JP3173684B2 - Lubricating oil for compression refrigerators - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel lubricating oil for compression refrigerating machines, and more particularly, to dichlorofluoromethane (hereinafter referred to as chlorofluorocarbon (CFC)) which is a problem of environmental pollution.
1,1,1,2-tetrafluoroethane, difluoromethane, pentafluoroethane (hereinafter, Freon 134a, Freon 32,
A hydrogen-containing freon compound such as freon 125 [here, the freon compound is a general term for chlorofluorocarbon (CFC), hydrofluorocarbon (HFC) and hydrochlorofluorocarbon (HCFC). Good compatibility with, and excellent lubrication performance,
The present invention relates to a lubricating oil for a compression type refrigerator mainly containing a polyvinyl ether compound.

[0002]

2. Description of the Related Art Generally, a compression refrigerating machine comprises a compressor, a condenser, an expansion valve, and an evaporator, and has a structure in which a mixed liquid of a refrigerant and a lubricating oil circulates in this closed system. In such a compression refrigerator, although it depends on the type of the device, generally, the temperature is high in the compressor and low in the cooler, so that the refrigerant and the lubricating oil undergo phase separation in a wide temperature range from low to high. It is necessary to circulate in this system without having to. If phase separation occurs during the operation of the refrigerator, the life and efficiency of the device will be significantly adversely affected. For example, when the phase separation of the refrigerant and the lubricating oil occurs in the compressor part, the moving part becomes inadequately lubricated, causing seizure or the like to significantly shorten the life of the device, while the phase separation occurs in the evaporator, The presence of the lubricating oil having a high viscosity causes a reduction in the efficiency of heat exchange.

[0003] Further, since lubricating oil for refrigerators is used for lubricating movable parts of the refrigerator, lubrication performance is naturally important. In particular, since the temperature inside the compressor becomes high, a viscosity capable of holding an oil film required for lubrication is important. The required viscosity varies depending on the type of compressor used and operating conditions, but usually the viscosity (kinematic viscosity) of the lubricating oil before mixing with the refrigerant is preferably 5 to 1000 cSt at 40 ° C. If the viscosity is lower than this, the oil film becomes thin and lubrication failure easily occurs, and if it is higher, the efficiency of heat exchange decreases. Further, in the electric refrigerator, since the motor and the compressor are integrated, the lubricating oil is required to have high electric insulation.
Generally, the volume resistivity at 80 ° C. is 10 ¹² Ω · cm
The above is required, and if it is lower than this, there is a risk of electric leakage. Further, lubricating oils are required to have high stability. For example, when an organic acid is generated by hydrolysis or the like, the corrosion or abrasion of the device is easily caused, depending on the amount thereof.

Conventionally, Freon 12 has been widely used as a refrigerant for compression refrigerators, and various mineral oils and synthetic oils satisfying the above-mentioned required characteristics have been used as lubricating oils.
However, Freon 12 has a possibility of causing environmental pollution such as destruction of the ozone layer, and thus its regulation has recently become stricter worldwide. Therefore, Freon 134a, Freon 32, Freon 125 are used as new refrigerants.
Attention has been paid to hydrogen-containing Freon compounds typified by the above. This hydrogen-containing Freon compound, particularly Freon 134a, has a low risk of destruction of the ozone layer and has almost no change in the structure of a conventional refrigerator.
It is preferable as a refrigerant for a compression-type refrigerator, because it can be replaced with Freon 12. When a hydrogen-containing chlorofluorocarbon compound such as chlorofluorocarbon 134a is used instead of chlorofluorocarbon 12 as the refrigerant for the compression refrigerator, the lubricating oil naturally contains the chlorofluorocarbon compound such as fluorocarbon 134a, fluorocarbon 32, fluorocarbon 125 and the like. It is required to be excellent in compatibility with, and excellent in lubricating performance capable of satisfying the above-mentioned required performance. However, the lubricating oil used together with the conventional Freon 12 has poor compatibility with hydrogen-containing Freon compounds such as Freon 134a, Freon 32 and Freon 125.
New lubricating oils suitable for these compounds are needed. In this case, it is demanded that the structure of the device is hardly changed, especially when the CFC 12 is replaced, and it is not desirable to change the structure of the current device significantly for lubricating oil.

As a lubricating oil compatible with Freon 134a, for example, a polyoxyalkylene glycol type is known. For example, Research Disclosure, No. 17463
No. (Oct. 1978), U.S. Pat.
6, JP-A-1-256594, JP-A-1-25
No. 9093, Japanese Unexamined Patent Publication No. 1-259094, Japanese Unexamined Patent Publication No. 1-271491, Japanese Unexamined Patent Publication No. 2-43290, Japanese Unexamined Patent Publication No. 2-84491, Japanese Unexamined Patent Publication No. Hei 2-13221.
76-132178, JP-A-2-132179, JP-A-2-173195, JP-A-2-18
0986-180987, JP-A-2-18278
Nos. 0 to 182781, JP-A-2-242888, JP-A-2-258895, and JP-A-2-269.
195, JP-A-2-272097, JP-A-2-305893, JP-A-3-28296, JP-A-3-33193, JP-A-3-1034
96-103497, JP-A-3-50297, JP-A-3-52995, JP-A-3-7079
JP-A-4-70795, JP-A-3-79696,
JP-A-3-106992, JP-A-3-10949
No. 2, Japanese Unexamined Patent Application Publication No. 3-121195, Japanese Unexamined Patent Application Publication No.
No. 205492, JP-A-3-231929,
JP-A-3-231994, JP-A-4-15295
JP, JP-A-4-39394, JP-A-4-41
No. 591-41592. But,
Polyoxyalkylene glycols generally have low volume resistivity, and no examples have been shown which satisfy a value of 10 ¹² Ω · cm or more at 80 ° C. In addition to polyoxyalkylene glycol, as a compound having compatibility with Freon 134a, an ester-based compound is disclosed in British Patent Publication No. 221654.
No. 1, WO6979 (1990), Japanese Patent Laid-Open No. 2-2
768894, JP-A-3-128992, JP-A-3-88892, JP-A-3-179909, JP-A-3-252497, JP-A-3-27
5799, JP-A-4-4294, JP-A-4-4294.
-20597 and US Pat. No. 5,021,179. However, ester-based lubricating oils are unavoidably structurally liable to produce carboxylic acids by hydrolysis, which causes corrosion of equipment. For example, a rubber hose is used in an automobile air conditioner, but cannot be used because water is mixed therein. In addition, in an electric refrigerator, there is no danger of water being mixed during use, but since the lubricating oil is used for a long time without being replaced, most of the water mixed during production is subjected to hydrolysis. This is a problem. Due to these problems, when an ester-based lubricating oil is used in a compression refrigerator, it is necessary to greatly improve the existing apparatus or the manufacturing apparatus, which is not preferable. Here, as an ester-based refrigerating machine oil having good hydrolysis resistance, JP-A-3-275799 discloses a refrigerating machine oil composition characterized by containing an epoxy compound. The hydrolysis resistance of the epoxy group reacts with water to form an alcohol, so if the amount of water is large, the refrigerating machine oil composition may change drastically, and even if the amount of water is small, the alcohol formed is transesterified. This is not preferable because the refrigerating machine oil composition may greatly change due to the reaction.

[0006] As carbonate-based compounds, Japanese Patent Laid-Open Publication No.
149295, EP 421298,
JP-A-3-217495, JP-A-3-24769
No. 5, JP-A-4-18490, JP-A-4-6
No. 3893, and the like. However, carbonates also have a problem of hydrolysis, similar to esters. As described above, a lubricating oil for a compression refrigerating machine having sufficiently good compatibility with Freon 134a, excellent stability and lubricating performance, and having a volume specific resistance of 10 ¹² Ω · cm or more at 80 ° C. is not yet available. At present, it has not been found, and its development is strongly desired.

