CN1083538C - Lubricant for refrigeration compressors - Google Patents

Abstract

A lubricant composition comprising as a base oil one or more ester oils, alkylbenzene oils and mineral oils, and a glycidyl ether compound having at least two epoxy groups is miscible in hydrofluorocarbon and hydrochlorofluorocarbon refrigerants such as R[134]alpha, etc. as replacing refrigerants of R[12] and provides a stable operation of refrigeration compressor for a long period of time without causing corrosion and wear of a sliding portion of the compressor.

Description

Compressor and the application in refrigerator thereof

The application submitted, is entitled as the dividing an application of No. 92104216.7 applications for a patent for invention of " oiling agent that is used for refrigeration compressor " on April 30th, 1992.

The present invention relates to a kind of solvable mixing in the lubrication preparation of carbon-fluorine-hydrogen compound and carbon-fluorine-chlorine-hydrogen compound refrigerant, and a kind of method of in refrigeration compressor and the inner refrigerating device that refrigeration compressor is installed, using this lubrication preparation.More particularly, the present invention relates to a kind of lubrication preparation, said preparation when under higher temperature when refrigerant in the freezer contacts the performance degradation degree lower and be suitable for improving the reliability of freezer, the invention still further relates to a kind of method of in refrigeration compressor and the inner refrigerating device that refrigeration compressor is housed, using this lubrication preparation.

Recently, for avoiding occurring the cavity in the ozonosphere in the stratosphere, the use of compound chlorine of fluorocarbon (CFC) will be forbidden.Such CFC comprises R ₁₁(F-11), R ₁₂(freon), R ₁₁₃, R ₁₁₄, R ₁₁₅Deng.Such as, be used for the R in refrigerating device (as the refrigerator) refrigeration cycle ₁₂It is exactly a target to be prohibited.Refrigerant as an alternative, the carbon-fluorine-chlorine-hydrogen compound (HCFC) that contains one or more hydrogen atoms in the molecule is (such as R ₂₂And R ₅₀₂-promptly contain the R of 48.8% weight ₂₂And the R of 51.2% weight ₁₁₅Azeotropic refrigerant) just studied by people.If R ₁₂The ozone hole coefficient be 1, R then ₂₂The ozone hole coefficient be 0.05, R ₅₀₂The ozone hole coefficient be 0.3.The carbon fluorine hydrogen (HFC) that will adopt in the future will be the compound of chloride atom not in those molecules forever.The typical example of HFC is R _134a, the ozone hole coefficient of this compound is 0, and nonflammable, its thermodynamic property and R ₁₂Basic identical.Like this, in fact the structure that does not need to change refrigerating device (as refrigerator and dehumidifier) refrigeration compressor to a great extent can be used R _134aBut, because chemical structure is special, R _134a(CH ₂FCF ₃) character is very unique, so it can not moltenly mix in using R ₁₂Refrigeration system in refrigeration machine oil in, these machine oil for example can be mineral oil (naphthenic oil, paraffin oil) and artificial oil (as alkylbenzene).Like this, variety of issue has just appearred, the situation of returning of oil degenerates when flowing in the refrigeration system when oil, refrigeration makes trapped fuel in the heat exchanger, reduced thermal heat transfer capability, and in the worst case, the low on fuel of compressor, because lubricated not enough, cause sliding parts to be stuck or inordinate wear occurs.Therefore, need exploitation to be applicable to refrigerant R _134aRefrigeration machine oil (or at some oiling agents of the some other refrigerant).

Because oiling agent is solvable to be mixed in R _134aIn, existing people proposes to adopt polyethyleneglycol oil, and (publication number is 1-259093.1-259094, the unexamined Japanese patent application of 1-259095 etc.) and ester oil (as Reito the 65th volume 756 phase 47-52 pages or leaves of publishing October nineteen ninety).But polyethyleneglycol oil has following deficiency: (i) big (the saturation water absorptivity is 10000-30000ppm to hygroscopicity, and (ii) low (volume resistivity is 10 in the electrical insulation impedance ¹²Ω cm or lower), and (iii) the degeneration that causes of oxidation is very serious.To adopting the situation of the air-tight compressor that a motor driven source wherein is housed, the insulating property of motor coil and electrode may reduce, and the result can bring the problem of reliability aspect.On the other hand, to using the situation of ester oil, though with the polyethyleneglycol oil phase than obtaining some improvement (volume resistivity 10 aspect electrical insulation properties and the hygroscopicity ¹²Ω cm, saturation water absorptivity 1000-5000ppm), but hygroscopicity is still greater than the saturation water absorptivity of mineral oil and alkylbenzene 50-100ppm, and these mineral oil and alkylbenzene are exactly R ₁₂Used refrigeration machinery oil in the system, and because its structure of molecule, these ester oil generation hydrolysis are inevitable.So, when the ester oil of high water content is used as the refrigeration machinery oil, hydrolysis takes place near the sliding parts of the ester oil compressor that temperature is the highest in refrigeration system, form organic acid, cause total acid number raising in the refrigeration machinery oil, the corrosion or the damage of compressor sliding material can take place in the result, forms the copper coating layer, owing to the saponified locomitivity that reduces sliding parts of the metal that has formed viscosity (the unusual increase appears in the moment of torsion that axle is rotated), make the capillary tube in the refrigeration cycle blocked.So just damaged the long-term reliability of compressor and refrigerating device widely, therefore need make improvement this.

