst.

If necessary, various additives for conventional lubricating oils, such as anti-carrying agent, chlorine capture agent, antioxidant, metal deactivator, defoamer, can be added to lubricating oil II of the present invention in the same manner as above lubricating oil I , Cleaning and dispersing agent, viscosity index improver, oily additive, antiwear agent, extreme pressure agent, rust inhibitor, corrosion inhibitor, pour point depressant, etc. Their specific examples are as mentioned above.

Lubricating oil III of the present invention is described in detail below

Lubricating oil III contains a polyoxyalkylene glycol derivative as a main component, and said derivative contains an ethylene oxide-propylene oxide copolymer represented by general formula (III) and/or (IV), wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each represent hydrogen or C _1-3 alkyl (methyl, ethyl, n-propyl, isopropyl). In particular, R ⁶ and R ⁷ or R ⁸ , R ⁹ and R ¹⁰ are preferably all alkyl groups, especially methyl groups. A is a copolymer chain of p times ethylene oxide units and q times propylene oxide units, and the form of the copolymer can be any block copolymer, random copolymer, alternating copolymer and the like. p and q satisfy the following relationship: 0.1≤p/q≤10, preferably 0.1≤p/q≤3, best 0.2≤p/q≤2, and 5≤p+q≤100, best 5≤p +q≤50. Thus, the polyoxyalkylene glycol derivatives of the general formulas (III) and/or (IV) used in the lubricating oil III of the present invention must contain ethylene oxide units and propylene oxide units in specified portions. If p/q is smaller than 0, 1, there may be such a problem that the viscosity index decreases and also the solubility decreases. If p/q is higher than 10, there is a problem that the product becomes paraffin-like and the solubility decreases. In addition, if p+q is less than 5, there is a problem that lubricity decreases due to too low viscosity. If p+q is higher than 100, the solubility and heat exchange efficiency will drop annoyingly.

For the sake of simplicity, the ethylene oxide unit is called EO, the propylene oxide unit is called PO, and A is called -(EO)m-(PO)n-. They are not limited to block copolymers, but are widely applied to random copolymers, alternating copolymers, and the like.

Specific examples of polyoxyalkylene glycol derivatives of the general formulas (III) and (IV) used in the present invention are: H ₃ CO-(EO) ₂₀ -(PO) ₂₀ -CH ₃ ,

HO-(EO) ₄ -(PO) ₁₄ -CH ₃ ,

HO-(EO) ₁₅ -(PO) ₁₅ -H,

The above repeating unit numbers of EO and PO are given as examples only, and are not limited as long as the above conditions are satisfied.

In the lubricating oil III of the present invention, the polyoxyalkylene glycol derivatives of the above general formulas (III) and (IV) may be used alone or in the form of a mixture of two or more thereof.

The lubricating oil III of the present invention contains the above-mentioned polyoxyalkylene glycol derivative as a main component. In the same manner as the above lubricating oil I, if necessary, various additives used in conventional lubricating oils, such as anti-carriers, chlorine capture agents, antioxidants, metal deactivators, defoamers, cleaning and dispersing agents, viscosity Index improvers, oily additives, antiwear agents, extreme pressure agents, rust inhibitors, corrosion inhibitors, pour point depressants, etc. In addition, mineral oils and synthetic oils used as lubricating base oils can also be added. Examples of various additives are described above.

Next, the lubricating oil IV of the present invention will be described.

The lubricating oil IV of the present invention contains a polyoxyalkylene glycol derivative represented by the foregoing general formula (V) and/or (IV) as a main component, wherein, R ¹¹ , R ¹² R ¹³ , R ¹⁴ and R ¹⁵ represent hydrogen or C _1-3 alkyl (methyl, ethyl, n-propyl, isopropyl) respectively. Specifically, R ¹¹ -R ¹⁵ are all preferably alkyl, most preferably methyl. A ¹ -A ³ are (co)polymer chains composed of 3-100, preferably 3-50, one, two or more C _2-4 alkylene oxide units. Numerals 3-100 representing the above unit numbers indicate the average value of the polymerization number of alkylene oxide units (ethylene oxide, propylene oxide, butylene oxide units) and the actual number including integers. That is, they are those containing d oxyalkylene units represented by the general formula,

-(R ^d O)-(wherein R ^d is a C _2-4 alkylene group) and an epoxide unit represented by the following general formula

-(R ^e O)-(wherein R ^e is a C _2-4 alkylene) block copolymer chain, random copolymer chain or alternating copolymer chain, d and e are 0-100 respectively, satisfying the relationship d+e=3-100. When d or e are 0, they become homopolymer chains of other alkylene oxide units. If d+e exceeds 100, compatibility decreases so that separation occurs undesirably.

Specific examples of polyoxyalkylene glycols represented by the general formula (V) or (VI) used in the present invention are

HO(C ₃ H ₆ O) _4～40H

H ₃ CO(C ₃ H ₆ O) _4～40 CH ₃

HO(C ₃ H ₆ O) _2～30 -(C ₂ H ₄ O) _2～30 CH ₃

涉及以上嵌段共聚合反应的共聚物不仅包括嵌段共聚物，而且还包括无规共聚物或交替共聚物。H ₃ CO(C ₃ H ₆ O) _2～30 -(C ₂ H ₄ O) _2～30 CH ₃

The copolymers involved in the above block copolymerization include not only block copolymers but also random copolymers or alternating copolymers.

In the lubricating oil IV of the present invention, the polyoxyalkylene glycol derivatives of the above formula (VI) or (VII) may be used either alone or as a mixture of two or more types.