[0007]

SUMMARY OF THE INVENTION The present invention satisfies such a demand, and in particular, Freon 134a, Freon 32, which can be used as a substitute for Freon 12 or another Freon compound which is difficult to decompose, which is a problem due to environmental pollution. Freon 125
Compatibility with hydrogen-containing fluorocarbon compounds such as the above, is excellent over the entire operating temperature range, is excellent in stability and lubricity, and has a volume resistivity at 80 ° C. of 10 ¹² Ω · cm.
The object of the present invention is to provide a lubricating oil for a compression refrigerator as described above.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to develop a lubricating oil for a compression type refrigerator having the above-mentioned preferable properties. It has been found that the purpose can be achieved by lubricating oil as a component. The present invention has been completed based on such findings. That is, the present invention provides a compound represented by the general formula (I):

[0009]

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Wherein R ¹ , R ² and R ³ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ⁴ is A divalent hydrocarbon group having 2 to 10 carbon atoms, and R ⁵ has 1 to 1 carbon atoms
A hydrocarbon group of 0, m represents a number having an average value of 0 to 10, R ^{1 to} R ⁵ may be the same or different for each structural unit, and when there are a plurality of R ⁴ O A plurality of R ⁴ O may be the same or different. The present invention provides a lubricating oil for a compression refrigerator mainly comprising a polyvinyl ether compound having a structural unit represented by the formula (1).

The lubricating oil for a compression type refrigerator of the present invention comprises a polyvinyl ether compound having a structural unit represented by the above general formula (I) as a main component. The above general formula (I)
R ¹ , R ² and R ³ in the above each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different. Here, the hydrocarbon group specifically means a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, various hexyl groups. Group, various heptyl groups, alkyl groups of various octyl groups,
Cycloalkyl groups such as cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups,
It represents an arylalkyl group of various dimethylphenyl groups, a benzyl group, various phenylethyl groups, and various methylbenzyl groups. Note that these R ¹ , R ² , R
³ is preferably a hydrogen atom or an aliphatic hydrocarbon group having 5 or less carbon atoms, particularly preferably a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms.

On the other hand, R ⁴ in the general formula (I) has 2 carbon atoms.
A divalent hydrocarbon group having 10 to 10 carbon atoms is shown.
The divalent hydrocarbon group of 10 is specifically an ethylene group;
Phenylethylene group; 1,2-propylene group; 2-phenyl-1,2-propylene group; 1,3-propylene group;
Various butylene groups; various pentylene groups; various hexylene groups; various heptylene groups; various octylene groups; various nonylene groups; divalent aliphatic groups of various decylene groups, cyclohexane; methylcyclohexane; ethylcyclohexane; dimethylcyclohexane; An alicyclic group having two binding sites in an alicyclic hydrocarbon, various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, divalent aromatic hydrocarbon groups such as various naphthylenes, Toluene; Xylene; Alkyl group of alkylaromatic hydrocarbon such as ethylbenzene and alkylaromatic group having a monovalent bonding site on each aromatic part; xylene; Alkyl group of polyalkylaromatic hydrocarbon such as diethylbenzene A having a binding site And the like Kill aromatic group. Of these, aliphatic groups having 2 to 4 carbon atoms are particularly preferred. A plurality of R ⁴ Os may be the same or different. In addition, m in general formula (I) shows the number of repetitions, and the average value is a number in the range of 0 to 10, preferably 0 to 5.

Further, R ⁵ in the general formula (I) represents a hydrocarbon group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec
-Butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl alkyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups,
Various cycloalkyl groups such as various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butyl groups Aryl groups such as phenyl group and various naphthyl groups, benzyl group, various phenylethyl groups, various methylbenzyl groups,
It represents an arylalkyl group of various phenylpropyl groups and various phenylbutyl groups. Among them, a hydrocarbon group having 8 or less carbon atoms is preferable, and when m is 0, an alkyl group having 1 to 6 carbon atoms is preferable, and when m is 1 or more, an alkyl group having 1 to 4 carbon atoms is particularly preferable.

The polyvinyl ether compound of the present invention is
It has a structural unit represented by the general formula (I), and the number of repetitions (that is, the degree of polymerization) may be appropriately selected according to the desired kinematic viscosity, but is usually 5 to 1000.
cSt (40 ° C.), preferably 5 to 800 cSt (40
° C).

The polyvinyl ether compound of the present invention comprises
It can be produced by polymerization of a corresponding vinyl ether monomer. The vinyl ether-based monomer that can be used here has the general formula (VI)

[0016]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and m are the same as described above). As the vinyl ether-based monomer, there are various kinds corresponding to the above-mentioned polyvinyl ether-based compounds. Examples thereof include vinyl methyl ether; vinyl ethyl ether; vinyl-n-propyl ether; vinyl-isopropyl ether; vinyl-n-butyl ether; -Isobutyl ether; vinyl-sec-butyl ether; vinyl-tert-butyl ether; vinyl-n-pentyl ether; vinyl-n-hexyl ether; vinyl-2-
Methoxyethyl ether; vinyl-2-ethoxyethyl ether; vinyl-2-methoxy-1-methylethyl ether; vinyl-2-methoxy-propyl ether; vinyl-3,6-dioxaheptyl ether;
3,6,9-trioxadecyl ether; vinyl-1,
4-dimethyl-3,6-dioxaheptyl ether; vinyl-1,4,7-trimethyl-3,6,9-trioxadecyl ether; vinyl-2,6-dioxa-4-heptyl ether; vinyl-2 , 6,9-Trioxa-4
1-methoxypropene; 1-ethoxypropene; 1-n-propoxypropene; 1-isopropoxypropene; 1-n-butoxypropene; 1-isobutoxypropene; 1-sec-butoxypropene;
1-tert-butoxypropene; 2-methoxypropene; 2-ethoxypropene; 2-n-propoxypropene; 2-isopropoxypropene; 2-n-butoxypropene; 2-isobutoxypropene; 2-sec-butoxypropene; 2-tert-butoxypropene; 1-
Methoxy-1-butene; 1-ethoxy-1-butene; 1
-N-propoxy-1-butene; 1-isopropoxy-
1-butene; 1-n-butoxy-1-butene; 1-isobutoxy-1-butene; 1-sec-butoxy-1-butene; 1-tert-butoxy-1-butene; 2-methoxy-1-butene; 2-ethoxy-1-butene; 2-n
-Propoxy-1-butene; 2-isopropoxy-1-
2-butene; 2-n-butoxy-1-butene; 2-isobutoxy-1-butene; 2-sec-butoxy-1-butene; 2-tert-butoxy-1-butene; 2-methoxy-2-butene; Ethoxy-2-butene; 2-n-
2-propene-2-butene; 2-isopropoxy-2-butene; 2-n-butoxy-2-butene; 2-isobutoxy-2-butene; 2-sec-butoxy-2-butene;
2-tert-butoxy-2-butene and the like.
These vinyl ether monomers can be produced by a known method.

The polyvinyl ether compound having the structural unit represented by the general formula (I) used as a main component in the lubricating oil of the present invention has its terminal terminated by the method shown in the present disclosure and a known method. It can be converted to a desired structure. Examples of the group to be converted include a saturated hydrocarbon, ether, alcohol, ketone, amide, nitrile and the like. As the polyvinyl ether compound as a main component of the lubricating oil of the present invention, those having the following terminal structure are preferably used. That is, (1) the one end is represented by the general formula (II)

[0019]

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[0020] (wherein, R ^6, R ⁷ and R ⁸ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, they may be different even identical to each other, R ⁹ Is a divalent hydrocarbon group having 2 to ¹⁰ carbon atoms, and R ¹⁰ is
10 hydrocarbon group, n average value thereof indicates the number of 0, a plurality of R ⁹ O if R ⁹ O there are a plurality may be the same or different. ) And the remaining terminal is represented by the general formula (III)

[0021]

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[0022] (wherein, R ^11, R ¹² and R ¹³ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, they may be different even identical to each other, R ¹⁴ Is a divalent hydrocarbon group having 2 to 10 carbon atoms, and R ¹⁵ is
10 hydrocarbon group, p is an average value thereof indicates the number of 0, a plurality of R ¹⁴ O in the case of R ¹⁴ O there are a plurality may be the same or different. (2) one end of which is represented by the general formula (II) and the other end is represented by the general formula (IV)

[0023]

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[0024] (wherein, R ^16, R ¹⁷ and R ¹⁸ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, they may be different even identical to each other, R ¹⁹ And R ²¹ each represent a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different, and R ²⁰ and R ²² each represent a hydrocarbon group having 1 to 10 carbon atoms. And they may be the same or different, and q and r each have an average value of 0 to 10
Which may be the same or different, and when there are a plurality of R ¹⁹ O, a plurality of R ¹⁹ O
¹⁹ O may be the same or different;
^When there is ²¹ O, a plurality of R ²¹ Os may be the same or different. ) Having the structure represented by
(3) one having one terminal represented by the general formula (II) and the other terminal having an olefinically unsaturated bond;
(4) One terminal is represented by the above general formula (II) and the other terminal is represented by the general formula (V)

[0025]

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(In the formula, R ²³ , R ²⁴ and R ²⁵ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different.) Of the structure represented. The polyvinyl ether-based compound may be a mixture of two or more kinds selected from those having the terminal structures of (1) to (4). Preferred examples of such a mixture include, for example, a mixture of the above (1) and (4) and a mixture of the above (2) and (3).