On the other hand, also propose in the refrigeration machinery oil, to add the suggestion of epoxide.For example, publication number is to propose to add a kind of olefinated oxygen compound in the unexamined Japanese patent application of 57-10694 to improve the thermostability of CFCs in mineral oil or artificial oil.Point out that in the document styrene oxide and phenyl glycidyl ether are because toxicity is big and skin is had extremely strong strong excitant thereby can not use, the epoxidized soybean oil thermostability is very poor, and is easy to generate from oil bits when coexisting as the CFC freezer; And opposite with these compounds, the low thermostability that also can improve freezer of some specific olefinated oxygen compound toxicity.But used freezer has only R in the example of work ₁₂Type is a kind of, but R ₁₂The use that will be under an embargo of this compound.Both do not describe how to replace refrigerant in the document, also not mentioned employing olefinated oxygen compound can bring any effect.In fact, the effect of olefinated oxygen compound is not enough to and R _134aCompare.

In addition, publication number is to have proposed a kind of refrigeration machinery oil in the unexamined Japanese patent application of 62-292895, obtain this machinery oil and be by add in a kind of polyol ester or in the mixture formed of polyol ester and a kind of mineral oil or artificial oil a kind of with 8-18 carbon atom straight chain or the ethylene oxidic ester of the ethylene oxidic ester of side chain saturated fatty acid or a kind of straight chain unrighted acid with 14-18 carbon atom.This piece document is pointed out, because in some cases, existence has very strong stimulation to skin, bad and other factors of effect, add glycidol ether, for example phenyl glycidyl ether, epoxidized fatty acid ester, epoxidized vegetable oil and glycidyl acrylate are also inadvisable, and adding long-chain alcohol glycidol ether (being with an epoxy group) also phenomenons such as copper plating, copper corrosion can occur fallaciously.Yet, even what use under harsh high temperature condition is the sweet and ester of a kind of effective fatty acid shrink, also can occur the acid content formation reaction that the fatty acid glycidyl ester hydrolysis brings and the sour capture reaction of glycidyl simultaneously, the result has reduced acid on the whole and has captured effect.Like this, the metal part branch of compressor is because the not corrosion of captive acid content and wearing and tearing and damage, cause the passage of refrigerant in all plug refrigerating devices of product of fatty acid and metal reaction, and cause thus because the problem that the device performance that the refrigeration deficiency is brought reduces.

In addition, adopting R ₂₂Or R ₅₀₂Make refrigerant and mineral oil or alkylbenzene and do in the such refrigeration cycle of machinery oil, the copper plating takes place in the slide part branch of compressor, brings the problem of compressor reliability difference.

An object of the present invention is to provide a kind of circulation and compress a kind of compressor of refrigerant and the application in refrigerator thereof in refrigerator.

The invention provides a kind of circulation and compress a kind of compressor of refrigerant and the application in refrigerator thereof in refrigerator, described compressor comprises that one accommodates a kind of refrigeration machine oil, and the seal container of a motor is housed therein in its bottom, and described motor is made of stator and rotor; Also be equipped with one and be fixed on described epitrochanterian rotating shaft; A compression set that links to each other with described motor through described rotating shaft, described refrigeration machine oil comprise as base oil, be selected from least a in one group of material that ester oil, alkylbenzene oil and mineral oil forms and a kind of epoxide with at least two epoxide groups.

In a kind of preferred embodiment of the present invention, refrigerant is that at least a to be selected from critical temperature be 40 ℃ or the higher carbon-fluorine-hydrogen compound and the refrigerant of carbon-fluorine-chlorine-hydrogen compound.

