CN101851545A - Refrigerator oil composition - Google Patents
Refrigerator oil composition Download PDFInfo
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- CN101851545A CN101851545A CN 200910131994 CN200910131994A CN101851545A CN 101851545 A CN101851545 A CN 101851545A CN 200910131994 CN200910131994 CN 200910131994 CN 200910131994 A CN200910131994 A CN 200910131994A CN 101851545 A CN101851545 A CN 101851545A
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Abstract
The invention relates to a refrigerator oil composition, which comprises polyol ester, (3,5-dialkyl-4-hydroxyphenyl) carboxylic thiophenyl alkyl ester, an antiwear agent, a metal passivator and an acid catching agent, wherein the polyol ester is pentaerythritol tetranitrate generated by reacting pentaerythritol with a mixture of isononanoic acid and diethyl caproic acid. The refrigerator oil composition provided by the invention has excellent oxidation stability. Compared with that of the refrigerator oil using the conventional antioxidant, the oxidative induction time of the refrigerator oil composition is obviously prolonged.
Description
Technical field
The present invention relates to a kind of refrigerated machine oil composition.
Background technology
Widely used in the past Chlorofluorocarbons (CFCs), Hydrochlorofluorocarbons refrigeration agent chemical stability are good, leak into and be difficult in the air decomposing in the troposphere, in case when entering into the stratosphere at ozonosphere place by general circulation, under the irradiation of short wave ultraviolet, can decomposite chlorine radical, participated in the consumption of ozone, ozonosphere in the atmosphere is produced destruction, replaced at present by not chloride hydrogen fluorohydrocarbon (HFCs) refrigeration agent.
Synthetic ester (POE) has good mutual solubility, stability and material compatibility, and the reliable and safety of lubricity, environmental protection have become the first-selected lubricating oil of hydrogen fluorohydrocarbon (HFCs) class material.
Different with general lubricating oil, refrigerator oil is with refrigeration agent circulation continuously between the vaporizer of the compressor outlet of high-temperature zone and cold zone, its operating temperature range very wide and with the same life-span of compressor, therefore for refrigerator oil, except should having good lubricated, sealing, cooling and antiseptic property, oxidation stability is even more important.
One of approach that improves the oil product life-span is to add oxidation inhibitor.The kind of oxidation inhibitor is a lot, mainly comprises phenol type, amine type, phenolic ester type, monothioester type, phosphite type etc.Wherein, the hindered phenol type antioxidant refrigerator oil that is widely used, Te Xu Gong Open 2001-226690 for example, CN1135594A, it is primary antioxidant that CN1157848A, CN1836030A, CN1930276A, CN101018844A etc. all adopt hindered phenol type antioxidant.But,, therefore adopt general hindered phenol type antioxidant may be difficult to satisfy the stable and long lifetime requirement of oxidation owing to compressor operating pressure and the working temperature with the fluoroether refrigerant coupling all will be higher than former compressor.CN1235191A has adopted the sulfur-bearing phenol type antioxidant, and its antioxidant property is not outstanding.
For with (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester as refrigerator oil oxidation inhibitor, still do not have bibliographical information both at home and abroad.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of refrigerated machine oil composition, and said composition has good oxidative stability.
Refrigerated machine oil composition provided by the invention is 100% in the weight of polyol ester, comprising:
(1) polyol ester;
(2) (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester, content are 0.01～2 heavy %;
(3) anti-wear agent, content are 0.05～2 heavy %;
(4) metal passivator, content are 0.01～0.2 heavy %;
(5) acid-capture agent, content are 0.01～1 heavy %;
Described polyol ester is four esters of tetramethylolmethane and different n-nonanoic acid and diethyl caproic acid mixture reaction, and the ratio of wherein different n-nonanoic acid and diethyl caproic acid is 10: 1～1: 10;
Described (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester structural formula is:
Wherein, R
1Be C
1～C
5Alkyl, R
2Be C
1～C
4Alkyl, R
3, R
4Be C
1～C
8Alkyl.
Described polyol ester is four esters of tetramethylolmethane and different n-nonanoic acid and diethyl caproic acid mixture reaction, the ratio of wherein different n-nonanoic acid and diethyl caproic acid is preferably 4: 6～and 6: 4.
In described (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester, R
1Be preferably ethyl, propyl group or butyl, R
2Be preferably ethyl or propyl group, R
3, R
4Be preferably the tertiary butyl.
In base oil weight is 100%, and the content of (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester is preferably 0.05～1.5%, more preferably 0.2～1%.
The preparation method of (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester mixes thiophenyl alkyl alcohol and (3,5-dialkyl group-4-hydroxy phenyl) alkyl carboxylates, in the presence of the lithium hydroxide catalyzer, reacts and separated product.
Reaction conditions is pressure 0.0001～0.1MPa, is preferably 0.001～0.09MPa, and temperature of reaction is 60 ℃～220 ℃, is preferably 100 ℃～200 ℃.Reaction times is 1～30 hour, is preferably 3～8 hours.