In the present invention, the phosphate represented by the above formula (V) is blended with a base oil containing the above polyoxyalkylene glycol as a main component. R ¹⁶ and the above R ¹¹ -R ¹⁵ represent hydrogen or C _-2 alkyl, and r represents an integer of 1 or 2. If there are two R ¹⁶ , they can represent different alkyl groups, but the total number of carbon atoms must be 3 or less.

Specific examples of such phosphate represented by the general formula (V) are tricresyl phosphate (TCP), triphenyl phosphate, triisopropylphenyl phosphate and the like. Among them, tricresyl phosphate is preferred.

In the present invention, the amount of the above phosphoric acid ester to be blended is not critical. Usually, based on the total amount of cold machine oil to be prepared, it is more appropriate to determine 0.1-5wt%, preferably 0.2-3wt%.

In the lubricating oil IV of the present invention, by combining the polyoxyalkylene glycol derivative having the above-mentioned structure with the above-mentioned phosphoric acid ester, the effect of the phosphoric acid ester as an antiwear agent can be fully exhibited, and the tear resistance can be improved. At the same time, adverse effects such as damage to the appearance and lowering of the high critical solution temperature are reduced, and the lubricity as a refrigerator oil is also improved.

The lubricating oil of the present invention generally contains the above-mentioned polyoxyalkylene glycol derivative as a main component, into which the phosphoric acid ester of the general formula (V) is incorporated. In addition, various additives used in conventional lubricating oils can also be blended, such as anti-carriers, chlorine traps, antioxidants, metal deactivators, antifoaming agents, detergent dispersants, viscosity index improvers, oily dispersants , Antiwear agent, extreme pressure agent, rust inhibitor, corrosion inhibitor, pour point depressant, etc.

Furthermore, in addition to the above-mentioned polyoxyalkylene glycol derivatives as base oils, mineral oils and synthetic oils may be added as base oils for lubricating oils, if desired. Specific examples of them have been described above.

The lubricating oil V of the present invention will be described below.

As shown in the general formula (Ⅷ), this lubricating oil V is a compound obtained by adding alkylene oxidation to glycerin, wherein R ¹⁷ , R ¹⁸ and R ¹⁹ can be the same alkylene or different alkylene alkyl.

Alkylene oxides (for the present invention, having 2 to 6 carbon atoms) added to polyoxyalkylene glycol derivatives such as ethylene oxide, propylene oxide, butylene oxide, etc. can be used .

In the general formula, the additional values s, t and u are an integer of 1-30, preferably 2-15.

The polyoxyalkylene glycol derivatives of the general formula (VIII) can be used in the form of mixtures with different additions.

The viscosity of polyethylene glycol derivatives depends on the type of alkylene group and the number of additions (s, t, u).

The polyethylene glycol compound used in the present invention must have a viscosity of 50-250 cst, preferably 60-200 cst (at 40°C). If the viscosity is lower than 50 cst, the sealing property will be poor, and if the viscosity is higher than 250 cst, the polyoxyalkylene glycol derivative will be insoluble in the refrigerant.

Depending on the desired viscosity, the average number and type of additions can be determined.

Such polyoxyalkylene glycol derivatives obtained by adding propylene oxide or ethylene oxide to glycerin are preferably used.

For example, the viscosity of the propylene oxide adduct of glycerol represented by the general formula on the left is 116 cst at 40°C. The propylene oxide adduct of glycerol represented by the general formula on the right is 103cst at 40°C. It is best to use these two compounds.

Preferably, the polyoxyalkylene glycol derivative used in the present invention has a purity of 70% by weight or higher.

In the lubricating oil V of the present invention, mineral oil or synthetic oil may be blended into the above-mentioned polyglycol compound in an amount of 50% by weight or less.

Preferably blended with mineral oil or synthetic oil with a viscosity of 5-500 cst at 40°C. For example, (i) paraffinic mineral oils, (ii) naphthenic mineral oils, (iii) polyalphaolefins, (iv) alkylbenzenes, (v) alkylbiphenyls, (ⅵ) esters (hindered esters, dibasic acid esters, polyhydroxyl esters, phosphate esters), (vii) polyglycols (polyphenylene glycols, monofunctional and difunctional polyglycols), and the like. Among them, it is preferable to incorporate synthetic oils (ⅳ)-(ⅶ) having high solubility in refrigerants.

If the viscosity of these mixtures becomes lower than 5 cst, the amount of circulating oil increases, the loss due to evaporation increases, and thus there arises a problem of poor sealing performance.

In the lubricating oil V, it is preferable to keep the water content at 500 ppm or less, more preferably 300 ppm or less, more preferably 200 ppm or less, most preferably 100 ppm or less.

If the water content increases, rust will easily form, and the solubility will decrease. Although lubricating oil V is excellent in the above-mentioned various characteristics, it is relatively poor in wear resistance compared with other lubricating oils (lubricating oils 1-IV and VI).

In the lubricating oil of the present invention, various additives such as antiwear agents, antioxidants, metal deactivators, chlorine capture agents, defoamers, and other additives may be added appropriately if necessary.

The lubricating oil VI of the present invention will be described below. In said lubricating oil VI, the polyoxyalkylene glycol derivative used as component (a) is not critical, but at least one compound selected from the group represented by the following general formula is preferably selected.