Fig. 1 is the front cross-sectional view of an airtight rotation refrigeration compressor theme part.

Fig. 2 is a refrigeration circuit sketch map in the expression refrigerating device.

The present inventor notices, joins the epoxide in the refrigeration machinery oil owing to only do not attain the results expected with an epoxy radicals result, just finishes thus the present invention.

With being selected from by ester oil, at least one component in one group of material that alkylbenzene oil and mineral oil form is as the base oil of lubricant formulations. Specifically, for ester oil, preferably adopt by the be obstructed ester oil of a kind of organic (fat) acid with a kind of acidification reaction generation of polyalcohol, and by a kind of polyalcohol, a kind of polyacid and a kind of organic (fat) sour compound ester oil that obtains, above ester oil can use separately or adopt the mixture of the two.

As for epoxide, adopt all with two or more epoxy radicals. Such epoxide for example a kind of glycidyl ether compound does not have toxicity, and (not resembling phenyl glycidyl ether) do not have excitant to skin, so safer when operating.

Preferred glycidyl ether compound for example comprises aklylene glycol diglycidyl ether and alicyclic epoxide compound.

The preferred embodiment of aklylene glycol diglycidyl ether is represented with following structural formula:

R wherein ₁Be an alkylidene, this base preferably is with 1 to 5 carbon atom, R ₂Be a hydrogen atom or one preferably with the alkyl of 1 to 5 carbon atom, n is the integer between 1 to 22

(neopentyl glycol diglycidyl ether)

(1,6-hexylene glycol diglycidyl ether)

(the many Synthesis of Oligo Ethylene Glycol of sorbitol)

In the compound of structural formula (1) expression, those use CH ₂As R ₁, H or CH ₃As R ₂And desirable especially with the compound of structural formula (6) and (7) representative:

The preferred example of alicyclic ring epoxy compound is following formula (3, the 4-epoxy) cyclohexane-carboxylic acid (3, a 4-epoxy) cyclohexyl methyl fat: Interior epoxide with following chemical formulation:

Ring epoxy and glycidyl ether compound in the following formula:

The following formula epihydric alcohol ester compound:

Following formula hydrantoin compound:

Wherein R is for preferably with the alkylidene of 1 to 5 carbon atom; R ₃And R ₄Be respectively a hydrogen atom or one preferably with the alkyl of 1 to 5 carbon atom.

Be used for epoxide of the present invention and be characterised in that molecule is with two epoxy group at least.For example, glycidol ether acid capture aspect than only with the epoxide of an epoxy group (as 2-ethylhexyl glycidol ether or glycidyl 2 ethyl hexanoic acid ester better effects if.

To the sour capture effect of various epoxides (in lubrication preparation, accounting for 1% weight) (being a kind of effect of removing harmful acid that the ester oil hydrolysis produced), test, the results are shown in the table 1.

In the teat glass of an internal diameter 10mm, put into the oil that 5ml contains the epoxide to be measured of 1% (weight), its water content is 700ppm, and also puts into iron simultaneously, the metal fillings of copper and aluminium seals test tube then.Open test tube in heating under 175 ℃ after 336 hours, measure the total acid number of this oil sample and the extent of corrosion of metal fillings.

Measure total acid number with the method (JISK2501) of measuring the petroleum products neutralization value.

The extent of corrosion of metal fillings is comprehensively by the surface state of observing the state that corrodes the product suspension that generated or precipitation in the oil and metal fillings to determine.The evaluation of being done is as follows:

◎ does not corrode

Zero not corrosion basically

△ slightly corrodes

* obviously corrosion

Table 1

Epoxide		Total acid number (mgKOH/g)	Corrosion of metal	Remarks
					Glycidol ether	The malonic acid diglycidyl ether, (1) 2-ethylhexyl glycidol ether, (2) neopentyl glycol diglycidyl ether, (3) phenyl glycidyl ether, (4) iso stearate glycidol ether, (long-chain alcohol glycidol ether)	1.0 1.4 1.0 0.65 1.35	○ △ ○ ◎ △	* has very strong and stimulating to skin
The fatty acid epoxide	3,4-7-oxa-bicyclo[4.1.0 carboxylic acid (3) 4-epoxy) cyclohexyl methyl ester (5) 7-oxa-bicyclo[4.1.0 (6)	0.61 0.30	◎ ◎	Skin is not stimulated low ignition point
						Epoxidised linseed oil 2-ethyl-caproic acid ethylene oxidic ester (7)	1.50 1.42	△ △
(reference) ester oil (not adding epoxide)		2.0	×

Annotate) *: the label in the used epoxide table 1 of the present invention:

Obviously as seen, used epoxide can obtain fabulous sour removal effect among the present invention, and skin is not had excitant from table 1.

