CN1031758C - 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 R134a, etc. as replacing refrigerants of R12 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

The lubricant that is used for refrigerating compressor

The present invention relates to a kind of solvable mixing in the lubricant formulations of carbon-fluorine-hydrogen compound and carbon-fluorine-chlorine-hydrogen compound cooling agent, and a kind of method of in refrigerating compressor and the inner refrigeration unit that refrigerating compressor is installed, using this lubricant formulations.More particularly, the present invention relates to a kind of lubricant formulations, said preparation when under comparatively high temps when cooling agent in the refrigerator contacts the performance degradation degree lower and be suitable for improving the reliability of refrigerator, the invention still further relates to a kind of method of in refrigerating compressor and the inner refrigeration unit that refrigerating compressor is housed, using this lubricant formulations.

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(Trichloromonofluoromethane), R ₁₂(Refrigerant 12), R ₁₁₃, R ₁₁₄, R ₁₁₅Deng.Such as, be used for the R in refrigeration unit (as the refrigerator) refrigerant cycles ₁₂It is exactly a target to be prohibited.Cooling agent 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 ₁₃₄, the ozone hole coefficient of this compound is 0, and nonflammable, its thermomechanical property and R ₁₂Basic identical.Like this, in fact the structure that does not need to change refrigeration unit (as refrigerator and dehumidifier) refrigerating 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 ₁₂Refrigerating system in refrigeration machine oil in, these machine oil for example can be mineral oil (naphthenic oil, paraffin oil) and synthetic oil (as alkylbenzene).Like this, variety of issue has just appearred, the situation of returning of oil degenerates when flowing in the refrigerating 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 slipper to be stuck or inordinate wear occurs.Therefore, need exploitation to be applicable to cooling agent R _134aRefrigeration machine oil (or at some lubricants of the some other cooling agent).

Because lubricant is solvable to be mixed in R _134aIn, existing people proposes to adopt polyoxyethylene glycol oil, and (publication number is 1-259093.1 one 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 polyoxyethylene glycol oil has following deficiency: (i) big (the saturation water specific absorption is 10000-30000ppm to water absorbability, and (ii) low (volume specific resistance is 10 in the electrical isolation 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 drive 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 polyoxyethylene glycol oil phase than obtaining some improvement (volume specific resistance 10 aspect electrical insulation properties and the water absorbability ¹²Ω cm, saturation water specific absorption 1000-5000ppm), but water absorbability is still greater than the saturation water specific absorption 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 molecular structure, 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 slipper of the ester oil compressor that temperature is the highest in refrigerating system, form organic acid, cause total acid value raising in the refrigeration machinery oil, the corrosion or the damage of compressor sliding material can take place in the result.Form the copper coating layer.Owing to the saponified motor capacity that reduces slipper of the metal that has formed viscosity (the unusual increase appears in the moment of torsion that axle is rotated), make the kapillary in the refrigerant cycles blocked.So just damaged the long-term reliability of compressor and refrigeration unit widely, therefore need make improvement this.

On the other hand, also propose in the refrigeration machinery oil, to add the suggestion of epoxy compounds.For example, publication number is to propose to add a kind of olefinated oxygen compound in 57-10694 the unexamined Japanese patent application to improve the thermostability of CFCs in mineral oil or synthetic oil.Point out that in the document Styrene oxide 98min. and phenyl glycidyl ether are because toxicity is big and skin is had extremely strong strong pungency 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 refrigerator; And opposite with these compounds, the low thermostability that also can improve refrigerator of some specific olefinated oxygen compound toxicity.But used refrigerator 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 cooling agent 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 _134aRatio.

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 synthetic oil a kind of with 8-18 carbon atom straight chain or the glycidyl ester of the glycidyl ester of side chain saturated fatty acid or a kind of straight chain unsaturated fatty acids 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 glycidyl ether, for example phenyl glycidyl ether, epoxidized fatty acid ester, epoxidized vegetable oil and glycidyl acrylate are also inadvisable, and adding long-chain alcohol glycidyl ether (being with an epoxy group(ing)) also phenomenons such as copper plating, copper corrosion can occur fallaciously.Yet, even what use under harsh hot conditions is the sweet and ester of a kind of effective lipid acid shrink, also can occur the acid 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 and wearing and tearing and damage, cause the product of lipid acid and metal reaction to stop up the passage of cooling agent in the refrigeration unit, and cause thus because the problem that the device performance that the refrigeration deficiency is brought reduces.