The lubricating oil for refrigerators of the present invention contains the above-mentioned polyvinyl ether compound as a main component. The kinematic viscosity of the lubricating oil before mixing with the refrigerant is 5 to 1000 at 40 ° C.
Since cSt is preferable, it is preferable to select the raw materials, the initiator, and the reaction conditions so as to generate a polyvinyl ether-based compound having this viscosity range. The average molecular weight of this polymer is usually from 150 to 4000. In addition,
It is also possible to adjust the viscosity within the above kinematic viscosity range by mixing a polymer having a kinematic viscosity outside the above range with another polymer having another kinematic viscosity. In the lubricating oil for refrigerators of the present invention, the above polyvinyl ether-based compounds may be used alone or in combination of two or more. Furthermore, it can be used by mixing with other lubricating oils.

The lubricating oil for refrigerators of the present invention includes various additives used in conventional lubricating oils, such as load-bearing additives, chlorine scavengers, antioxidants, metal deactivators, Foaming agents, cleaning dispersants, viscosity index improvers, oil agents, antiwear additives, extreme pressure agents, rust inhibitors, corrosion inhibitors, pour point depressants and the like can be added as desired. Examples of the load-bearing additives include organic sulfur compounds such as monosulfides, polysulfides, sulfoxides, sulfones, thiosulfinates, sulfurized fats and oils, thiocarbonates, thiophenes, thiazoles, and methanesulfonic acid esters. Phosphoric acid esters, such as phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid triesters (tricresyl phosphate), phosphite monoesters, phosphite diesters, phosphorous acid Phosphites such as acid triesters, thiophosphates such as thiophosphate triesters, higher fatty acids, hydroxyaryl fatty acids, carboxylic acid-containing polyhydric alcohol esters, acrylic acid esters, etc. Fatty acid esters, chlorinated hydrocarbons, chlorinated carboxylic acids Organochlorine compounds such as conductors, fluorinated aliphatic carboxylic acids, fluorinated ethylene resins, fluorinated alkylpolysiloxanes, organic fluorinated compounds such as fluorinated graphite, alcoholic compounds such as higher alcohols, naphthenes Acid salts (lead naphthenate), fatty acid salts (lead fatty acid), thiophosphates (zinc dialkyldithiophosphate), thiocarbamates, organic molybdenum compounds,
Metal compounds such as organic tin compounds, organic germanium compounds, and borate esters are available. Examples of the chlorine scavenger include glycidyl ether group-containing compounds, epoxidized fatty acid monoesters, epoxidized oils and fats, and epoxycycloalkyl group-containing compounds. As the antioxidant, phenols (2,6-di-tert-butyl-p
-Cresol) and aromatic amines (α-naphthylamine). Examples of the metal deactivator include a benzotriazole derivative. Examples of the antifoaming agent include silicone oil (dimethylpolysiloxane) and polymethacrylates. Detergents include sulfonates, phenates, succinimides and the like. Examples of the viscosity index improver include polymethacrylate, polyisobutylene, an ethylene-propylene copolymer, and a styrene-diene hydrogenated copolymer.

The lubricating oil of the present invention has excellent compatibility with a refrigerant and excellent lubricating performance, and is therefore used as a lubricating oil for a compression refrigerator. Unlike conventional lubricating oils, hydrogen-containing freon compounds such as freon 134a (specifically, in addition to freon 134a, 1,1-dichloro-2,2,2-trifluoroethane (freon-12)
3); 1-chloro-1,1-difluoroethane (Freon-142b); 1,1-difluoroethane (Freon-1
52a); chlorodifluoromethane (CFC-22);
Good compatibility with trifluoromethane (Freon-23); difluoromethane (Freon 32) or pentafluoroethane (Freon 125). Further, for the purpose of improving the compatibility with the refrigerant, it can be used by mixing with other lubricating oils for compression refrigerators.

[0030]

The present invention will be described in more detail with reference to Preparation Examples, Production Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. Preparation Example 1 Raney nickel (manufactured by Kawaken Fine Chemicals Co., Ltd., trade name:
M300T) 100 g (hydrated state) is placed in a flask,
100 g of absolute ethanol was added and mixed well. Thereafter, the mixture was allowed to stand to settle Raney nickel, and the supernatant was removed by decantation. The above operation was performed five times on Raney nickel remaining in the flask. In addition,
The Raney nickel used in the production example is wet with the ethanol obtained in this preparation example.

Preparation Example 2 Zeolite (manufactured by Tosoh Corporation, trade name: HSZ330HUA)
Put 20 g in a 100 ml eggplant-shaped flask,
It was immersed in an oil bath at 150 ° C., and the pressure was reduced by an oil rotary vacuum pump for 1 hour. After cooling to room temperature, the pressure was adjusted to normal pressure with dry nitrogen. The zeolite used in the production examples was obtained in this preparation example.

Production Example 1 Ethyl vinyl ether 600 was placed in a 5-liter glass flask equipped with a dropping funnel, a condenser and a stirrer.
g, 72 g of methanol and 2400 g of hexane were added, and the mixture was cooled with water while stirring. When the temperature of the solution reached 5 ° C., a solution of 3.6 g of boron trifluoride diethyl ether complex dissolved in 20 g of tetrahydrofuran was added, and the mixture was stirred for 1 hour. did. During this time, the reaction started, the temperature of the reaction solution increased, and reflux of ethyl vinyl ether was observed in the cooling tube. The reaction mixture was transferred to a washing tank, washed three times with 1500 ml of a 3 wt% aqueous sodium hydroxide solution, and further washed with 150 ml of water.
Washed three times with 0 ml. After concentration using a rotary evaporator, the residue was dried at 50 ° C. under reduced pressure (0.2 mmHg) for 1 hour to obtain 468 g of a crude product. 400 g of the obtained crude product, 500 g of acetone, 800 g of water, and 10 g of concentrated hydrochloric acid (35 wt%) were placed in a 5-liter glass flask equipped with a dropping funnel, a condenser, and a stirrer.
Stirred at 60 ° C. for 3 hours. After neutralizing hydrochloric acid with sodium hydrogen carbonate, acetone and the like were removed under reduced pressure using a rotary evaporator, and the mixture was poured into 400 ml of hexane. After removing the aqueous phase, it was washed once with 400 ml of water. Put the hexane phase in an autoclave and add platinum oxide
0.8 g as a catalyst, hydrogen pressure 20 kg / cm ² , 50 ° C.
For 1 hour. After filtering off the platinum oxide, it was transferred to a 2 liter glass flask, and methanol was added at room temperature.
0 g and 8 g of sodium borohydride were added and stirred for 1 hour. After weak acidification with an aqueous acetic acid solution, acetic acid was neutralized with sodium bicarbonate. This was washed once with 400 ml of water, and the solvent and water were removed under reduced pressure using a rotary evaporator. The obtained residue was dissolved in 300 ml of tetrahydrofuran and reacted with 12 g of sodium hydride for 1 hour. At this time, generation of hydrogen gas was recognized. Then, 120 g of methyl iodide
Was added dropwise in 30 minutes. At this time, heat generation was observed. After dropwise addition of methyl iodide, the mixture was stirred for 1 hour. The solvent and unreacted raw materials were removed under reduced pressure using a rotary evaporator. The residue was transferred to a 2 liter washing tank and hexane 400
After dissolving in milliliter, it was washed 5 times with 400 milliliters of water. Further, 40 g of an ion exchange resin was added and stirred for 3 hours. After filtering off the ion exchange resin, hexane was removed under reduced pressure using a rotary evaporator. The yield of the obtained lubricating oil of the present invention was 200 g. As a result of measurement of a nuclear magnetic resonance spectrum (hereinafter, referred to as NMR) and an infrared absorption spectrum (hereinafter, referred to as IR), one of the terminal structures of the polymer was (A) and the other was (B).