As mentioned above, by to containing one or more ester oil, add at least epoxide in the base oil of alkylbenzene oil and mineral oil (separately a kind of or their mixture) with two epoxy group, the organic acid that the ester oil hydrolysis is produced is captured by epoxy group, thereby controlled the increase of total acid number, avoided corrosion and wearing and tearing, avoided the generation of copper plating phenomenon and metallic soap, guaranteed the proper functioning of compressor the compressor sliding material.More particularly, when the ester oil hydrolysis, generated acid and pure sometimes.When epoxy group, epoxy group is opened, and has captured organic acid.This reaction mechanism can be represented with following reaction equation (14): (ester is obstructed)

To the situation of the composition that uses alkylbenzene oil, mineral oil and a kind of carbon fluorine chlorine hydrogen refrigerant, refrigerant generates hydrochloric acid with the oil reaction under harsh condition, cause the corrosion and the wearing and tearing of sliding material, and copper plating phenomenon occurs.In this case, epoxy group is opened, and has captured hydrochloric acid, has kept the normal performance of compressor.Under the situation of using the epoxide only have an epoxy group, can think that such effect is arranged, and when the epoxide that adopts at least with two epoxy group this effect will be strong more than.

Used at least can be preferably between 0.05-10% (weight) in the weight of lubrication preparation with the amount of the epoxide of two epoxy group, better between 0.1-1.0% (weight).When institute's consumption was less than 0.05% (weight), it is insufficient that effect is captured in acid, and when used amount surpasses 10% weight, then be easy to damage the function as the base oil of refrigeration machinery oil, also just lost use value.

When with propylene glycol or polypropylene glycol diglycidyl ether or (3, the 4-epoxy)-cyclohexane-carboxylic acid (3, when the 4-epoxy) conduct of cyclohexyl methyl ester brings to the glycidyl ether compound of few two epoxy group, the amount that is adopted equally can be preferably between 0.05-10% (weight) in the weight of lubrication preparation, and is better between 0.1-1% (weight).

Do not hindering under realization the object of the invention prerequisite, lubrication preparation of the present invention can contain one or more antioxidants, extreme pressure additive, materials such as antifoaming agent.

For antioxidant, comparatively effective with phenol compound.For preventing that base oil character from changing and durability rotten and the maintenance base oil, preferably add phenol compound fully.The addition of antioxidant is preferably between the 0.01-5% (weight) by the weight of lubrication preparation.

The most preferred embodiment of phenol antioxidant is represented with structural formula (8) and (9): X is an integer of 1 to 3

X is an integer of 1 to 3

For refrigerant used in refrigeration compressor and the refrigerating device, its critical temperature is preferably 40 ℃ or higher.

Critical temperature is that the example of 40 ℃ or higher carbon fluorine hydrogen refrigerant is difluoromethane (R ₃₂), pentafluoroethane (R125), 1,1,2,2-HFC-134a (R ₁₃₄), 1,1,1,2-HFC-134a (R _134a), 1,1,2-HFC-143a (R ₁₄₃), 1,1,1-HFC-143a (R _143a), 1,1-Difluoroethane (R _152a), a fluoroethane (R ₁₆₁), or the like.

Critical temperature is that the example of 40 ℃ or higher carbon-fluorine-chlorine-hydrogen compound refrigerant is Dichloromonofluoromethane (R ₂₁), F-22 (R ₂₂), a chloro-1,2,2,2-HFC-134a (R ₁₂₄), 1-chloro-1,1,2,2-HFC-134a (R _124a), pentafluoroethane (R ₁₂₅), 1-chloro-1,1-Difluoroethane (R _142b), F-22 (R ₂₂) and a chloropentafluoroethane (R ₁₁₅) azeotropic mixture (R ₅₀₂), or the like.

In these refrigerant, R ₁₃₄, R _134a, R ₁₄₃And R _143aBe comparatively desirable alternative R ₁₂Refrigerant because the boiling point of these refrigerant and R ₁₂Boiling point approaching.In addition, R ₂₂With azeotropic mixture R ₅₀₂(R ₂₂With R ₁₁₅Mixture) though the ozone hole coefficient non-vanishing, still use in reality their today, therefore, can be used as in a short time and substitute R ₁₂Effective refrigerant.