(其中R²³、R²⁴和R²⁶分别是C_2-6亚烷基，它们可相同或不同，R²⁶、R²⁷和R²⁸分别是氢原子、烃基或酰基，它们可相同或不同；X、Y和Z分别是2或以上的一个数，它们可相同或不同)中的化合物。R ²⁰ -O-(R ²¹ O) _W R ²² ... (IX) (wherein R ²⁰ and R ²² are hydrogen, hydrocarbon group or acyl group respectively, they can be the same or different, R ²¹ is a C _2-6 alkylene group, W is a number of 2 or more) and compounds represented by the following general formula

(wherein R ²³ , R ²⁴ and R ²⁶ are C _2-6 alkylene groups, which may be the same or different; R ²⁶ , R ²⁷ and R ²⁸ are hydrogen atoms, hydrocarbon groups or acyl groups, which may be the same or different; X , Y and Z are each a number of 2 or more, and they may be the same or different).

R ²⁰ and R ²² in the general formula (IX), R ²⁶ , R ²⁷ and R ²⁹ in the general formula (X) are hydrogen atoms, hydrocarbon groups or acyl groups respectively, and the hydrocarbon groups include alkyl, cycloalkyl or acyl groups ( each having 1-30, preferably 1-12 carbon atoms). Examples of such hydrocarbyl groups are methyl, ethyl, n-propyl, isopropyl, different butyl groups, different pentyl groups, different hexyl groups, different heptyl groups, different octyl groups, different arbitrary groups, different Decyl, different undecyl, different dodecyl, different cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, tolyl, benzyl, phenethyl and so on.

Acyl groups include those derived from aliphatic carboxylic acids, alicyclic compounds or aromatic carboxylic acids (having 1-30, preferably 1-12 carbon atoms, respectively). Examples of such acyl groups are those derived from carboxylic acids including formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, lauric acid, cyclohexanecarboxylic acid and benzoic acid.

R ²¹ in general formula (IX), R ²³ , R ²⁴ and R ²⁵ in general formula (X) are C _2-6 alkylene, preferably vinyl, propenyl or butenyl. In the polyoxyalkylene glycol derivatives represented by the general formulas (IV) and (X), the repeating units of oxyalkylene contained in one molecule may be the same or different.

R ²⁰ and R ²² in the general formula (IX) may be the same or different from each other, but one of them is preferably a hydrocarbon group, most preferably an alkyl group. Specific examples of polyglycol compounds represented by the general formula (IX) are

C ₈ H ₁₀ O (C ₃ H ₆ O) ₁₀ H

C ₄ H ₈ O(C ₃ H ₆ ) ₁₈ H

HO(C ₃ H ₆ O) ₁₇ H

R ²³ , R ²⁴ and R ²⁵ in the general formula (X) may be the same as or different from each other. R ²⁰ , R ²⁷ and R ²⁸ may be the same or different from each other, but these three groups are preferably hydrogen atoms. In addition, X, Y and Z may be the same as or different from each other. Specific examples of such compounds are

The polyoxyalkylene glycol derivatives represented by the general formulas (IX) and (X) can be prepared according to conventional methods. For example, in the method for preparing polyoxyalkylene glycol derivatives represented by general formula (IX), the C _2-6 alkylene oxide (such as ethylene oxide or propylene oxide) and water or alkali metal Hydroxide initiators are polymerized to obtain polyglycols with hydroxyl groups at both ends. If one or two hydroxyl groups of the polyglycols thus obtained are etherified or esterified by conventional methods, the polyglycols with ether bonds at the ends can be obtained. or ester bonded polyoxyalkylene glycol derivatives.

In addition, if the _C2-6 alkylene oxide is polymerized with the alcohol or phenol or its metal salt initiator having the required carbon atoms used, a polyoxyalkylene glycol with an ether bond at one end and a hydroxyl group at the other end can be obtained derivative. If the hydroxyl group of the derivative is etherified or esterified, a polyoxyalkylene glycol derivative having an ether bond or an ether bond and an ester bond at both ends can be obtained.

In the method for preparing the polyoxyalkylene glycol derivatives represented by the general formula (X), if the _C2-6 alkylene oxide is polymerized with the glycerol or its alkali metal salt initiator used, the two ends can be obtained Polyethylene glycol ethers of glycerin having three hydroxyl groups, and if the hydroxyl groups of the polyglycol ethers are etherified or esterified in a conventional manner, polyethylene glycol ethers of glycerin having ether bonds or ester bonds at both ends can be obtained. Glycol ethers (polyoxyalkylene glycol derivatives).

In the lubricating oil VI of the present invention, one of the above-mentioned components (a) may be used alone, or two or more kinds may be used in combination.

In lubricating oil VI of the present invention, at least one compound selected from (i) dibasic acid esters, (ii) fluorinated oils, (iii) polyol esters and (iv) fluorosiloxanes is used as a component ( b).

For example, a compound represented by the following general formula is used as the dibasic acid ester of component (i):

R ²⁹ OOO-A ⁴ -COOR ³⁰ ... (Ⅺ) wherein R ²⁹ and R ³² are alkyl, cycloalkyl or aryl groups with 1-20 carbon atoms respectively, and may be the same or different, and A ⁴ is alkylene group, cycloalkylene or phenylene. Typical examples of such dibasic acid esters are adipate-di-2-ethylhexyl, sebacate-di-2-ethylhexyl, cyclohexane-1,4-dicarboxylic acid di-2 - Ethylhexyl ester, diisodecyl phthalate, etc.

A preferred example of the fluorinated oil used as the component (ii) is - chlorotrifluoroethylene copolymer represented by the general formula (VII) Wherein X ¹ and X ² are halogen atoms respectively, they may be the same or different from each other, and j is a number whose average molecular weight is 250-1500. Commercially available Daifloil 10 and Daifloil 20 (trademarks, both produced by Daikin Industries Co., Ltd.) can be used as the chlorotrifluoroethylene polymer.

Preferred examples of polyhydric alcohol esters used as component (iii) are monovalent or divalent aliphatic polyhydric alcohols such as neopentyl glycol, glycerol, trihydroxyethane, trimethylolpropane, pentaerythritol and sorbitol. ester.