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

An object of the present invention is to provide a kind of lubricant formulations (a kind of refrigeration machinery oil formulation), said preparation is solvable to be mixed in carbon-fluorine-chlorine-hydrogen compound and carbon-fluorine-hydrogen compound cooling agent (the alternative R of this two classes cooling agent ₁₂Cooling agent) in, fabulous thermostability and wear resistance are arranged, overcome problem above-mentioned.Another object of the present invention provides a kind of in refrigerating compressor or comprised the method that adopts such lubricant formulations in the refrigeration unit of such refrigerating compressor therein.

The invention provides a kind of lubricant formulations, said preparation is solvable to be mixed in carbon-fluorine-hydrogen compound and carbon fluorine chlorine hydrogen cooling agent, and said preparation is by being selected from least a in the middle of one group of material being made up of ester oil, alkylbenzene oil and mineral oil and a kind ofly constituting with the epoxy compounds of two epoxy group(ing) at least as base oil.

It is a kind of in refrigerating compressor or comprised the method that adopts such lubricant formulations in the refrigeration unit of such refrigerating compressor therein that the present invention also provides.

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

Fig. 2 is a refrigeration round-robin sketch map in the expression refrigeration unit.

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 esterification 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 group, this base preferably is with 1 to 5 carbon atom, R ₂Be that a hydrogen atom or one are 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 sorbyl alcohol)

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:

(n=1 to 22) (n=1 to 20)

The preferred example of alicyclic ring epoxy compound is following formula (3, the 4-epoxy) hexahydrobenzoic acid (3, a 4-epoxy) cyclohexyl methyl fat:

Interior epoxy compounds 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 group 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 epoxy compounds of the present invention and be characterised in that molecule is with two epoxy group(ing) at least.For example, glycidyl ether acid capture aspect than only with the epoxy compounds of an epoxy group(ing) (as 2-ethylhexyl glycidyl ether or glycidyl 2-ethylhexanoate better effects if.

The sour capture effect of various epoxy compoundss (accounting for 1% weight in lubricant formulations) (being a kind of effect of removing harmful acid that the ester oil hydrolysis produced) is tested, the results are shown in the table 1.

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

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

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

◎ does not corrode

Zero not corrosion basically

△ slightly corrodes

* obviously corrosion

Table 1

Epoxy compounds		Total acid value (mgKOH/g)	Corrosion of metal	Remarks
					Glycidyl ether	The propanedioic acid diglycidyl ether, (1) 2-ethylhexyl glycidyl ether, (2) neopentyl glycol diglycidyl ether, (3) phenyl glycidyl ether, (4) iso stearate glycidyl ether, (long-chain alcohol glycidyl ether)	1.0 1.4 1.0 0.65 1.35	○ △ ○ ◎ △	* has very strong and stimulating to skin
The lipid acid epoxy compounds	3,4-epoxy cyclohexane carboxylic acid (3) 4-epoxies) cyclohexyl methyl vinegar (5) epoxy cyclohexane (6)	0.61 0.30	◎ ◎	Skin is not stimulated low ignition point
						Epoxidised linseed oil 2-ethyl-caproic acid Racemic glycidol vinegar (7)	1.50 1.42	△ △
(reference) ester oil (not adding epoxy compounds)		2.0	×

Annotate) *: the epoxy compounds that the present invention is used

Label in the table 1:

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

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

(ester is obstructed)

(acid) (alcohol) (acid) (open loop of epoxy group(ing))

To the situation of the composition that uses alkylbenzene oil, mineral oil and a kind of carbon fluorine chlorine hydrogen cooling agent, cooling agent 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(ing) is opened, and has captured hydrochloric acid, has kept the normal performance of compressor.Under the situation of using the epoxy compounds only have an epoxy group(ing), can think that such effect is arranged, and when the epoxy compounds that adopts at least with two epoxy group(ing) this effect will be strong more than.

Used at least can be preferably between 0.05-10% (weight) in the weight of lubricant formulations with the amount of the epoxy compounds of two epoxy group(ing), 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 practical value.

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

Do not hindering under realization the object of the invention prerequisite, lubricant formulations of the present invention can contain one or more antioxidants, extreme pressure additive, materials such as antifoams.

For antioxidant, comparatively effective with phenolic compound.For preventing that base oil character from changing and weather resistance rotten and the maintenance base oil, preferably add phenolic compound fully.The add-on of antioxidant is preferably between the 0.01-5% (weight) by the weight of lubricant formulations.

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 cooling agent used in refrigerating compressor and the refrigeration unit, its critical temperature is preferably 40 ℃ or higher.