Can use these carbon-fluorine-hydrogen compounds and carbon-fluorine-chlorine-hydrogen compound separately, perhaps use their mixture.

Requiring critical temperature is 40 ℃ or higher, and this is because refrigerating device keeps 40 ℃ or higher condensing temperature in condenser.

This lubrication preparation is used as the lubricant oil in the compressor (this refrigeration agent just circulates therein and is compressed).As for compressor, can adopt rotary, reciprocating type, spiral and scroll compressor.Such as, such compressor comprises a seal container, this container bottom accommodates refrigeration machine oil, be equipped with wherein that a motor that is made of rotor and stator, one are installed in compression set that epitrochanterian rotatingshaft, one be connected with motor by rotatingshaft and at least a to be selected from critical temperature be 40 ℃ or the higher carbon-fluorine-hydrogen compound and the refrigerant of carbon-fluorine-chlorine-hydrogen compound, described refrigeration machine oil is exactly above-described lubrication preparation.

According to the present invention, carbon-fluorine-hydrogen compound or carbon-fluorine-chlorine-hydrogen compound were used under quite high temperature since between base oil and the refrigerant or the reaction between base oil and the water be suppressed, coolant compressor can be worked under sufficiently stable state.So the refrigerating device that has such coolant compressor also can stably be worked.Such refrigerating device comprises compressor above-mentioned, a condenser, an expansion assembly, a vaporizer and these parts of some connections and makes the pipe of refrigerant cycle.

Such refrigerating device can be used as household electric appliance, as refrigerator, dehumidifier, air conditioner, or the like; Can be used for being equipped with in showcase and the beverage storage storehouse refrigerating device of refrigeration cycle; And the refrigerating device that needs refrigeration cycle, as self-contained air-conditioner and assembling type Air Conditioner.

The present invention will be illustrated by following example, in the example all composition and percentage all by weight, except as otherwise noted.

Example 1 to 10, comparative example 1 to 3

Make lubrication preparation listed in the table 2 all accept the check of refrigerant thermostability.The results are shown in Table 2.

Check the thermostability of refrigerant by the following formula mode.In the test tube of the thick 2mm of internal diameter 6mm that the withstand voltage glass of usefulness is made, put into 0.5ml sample oil (having added or do not added additive), put into some iron of using as catalyzer, copper and aluminum metal bits simultaneously, add 0.5ml refrigerant then, seal with the dry ice cooling and with test tube simultaneously.Test tube heated 960 hours down at 175 ℃ or 200 ℃.After the heating, the color of oil and refrigerant mixture in the observation test tube, and the comparison of ASTM standard color is to estimate the degree that chemical reaction carries out between this oil and the refrigerant.

In addition, detect by an unaided eye and estimate the degree of copper plating phenomenon (being that copper is deposited on the surface of iron plate) by 5 ranks, promptly (+) slight copper is plated on the whole surface that (5+) copper is plated on iron plate.

In addition, also estimated should oil and refrigerant between the sedimental situation that exists that chemical reaction produced.

(example 1) that obviously as seen add with 0.25% amount from table 2 is by the oiling agent that is obstructed ester oil and forms with propylene glycol/polypropylene glycol diglycidyl ether (epoxy 1.) that structural formula (7) is represented, and (example 2) that add with 0.25% amount, by ester oil and (3 of being obstructed, the 4-epoxy)-cyclohexane-carboxylic acid (3, the 4-epoxy) the lubrication preparation base oil change in color of cyclohexyl methyl ester (epoxy 2.) composition is slight, and have formation copper coating layer in the situation that has R134a, also do not form sediments.In contrast, the sample in comparative example 1 does not contain any additives, has then formed copper coating and sediments loathsomely.Like this, the stability of the refrigerant in example 1 and the example 2 is significantly improved.

, to example 6,2. 1. epoxy joined in alkylbenzene oil and the naphthenic mineral oil with epoxy in example 3, R is being arranged ₂₂Do not form copper coating and sediments under the condition that exists.This shows with comparative example 2 compares with 3, and the stability of refrigerant obviously improves.

In addition, in example 7 to 10,2 of usefulness structural formula (8) expression of the amount with 0.25% is after 6-d-tert-butyl-p-cresol (DBPC) adds as antioxidant, with only add epoxy 1. or epoxy situation 2. compare the further raising of having got back of the thermostability of refrigerant.9. structural formula represents that phenolic antioxidant also shows the effect (result be not listed in table 2) identical with the phenol compound of structural formula (3).