Typical examples of such polyol esters are trimethylolpropane hexanoate, pentaerythritol propionate, pentaerythritol hexanoate, trimethylolpropane adipate, and the like.

Examples of fluorosilicone used as component (iv) are compounds represented by the general formula (VIII): Wherein at least one of R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ is a C _1-30 fluorocarbon group, and the others are C _1-30 hydrocarbon groups, acyl groups, alkoxy groups or fluorocarbon groups, and they are mutually They may be the same or different, and v is 0 or an integer of 1 or more.

The hydrocarbon group in the fluorosilicone represented by the general formula (VIII) is an alkyl group, a cycloalkyl group or an aryl group, and in the fluorocarbon group, at least one hydrogen atom of these hydrocarbon groups is replaced by a fluorine atom.

In addition, in the alkoxy group and acyl group, when an oxygen atom or a carboxyl group is removed, the remaining group includes an alkyl group, a cycloalkyl group or an aryl group. A typical example of such fluorosilicone is commercially available LS-8210 (trademark, manufactured by Shin-etsu Chemical Industry Co., Ltd.).

In lubricating oil VI of the present invention, at least one compound selected from component (i), component (ii), component (iii) and component (iv) is used as component (b) and component (a ) combination. The amount of component (b) is limited to 0.01-50 wt%, especially 0.1-30 wt% (based on the total amount of component (a) and component (b)). If the amount is less than 0.01 wt%, the effect of improving the solubility of the halothane refrigerant at high temperature is not obvious, and if the amount exceeds 50 wt%, the solubility or the stability of the mixture will decrease.

Various additives commonly used in refrigerator oils may be added to the lubricating oil VI of the present invention as long as the object of the present invention is not hindered. Examples of such additives are antiwear agents, antioxidants, metal deactivators, chlorine traps, defoamers, pour point depressants, viscosity index improvers, and the like.

The lubricating oil of the present invention has excellent lubricity and compatibility with refrigerants, so it can be used as a lubricating oil for various refrigerators (including compression refrigerators) using flon refrigerants. Specifically, the lubricating oil of the present invention is different from conventional lubricating oils, and is different from hydrogen-containing fluorocarbon compounds [such as Flon134a, etc., such as 1,1,2,2-tetrafluoroethane (Flon-134), 1,1- Dichloro-2,2,2-trifluoroethane (Flon-123), 1-chloro-1,1-difluoroethane (Flon-142b), 1,1-difluoroethane (Flon-152a) , Chlorodifluoromethane (Flon-22), trifluoromethane (Flon-23)] good compatibility. This solubility is satisfactory over the entire temperature range.

Therefore, it is expected that the lubricating oil of the present invention can be effectively used as a lubricating oil for refrigerators, coolers (especially air conditioners), heat pumps, etc. using various halothane compound refrigerants. This lubricating oil can be mixed with other lubricating oils for compression refrigerators.

The present invention is illustrated in more detail with reference to the following examples.

Preparation Example 1

In a 200 ml three-neck glass flask equipped with a stirrer and a dropping funnel, add 50 gram Unilube MB-11 (polyoxypropylene glycol-n-butyl ether, average molecular weight: 1000, produced by Nippon Oil & Fats Co., Ltd.), 9.5 gram ( 0.12 mol) pyridine and 100 ml ether. Then, within 30 minutes, 9.4 g (0.12 mol) of acetyl chloride were added via the dropping funnel while stirring at room temperature. After heating to reflux for 2 hours, the reaction mixture was cooled to room temperature, transferred to a separatory funnel and washed 5 times with 50 mL of saturated brine each time. After distilling off the ether, the residue was dried at 100°C for 1 hour under reduced pressure using a vacuum pump to obtain 49.0 g of the desired acetate of Unilube MB-11.

Preparation example 2

In a 300 ml three-neck glass flask equipped with a stirrer and a distillation apparatus, add 75 g of Unilube MB-11 (manufactured by Nippon Oil & Fats Co., Ltd.) and 50 ml of toluene, and distill off 20 ml while heating and stirring Toluene to remove water content. Then, the distillation apparatus was removed, a cooler and a dropping funnel were installed, and then 11.9 g (0.15 mol) of pyridine and 50 ml of toluene were added. While stirring at room temperature, 16.0 g (0.15 mol) of n-butyryl chloride was added through the dropping funnel over 30 minutes. After heating to reflux for 4 hours, the reaction mixture was cooled to room temperature, poured into a separatory funnel and washed 5 times with 50 ml of saturated brine each time. After distilling off the toluene, the residue was dried at 100°C for 1 hour under reduced pressure using a vacuum pump to obtain 70.5 g of the desired n-butyrate of Unilube MB-11.

Preparation example 3

Repeat the same procedure of Preparation Example 2, except that 16.0 grams (0.15 moles) of isobutyryl chloride is used instead of n-butyryl chloride to obtain 74 grams of isobutyryl ester of Unilube MB-11.

Reference example 1

The same procedure of Preparation Example 1 was repeated, except that 16.9 grams (0.12 moles) of benzoyl chloride were used instead of acetyl chloride to obtain 5 to 7.0 grams of benzoate esters of Unilube MB-11.