Wherein the lithium hydroxide catalyst consumption is 0.1～10% of (3,5-dialkyl group-4-hydroxy phenyl) alkyl carboxylates weight, is preferably 0.2～3%.
Obtain thick material after reaction is finished, can remove unreacted raw material, obtain the transparent thick liquid of red-brown by underpressure distillation.With the transparent thick liquid organic solvent dissolution of red-brown, remove by filter catalyzer, remove then and desolvate, obtain (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester (hereinafter to be referred as the sulfur-bearing phenolic ester).
Said solvent can be selected from toluene, ethanol, one or more in ethyl acetate, acetone, the chloroform.
Reaction formula is as shown below:
Anti-wear agent is one or more in alkyl zinc dithiophosphate, benzyl disulfide thing, sulfide isobutene, tritolyl phosphate (T306), triphenylphosphate and the boronation oleylamide, preferably tritolyl phosphate.The content of anti-wear agent is preferably 0.5～1.5 heavy %.
Metal passivator is selected from 124 Triazole derivative (T551) and/or thiadiazoles derivative (T561), is preferably T551.The content of metal passivator is preferably 0.02～0.1 heavy %.
Acid-capture agent is selected from one or more in alkyl glycidyl ether type epoxy compounds and the epoxidized vegetable oil, be preferably in phenyl glycidyl ether, decyl glycidyl ether, tetramethylolmethane four glycidyl ethers, epoxy soybean oil, epoxy rapeseed oil, the epoxy Oleum Gossypii semen one or more, more preferably epoxy soybean oil.Acid-capture agent in composition content be preferably 0.2～1 heavy %.
The present invention is base oil with the polyol ester, with (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester is an oxidation inhibitor, provide a kind of oxidation stability energy excellent refrigerated machine oil composition, compared with the refrigerator oil that uses conventional oxidation inhibitor, oxidation induction period obviously prolongs.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.
Embodiment 1
(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate of 0.2mol (30.8g) thiophenyl ethanol and 0.24mol (70.08g) is put into three mouthfuls of reaction flasks of 250ml, add the 0.4gLiOH catalyzer, stir, heat.Be decompressed to 0.02Mpa, temperature is 120 ℃, reacts 3 hours.Obtain thick material, color is a light brown.Heat up 260 ℃, the raw material that there is not reaction is removed in underpressure distillation.Obtain the transparent thick liquid of red-brown.Product yield is 83.6%.
Embodiment 2
(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate of 0.2mol (30.8g) thiophenyl ethanol and 0.24mol (70.08g) is put into three mouthfuls of reaction flasks of 250ml, add the 0.8gLiOH catalyzer, stir, heat.Be decompressed to 0.085Mpa, temperature is 180 ℃, reacts 5 hours.Obtain thick material, color is a light brown.Heat up 260 ℃, the raw material that there is not reaction is removed in underpressure distillation.Obtain the transparent thick liquid of red-brown.Product yield is 95.1%.
Embodiment 3
(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate of 0.2mol (30.8g) thiophenyl ethanol and 0.24mol (70.08g) is put into three mouthfuls of reaction flasks of 250ml, add the 1gLiOH catalyzer, stir, heat.Be decompressed to 0.005Mpa, temperature is 160 ℃, reacts 8 hours.Obtain thick material, color is a light brown.Heat up 260 ℃, the raw material that there is not reaction is removed in underpressure distillation.Obtain the transparent thick liquid of red-brown.Product yield is 95.7%.
Embodiment 4～7
(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid thiophenyl ethyl ester (being called for short the sulfur-bearing phenolic ester) that embodiment 1 is obtained joins in the base oil according to ratio shown in the table 1, is deployed into refrigerated machine oil composition.The performance test results sees Table 3.
Table 1
Comparative example 1～3
Be deployed into the prescription of refrigerator oil according to ratio shown in the table 2, The performance test results sees Table 3.
Table 2
Composition to the foregoing description and comparative example carries out performance test, the results are shown in following table 3.
Table 3
Test condition: 190 ℃, 0.5MPa, heat-up rate are 50 ℃/min
Claims (10)
1. refrigerated machine oil composition is 100% in the weight of polyol ester, comprising:
(1) polyol ester;
(2) (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester, content are 0.01～2 heavy %;
(3) anti-wear agent, content are 0.05～2 heavy %;
(4) metal passivator, content are 0.01～0.2 heavy %;
(5) acid-capture agent, content are 0.01～1 heavy %;
Described polyol ester is four esters of tetramethylolmethane and different n-nonanoic acid and diethyl caproic acid mixture reaction, and the ratio of wherein different n-nonanoic acid and diethyl caproic acid is 10: 1～1: 10;
Described (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester structural formula is:
Wherein, R
1Be C
1～C
5Alkyl, R
2Be C
1～C
4Alkyl, R
3, R
4Be C
1～C
8Alkyl.
2. according to the described composition of claim 1, it is characterized in that described polyol ester is four esters of tetramethylolmethane and different n-nonanoic acid and diethyl caproic acid mixture reaction, the ratio of wherein different n-nonanoic acid and diethyl caproic acid is 4: 6～6: 4.