Table 2

Routine number of test	Base oil	Viscosity (40 ℃ of following cst)	Additive *	Refrigerant	Probe temperature (℃)	The thermostability of refrigerant
									The color (ASTM) of oil	Copper coating * *	Sediments
						Example 1 example 2 examples 3 examples 4 examples 5 examples 6	The hard ester acid oil that the is obstructed oily alkylbenzene alkylbenzene alicyclic hydrocarbon mineral grease cyclic hydrocarbon mineral oil of hard ester acid that is obstructed	32 32 60 60 56 56				Epoxy 1. epoxy 2. epoxy 1. epoxy 2. epoxy 1. epoxy is 2.	R 134aR 134aR 22R 22R 22R 22	175 200 175 200 200 200 200 200	0.5 1.5 0.5 1.5 0.5 0.5 1.0 1.0	Do not have++	Do not have
Comparative example 1 comparative example 2 comparative examples 3	Stearic acid oil alkylbenzene oil alicyclic hydrocarbon mineral oil is obstructed	32 60 56	Do not have	R 134aR 22R 22	175 200 200 200				0.5 2.0 0.5 1.0	+ 3+ 3+ 3+	Do not have and have or not nothing
						Example 7 examples 8 examples 9 examples 10	The ester oil that the is obstructed ester oil ester oil ester oil that is obstructed that is obstructed that is obstructed	32 32 15 15				Epoxy is 2. 1. 2. DBPC of DBPC epoxy of DBPC epoxy of DBPC epoxy 1.	R 134aR 134aR 134aR 134a	175 200 175 200 175 200 175 200	0.5 1.0 0.5 0.5 0.5 0.5 0.5 0.5	Do not have	Do not have

The explanation of his-and-hers watches 2:

Additive *:

Epoxy 1.=propylene glycol/polypropylene glycol diglycidyl ether (0.25%)

Epoxy 2.=3,4-epoxy-cyclohexane-carboxylic acid (3, the 4-epoxy) cyclohexyl methyl ester (0.25%)

DBPC=2,6-d-tert-butyl-p-cresol (0.25%)

Copper coating * *: with the naked eye divide 5 grades to estimate the lip-deep copper coating of iron plate: (+) a little copper coating to (5+) copper is plated on the whole surface.

Example 11 to 17, comparative example 4 and 5

Make lubrication preparation listed in the table 3 accept hydrolysis experiment by following mode.

In the withstand voltage glass of usefulness test tube that make, internal diameter 10mm, thick 2mm, putting into the 5ml water content is the sample oil of 3000ppm, and puts into some iron, copper and aluminum metal bits, adds 2ml refrigerant R then _134a, seal with the dry ice cooling and with test tube simultaneously.Heated 7 to 21 days down at 150 ℃.After the heating, estimate oil and the color of refrigerant mixture and the degree of copper plating.Seal test tube then,, measure the total acid number of oil and refrigerant mixture according to the method (JIS K 2501) of testing stone oil product neutralization value.

The results are shown in Figure 3.

Table 3

Routine number of test	Base oil	Viscosity (40 ℃ of following cst)	Additive *	The test fate (my god)	Character after the heating
								Total acid number (mg K0H/g)	The color (ASTM) of oil	Copper coating
					Example 11 examples 12 examples 13	Ester oil (water 3000 ppm are obstructed	32 32 15				Epoxy is 2. (0.25%) epoxy 1. (0.25%) of (0.25%) epoxy 1.	7 21 7 21 7 21	0.019 0.112 0.018 0.100 0.027 0.280	0.5 0.5 0.5 0.5 0.5 0.5	Do not have
Comparative example 4 comparative examples 5			Do not have	7 21 7 21				0.066 0.585 0.056 0.344	0.5 0.5 0.5 0.5	Do not have
					Example 14 examples 15 examples 16 examples 17						Epoxy is 2. 1. 2. DBPC of DBPC epoxy of DBPC epoxy of DBPC epoxy 1.	7 21 7 21 7 21 7 21	0.010 0.080 0.010 0.061 0.010 0.120 0.010 0.096	0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5	Do not have

Can find out significantly that from table 3 example 11 and 12 total acid number are starkly lower than the total acid number of comparative example 4 and 5.This organic acid that clearly illustrates that the ester oil hydrolysis is produced is captured by glycidyl ether compound.Therefore, its anti-hydrolysis ability improves greatly because of the present invention.