Reference example 2

In a 200 ml three-necked glass flask equipped with a stirrer and a dropping funnel, 50 g of Unilube MB-11 (manufactured by Nippon Oil & Fast Co., Ltd.), 7.9 g (0.14 mol) of potassium hydroxide and 80 ml of toluene were charged. Then, 15.2 g (0.12 mol) of benzyl chloride was added through the dropping funnel over 30 minutes while heating and refluxing toluene with stirring. After that, the mixture was heated and refluxed for 4 hours, cooled to room temperature, and then the reaction mixture was poured into a separatory funnel and washed 5 times with 50 ml of saturated brine each time. After distilling off the toluene, the residue was dried at 100°C for 1 hour under reduced pressure (0.1 mmHg) using a vacuum pump to obtain 49.0 g of the desired benzyl ether of Unilube MB-11.

Preparation Example 4

In a 300 ml three-neck glass flask equipped with a stirrer and distillation equipment, add 65 g of polyoxypropylene glycol-n-butyl ether (average molecular weight 1120) and 70 ml of toluene, and distill off about 20 ml of toluene to remove moisture, Heat and stir simultaneously. After cooling, 25 g (0.13 mol) of sodium methoxide in methanol (28 wt%) was added and heated to distill off methanol and about 20 ml of toluene. After cooling, remove the distillation equipment and install a cooler and dropping funnel. Then, 30 g (0.19 mol) of ethyl iodide was added through the dropping funnel over 30 minutes while heating and stirring at 50°C. After heating and stirring at 50°C for 1 hour, at 70°C for 3 hours and at 105°C for 1.5 hours, the mixture was cooled to room temperature. After that, the reaction mixture was poured into a separatory funnel and washed 5 times with 50 mL of saturated brine each time. After distilling off the toluene, the residue was dried at 100°C for 1 hour under reduced pressure using a vacuum pump to obtain 58 g of the desired ether derivative of polyoxypropylene glycol-n-butyl ether.

Preparation Example 5

Repeat the same procedure of Preparation Example 4, but the difference is to replace polyoxypropylene glycol-n-butyl ether with 65 grams of polyoxypropylene glycol (average molecular weight is 1100) with hydroxyl groups at each end, and use 50 grams (0.27 moles) of ethanol solution of sodium methylate (28wt%) and 60 grams (0.38 mole) ethyl iodide, obtain 6 2 grams required polyoxypropylene glycol ethers.

Preparation Example 6

Repeat the same procedure of Preparation Example 4, except that there are three hydroxyl polyoxypropylene glycol (average molecular weight is 1000) derivatives (using glycerol as initiator polymerization propylene oxide to obtain) to replace polyoxypropylene glycol- n-Butyl ether, and with 50 g (0.26 mol) of sodium methoxide in methanol (28% by weight) and 90 g (0.58 mol) of ethyl iodide, 61 g of the desired polyoxypropylene glycol triethyl ether derivative was obtained.

Preparation Example 7

In a 300 ml three-necked glass flask equipped with a stirrer and a distillation apparatus, 50 g of Sannixpp-1000 (polyoxypropylene glycol having -hydroxyl groups at each end, average molecular weight 1000, produced by Sanyo Chemical Industry Co., Ltd.) and 80 ml of toluene were added , Evaporate 20 ml of toluene to remove moisture while heating and stirring.

After cooling, 25 g (0.13 mol) of sodium methoxide in methanol (28 wt%) was added, and the mixture was heated to distill off methanol and about 20 ml of toluene.

After cooling, the mixture in the flask was poured into a 300 ml stainless steel autoclave equipped with a stirrer, 36.8 g (0.26 mol) of methyl iodide was added and sealed. Then, the mixture was heated at 50°C-70°C for 4.5 hours, and reacted at 85°C for 4 hours. After cooling to room temperature, the reaction mixture was dissolved in a mixture of 100 ml of water and 200 ml of methanol, and passed through a 200 ml column of cation exchange resin and then a column of 200 ml of anion exchange resin.

After distilling off the solvent, the residue was dried under reduced pressure (0.1 mmHg) with a vacuum pump for 1 hour to obtain 42.5 g of the desired dimethyl ether derivative of Sannix pp-1000. In this derivative, the infrared absorption spectrum (3450 cm ^-1 ) is lost due to the hydroxyl group.

Preparation example 8

Repeat the same procedure of Preparation Example 7, except that 60 grams of Nissan Uniol D-1200 (polyoxypropylene glycol with a hydroxyl group at each end, average molecular weight 1200, produced by Nippon Oil & Fats Co., Ltd.) replace Sannispp-1000 to obtain 49 grams of Nissan Uniol D- 1200 dimethyl ether derivatives. In this derivative, the infrared absorption spectrum (3450 cm ^-1 ) (3450 cm ^-1 ) is lost due to the hydroxyl group.

Embodiment 1-8, comparative example 1-4

The compatibility of the raw material polyglycols in Preparation Examples 1 and 4, the compounds prepared in Preparation Examples 1-8, and Reference Examples 1-2 with Flon134a was determined.

A certain sample is added to a pressure glass bottle so that the amount of the sample accounts for 10wt% or 20wt% of Flon 134a (1,1,1,2-tetrafluoroethane), and the bottle is connected to a vacuum pump and Flon134a Gas tube, after which the bottle was vacuum degassed at room temperature and cooled with liquid nitrogen to bring out the prescribed Flon134a. The vial was then sealed, heated in a thermostat from -40°C and the onset temperature of phase separation was determined. Higher temperatures for phase separation are preferred. The results are shown in Table 1.