[0033]

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Production Example 2 Ethyl vinyl ether 600 was placed in a 5 liter glass flask equipped with a dropping funnel, a condenser and a stirrer.
g, methanol 60 g and hexane 2400 g, and water-cooled with stirring. When the temperature of the solution reached 5 ° C., a solution prepared by dissolving boron trifluoride diethyl ether complex 3.6 g in tetrahydrofuran 20 g was added and stirred for 1 hour. did. During this time, the reaction started, the temperature of the reaction solution increased, and reflux of ethyl vinyl ether was observed in the cooling tube. The reaction mixture was transferred to a washing tank, washed three times with 1500 ml of a 3 wt% aqueous sodium hydroxide solution, and further washed with 150 ml of water.
Washed three times with 0 ml. After concentration using a rotary evaporator, the residue was dried at 50 ° C. for 1 hour under reduced pressure (0.2 mmHg) to obtain 452 g of a crude product. 400 g of the obtained crude product, 500 g of acetone, 800 g of water and 10 g of concentrated hydrochloric acid (35 wt%) were placed in a 5-liter glass flask equipped with a dropping funnel, a condenser and a stirrer.
The mixture was stirred at 0 to 60 ° C for 3 hours. After neutralizing hydrochloric acid with sodium hydrogen carbonate, acetone and the like were removed under reduced pressure using a rotary evaporator, and the mixture was poured into 400 ml of hexane. After removing the aqueous phase, add 400 ml of water to 1
Washed twice. The hexane phase was put into an autoclave, and hydrogen pressure was set to 20 kg / cm ² , 5, using 0.8 g of platinum oxide as a catalyst.
Hydrogenation was performed at 0 ° C. for 1 hour. After filtering off the platinum oxide, 2
The mixture was transferred to a 1-liter glass flask, and 40 g of methanol and 8 g of sodium borohydride were added at room temperature and stirred for 1 hour. After weak acidification with an aqueous acetic acid solution, acetic acid was neutralized with sodium bicarbonate. This was washed once with 400 ml of water, and the solvent and water were removed under reduced pressure using a rotary evaporator. The obtained residue was dissolved in 300 ml of tetrahydrofuran and reacted with 12 g of sodium hydride for 1 hour. At this time, generation of hydrogen gas was recognized. Then, methyl iodide 120
g was added dropwise in 30 minutes. At this time, heat generation was observed. After dropwise addition of methyl iodide, the mixture was stirred for 1 hour. The solvent and unreacted raw materials were removed under reduced pressure using a rotary evaporator. The residue was transferred to a 2 liter washing tank and hexane 40
After dissolving in 0 ml, it was washed 5 times with 400 ml of water. Further, 40 g of an ion exchange resin was added and stirred for 3 hours. After filtering off the ion exchange resin, hexane was removed under reduced pressure using a rotary evaporator. The yield of the obtained lubricating oil of the present invention was 208 g. As a result of NMR and IR measurements, one of the terminal structures of the polymer was (A) and the other was (B).

Production Example 3 A 5-liter glass flask equipped with a dropping funnel, a condenser and a stirrer was charged with 500 g of hexane, and a solution of 12 g of boron trifluoride diethyl ether complex dissolved in 24 g of tetrahydrofuran was added thereto. Cooled to 5 ° C. in bath. Ethyl vinyl ether 2 in dropping funnel
000 g and methanol 120 g were added, and this was added dropwise over 1 hour and 30 minutes. During this time, the reaction started and the temperature of the reaction solution rose. The temperature was kept at about 30 ° C. while cooling in an ice water bath. After completion of the dropwise addition, the mixture was stirred for 30 minutes. The reaction mixture was transferred to a washing tank, washed three times with 1500 ml of a 3 wt% aqueous sodium hydroxide solution, and further washed three times with 1500 ml of water. Using a rotary evaporator,
The solvent and unreacted raw materials were removed under reduced pressure to obtain a crude product 1806.
g was obtained. Next, 400 g of the obtained crude product and 300 g of tetrahydrofuran were placed in a 2-liter glass flask equipped with a dropping funnel, a condenser and a stirrer, followed by 15 g of lithium aluminum hydride and stirred for 30 minutes. 196 g of boron trifluoride diethyl ether complex was placed in the dropping funnel, and dropped over 1 hour. At this time, although heat generation was observed, the mixture was cooled in an ice water bath and kept at 10 to 20 ° C. After completion of the dropwise addition, the mixture was stirred for 30 minutes. Next, a sodium hydroxide solution was added to make the solution neutral. The resulting precipitate was filtered off, and the liquid phase was applied to a rotary evaporator to remove the formed alcohol, solvent and water under reduced pressure. 2 remaining
And dissolved in 500 ml of hexane.
After washing 10 times with 0 milliliter, it was washed 3 times with 200 ml of water. Further, 100 g of ion exchange resin was added and stirred for 3 hours. After filtering off the ion exchange resin, hexane was removed under reduced pressure using a rotary evaporator. The yield of the obtained lubricating oil of the present invention was 235 g. As a result of NMR and IR measurements, one of the terminal structures of the polymer was (A) and the other was a mixture of (B) and (C).

[0036]

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Production Example 4 A 5-liter glass flask equipped with a dropping funnel, a condenser and a stirrer was charged with 1,000 g of toluene, 500 g of acetaldehyde diethyl acetal and 5.0 g of a boron trifluoride diethyl ether complex. 2500 g of ethyl vinyl ether was placed in the dropping funnel and dropped over 2 hours and 30 minutes. During this time, the reaction started and the temperature of the reaction solution rose. The temperature was kept at about 25 ° C. while cooling in an ice water bath. After completion of the dropwise addition, the mixture was stirred for 5 minutes. Transfer the reaction mixture to the washing tank,
The solution was washed three times with 1000 ml of a 10% aqueous sodium hydroxide solution, and further washed three times with 1000 ml of water. Using a rotary evaporator, the solvent and unreacted raw materials were removed under reduced pressure to obtain 2833 g of a crude product. SUS
-600L crude product in 2-liter autoclave made of 316L
g, hexane 600 g, Raney nickel 60 g and zeolite 60 g. Hydrogen was introduced into the autoclave to a hydrogen pressure of 20 kg / cm ² , stirred for about 30 seconds, and then depressurized. Introduce hydrogen into the autoclave again,
The hydrogen pressure was adjusted to 20 kg / cm ^2, and the mixture was stirred for about 30 seconds and then depressurized. After performing this operation once more, the hydrogen pressure was increased to 50%.
The temperature was raised to 130 ° C. in 30 minutes with stirring at kg / cm ² . The reaction was performed at 130 ° C. for 1 hour. A reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. In addition, the pressure was increased and the pressure decreased due to the temperature increase, and the pressure was reduced and pressurized as appropriate to carry out the reaction at a hydrogen pressure of 50 kg / cm ² . After completion of the reaction, the resultant was cooled to room temperature and reduced to normal pressure. The mixture was allowed to stand for 1 hour to settle the catalyst, and the reaction solution was removed by decantation.
The catalyst was washed twice with 100 ml of hexane, the washing solution was combined with the reaction solution, and filtered using filter paper. It was transferred to a washing tank and washed three times with 500 ml of a 5 wt% aqueous sodium hydroxide solution, and then washed five times with 500 ml of distilled water. Hexane, water and the like were removed under reduced pressure using a rotary evaporator. The yield was 468 g. As a result of NMR and IR measurements, one of the terminal structures of the polymer was mostly (C). It was also confirmed that a small amount of the terminal was (D).

[0038]

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Production Example 5 Using the catalyst removed by decantation in Production Example 4,
600 g of the crude product produced in Production Example 4 was reacted in the same manner as in Production Example 4. The yield was 501 g. The catalyst was recyclable. NMR, IR
As a result of the measurement, one of the terminal structures of the polymer was (A) and the other was mostly (C). It was also confirmed that a small amount of the terminal was (D).