In addition, as shown in example 14 and 17, when adding phenolic antioxidant DBPC, anti-hydrolysis ability than only in base oil, add epoxy 1. or epoxy situation 2. further improvement has been arranged again.

The represented phenolic antioxidant of structural formula (9) also has the effect (result exclude in table 3) identical with the phenol compound of chemical formula (8).

Example 18 to 21, comparative example 6 and 7

Carry out oxidation-stabilized property testing according to listed lubrication preparation in JIS K 2514 methods (method of the test oil ageing stability) his-and-hers watches 4.

The results are shown in Table 4.

Table 4

Routine number of test	Base oil	Viscosity (40 ℃ of following cst)	Additive	Character after the heating
							Total acid number (mg KOH/g)	The color (ASTM) of oil	Copper coating
				Example 18 examples 19 examples 20 examples 21	Alkylbenzene alkylbenzene alicyclic hydrocarbon mineral grease cyclic hydrocarbon mineral oil	60 60 56 56				Epoxy is 2. 1. (0.5%) epoxy 2. (0.5%) of (0.5%) epoxy of (0.5%) epoxy 1.	0.012 0.004 0.018 0.015	0.5 0.5 1.0 1.0	Do not have
Comparative example 6 comparative examples 7	Alkylbenzene alicyclic hydrocarbon mineral oil	60 56	Do not have				0.156 0.128	1.0 1.5	Do not have

1. or epoxy 2. the time from table 4, can obviously find out,, compare with 7 situation with comparative example 6 when adding epoxy with 0.5% amount, the total acid number after the heating only be about total acid number in 18 to 21 1/10 or lower.

This clearly illustrates that lubrication preparation of the present invention can also prevent oxidation deterioration effectively.

Example 22

Fig. 1 is the front sectional elevation of a hermetically sealed rotary coolant compressor major component.Fig. 2 is the sketch map of refrigeration cycle that expression has a kind of refrigerating device of compressor shown in Figure 1.

In Fig. 1, cabinet of numbering 1 expression, this cabinet is one to can be used as the seal container of oil sump, accommodates motor part 22 and compressor section 23.Motor 22 comprises stator 19 and rotor 20, and rotor 20 is fixed on the rotating shaft 4A.One eccentric part 3 is arranged on the rotating shaft 4A, an axocoel 17 is arranged in the vacancy of one end.The coiler part 19a of stator 19 has a magnetic coil, scribbles ester acid imide enamel paint on the coil.The core of stator and coiler part are isolated with the polyethylene terephthalate electrical insulating film.Fine finishing is carried out on surface with polishing method countershaft 4A.Compressor section 23 comprises that a cylinder body made from sintered iron 2, one stretch in the eccentric part 3 of rotating shaft 4A and the roller that rotates along the inboard of cylinder body 27, a slide block (Vane) 10 made from high speed steel, this slide block moves reciprocatingly in a groove 8 of cylinder body 2, the one end contacts with roller 7 simultaneously, and its other end is promoted by spring 9, and a main bearing 5 and a supplementary bearing 6, they are made with sintered iron or cast iron, constitute the bearing of rotating shaft 4A and the sidewall of cylinder body 2, and be positioned the two ends of cylinder body.

A delivery valve 27 is arranged on the supplementary bearing 6 and be stamped a conveying cover plate 25, to constitute a silencing apparatus 28.Main bearing 5, cylinder body 2 and Volt nip of supplementary bearing 6 usefulness.Oil pump room 12 by groove 8, main bearing 5 and the supplementary bearing of the rear side 11 of slide block 10, cylinder body 2 around forming.One suction device 14 is arranged on the main bearing 5, and this device can extract the lubrication preparation of depositing cabinet 1 bottom 13 and the refrigerant that can isolate is wherein sent in the pump chamber 12.A delivery port 16 is arranged on the supplementary bearing 6, and it can deliver to a transport pipe 15 to lubrication preparation 13 from pump chamber 12.The axle cavity 17 of rotating shaft 4A delivered to lubrication preparation 13 by transport pipe 15.Lubrication preparation 13 passes a cavity 17 and and diverges hole 18 to the sliding parts that will lubricate.

The function of the rotary compressor that explained later constitutes like this.