Table 1 serial number sample from Viscosity (cst) Viscosity index Onset temperature of phase separation (°C) The ratio of polyglycol to 1,1,1,2-tetrafluoroethane (wt.%) 40℃ 100°C 10% 20% Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 4 Comparative Example 4 Example 5 Example 6 Example 7 Example 8 Acetate of Unilube MB-11 Isobutyrate of "n-butyrate" Benzyl ether of "benzoate" Ethyl ether derivative of monohydroxypolyoxypropylene glycol monohydroxypolyoxypropylene glycol dihydroxypolyoxypropylene glycol Ether derivatives of trihydroxypolyoxypropylene glycol ether derivatives of dihydroxypolyoxypropylene glycol methyl ether derivatives of dihydroxypolyoxypropylene glycol methyl ether derivatives of dihydroxypolyoxypropylene glycol Product of Preparation 1 Product of Preparation 2 Product of Preparation 3 Product of Preparation 1 Product of Reference 2 Product of Reference 2 Product of Preparation 4 Material of Preparation 5 Product of Preparation 6 Product of Preparation Example 7 Product of Preparation Example 8 48.2346.7245.4456.1072.0349.3538.7053.041.5020.7632.047.56 9.779.969.6110.812.589.908.7110.069.018.107.509.70 194207203187175192214185206177214195 71.066.566.551.515.032.063.055.570.073.079.570.5 74.066.567.054.0-3.028.566.557.573.074.580.570.5

Preparation Example 9

In a 200 ml stainless steel autoclave equipped with a stirrer and isolating tube, add 3.0 g of sodium methoxide powder, seal and heat at 105 ° C, and add 100 g of propylene oxide to the autoclave under pressure through the catheter , which lasted 9 hours while stirring.

After adding 100 ml of water and 200 ml of methanol and dissolving in the reaction mixture, the solution was passed through a 200 ml column of cation exchange resin and then through a column of 200 ml anion exchange resin to remove sodium ions. After methanol and water were distilled off, the residue was dried at 100°C under reduced pressure (0.4 mmHg) for 1 hour to obtain 96 g of the desired polyoxypropylene glycol monomethyl ether.

Preparation Example 10

In a 200 ml stainless steel autoclave equipped with a stirrer and a conduit, add 1.6 g of methanol and 0.2 g of sodium hydroxide, seal, heat at 105°C and introduce 129.6 g of propylene oxide under pressure into the autoclave through the conduit device.

After 100 ml of water and 200 ml of methanol were added and dissolved in the reaction mixture, the solution was passed through a 200 ml cation exchange column and then a 200 ml anion exchange column to remove sodium ions. After methanol and water were distilled off, the residue was dried at 100°C for 1 hour under reduced pressure (0.4 mmHg) using a vacuum pump to obtain 115 g of the desired polyoxypropylene glycol-methyl ether.

Preparation Example 11

Repeat the same procedure of Preparation Example 1, except that 4.42 g of sodium ethoxide is used instead of sodium methoxide and the amount of cyclopropane is changed to 100 g to obtain 97 g of the desired polyoxypropylene glycol-ether.

Embodiment 9-11 and comparative example 5

The compatibility of the compounds prepared in Preparation Examples 9-11 and polyoxypropylene glycol having a butyl ether group at one end and a hydroxyl group at the other end with Flon134a was determined.

Add the prescribed sample to a pressure glass bottle so that the amount of the sample accounts for 10wt% or 20wt% of Flon134a (1,1,1,2-tetrachloroethane), and connect the bottle to a vacuum pump and Flon134a air tube. Afterwards, the bottle was vacuum degassed at room temperature and cooled with liquid nitrogen to bring out some Flon134a. Then, the bottle was sealed, heated in a thermostat from -40°C and the onset temperature of phase separation was measured. The results are shown in Table 2. Higher separation temperatures are preferred.

Table 2 serial number sample from Viscosity (cst) Viscosity index dispersion Onset temperature of phase separation (°C) The ratio of polyglycol to 1,1,1,2-tetrafluoroethane (wt.%) 40℃ 100°C 10% 20% Example 9 Example 10 Example 11 Comparative Example 5 Polyoxypropylene glycol-methyl ether Polyoxypropylene glycol-methyl ether Polyoxypropylene glycol-ethyl ether Polyoxypropylene glycol-n-butyl ether Product of Preparation Example 9 Product of Preparation Example 10 Product of Preparation Example 11 UnilubeMB-11 manufactured by Nippon oil dFats Co., Ltd. 48.257.262.1356.1 9.4510.9811.7010.8 184186187187 71.562.558.051.5 74.066.560.054.0 Embodiment 12-16 and contrast 6-9

Using various polyoxyalkylene glycol derivatives as sample oils, the phase separation initiation temperature (critical solution temperature) was measured according to the following test method.

In a 10 ml glass autoclave, add sample oil and refrigerant (Flon134a), the weight ratio of the two is 1:9, then seal and gradually heat from a homogeneous solution state, and determine that the sample oil and refrigerant begin to separate The temperature is taken as the critical solution temperature. The results are shown in Table 3.

table 3 serial number Polyoxyalkylene glycol derivatives of general formula (Ⅲ) Dynamic viscosity (cst) Critical solution temperature (°C) R ⁶ R ⁷ p+q p+q 100°C Example 12 Comparative Example 6 Comparative Example 7 Comparative Example 8 Example 13 Example 14 Example 15 Comparative Example 9 Example 16 methyl methyl butyl butyl methyl methyl methyl methyl methyl methyl methyl hydrogen methyl methyl hydrogen hydrogen 40403634206323222 101011101 24.022.425.721.89.502.8621.922.99.45 49.09.532.0 separates 74.090.0 or higher 41.05.073.0

As shown in Table 3, the comparison of the sample oils with similar values of dynamic viscosities shows that the critical solution temperature of the sample oils in the Examples is higher than that of the Control Examples (such as Example 12 and Comparative Examples 6-8, Example 12 and Comparative Examples 9) the critical solution temperature of the sample oil is higher.