Production Example 6 A 1-liter glass flask equipped with a dropping funnel, a condenser and a stirrer was charged with 250 g of toluene, 36.82 g of isopropyl alcohol and 4.35 g of a boron trifluoride diethyl ether complex. 500 g of isopropyl vinyl ether was put into the dropping funnel, and dropped in 30 minutes. During this time, the reaction started and the temperature of the reaction solution rose. The temperature was kept at about 30 ° C. while cooling in an ice water bath. After completion of the dropwise addition, the mixture was stirred for 5 minutes. The reaction mixture was transferred to a washing tank and washed three times with 130 ml of a 3 wt% aqueous sodium hydroxide solution, and further washed three times with 200 ml of water. Using a rotary evaporator, the solvent and unreacted raw materials were removed under reduced pressure to obtain 475.3 g of a crude product. In a SUS-316L 1 liter autoclave, 380 g of crude product, 10 hexane
0 g, Raney nickel 45 g and zeolite 45 g. Hydrogen was introduced into the autoclave and the hydrogen pressure was increased to 20.
kg / cm ^2, and the mixture was stirred for about 30 seconds and then depressurized. Hydrogen was introduced again into the autoclave, and the hydrogen pressure was 20 kg /
cm ² , the mixture was stirred for about 30 seconds, and then depressurized. After this operation was performed once more, the temperature was increased to 130 ° C. in 30 minutes with stirring under a hydrogen pressure of 50 kg / cm ² . The reaction was performed at 130 ° C. for 1 hour. A reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. In addition, increase in pressure due to temperature rise,
The pressure decrease accompanying the reaction is reduced and pressurized as appropriate to reduce the hydrogen pressure to 5
The reaction was performed at 0 kg / cm ² . After completion of the reaction, the resultant was cooled to room temperature and reduced to normal pressure. The mixture was allowed to stand for 1 hour to settle the catalyst, and the reaction solution was removed by decantation. Hexane 1 catalyst
After washing twice with 00 ml, the washing solution was combined with the reaction solution, and filtered using a filter paper. The catalyst was recyclable. The reaction solution and the washing solution were transferred to a washing tank, washed three times with 200 ml of a 5 wt% aqueous sodium hydroxide solution, and then washed with 200 ml of distilled water.
Washed twice. Using a rotary evaporator under reduced pressure,
Hexane, water and the like were removed. The yield was 287 g. As a result of NMR and IR measurement, one of the terminal structures of the polymer was (E) and the other was mostly (F). It was also confirmed that a small amount of the terminal was (D).

[0041]

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Production Example 7 In a 1-liter autoclave, 200 g of toluene, 5.5 g of methanol and boron trifluoride-diethyl ether complex 1.
2 g was charged, and the inside of the autoclave was replaced with nitrogen. While stirring inside the autoclave, methyl vinyl ether 200
g in 4 hours. During this time, the reaction occurred and heat generation was observed. Therefore, the reaction was carried out while maintaining the inside of the autoclave at about 5 ° C. while cooling the autoclave with an ice water bath. After the injection of methyl vinyl ether was completed, the mixture was stirred for 5 minutes. The reaction mixture was transferred to a washing tank, washed three times with 100 ml of a 5 wt% aqueous sodium hydroxide solution, and further washed three times with 100 ml of water. Using a rotary evaporator, the solvent and unreacted raw materials were removed under reduced pressure to obtain a crude product of 165
g was obtained. In an autoclave, 165 g of crude product, 200 g of hexane, 15 g of Raney nickel and 15 zeolite
g. Hydrogen was introduced into the autoclave to a hydrogen pressure of 20 kg / cm ² , stirred for about 30 seconds, and then depressurized. Hydrogen was introduced again into the autoclave, and the hydrogen pressure was increased to 20.
kg / cm ^2, and the mixture was stirred for about 30 seconds and then depressurized. After performing this operation once more, the hydrogen pressure was set to 50 kg / cm ^2.
The temperature was raised to 130 ° C. in 30 minutes while stirring. 130
The reaction was performed at a temperature of 1 ° C. for 1 hour. The reaction occurs during and after the temperature rise,
A decrease in hydrogen pressure was observed. In addition, the pressure was increased and the pressure decreased due to the temperature increase, and the pressure was reduced and pressurized as appropriate to carry out the reaction at a hydrogen pressure of 50 kg / cm ² . After completion of the reaction, the resultant was cooled to room temperature and reduced to normal pressure. The mixture was allowed to stand for 1 hour to settle the catalyst, and the reaction solution was removed by decantation. The catalyst was washed twice with 50 ml of hexane, the washing solution was combined with the reaction solution, and the solution was filtered using filter paper. After removing hexane under reduced pressure using a rotary evaporator, 300 g of chloroform was added. It was transferred to a washing tank and washed three times with 100 ml of a 5 wt% sodium hydroxide aqueous solution, and then washed five times with 100 ml of distilled water. Chloroform water and the like were removed under reduced pressure using a rotary evaporator. The yield was 150 g. As a result of NMR and IR measurements, one of the terminal structures of the polymer was (G) and the other was mostly (B). It was also confirmed that a small amount of the terminal was (D).

[0043]

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Production Example 8 A 5-liter glass flask equipped with a dropping funnel, a condenser and a stirrer was charged with 1,000 g of toluene, 500 g of acetaldehyde diethyl acetal and 5.0 g of a boron trifluoride diethyl ether complex. 2500 g of ethyl vinyl ether was placed in the dropping funnel and dropped over 2 hours and 30 minutes. During this time, the reaction started and the temperature of the reaction solution rose. The temperature was kept at about 25 ° C. while cooling in an ice water bath. After completion of the dropwise addition, the mixture was stirred for 5 minutes. Transfer the reaction mixture to the washing tank,
The solution was washed three times with 1000 ml of a 10% aqueous sodium hydroxide solution, and further washed three times with 1000 ml of water. Using a rotary evaporator, the solvent and unreacted raw materials were removed under reduced pressure to obtain 2833 g of a crude product. NM
As a result of R and IR measurement, one of the terminal structures of the polymer is (A)
And the other was a mixture of (H) and (I), and the ratio was (H) / (I) = 1 / 4.5.

[0045]

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Production Example 9 A 2-liter autoclave made of SUS-316L was charged with 700 g of the ethyl vinyl ether polymer obtained in Production Example 8, 35 g of Raney nickel, 35 g of zeolite and 1.5 g of water. Hydrogen is introduced into the autoclave and the hydrogen pressure is set to 10
kg / cm ^2, and the mixture was stirred for about 30 seconds and then depressurized. Hydrogen was introduced again into the autoclave, and the hydrogen pressure was 10 kg /
cm ^2, and the pressure was released after stirring for about 30 seconds. After this operation was performed once more, the temperature was raised to 140 ° C. in 30 minutes with stirring at a hydrogen pressure of 35 kg / cm ² . The reaction was performed at 140 ° C. for 2 hours. A reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. In addition, increase in pressure due to temperature rise,
The pressure decrease accompanying the reaction is reduced and pressurized as appropriate to reduce the hydrogen pressure by 3
The reaction was performed at 5 kg / cm ² . After completion of the reaction, the resultant was cooled to room temperature and reduced to normal pressure. Filtration was performed using filter paper.
Transfer to a 2 liter washing tank, dilute with 300 g of hexane,
Washing was performed three times with 250 ml of a 5 wt% aqueous sodium hydroxide solution, and then five times with 250 ml of distilled water. Hexane, water and the like were removed under reduced pressure using a rotary evaporator. The yield was 550 g. NM
As a result of R and IR measurements, one of the terminal structures of the polymer was (A) and the other was a mixture of (C) and (D).

Production Example 10 50 g of toluene, 17.7 g of acetaldehyde diethyl acetal and 1.5 g of boron trifluoride diethyl ether complex were placed in a 500 ml glass flask equipped with a dropping funnel, a condenser and a stirrer. 43 g of ethyl vinyl ether was put into the dropping funnel, and 65 g of isopropyl vinyl ether was added and dropped in 50 minutes. Although the temperature of the reaction solution increased due to the heat of the reaction, the temperature was maintained at about 30 ° C. while cooling in an ice water bath. After completion of the dropwise addition, the mixture was stirred for 5 minutes. The reaction mixture was transferred to a washing tank, washed three times with 100 ml of a 5 wt% aqueous sodium hydroxide solution, and further washed three times with 150 ml of water. Using a rotary evaporator, the solvent and unreacted raw materials were removed under reduced pressure to obtain a crude product.
20 g were obtained. The kinematic viscosity at 40 ° C. of the crude product is 48.8 c.
St. As a result of NMR and IR measurements, one of the terminal structures of the polymer is a mixture of (A) and (E), and the other is a mixture of (H) and (I) and the oxyethyl group portion of (H) and (I). It was a mixture of structures of oxyisopropyl.