When the rotating shaft 4A of compressor start and cast iron rotation, also rotate simultaneously with roller 7 through heat treated cast iron.When at one end contacting with roller 7, the slide block 10 that high speed steel is made promoted to-and-fro motion in the groove 8 of the cylinder body 2 of sintered iron or cast iron by spring.Transfer out mouthful 24 outflow compressors from a delivery pipe 29 through a refrigerant from the refrigerant of refrigerant suction port (not shown in figure 1) inflow is compressed.The coiler part 19a of stator 19 and electrical insulating film (not shown in figure 1) are immersed in the lubrication preparation that is dissolved with refrigerant or are exposed in the environment of spraying formation.

As use-case 1-6, when the lubrication preparation shown in 11-13 and the 18-21 makes compressor operating as refrigeration machine oil, even also can work highly reliably for a long time at harsh condition lower compression machine, and can not damage the sliding parts of compressor, for example can not make bearing corrosion and block, can not make the failure of insulation in the electric system, and, can not damage the resistance to heat and the anti-oxidant rotten performance of lubrication preparation yet owing to have fabulous thermostability.

Fig. 2 is the sketch map of refrigeration system in the refrigerating device.In the drawings, label 40 expression compressors, label 41 expression condensers, label 45 expression exsiccators, label 42 expression expansion gears, label 43 expression vaporizers.Shown in example 21, irritate with lubrication preparation used among the routine 1-21 in the coolant compressor 40.Refrigerant gas under the low-temp low-pressure is compressed, and the refrigerant gas that becomes High Temperature High Pressure is discharged from delivers to condenser 41.The refrigerant gas that arrives condenser 41 becomes the refrigerant liquid of High Temperature High Pressure, and the while in atmosphere, removes heat release then and anhydrates in exsiccator 45.Subsequent refrigerant liquid is sent to expansion gear 42 (for example an expansion valve or a capillary tube).The High Temperature High Pressure refrigerant liquid that passes expansion gear becomes the damp steam of low-temp low-pressure and is sent to vaporizer 43 owing to extrusion effect.Refrigerant in the vaporizer 43 absorbs heat from environment so that evaporation.The refrigerant gas of low-temp low-pressure is discharged from from vaporizer 43 and is sucked into compressor 40.Same cyclic process is carried out in refrigerating device repeatedly.

When being applied in above-mentioned refrigeration cycle on the family expenses refrigerator, it is fine that the performance of the coolant compressor 40 shown in Fig. 1 demonstrates in this refrigeration cycle oil backflow performance of 40 from the vaporizer to the coolant compressor, the result realized freezer reliably and with long-term, durable in use.Life test to this refrigeration cycle has obtained gratifying result.

The condition of life test is as follows:

Motor coil temperature: 125 ℃

The outlet pressure of compressor: 13kg/cm ²G

Capillary tube in the refrigeration cycle: internal diameter 0.65mm

Refrigerant: R _134a

Ambient temperature: 40 ℃

Lubrication preparation: example 7 or 9

This test was equivalent to the freezer real work 10 years.

Result: work and do not find in 90 days to change.

In contrast, when in lubrication preparation, not adding glycidyl ether compound, the metallic soap deposition in capillary tube, occurs, stopped up passage.

As mentioned above, lubrication preparation of the present invention and carbon fluorine hydrogen and carbon fluorine chlorine hydrogen refrigerant are united use, demonstrate fabulous thermostability, anti-hydrolysis and anti-oxidant rotten performance.So such lubrication preparation has significant effect to keeping the compressor long-term work.Therefore, by refrigerating device that the coolant compressor that is filled with lubrication preparation of the present invention is packed into, can make refrigerating device not use R ₁₂And has a very high reliability.

Claims (3)

1. circulation and compress a kind of compressor of refrigerant in refrigerator, described compressor comprise that one accommodates a kind of refrigeration machine oil, and the seal container of a motor is housed therein in its bottom, and described motor is made of stator and rotor; Also be equipped with one and be fixed on described epitrochanterian rotating shaft; A compression set that links to each other with described motor through described rotating shaft, described refrigeration machine oil comprise as base oil, be selected from least a in one group of material that ester oil, alkylbenzene oil and mineral oil forms and a kind of epoxide with at least two epoxide groups.

2. according to the circulation in refrigerator of claim 1 with compress a kind of compressor of refrigerant, it is characterized in that described refrigerant is that at least a to be selected from critical temperature be 40 ℃ or the higher carbon-fluorine-hydrogen compound and the refrigerant of carbon-fluorine-chlorine-hydrogen compound.

3. the application of the compressor of claim 1 in refrigerator.

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