CN1315492A - Lubricating oil for refrigerating machine - Google Patents

Lubricating oil for refrigerating machine Download PDF

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CN1315492A
CN1315492A CN 00105312 CN00105312A CN1315492A CN 1315492 A CN1315492 A CN 1315492A CN 00105312 CN00105312 CN 00105312 CN 00105312 A CN00105312 A CN 00105312A CN 1315492 A CN1315492 A CN 1315492A
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acidic group
formula
fatty acid
acid
unary fatty
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CN1101459C (en
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丁铭
刘国文
张天巧
杨娟
徐珂
张士赢
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
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Abstract

A novel polyolester oil for refrigerating machine is prepared through the reaction of trihydroxymethylpropane or pentaerythritol on equivalent naphthenic acid and further reaction with excess saturated monoacid. The composition of the working fluid containing polyol ester for refrigerating machine is also disclosed.

Description

Refrigerator oil
The present invention relates to novel refrigerator oil, specifically the present invention relates to the polyol ester refrigerator oil.
For the protection ozonosphere, limited the Refrigerant 12 (CFCl2) that uses as refrigeration agent.Now developed the hydrogen fluorohydrocarbon as 1,1,1,2-Tetrafluoroethane (HFC134a) as refrigeration agent with substitute CFC l2.Because the polarity of HF134a is much larger than CFCl2, so lubricating oil and the HFC134a that uses with CFCl2 was incompatible originally, so need are researched and developed new lubricating oil.
EP 0501 440A1 discloses a kind of polyol ester refrigerator oil, and ester cpds wherein is by aliph polyols and the reaction of straight or branched saturated fatty monoprotic acid or derivatives thereof, and reaction makes with straight or branched saturated fatty diprotic acid or derivatives thereof again; Or by aliph polyols and the reaction of straight or branched saturated fatty diprotic acid or derivatives thereof, reaction makes with straight or branched saturated fatty monohydroxy-alcohol again.But the viscosity and the viscosity-temperature index of product are not ideal enough.
EP 0632 124A1 also discloses a kind of polyol ester class lubricating oil, and ester cpds is wherein made with the first acid-respons of fat by saturated fatty monohydroxy-alcohol or aliph polyols and the reaction of carboxyl carboxylic acid condenses again.
Do not see in the prior art to have by naphthenic acid to prepare polyol ester, the polyol ester viscosity-temperature index that makes with the present invention makes moderate progress, and viscosity reaches requirement, and thermostability also increases, and also increases with the intermiscibility of refrigeration agent HFC134a.
Therefore, the invention provides a kind of polyol ester on the one hand as refrigerator oil with following formula
R wherein, R 1, R 2And R 3Be 4～10 the saturated unary fatty acid base of straight or branched for containing the cycloalkanes acidic group of 4～9 yuan of rings or carbonatoms independently, supplementary condition are for formula I, R, R 1, R 2One of be the cycloalkanes acidic group, all the other are the unary fatty acid base; For formula (2), R, R 1, R 2, R 3One of be the cycloalkanes acidic group, all the other are the unary fatty acid base.
On the other hand, the invention provides a kind of method for preparing the following formula polyol ester.
Figure A0010531200051
This method comprise with TriMethylolPropane(TMP) or tetramethylolmethane earlier with the naphthenic acid reaction of equivalent, be the saturated unary fatty acid reaction of straight or branched of 4-10 with excessive carbonatoms again, reclaim the polyol ester of prepared formula I or formula II.
The term naphthenic acid that is used for herein refers to saturated monobasic alicyclic acid, preferably contain 5 yuan of rings or 6 yuan of rings and be cyclopentyl formic acid or hexahydrobenzoic acid, and composition thereof.
Carbonatoms is the mixture that 4～10 the saturated unary fatty acid of straight or branched comprises butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid and isomers or two or more unary fatty acids.
Esterification of the present invention is by pure and mild acid-respons, and catalyst-free also can carry out, but preferably adds catalyzer.Catalyzer commonly used is an an acidic catalyst, preferred p-methyl benzenesulfonic acid.
TriMethylolPropane(TMP) or tetramethylolmethane earlier with the naphthenic acid reaction of equivalent with its on a hydroxyl become ester, make the hydroxyl of remainder become ester with excessive unary fatty acid reaction again.Reclaim product with ordinary method then.