Production Example 11 In a 1-liter autoclave made of SUS-316L, 110 g of the ethyl vinyl ether / isopropyl vinyl ether copolymer obtained in Production Example 10 and 300 hexanes
g, Raney nickel 5.5 g and zeolite 5.5 g. Hydrogen is introduced into the autoclave and the hydrogen pressure is 20k
g / cm ^2, and the pressure was released after stirring for about 30 seconds. Hydrogen was introduced again into the autoclave, and the hydrogen pressure was 20 kg / c.
m ^2, and the pressure was released after stirring for about 30 seconds. After this operation was performed once more, the temperature was raised to 140 ° C. in 30 minutes with stirring at a hydrogen pressure of 50 kg / cm ² . 2 at 140 ° C
Reacted for hours. A reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. The pressure increase due to the temperature rise and the pressure decrease due to the reaction are reduced and pressurized as appropriate to reduce the hydrogen pressure to 50%.
The reaction was carried out at a pressure of kg / cm ² . After completion of the reaction, the resultant was cooled to room temperature and reduced to normal pressure. Filtration was performed using filter paper. It was transferred to a washing tank and washed three times with 100 ml of a 5 wt% sodium hydroxide aqueous solution, and then washed five times with 150 ml of distilled water. Hexane, water and the like were removed under reduced pressure using a rotary evaporator. The yield was 97 g. As a result of NMR and IR measurements, one of the terminal structures of the polymer was a mixture of (A) and (E), and the other was mostly a mixture of (C) and (F). It was also confirmed that a small amount of the terminal was (D).

Production Example 12 80 g of toluene, 40 g of propionaldehyde diethyl acetal and 0.4 g of boron trifluoride diethyl ether complex were placed in a 500 ml glass flask equipped with a dropping funnel, a condenser and a stirrer. 116 g of 1-ethoxy-1-propene was put in the dropping funnel and dropped in 60 minutes. Although the temperature of the reaction solution increased due to the heat of the reaction, the temperature was maintained at about 30 ° C. while cooling in an ice water bath. After completion of the dropwise addition, the mixture was stirred for 40 minutes. Transfer the reaction mixture to the washing tank and
Washing was performed three times with 150 ml of a t% aqueous sodium hydroxide solution, and further three times with 200 ml of water. The solvent and unreacted raw materials were removed under reduced pressure using a rotary evaporator to obtain 140 g of a crude product. The kinematic viscosity at 40 ° C. of the crude product was 34.4 cSt. SUS
-1 liter of 316L, 120 g of crude product, 3 hexanes
00 g, Raney nickel 6 g and zeolite 6 g. Hydrogen is introduced into the autoclave and the hydrogen pressure is 20k
g / cm ^2, and the pressure was released after stirring for about 30 seconds. Hydrogen was introduced again into the autoclave, and the hydrogen pressure was 20 kg / c.
m ^2, and the pressure was released after stirring for about 30 seconds. After this operation was performed once more, the temperature was increased to 130 ° C. in 30 minutes with stirring at a hydrogen pressure of 50 kg / cm ² . 2 at 130 ° C
Reacted for hours. A reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. The pressure increase due to the temperature rise and the pressure decrease due to the reaction are reduced and pressurized as appropriate to reduce the hydrogen pressure to 50%.
The reaction was carried out at a pressure of kg / cm ² . After completion of the reaction, the resultant was cooled to room temperature and reduced to normal pressure. The mixture was allowed to stand for 1 hour to settle the catalyst, and the reaction solution was removed by decantation. Hexane 50 catalyst
After washing twice with milliliters, the washing solution was combined with the reaction solution, and filtered using a filter paper. Transfer to 1 liter washing tank, 5
3% with 150 ml of wt% sodium hydroxide aqueous solution
Washing was carried out once and then 5 times with 200 ml of distilled water. Hexane, water and the like were removed under reduced pressure using a rotary evaporator. The yield was 95 g. NM
As a result of R and IR measurements, one of the terminal structures of the polymer was (J) and the other was mostly (K). It was also confirmed that a small amount of the terminal was (L).

[0050]

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Production Example 13 1000 g of toluene, 304 g of ethanol and 7.8 parts of boron trifluoride-diethyl ether complex were placed in a 5-liter glass flask equipped with a dropping funnel, a condenser and a stirrer.
g. Ethyl vinyl ether 328 in the dropping funnel
4 g was added and added dropwise over 4 hours and 30 minutes. During this period, the temperature of the reaction solution increased due to the heat of the reaction. After completion of the dropwise addition, the mixture was stirred for 5 minutes. The reaction mixture was transferred to a washing tank, washed three times with 1100 ml of a 5 wt% aqueous sodium hydroxide solution, and further washed with water 1
Washed three times with 100 ml. The solvent and unreacted raw materials were removed under reduced pressure using a rotary evaporator to obtain 3397 g of a crude product. SUS-316L made 2 liters of crude autoclave 600g, hexane 600
g, Raney nickel 18 g and zeolite 18 g. Hydrogen is introduced into the autoclave and the hydrogen pressure is 20k
g / cm ^2, and the pressure was released after stirring for about 30 seconds. Hydrogen was introduced again into the autoclave, and the hydrogen pressure was 20 kg / c.
m ^2, and the pressure was released after stirring for about 30 seconds. After this operation was performed once more, the temperature was raised to 140 ° C. in 30 minutes with stirring at a hydrogen pressure of 50 kg / cm ² . 2 at 140 ° C
Reacted for hours. A reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. The pressure increase due to the temperature rise and the pressure decrease due to the reaction are reduced and pressurized as appropriate to reduce the hydrogen pressure to 50%.
The reaction was carried out at a pressure of kg / cm ² . After completion of the reaction, the resultant was cooled to room temperature and reduced to normal pressure. The mixture was allowed to stand for 1 hour to settle the catalyst, and the reaction solution was removed by decantation. Hexane catalyst 10
Wash twice with 0 ml and combine the washing solution with the reaction solution,
Filtration was performed using filter paper. Transfer to a washing tank and wash 3 times with 500 ml of 5 wt% sodium hydroxide aqueous solution,
Then, it was washed five times with 500 ml of distilled water. Hexane, water and the like were removed under reduced pressure using a rotary evaporator. The yield was 492 g. As a result of NMR and IR measurements, one of the terminal structures of the polymer is (A),
Most of the other was (C). It was also confirmed that a small amount of the terminal was (D).

Production Example 14 A 5-liter glass flask equipped with a dropping funnel, a condenser and a stirrer was charged with 1,000 g of toluene, 500 g of acetaldehyde diethyl acetal and 5.0 g of a boron trifluoride diethyl ether complex. 2700 g of ethyl vinyl ether was put into the dropping funnel and dropped over 3 hours. Although the temperature of the reaction solution increased due to the heat of the reaction, it was kept at about 25 ° C. while cooling in an ice water bath. After completion of the dropwise addition, the mixture was stirred for 5 minutes. The reaction mixture was transferred to a washing tank, washed three times with 1000 ml of a 5 wt% aqueous sodium hydroxide solution, and further washed three times with 1000 ml of water. The solvent and unreacted raw materials were removed under reduced pressure using a rotary evaporator to obtain 3040 g of a crude product. 40 ° C of the composition
Was 42.1 cSt. In a 2-liter autoclave made of SUS-316L, 600 g of crude product, 600 g of hexane, 18 g of Raney nickel and 18 zeolite
g. Hydrogen was introduced into the autoclave to a hydrogen pressure of 20 kg / cm ² , stirred for about 30 seconds, and then depressurized. Hydrogen was introduced again into the autoclave, and the hydrogen pressure was increased to 20.
kg / cm ^2, and the mixture was stirred for about 30 seconds and then depressurized. After performing this operation once more, the hydrogen pressure was increased to 50 kg / cm.
^The temperature was raised to 140 ° C. in 30 minutes with stirring. 14
The reaction was performed at 0 ° C. for 2 hours. A reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. In addition, the pressure was increased and the pressure decreased due to the temperature increase, and the pressure was reduced and pressurized as appropriate to carry out the reaction at a hydrogen pressure of 50 kg / cm ² . After completion of the reaction, the resultant was cooled to room temperature and reduced to normal pressure. The mixture was allowed to stand for 1 hour to settle the catalyst, and the reaction solution was removed by decantation. The catalyst was washed twice with 100 ml of hexane, the washing solution was combined with the reaction solution, and the solution was filtered using filter paper. Transfer to washing tank,
Washing was performed three times with 500 ml of a 5 wt% sodium hydroxide aqueous solution, and then five times with 500 ml of distilled water. Hexane, water and the like were removed under reduced pressure using a rotary evaporator. The yield was 495 g. The terminal structure of the polymer was the same as in Production Example 4.