Critical temperature is that the example of 40 ℃ or higher carbon fluorine hydrogen cooling agent is methylene fluoride (R ₃₂) pentafluoride ethane (R125), 1,1,2,2-Tetrafluoroethane (R ₁₃₄), 1,1,1,2-Tetrafluoroethane (R _134a), 1,1,2-Halothane (R ₁₄₃), 1,1,1-Halothane (R _143a), 1,1-C2H4F2 C2H4F2 (R _152a), a fluoroethane (R ₁₆₁), or the like.

Critical temperature is that the example of 40 ℃ or higher carbon-fluorine-chlorine-hydrogen compound cooling agent is Dichloromonofluoromethane (R ₂₁), monochlorodifluoromethane (R ₂₂), a chlorine-1,2,2,2-Tetrafluoroethane (R ₁₂₄), 1-chlorine-1,1,2,2-Tetrafluoroethane (R _124a), pentafluoride ethane (R ₁₂₅), 1-chlorine-1,1-C2H4F2 C2H4F2 (R _142b), monochlorodifluoromethane (R ₂₂) and a chloropentafluoroethane (R ₁₁₅) azeotropic mixture (R ₅₀₂), or the like.

In these cooling agent, R ₁₃₄, R _134a, R ₁₄₃And R _143aBe comparatively desirable alternative R ₁₂Cooling agent because the boiling point of these cooling agent 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 cooling agent.

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 refrigeration unit keeps 40 ℃ or higher condensing temperature in condenser.

This lubricant formulations is used as the lubricating 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 sealed vessel, 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 rotation axis, one be connected with motor by rotation axis and at least a to be selected from critical temperature be 40 ℃ or the higher carbon-fluorine-hydrogen compound and the cooling agent of carbon-fluorine-chlorine-hydrogen compound, described refrigeration machine oil is exactly above-described lubricant formulations.

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 cooling agent or the reaction between base oil and the water be suppressed, coolant compressor can be worked under sufficiently stable state.So the refrigeration unit that has such coolant compressor also can stably be worked.Such refrigeration unit 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 refrigeration unit can be used as household electrical appliance, as refrigerator, dehumidifier, conditioner, or the like; Can be used for being equipped with in display stands and the beverage storage storehouse refrigeration unit of refrigeration cycle; And the refrigeration unit that needs refrigerant cycles, as self-contained air-conditioner and assembled Air Conditioner.

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

Example 1 to 10, comparative example 1 to 3

Make lubricant formulations listed in the table 2 all accept the check of cooling agent thermostability.The results are shown in Table 2.

Check the thermostability of cooling agent 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 cooling agent 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 reference colour is to estimate the degree that chemical reaction carries out between this oil and the cooling agent.

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 cooling agent 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 lubricant 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, 4-epoxy)-hexahydrobenzoic acid (3,4-epoxy) the lubricant formulations base oil colour-change 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 settling.In contrast, the sample in comparative example 1 does not contain any additives, has then formed copper coating and settling loathsomely.Like this, the stability of the cooling agent 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 settling under the condition that exists.This shows with comparative example 2 compares with 3, and the stability of cooling agent obviously improves.

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

Table 2

Routine number of test	Base oil	Viscosity (40 ℃ of following cst)	Additive *	Cooling agent	Probe temperature (℃)	The thermostability of cooling agent
									The color (ASTM) of oil	Copper coating * *	Settling
						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 134a R 134a R 22 R 22 R 22 R 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 134a R 22 R 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 134a R 134a R 134a R 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-hexahydrobenzoic acid (3,4-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 lubricant formulations 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 cooling agent 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 value of oil and refrigerant mixture according to the method (JIS K2501) of testing stone oil production 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 value (mg KOH/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 value are starkly lower than the total acid value 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 phenolic compound of chemical formula (8).

Example 18 to 21, comparative example 6 and 7

Carry out oxidation-stabilized property testing according to listed lubricant formulations 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 value (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 value after the heating only be about total acid value in 18 to 21 1/10 or lower.

This clearly illustrates that lubricant formulations of the present invention can also prevent deterioration by oxidation effectively.

Example 22

Fig. 1 is the front sectional elevation of a hermetically sealed rotary coolant compressor major portion.Fig. 2 is the sketch map of refrigerant cycles that expression has a kind of refrigeration unit of compressor shown in Figure 1.