Catalyst levels accounts for 0.1%～3% of charging capacity weight.The mol ratio of polyvalent alcohol and naphthenic acid is 1: 1～1: 1.2.The more theoretical consumption of the consumption of unary fatty acid excessive at least 10%, preferred excessive 50%.Adopt toluene as azeotropic agent, institute's consumption accounts for 60% of used sour volume.Reacted the back by with alkali as the washing of 5% sodium carbonate solution, catalyzer and excessive acid are removed in washing then, and is clay-filtered, often, underpressure distillation removes azeotropic agent and acid, obtains target product.
But be used for buying on the unary fatty acid of the present invention market.
Being used for naphthenic acid of the present invention can or buy from the market by the means known in the art preparation.
In an embodiment preferred, naphthenic acid is a kind of by product that extract from refinery alkali cleaning waste residue, mainly contains cyclopentyl formic acid, a small amount of hexahydrobenzoic acid and encircle carboxylic acid more.
Naphthenic acid from refinery comes out wherein contains many impurity, generally passes through decolouring and deodorizing, removes neutral oil and takes off the refining course of processing of lipid acid three parts, obtains refining naphthenic acid to reach the quality index of the market requirement.
If the refining naphthenic acid impurity component on the market is more, hydro carbons especially, will to the performance of polyol ester particularly condensation point bigger influence is arranged.Therefore, further refining to naphthenic acid with this area routine techniques such as saponifiable extraction, acidifying washing and rectifying.
Naphthenic acid after preferably being made with extra care by the refinery byproduct has as the routine performance of following table I:
The table I
Density (20 ℃) kg/m 3 Acid number mgKOH/g Naphthenic acid content weight % Fatty acid content weight % Phenol content weight % Moisture weight % Boiling range ℃
960.4 217.19 91.01％ 2.41％ 1.97％ 0.12％ 220-320
Derive from the by-product cyclic alkanoic acid aboundresources of refinery, produce naphthenate but be mainly used at present, added value is not high, as is used for the present invention and can improves added value greatly.
Polyol ester of the present invention can be used as machine oil or lubricating oil in the working fluid of refrigerator or automative air conditioning.
The polyol ester of formula I can be used the refrigerator oil of rotary compressor home freezer.
The polyol ester of formula II can be used as inclined disc type and the refrigerator oil reciprocation compressor automative air conditioning.
Therefore, the present invention further provides a kind of composition as hydraulic fluid for refrigerator, said composition comprises the polyol ester of (a) following formula I or II
Figure A0010531200061
R wherein, R 1, R 2And R 3Be 4～10 straight or branched unary fatty acid base for containing the cycloalkanes acidic group of 4～9 yuan of rings or carbonatoms independently, supplementary condition are for formula I, R, R 1, R 2One of be the cycloalkanes acidic group, all the other are the unary fatty acid base; For formula II, R, R 1, R 2, R 3One of be the cycloalkanes acidic group, all the other are the unary fatty acid base; With
(b)HFC134a
In the composition (a), (b) two kinds of material proportionings can change in wide range, and for example volume ratio is 1: 99～99: 1.
In composition of the present invention, also can contain the various conventional additives in this area, only otherwise have disadvantageous effect to get final product to the performance of the present composition.
The following examples further specify the present invention, but scope of the present invention is not subjected to the influence of these embodiment.The analytical procedure standard is as follows among the embodiment: viscosity adopts GB/T265, viscosity-temperature index adopts GB/T2541, condensation point adopts GB/T510, flash-point adopts GB/T3536, and acid number adopts GB/T4945, and density adopts GB/T1884, moisture adopts GB/T260, the intermiscibility measuring method is for to add a heavy wall Glass tubing (pipe range 300mm, external diameter 10mm, internal diameter 6mm) with 1ml product and 9ml refrigeration agent HFC134a.Put into a thermostatic bath then, whether temperature the isolating phenomenon of two-phase occurs from-50 ℃～+ 80 ℃ variations in the sight glass pipe.
Among the embodiment, used naphthenic acid is meant the naphthenic acid with the listed performance of table I below.
Embodiment 1
In being housed, two mouthfuls of flasks of branch water condenser and thermometer add TriMethylolPropane(TMP) 20.21g, naphthenic acid 34.36g, and toluene 32ml, catalyzer p-methyl benzenesulfonic acid 0.52g, reacting by heating is not till having water to generate.Cooling adds valeric acid 41ml then, catalyzer p-methyl benzenesulfonic acid 0.41g, and toluene 14ml, reacting by heating is not till having water to generate.Reactant washs to weakly alkaline with 5% sodium carbonate solution, and extremely neutral with saturated metabisulfite solution washing again, through clay-filtered, underpressure distillation (12mmHg) is to 200 ℃, and still liquid is product, the color golden yellow.Product analysis data such as following table 2.