Production Example 15 A 5-liter glass flask equipped with a dropping funnel, a condenser and a stirrer was charged with 1,000 g of toluene, 450 g of acetaldehyde diethyl acetal and 4.5 g of a boron trifluoride diethyl ether complex. 3200 g of ethyl vinyl ether was put into the dropping funnel and dropped over 4 hours and 10 minutes. Although the temperature of the reaction solution increased due to the heat of the reaction, it was kept at about 25 ° C. while cooling in an ice water bath. After completion of the dropwise addition, the mixture was stirred for 5 minutes. The reaction mixture was transferred to a washing tank, washed three times with 1000 ml of a 5 wt% aqueous sodium hydroxide solution, and further washed three times with 1000 ml of water.
The solvent and unreacted raw materials were removed under reduced pressure using a rotary evaporator to obtain 3466 g of a crude product. The viscosity at 40 ° C. of the crude product was 76.1 cSt. SUS-31
600 g of crude product, 600 hexane in 2 liters of 6L
g, Raney nickel 18 g and zeolite 18 g. Hydrogen is introduced into the autoclave and the hydrogen pressure is 20k
g / cm ^2, and the pressure was released after stirring for about 30 seconds. Hydrogen was introduced again into the autoclave, and the hydrogen pressure was 20 kg / c.
m ^2, and the pressure was released after stirring for about 30 seconds. After this operation was performed once more, the temperature was raised to 140 ° C. in 30 minutes with stirring at a hydrogen pressure of 50 kg / cm ² . 2 at 140 ° C
Reacted for hours. A reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. The pressure increase due to the temperature rise and the pressure decrease due to the reaction are reduced and pressurized as appropriate to reduce the hydrogen pressure to 50%.
The reaction was carried out at a pressure of kg / cm ² . After completion of the reaction, the resultant was cooled to room temperature and reduced to normal pressure. The mixture was allowed to stand for 1 hour to settle the catalyst, and the reaction solution was removed by decantation. Hexane catalyst 10
Wash twice with 0 ml and combine the washing solution with the reaction solution,
Filtration was performed using filter paper. Transfer to a washing tank and wash 3 times with 500 ml of 5 wt% sodium hydroxide aqueous solution,
Then, it was washed five times with 500 ml of distilled water. Hexane, water and the like were removed under reduced pressure using a rotary evaporator. The yield was 498 g. The terminal structure of the polymer was the same as in Production Example 4.

Production Example 16 (Comparative Production Example) To a 5-liter glass flask equipped with a Dean-Stark tube, a condenser and a stirrer were added 1091 g of pentaerythritol and 3909 g of n-hexanoic acid, and the mixture was heated while stirring. When the temperature of the solution reached 200 ° C., the temperature was maintained for 3 hours, and further raised to 220 ° C., and then maintained for 10 hours. During this time, the reaction started and water was generated. After the completion of the reaction, the temperature of the reaction solution was lowered to 150 ° C., and most of the unreacted n-hexanoic acid was recovered under reduced pressure. The remaining liquid was transferred to a washing tank, dissolved in 2 liters of hexane, washed three times with 1500 ml of a 3 wt% aqueous sodium hydroxide solution, and further washed with 1500 ml of water.
Washed twice. Further, 800 g of an ion exchange resin was added and stirred for 3 hours. After filtering off the ion exchange resin, hexane was removed under reduced pressure using a rotary evaporator. The yield of the obtained polyol ester-based lubricating oil is 3
390 g.

Example 1 Using the lubricating oil of the present invention produced in Production Example 1, the kinematic viscosity and
The compatibility with Freon 134a, volume resistivity, and hydrolysis stability were measured. Table 1 shows the obtained results. In addition,
Each measurement condition is as follows. Kinematic viscosity was measured using a glass capillary viscometer according to JIS K2283-1983. Compatibility (a) Freon 134a 1,1,1,2-tetrafluoroethane (Freon 134
A predetermined amount of a sample was added to a pressure-resistant glass ampule so as to be 5% by weight and 10% by weight with respect to a), and this was connected to a vacuum pipe and a Freon 134a gas pipe. After the ampoule was degassed in vacuum at room temperature, it was cooled with liquid nitrogen to collect a predetermined amount of Freon 134a. Then, the ampoule is sealed, and the compatibility on the low temperature side is gradually cooled from room temperature to −60 ° C. in a thermostat, while the compatibility on the high temperature side is gradually heated from room temperature to + 80 ° C. The temperature at which phase separation began was measured. The lower the phase separation temperature on the low temperature side, the higher the phase separation temperature on the high temperature side. (b) Freon 32 A predetermined amount of a sample was added to a pressure-resistant glass ampule so as to be 10% by weight and 20% by weight based on difluoromethane (Freon 32), and this was connected to a vacuum pipe and a Freon 32 gas pipe. After the ampoule was degassed in vacuum at room temperature, it was cooled with liquid nitrogen and a predetermined amount of Freon 32 was collected. Then
The ampoule is sealed and the compatibility on the low temperature side is gradually cooled from room temperature in a thermostat, while the compatibility on the high temperature side is gradually heated from room temperature to + 40 ° C to raise the temperature at which phase separation starts. It was measured. The lower the phase separation temperature on the low temperature side, the higher the phase separation temperature on the high temperature side. Volume resistivity The sample was dried at 100 ° C for 1 hour under reduced pressure (0.3 to 0.8 mmHg), and then sealed in a liquid cell for measuring volume resistivity in a constant temperature bath at 80 ° C. After being kept in a constant temperature bath at 80 ° C. for 40 minutes, the measurement was performed at an applied voltage of 250 V using an R8340 super insulation meter manufactured by Advantest Corporation. Hydrolysis stability 75 g of a sample, 25 g of water and copper (13 mm x 50 mm) were placed in a pressure-resistant bottle having a capacity of 250 ml, and the atmosphere in the vessel was set to a nitrogen atmosphere. The temperature was kept at 102 ° C. for 192 hours in a rotary thermostat. Thereafter, the appearance of the sample oil, the total acid value, and the state of the copper pieces were observed.

Examples 2 to 15 Using the lubricating oil of the present invention produced in Production Examples 2 to 15, kinematic viscosity, compatibility with Freon 134a, volume resistivity, and hydrolysis stability in the same manner as in Example 1. Was measured. Table 1 shows the obtained results. In Examples 14 and 15, the compatibility with Freon 32 was also measured. The result is
It is shown in the table.

Comparative Example 1 Using a commercially available paraffinic mineral oil (VG32),
Kinematic viscosity, compatibility with Freon 134a, volume resistivity, and hydrolysis stability were measured in the same manner as in Example 1. Table 1 shows the obtained results.

Comparative Example 2 Kinematic viscosity, compatibility with Freon 134a, specific volume resistance and hydrolysis stability were measured in the same manner as in Example 1 using polypropylene glycol (manufactured by NOF Corporation; Unilube MB11). did. Table 1 shows the obtained results.

Comparative Example 3 Using the polyol ester-based lubricating oil produced in Production Example 16, the kinematic viscosity and CFC 134a were obtained in the same manner as in Example 1.
Compatibility, volume resistivity, and hydrolysis stability were measured. Table 1 shows the obtained results.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

The lubricating oil of the present invention is a hydrogen-containing chlorofluorocarbon such as chlorofluorocarbon 134a, chlorofluorocarbon 32, chlorofluorocarbon 125, or the like, which can substitute for chlorofluorocarbon 12 or other chlorofluorocarbon compounds which are difficult to decompose, which are particularly problematic for environmental pollution. The compound has good compatibility with the compound over the entire operating temperature range, excellent stability and lubricating performance, and a volume resistivity at 80 ° C. of 10 ¹² Ω · cm or more. Used as oil.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C10N 40:30 (72) Inventor Nobuaki Shimizu 1280 Kamiizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd. (56) References JP JP-A-2-88607 (JP, A) JP-A-4-318004 (JP, A) JP-A-6-234805 (JP, A) JP-A-6-234814 (JP, A) JP-A-6-234815 (JP) U.S. Pat. No. 3,541,015 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C10M 107/24 C09K 5/00 C10N 20:02 C10N 30:00 C10N 40:30

Claims (13)