3. according to the described composition of claim 1, it is characterized in that, in described (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester, R
1Be ethyl, propyl group or butyl, R
2Be ethyl or propyl group, R
3, R
4Be the tertiary butyl.
4. according to claim 1,2 or 3 described compositions, it is characterized in that the content of (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester is 0.05～1.5%.
5. according to the described composition of claim 4, it is characterized in that the content of (3,5-dialkyl group-4-hydroxy phenyl) carboxylic acid thiophenyl alkyl ester is 0.2～1%.
6. according to the described composition of claim 1, it is characterized in that metal passivator is selected from 124 Triazole derivative and/or thiadiazoles derivative.
7. according to claim 1 or 6 described compositions, it is characterized in that the content of metal passivator is 0.02～0.1 heavy %.
8. according to the described composition of claim 1, it is characterized in that anti-wear agent is selected from one or more in alkyl zinc dithiophosphate, benzyl disulfide thing, sulfide isobutene, tritolyl phosphate, triphenylphosphate and the boronation oleylamide.
9. according to the described composition of claim 1, it is characterized in that acid-capture agent is selected from one or more in alkyl glycidyl ether type epoxy compounds and the epoxidized vegetable oil.
10. according to the described composition of claim 9, it is characterized in that acid-capture agent is selected from one or more in phenyl glycidyl ether, decyl glycidyl ether, tetramethylolmethane four glycidyl ethers, epoxy soybean oil, epoxy rapeseed oil, the epoxy Oleum Gossypii semen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910131994 CN101851545A (en) | 2009-03-31 | 2009-03-31 | Refrigerator oil composition |
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|---|---|---|---|
| CN 200910131994 CN101851545A (en) | 2009-03-31 | 2009-03-31 | Refrigerator oil composition |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453612A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method for biodiesel, and low freezing point biodiesel prepared by the same |
| CN104725222A (en) * | 2015-01-28 | 2015-06-24 | 黄小平 | Base oil of refrigerator oil, preparation method of base oil, refrigerator oil composition prepared from base oil and preparation method of refrigerator oil composition |
| CN106605108A (en) * | 2014-07-31 | 2017-04-26 | 江森自控日立空调技术（香港）有限公司 | Air conditioner |
| CN107406799A (en) * | 2015-03-30 | 2017-11-28 | 出光兴产株式会社 | Lubricant for refrigerator and mixed composition for refrigerator |
| CN108138073A (en) * | 2015-09-25 | 2018-06-08 | 爱德龙润滑油公司 | Lubricant compositions |
| CN108517247A (en) * | 2018-05-19 | 2018-09-11 | 武汉诺通润滑科技有限公司 | A kind of synthesis refrigerator oil and preparation method thereof |
| EP2771441B1 (en) | 2011-10-27 | 2018-10-03 | The Lubrizol Corporation | Lubricants with improved seal compatibility |
| CN114540108A (en) * | 2022-03-17 | 2022-05-27 | 江西苏克尔新材料有限公司 | Lubricating oil composition and preparation method and application thereof |
-
2009
- 2009-03-31 CN CN 200910131994 patent/CN101851545A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453612A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method for biodiesel, and low freezing point biodiesel prepared by the same |
| CN102453612B (en) * | 2010-10-26 | 2014-03-12 | 中国石油化工股份有限公司 | Preparation method for biodiesel, and low freezing point biodiesel prepared by same |
| EP2771441B1 (en) | 2011-10-27 | 2018-10-03 | The Lubrizol Corporation | Lubricants with improved seal compatibility |
| US10907112B2 (en) | 2011-10-27 | 2021-02-02 | The Lubrizol Corporation | Lubricants with improved seal compatibility |
| CN106605108A (en) * | 2014-07-31 | 2017-04-26 | 江森自控日立空调技术（香港）有限公司 | Air conditioner |
| CN104725222A (en) * | 2015-01-28 | 2015-06-24 | 黄小平 | Base oil of refrigerator oil, preparation method of base oil, refrigerator oil composition prepared from base oil and preparation method of refrigerator oil composition |
| CN107406799A (en) * | 2015-03-30 | 2017-11-28 | 出光兴产株式会社 | Lubricant for refrigerator and mixed composition for refrigerator |
| EP3279295A4 (en) * | 2015-03-30 | 2018-10-10 | Idemitsu Kosan Co.,Ltd. | Refrigerator lubricating oil and mixed composition for refrigerator |
| US10557103B2 (en) | 2015-03-30 | 2020-02-11 | Idemitsu Kosan Co., Ltd. | Refrigerator lubricating oil and mixed composition for refrigerator |
| CN108138073A (en) * | 2015-09-25 | 2018-06-08 | 爱德龙润滑油公司 | Lubricant compositions |
| CN108517247A (en) * | 2018-05-19 | 2018-09-11 | 武汉诺通润滑科技有限公司 | A kind of synthesis refrigerator oil and preparation method thereof |
| CN114540108A (en) * | 2022-03-17 | 2022-05-27 | 江西苏克尔新材料有限公司 | Lubricating oil composition and preparation method and application thereof |
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Application publication date: 20101006 |