Embodiment 17-21 and comparative example 10-24

Various polyoxyalkylene glycol derivatives and their mixtures with various additives were used as sample oils, and their critical solution temperature, stability, wear resistance and tear resistance were measured as follows.

The dynamic viscosities of all sample oils were uniform to about 10 cst (100°C).

(1) Critical solution temperature

In a glass autoclave with a capacity of about 10 ml, a sample and a refrigerant (Flon134a) in a weight ratio of 1:9 were added and sealed, and then gradually heated from a homogeneous solution state. The temperature at which the sample oil and the refrigerant begin to separate is measured and taken as the critical solution temperature.

(2) Stability

Evaluate by Shield Tube Test.

A 2:1 mixture of sample oil and refrigerant (Flon 134a) was added to a glass tube with iron, copper or aluminum catalyst and sealed, then heated at 175°C to 175°C. The appearance of the oil and catalyst was observed, and the total acid number was determined.

(3) Wear resistance

Evaluated by the Falex Wear Test.

The amount of rubbing is measured by blowing 10 liters of Flon 134a per hour and a load of 300 pounds for 1 hour.

(4) Tear resistance

Evaluated by the Falex Seizure Test.

Tear load (lbs) was determined according to ASTM D3233 by blowing in 10 liters of Flon 134a per hour. The results are shown in Table 4.

Table 4 Example Comparative example 17 18 19 20 twenty one 10 11 12 13 14 Dihydroxypolyoxypropylene glycol polyoxypropylene glycol monomethyl ether polyoxypropylene glycol dimethyl ether ethylene oxide propylene oxide copolymer dimethyl ether glycerol propylene oxide adduct polyoxypropylene glycol monobutyl ether polyoxypropylene glycol dibutyl ether tricresyl phosphate Ester Dylyl Phosphate Trinonylphenyl Phosphate Triphenyl Phosphite Zinc Dithiophosphate Dioctyl Sulfide Critical Solution Temperature (°C) Stability Appearance (Oil) (Refrigerant Flon134a) 99------1-----67.5 Good -99-----1-----67.5 good --99----1-----66.5 good ---98---2-----67.5 good ----99--1-----67.5 Good -----99-1-----58.5 Good ------991-----52.5 good -99------1----67.5 good -99----------- Room temperature (fuzzy) Untested -99--------1--67.5 good

Table 4 (continued) Example Control example 17 18 19 20 twenty one 10 11 12 13 14 Catalyst total acid value consumption (300 lbs x hours) (mg) tear resistance (lbs) Good 0.1 or below 3800 Good 0.1 or below 4800 Good 0.1 or below 5800 Good 0.1 or below 4800 Good 0.1 or below 5800 Good 0.1 or below 5800 Good 0.1 or below 5800 Good 0.5 or above 5800 untested untested untested untested Good 0.5 or above 5800

Table 4 (continued) Comparative example 15 16 17 18 19 20 twenty one twenty two twenty three twenty four Dihydroxypolyoxypropylene glycol polyoxypropylene glycol monomethyl ether polyoxypropylene glycol dimethyl ether ethylene oxide propylene oxide copolymer dimethyl ether glycerol propylene oxide adduct polyoxypropylene glycol monobutyl ether polyoxypropylene glycol dibutyl ether tricresyl phosphate Ester Dylyl Phosphate Trinonylphenyl Phosphate Triphenyl Phosphite Zinc Dithiophosphate Dioctyl Sulfide Critical Solution Temperature (°C) Stability Appearance (Oil) (Refrigerant Flon134a) -99---------1-67.5 coloring (yellow) -99----------167.5 coloring (yellow) -----99--1----58.5 good 100------------67.0 good -100-----------67.0 Good --100----------66.0 Good ---100---------67.0 Good ----100--------66.5 Good -----100-------57.5 good ------100------52.0 good

Table 4 (continued) Comparative example 15 16 17 18 19 20 twenty one twenty two twenty three twenty four Catalyst total acid value consumption (300 lbs x hours) (mg) tear resistance (lbs) Coloring (Fe) 0.5 or above 7650 Coloring (Fe) 0.1 or below 7500 Good 0.5 or above 7800 Good 0.1 or below 7600 Good 0.1 or below 7600 Good 0.1 or below 5600 Good 0.1 or below 5600 Good 0.1 or below 5600 Good 0.1 or below 5600 Good 0.1 or below 5600

It can be clearly seen from the above table 4 that the sample oil of the embodiment is higher than the critical solution temperature of the control, and the tear resistance is better.

Embodiment 22-24 and comparative example 27-31

For the components shown in Table 5, the sample oil and the fluorine-containing refrigerant Flon134a were mixed at a weight ratio of 1:9, and the critical solution temperature of the solution was measured. The results are shown in Table 5.

table 5 serial number Component Viscosity(40℃)cst critical solution temperature ¹ low temperature(℃) high temperature (℃) Example 22 Example 23 Example 24 Comparative Example 27 Comparative Example 28 Comparative Example 29 Comparative Example 30 Comparative Example 31 Glycerol propylene oxide adduct ² (trifunctional group) glycerol propylene oxide adduct ³ (") glycerol propylene oxide adduct ⁴ (") polypropylene glycol monobutyl ether ⁵ (monofunctional group) polypropylene glycol ⁶ ( Difunctional group) trimethylolpropane propylene oxide adduct ⁷ (trifunctional group) sorbitol propylene oxide adduct ⁸ (hexafunctional group) glycerol propylene oxide adduct ⁹ (trifunctional group) 116961031051501944275304 -50 or less -50"-50"-42-37 undissolved 10"" 8077578 Undissolved 10""

Note: the water content of each sample oil of the embodiment and the comparative example is 300ppm. Note:

1) Test method for critical solution temperature

In a glass pressure vessel with a capacity of about 10 ml, the sample oil and refrigerant (Flon134a) were charged at a ratio of 1:9 and sealed. Gradually cool the homogeneous solution on the low temperature side and observe the temperature at which the oil and refrigerant separate. On the high temperature side, gradually reduce its temperature, and observe the temperature at which the oil and refrigerant separate in a similar manner.