(57) [Claims] 1. A compound of the general formula (I) (In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ⁴ has 2 carbon atoms. -10
R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms, m is a number having an average value of 0 to 10, and R ^{1 to} R ⁵
It may be the or different from each be the same for each structural unit, and a plurality of R ⁴ O if R ⁴ O there are a plurality may be the same or different. A lubricating oil for a compression refrigerator mainly comprising a polyvinyl ether compound having a structural unit represented by the formula (1). 2. A poly (vinyl ether) compound, one end of which is represented by the general formula (II): (Wherein, R ⁶ , R ⁷ and R ⁸ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ⁹ represents a carbon atom 2-1
0 divalent hydrocarbon group, R ¹⁰ is a hydrocarbon group having 1 to 10 carbon atoms, n represents an average value thereof indicates the number of 0, a plurality of R ⁹ O if R ⁹ O is more May be the same or different. ), And the remaining terminal is represented by the general formula (III): (Wherein, R ¹¹ , R ¹² and R ¹³ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ¹⁴ represents a carbon atom 2-1
0 divalent hydrocarbon group, R ¹⁵ is a hydrocarbon group having 1 to 10 carbon atoms, p is an average value thereof indicates the number of 0, a plurality if R ¹⁴ O is more R ¹⁴ O May be the same or different. The lubricating oil according to claim 1, which has a structure represented by the formula: 3. A polyvinyl ether-based compound, of which one terminal is one general formula (II) ## STR4 ## (Wherein, R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
R ⁹ may be one or different, and R ⁹ has 2 to 1 carbon atoms.
0 is a divalent hydrocarbon group, and R ¹⁰ is a hydrocarbon having 1 to ¹⁰ carbon atoms.
Containing groups, n represents an average value thereof indicates the number of 0, the R ⁹ O
When there are a plurality of R ⁹ Os, they are different even if they are the same.
May be. ) And the remaining terminal is represented by the general formula (IV): (Wherein, R ¹⁶ , R ¹⁷ and R ¹⁸ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ¹⁹ and R ²¹ Each represents a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different, and R ²⁰ and R ²² each represent a hydrocarbon group having 1 to 10 carbon atoms. ,
They may be identical or different,
q and r each represent a number whose average value is from 0 to 10,
They may be identical or different,
Further to the plurality of R ¹⁹ O is when there are multiple R ¹⁹ O may be the same or different and also the plurality of R ²¹ O is when there are multiple R ²¹ O be the same It may be different. 2. The lubricating oil according to claim 1, which has a structure represented by the formula: 4. The polyvinyl ether compound, of which one terminal is one general formula (II) embedded image (Wherein, R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
R ⁹ may be one or different, and R ⁹ has 2 to 1 carbon atoms.
0 is a divalent hydrocarbon group, and R ¹⁰ is a hydrocarbon having 1 to ¹⁰ carbon atoms.
Containing groups, n represents an average value thereof indicates the number of 0, the R ⁹ O
When there are a plurality of R ⁹ Os, they are different even if they are the same.
May be. ) Is represented by, and the remaining terminal according to claim 1 lubricating oils described are those having an olefinic unsaturated bond. 5. The polyvinyl ether compound, of which one terminal is one general formula (II) embedded image (Wherein, R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
R ⁹ may be one or different, and R ⁹ has 2 to 1 carbon atoms.
0 is a divalent hydrocarbon group, and R ¹⁰ is a hydrocarbon having 1 to ¹⁰ carbon atoms.
Containing groups, n represents an average value thereof indicates the number of 0, the R ⁹ O
When there are a plurality of R ⁹ Os, they are different even if they are the same.
May be. ) , And the remaining terminal is represented by the general formula (V): (In the formula, R ²³ , R ²⁴ and R ²⁵ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different.) The lubricating oil according to claim 1, which is of a structure. 6. A polyvinyl ether-based compound, of which one terminal is one general formula (II) embedded image (Wherein, R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
R ⁹ may be one or different, and R ⁹ has 2 to 1 carbon atoms.
0 is a divalent hydrocarbon group, and R ¹⁰ is a hydrocarbon having 1 to ¹⁰ carbon atoms.
Containing groups, n represents the average value indicates the number of 0, the R ⁹ O
When there are a plurality of R ⁹ Os, they are different even if they are the same.
May be. ) , And the remaining terminal is represented by the general formula (III): (Wherein, R ¹¹ , R ¹² and R ¹³ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
R ¹⁴ may have one or two carbon atoms.
0 is a divalent hydrocarbon group, and R ¹⁵ is a hydrocarbon having 1 to 10 carbon atoms.
And p represents an average number of 0 to 10, and R ¹⁴ O represents
When there are a plurality of R ¹⁴ Os, they are different even if they are the same.
May be. ) Whose one end is represented by the general formula (II) and the other end is represented by the general formula (IV) (Wherein, R ¹⁶ , R ¹⁷ and R ¹⁸ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
R ¹⁹ and R ²¹ may be one or different.
Each represents a divalent hydrocarbon group having 2 to 10 carbon atoms;
Each may be the same or different, and R ²⁰ and
And R ²² each represent a hydrocarbon group having 1 to 10 carbon atoms;
They may be identical or different,
q and r each represent a number whose average value is from 0 to 10,
They may be identical or different,
The plurality of R ¹⁹ O is when there are multiple R ¹⁹ O are identical
May be different from each other, and if there are multiple R ²¹ O
A plurality of R ²¹ O may be the same or different
No. ) , One end of which is represented by the general formula (II), and the other end has a structure having an olefinically unsaturated bond, and one end of which is represented by the general formula (II) And the remaining terminal is represented by the general formula (V): (Wherein R ²³ , R ²⁴ and R ²⁵ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
They may be one or different. 2) a mixture of two or more selected from those having a structure represented by the formula:
The described lubricating oil. 7. A polyvinyl ether-based compound, of which one terminal is one general formula (II) embedded image (Wherein, R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
R ⁹ may be one or different, and R ⁹ has 2 to 1 carbon atoms.
0 is a divalent hydrocarbon group, and R ¹⁰ is a hydrocarbon having 1 to ¹⁰ carbon atoms.
Containing groups, n represents an average value thereof indicates the number of 0, the R ⁹ O
When there are a plurality of R ⁹ Os, they are different even if they are the same.
May be. ) , And the remaining terminal is represented by the general formula (III): (Wherein, R ¹¹ , R ¹² and R ¹³ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
R ¹⁴ may have one or two carbon atoms.
0 is a divalent hydrocarbon group, and R ¹⁵ is a hydrocarbon having 1 to 10 carbon atoms.
And p represents an average number of 0 to 10, and R ¹⁴ O represents
When there are a plurality of R ¹⁴ Os, they are different even if they are the same.
May be. ) And one end thereof is represented by the general formula (II), and the other end is represented by the general formula (V). (Wherein R ²³ , R ²⁴ and R ²⁵ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
They may be one or different. 2. The lubricating oil according to claim 1, wherein the lubricating oil is a mixture with one having a structure represented by the formula 8. A polyvinyl ether-based compound, of which one terminal is one general formula (II) embedded image (Wherein, R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
R ⁹ may be one or different, and R ⁹ has 2 to 1 carbon atoms.
0 is a divalent hydrocarbon group, and R ¹⁰ is a hydrocarbon having 1 to ¹⁰ carbon atoms.
Containing groups, n represents an average value thereof indicates the number of 0, the R ⁹ O
When there are a plurality of R ⁹ Os, they are different even if they are the same.
May be. ) And the remaining terminal is represented by the general formula (IV): (Wherein, R ¹⁶ , R ¹⁷ and R ¹⁸ are each a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms,
R ¹⁹ and R ²¹ may be one or different.
Each represents a divalent hydrocarbon group having 2 to 10 carbon atoms;
Each may be the same or different, and R ²⁰ and
And R ²² each represent a hydrocarbon group having 1 to 10 carbon atoms;
They may be identical or different,
q and r each represent a number whose average value is from 0 to 10,
They may be identical or different,
The plurality of R ¹⁹ O is when there are multiple R ¹⁹ O are identical
May be different from each other, and if there are multiple R ²¹ O
A plurality of R ²¹ O may be the same or different
No. 2. The lubricating oil according to claim 1, wherein the lubricating oil is a mixture of a structure represented by the formula (1) and a structure having one terminal represented by the general formula (II) and the other terminal having an olefinically unsaturated bond. oil. 9. A kinematic viscosity at a temperature of 40 ° C. of 5 to 10
The lubricating oil according to any one of claims 1 to 8, which is 00 cSt. 10. The lubricating oil according to claim 1, wherein the compression refrigerator uses hydrofluorocarbon as a refrigerant. 11. The compression refrigerator using hydrochlorofluorocarbon as a refrigerant.
9. The lubricating oil according to 9. 12. A compression refrigerator comprising: 1,1,
The lubricating oil according to any one of claims 1 to 9, wherein 1,2-tetrafluoroethane is used. 13. The lubricating oil according to claim 1, wherein the compression refrigerator uses difluoromethane as a refrigerant.