Embodiment 2
In being housed, two mouthfuls of flasks of branch water condenser and thermometer add TriMethylolPropane(TMP) 20.16g, naphthenic acid 34.72g, toluene 36ml, catalyzer p-methyl benzenesulfonic acid 0.54g, reacting by heating is not till having water to generate, and cooling adds caproic acid 47ml, catalyzer p-methyl benzenesulfonic acid 0.40g then, toluene 15ml, reacting by heating is not till having water to generate.Reactant washs to weakly alkaline with 5% sodium carbonate solution, and extremely neutral with saturated metabisulfite solution washing again, through clay-filtered, underpressure distillation (12mmHg) is to 200 ℃, and still liquid is product, the color golden yellow.Product analysis data such as following table 2.
Embodiment 3
In being housed, two mouthfuls of flasks of branch water condenser and thermometer add TriMethylolPropane(TMP) 20.11g, naphthenic acid 34.32g, toluene 36ml, catalyzer p-methyl benzenesulfonic acid 0.60g, reacting by heating is not till having water to generate, and cooling adds enanthic acid 54ml, catalyzer p-methyl benzenesulfonic acid 0.50g then, toluene 16ml, reacting by heating is not till having water to generate.Reactant washs to weakly alkaline with 5% sodium carbonate solution, and extremely neutral with saturated metabisulfite solution washing again, through clay-filtered, underpressure distillation (12mmHg) is to 200 ℃, and still liquid is product, the color golden yellow.Product analysis data such as following table 2.
Embodiment 4
In being housed, two mouthfuls of flasks of branch water condenser and thermometer add TriMethylolPropane(TMP) 20.13g, naphthenic acid 32.46g, toluene 36ml, catalyzer p-methyl benzenesulfonic acid 0.48g, reacting by heating is not till having water to generate, and cooling adds sad 59ml, catalyzer p-methyl benzenesulfonic acid 0.41g then, toluene 18ml, reacting by heating is not till having water to generate.Reactant washs to weakly alkaline with 5% sodium carbonate solution, and extremely neutral with saturated metabisulfite solution washing again, through clay-filtered, underpressure distillation (12mmHg) is to 200 ℃, and still liquid is product, the color golden yellow.Product analysis data such as following table 2.
Embodiment 5
In being housed, two mouthfuls of flasks of branch water condenser and thermometer add tetramethylolmethane 13.70g, naphthenic acid 26.65g, toluene 36ml, catalyzer p-methyl benzenesulfonic acid 0.51g, reacting by heating is not till having water to generate, and cooling adds caproic acid 49ml, catalyzer p-methyl benzenesulfonic acid 0.45g then, toluene 15ml, reacting by heating is not till having water to generate.Reactant washs to weakly alkaline with 5% sodium carbonate solution, and extremely neutral with saturated metabisulfite solution washing again, through clay-filtered, underpressure distillation (12mmHg) is to 200 ℃, and still liquid is product, the color golden yellow.Product analysis data such as following table 2.
Embodiment 6 adds tetramethylolmethane 13.69g in two mouthfuls of flasks of branch water condenser and thermometer are housed, naphthenic acid 27.00g, toluene 36ml, catalyzer p-methyl benzenesulfonic acid 0.51g, reacting by heating is not till having water to generate, and cooling adds caproic acid 54ml, catalyzer p-methyl benzenesulfonic acid 0.45g then, toluene 15ml, reacting by heating is not till having water to generate.Reactant washs to weakly alkaline with 5% sodium carbonate solution, and extremely neutral with saturated metabisulfite solution washing again, through clay-filtered, underpressure distillation (12mmHg) is to 200 ℃, and still liquid is product, the color golden yellow.Product analysis data such as following table 2.
Embodiment 7
In being housed, two mouthfuls of flasks of branch water condenser and thermometer add tetramethylolmethane 13.69g, naphthenic acid 26.55g, toluene 36ml, catalyzer p-methyl benzenesulfonic acid 0.51g, reacting by heating is not till having water to generate, and cooling adds sad 60ml, catalyzer p-methyl benzenesulfonic acid 0.45g then, toluene 15ml, reacting by heating is not till having water to generate.Reactant washs to weakly alkaline with 5% sodium carbonate solution, and extremely neutral with saturated metabisulfite solution washing again, through clay-filtered, underpressure distillation (12mmHg) is to 200 ℃, and still liquid is product, the color golden yellow.Product analysis data such as following table 2.
Table 2 product performance analytical table
Figure A0010531200091