2) Sannix GP400, produced by Sanyo Chemical Industry Co., Ltd.

3) Sanix GP600, produced by Sanyo Chemical Industry Co., Ltd.

4) Sannix GP1000, produced by Sanyo Chemical Industry Co., Ltd.

5) Uniilube MB19, produced by Nippon Oil & Fats Co., Ltd.

6) Sannx pp2000, produced by Sanyo Chemical Industry Co., Ltd.

7) Sanix TP400, produced by Sanyo Chemical Industry Co., Ltd.

8) Sannix SP750, produced by Sanyo Chemical Industry Co., Ltd.

9) Sanix GP4000, produced by Sanyo Chemical Industry Co., Ltd.

10) Insoluble with refrigerant (Flon134a) at normal temperature.

The components of Examples 22-24 have a low critical solution temperature at low temperatures and a high critical solution temperature at high temperatures. This shows that, at the operating temperature, operation can be performed satisfactorily without two-phase separation of the refrigerant and the refrigerating machine oil.

Examples 25-27 and Comparative Examples 32-34

In a glass tube, put a mixture of 6 grams of sample oil and Flon134a (the weight ratio of the two is 2:1) together with iron wires, copper wires and aluminum wires. The diameter of each wire is 1.5 mm and the length is 40 mm. and sealed. After 30 days and 60 days of heat preservation at 175°C, changes in the surface of each metal wire were observed with the naked eye.

No changes were observed on the surface of copper or aluminum wires, but some samples were observed to have changes on the surface of iron wires. The observation results of the iron wire are shown in Table 6. No change was confirmed with low water content.

Table 6 serial number Component Shielded tube test (refrigerant: Flon-134a) 170℃×30 days iron wire appearance 175℃×60 days iron wire appearance Example 25 Example 26 Comparative Example 32 Comparative Example 33 Comparative Example 34 Glycerol propylene oxide adduct (trifunctional group) (water content: 300ppm) glycerol propylene oxide adduct ¹ (trifunctional group) (water content: 150ppm) glycerol propylene oxide adduct ² (trifunctional group) (Water content: 1000ppm) Glycerin propylene oxide adduct ³ (trifunctional group) (water content: 1%) Glycerin propylene oxide adduct ³ (trifunctional group) (water content: 3%) No change (slight loss of gloss) No change No change (loss of gloss) Slight change Discoloration No change (slightly decreased gloss) no change (slightly decreased gloss) slight change decolorization Table 6 Note:

1 Example 27 was dehydrated, and the water content of the prepared samples was 50 and 150 ppm.

2 Example 27 was placed in an open state for 30 hours, and the water content of the prepared sample was 1000ppm.

3Example 27 was added with water, and the water contents of the prepared samples were 1% and 5%, respectively.

Embodiment 28-33 and comparative example 35

A refrigerating machine oil having the composition shown in Table 7 was prepared. In a 10 ml glass pressure vessel, respectively add refrigerating machine oil and Flon134a refrigerant (the weight ratio of the two is 1:9) and seal, then gradually heat from the homogeneous solution state. The measured temperature at which oil and refrigerant begin to separate is taken as the critical solution temperature. The results are shown in Table 7.

Table 7 serial number Composition of refrigerator oil (wt%) Critical solution temperature (°C) Component (a) Amount of component (b) Kind ^* Amount (ⅰ) (ii) (iii) (ⅳ) Example 28"29"30"31" 32 Comparative Example 35 Example 33 A-1A-1A-1A-1A-1A-1A-2 8776899099.910080 13------ -24--0.1-20 --11---- ---10--- 62.064.857.559.053.551.567.5

^* A-1: Unilube MB11

(Polypropylene glycol monobutyl ether, produced by Nippon & Fats Co., Ltd.) A-2: Sannix GP1000

(Glycerol cyclopropane adduct, produced by Sanyo Chemical Industry Co., Ltd.) Table 7 note (continued)

(i): Dioctyl adipate DOA

(Dibasic acid ester, manufactured by Mitsubishi Monsant Co., Ltd.)

(ⅱ):Daifloil 10

(Fluorinated oil, produced by Daikin Industries Co., Ltd.)

(Ⅲ): Unistar H-306

(Polyol Esters, Nippon Oil & Fats Co., Ltd.)

(ⅳ):LS-8210

(Fluorosilicone, manufactured by Shin-etsu Chemical Co., Ltd.)

Claims (2)

1. compression-type refrigerator, this refrigerator comprises compressor, wherein contain the refrigeration agent and the lubricant of hydrofluorocarbons compound, described lubricant contains lubricating oil, contains the polyoxyalkylene glycol derivative of the PEP-101 that following formula represents in the lubricating oil

R ⁶-0-A-R ⁷Or general formula

R wherein ⁶, R ⁷, R ⁸, R ⁹And R ¹⁰Be respectively C _1-3Alkyl, A are the copolymerization chains of oxyethane and propylene oxide, are made of p ethylene oxide unit and q propylene oxide units, and p and q are the numbers that satisfies following relation:

0.1≤p/q≤10 and 5≤p+q≤100.

2. according to the compression-type refrigerator of claim 1, R wherein ⁶To R ¹⁰Be methyl.