In Fig. 1, cabinet of numbering 1 expression, this cabinet is one to can be used as the encloses 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 imide enamel paint on the coil.The core of stator and coiler part are isolated with the polyethylene terephthalate electrical insulating film.Precision work 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 rapid 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 babbitting jig 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 sourdine 28.Main bearing babbitting jig 5, cylinder body 2 and Volt nip of supplementary bearing 6 usefulness.Oil pumping room 12 by groove 8, main bearing babbitting jig 5 and the supplementary bearing of the rear side 11 of slide block 10, cylinder body 2 around forming.One suction apparatus 14 is arranged on the main bearing babbitting jig 5, and this device can extract the lubricant formulations of depositing cabinet 1 bottom 13 and the cooling agent 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 transition pipeline 15 to lubricant formulations 13 from pump chamber 12.The axle cavity 17 of rotating shaft 4A delivered to lubricant formulations 13 by transition pipeline 15.Lubricant formulations 13 passes a cavity 17 and and diverges hole 18 to the slipper 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 rapid steel is made promoted to-and-fro movement 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 transfer lime 29 through a cooling agent from the cooling agent of cooling agent 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 lubricant formulations that is dissolved with cooling agent or are exposed in the environment of spraying formation.

When use-case 1-6, when the lubricant formulations shown in 11-13 and 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 slipper 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 toheat and the anti-oxidant rotten performance of lubricant formulations yet owing to have fabulous thermostability.

Fig. 2 is the sketch map of refrigerating system in the refrigeration unit.In the drawings, label 40 expression compressors, label 41 expression condensers, label 45 expression moisture eliminators, label 42 expression expansion gears, label 43 expression vaporizers.Shown in example 21, irritate with lubricant formulations 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 moisture eliminator 45.Subsequent refrigerant liquid is sent to expansion gear 42 (for example an expansion valve or a kapillary).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.Cooling agent 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 working cycle is carried out in refrigeration unit repeatedly.

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

The condition of life test is as follows:

Motor coil temperature: 125 ℃

The top hole pressure of compressor: 13kg/cm ²G

Kapillary in the refrigerant cycles: internal diameter 0.65mm

Cooling agent: R _134a

Envrionment temperature: 40 ℃

Lubricant formulations: example 7 or 9

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

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

In contrast, when in lubricant formulations, not adding glycidyl ether compound, the metallic soap deposition in kapillary, occurs, stopped up passage.

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

Claims (9)

1. solvable mixing in the lubricant formulations of carbon-fluorine-hydrogen compound and carbon-fluorine-chlorine-hydrogen compound cooling agent, comprise as base oil, be selected from least a in the one group of material that forms by ester oil, alkylbenzene oil and mineral oil, and a kind of have at least two epoxy group(ing), content is calculated as the epoxy compounds of 0.05 to 10% (weight) by the weight of this lubricant formulations.

2. a lubricant formulations as claimed in claim 1 is characterized in that also further comprising that a kind of content is calculated as the phenolic antioxidant of 0.01 to 5% (weight) by the weight of this lubricant formulations.

3. lubricant formulations as claimed in claim 1 is characterized in that described epoxy compounds is to be selected from least a in one group that is made up of aklylene glycol diglycidyl ether and alicyclic ring epoxy compound.

4. lubricant formulations as claimed in claim 3 is characterized in that described aklylene glycol diglycidyl ether is to be selected from least a in one group that is made up of the compound of following structural:

R wherein ₁It is an alkylidene group; R ₂Be a hydrogen atom or an alkyl, n is an integer of 1 to 22,

The compound that a kind of structural formula is following:

The compound that a kind of structural formula is following:

And the following compound of a kind of structural formula:

5. lubricant formulations as claimed in claim 3 is characterized in that described alicyclic ring epoxy compound is the compound that the structural formula below a kind of usefulness is represented:

6. lubricant formulations as claimed in claim 4, the compound that it is characterized in that structural formula (1) are to be selected from least a in the middle of one group that the compound represented by following structural forms:

Wherein n is an integer of 1 to 22, and the compound represented of following structural formula: Wherein n is an integer of 1 to 20.

7. lubricant formulations as claimed in claim 2 is characterized in that described phenolic antioxidant is to be selected from least a in the middle of one group that the compound represented by following structural forms:

Wherein X is an integer of 1 to 3, and the compound represented of following structural formula:

Wherein X is an integer of 1 to 3.

8. the application of the lubricant formulations of claim 1 is used for coolant compressor, and described coolant compressor comprises that one accommodates this lubricant formulations, and the encloses container of a motor is housed therein in the bottom, and described motor is made of rotor and stator; 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, and at least a to be selected from critical temperature be 40 ℃ or the higher carbon-fluorine-hydrogen compound and the cooling agent of carbon-fluorine-chlorine-hydrogen compound.

9. the application of the lubricant formulations of claim 1, be used for refrigeration unit, described refrigeration unit comprises that a compressor, condenser, expansion gear, vaporizer and some connect these parts and make a kind of cooling agent round-robin pipe between them.

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