Claims (7)

  1. One kind have following formula as the polyol ester class of refrigerator oil:
    Figure A0010531200021
    R wherein, R 1, R 2And R 3Be 4～10 straight or branched unary fatty acid base for containing the cycloalkanes acidic group of 4～9 yuan of rings or carbonatoms independently, supplementary condition are for formula I, R, R 1, R 2One of be the cycloalkanes acidic group, all the other are the unary fatty acid base; For formula II, R, R 1, R 2, R 3One of be the cycloalkanes acidic group, all the other are the unary fatty acid base.
  2. 2. according to the polyol ester of claim 1, wherein the cycloalkanes acidic group contains five yuan or six-ring.
  3. 3. according to the polyol ester of claim 1, wherein the cycloalkanes acidic group is the byproduct naphthenic acid deutero-by refinery.
  4. 4. the method for preparing the polyol ester that is used as refrigerator oil of following formula R wherein, R 1, R 2And R 3Be 4～10 straight or branched unary fatty acid base for containing the cycloalkanes acidic group of 4～9 yuan of rings or carbonatoms independently, supplementary condition are for formula I, R, R 1, R 2One of be the cycloalkanes acidic group, all the other are the unary fatty acid base; For formula II, R, R 1, R 2, R 3One of be the cycloalkanes acidic group, all the other are the unary fatty acid base,
    This method comprises the naphthenic acid reaction with TriMethylolPropane(TMP) or tetramethylolmethane elder generation and equivalent, is the saturated unary fatty acid reaction of straight or branched of 4-10 with carbonatoms again, reclaims the polyol ester of prepared formula I or formula II.
  5. 5. according to the method for claim 4, wherein naphthenic acid is cyclopentyl formic acid, hexahydrobenzoic acid and composition thereof.
  6. 6. according to the method for claim 4, wherein naphthenic acid is the naphthenic acid after being made with extra care by the refinery byproduct.
  7. 7. composition as hydraulic fluid for refrigerator, said composition comprises:
    (a) polyol ester of following formula I or II
    Figure A0010531200031
    R wherein, R 1, R 2And R 3Be 4～10 straight or branched unary fatty acid base for containing the cycloalkanes acidic group of 4～9 yuan of rings or carbonatoms independently, supplementary condition are for formula I, R, R 1, R 2One of be the cycloalkanes acidic group, all the other are the unary fatty acid base; For formula II, R, R 1, R 2, R 3One of be the cycloalkanes acidic group, all the other are the unary fatty acid base; With
    (b)HFC134a。
CN00105312A 2000-03-31 2000-03-31 Lubricating oil for refrigerating machine Expired - Lifetime CN1101459C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100344738C (en) * 2003-11-21 2007-10-24 日本油脂株式会社 Refrigeration lubricant composition
CN1869177B (en) * 2005-05-27 2012-01-04 日油株式会社 Refrigeration lubricant composition
CN101568625B (en) * 2007-03-27 2012-10-31 新日本石油株式会社 Refrigerator oil and working fluid composition for refrigerating machine
CN104145006A (en) * 2012-03-02 2014-11-12 吉坤日矿日石能源株式会社 Working fluid composition for refrigerator, refrigeration oil, and method for producing same
CN108676603A (en) * 2018-06-27 2018-10-19 中国石油化工股份有限公司 The fine purification treatment process and refined high viscosity esters base oil of a kind of high viscosity esters base oil

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0501440A1 (en) * 1991-02-26 1992-09-02 Kao Corporation Composition for refrigerator working fluid use
JPH0559038A (en) * 1991-09-06 1993-03-09 Terumo Corp Thiourea derivative and medicine preparation containing the same
SG59958A1 (en) * 1993-06-30 1999-02-22 Nof Corp Synthetic lubricating oil and working fluid composition for refrigeration machine

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100344738C (en) * 2003-11-21 2007-10-24 日本油脂株式会社 Refrigeration lubricant composition
CN1869177B (en) * 2005-05-27 2012-01-04 日油株式会社 Refrigeration lubricant composition
CN101568625B (en) * 2007-03-27 2012-10-31 新日本石油株式会社 Refrigerator oil and working fluid composition for refrigerating machine
CN104145006A (en) * 2012-03-02 2014-11-12 吉坤日矿日石能源株式会社 Working fluid composition for refrigerator, refrigeration oil, and method for producing same
US9469801B2 (en) 2012-03-02 2016-10-18 Jx Nippon Oil & Energy Corporation Working fluid composition for refrigerator, refrigeration oil, and method for producing same
CN108676603A (en) * 2018-06-27 2018-10-19 中国石油化工股份有限公司 The fine purification treatment process and refined high viscosity esters base oil of a kind of high viscosity esters base oil

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