阅读说明：本技术 一种合成植物型液压油 (Synthetic plant type hydraulic oil ) 是由 汤倩云 刘月皞 康涛 赵玉贞 马楷 于 2019-10-25 设计创作，主要内容包括：本发明提供了一种合成植物型液压油,按照以下步骤制得：A)将混合直链脂肪酸、多元醇和催化剂混合,进行酯化反应,得到酯化产物；所述混合直链脂肪酸为正癸酸及其同分异构体、正十四酸、正十六酸、正十八酸、油酸、亚油酸、亚麻酸中的一种或几种；所述多元醇为单季戊四醇、双季戊四醇、甘油、新戊二醇、三羟甲基丙烷中的一种或几种；所述混合直链脂肪酸与多元醇的质量比为(2～6)：1；B)将酯化产物、极压抗磨剂、抗氧剂和金属钝化剂混合,调配得到合成植物型液压油；所述抗氧剂为2,6-二叔丁基对甲酚、四(β-(3,5-二叔丁基-4-羟基苯基)丙酸)季戊四醇酯和二异辛基二苯胺多聚物中的一种或几种。(The invention provides synthetic plant type hydraulic oil which is prepared by the following steps: A) mixing the mixed straight-chain fatty acid, the polyol and the catalyst, and carrying out esterification reaction to obtain an esterification product; the mixed straight-chain fatty acid is one or more of n-decanoic acid and isomers thereof, n-tetradecanoic acid, n-hexadecanoic acid, n-octadecanoic acid, oleic acid, linoleic acid and linolenic acid; the polyhydric alcohol is one or more of monopentaerythritol, dipentaerythritol, glycerol, neopentyl glycol and trimethylolpropane; the mass ratio of the mixed straight-chain fatty acid to the polyhydric alcohol is (2-6): 1; B) mixing the esterification product, the extreme pressure antiwear agent, the antioxidant and the metal passivator, and blending to obtain synthetic vegetable hydraulic oil; the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and diisooctyl diphenylamine polymer.)

1. A synthetic plant type hydraulic oil is prepared by the following steps:

A) mixing the mixed straight-chain fatty acid, the polyol and the catalyst, and carrying out esterification reaction to obtain an esterification product;

the mixed straight chain fatty acid is two or more of n-decanoic acid, isomers of n-decanoic acid, n-tetradecanoic acid, n-hexadecanoic acid, n-octadecanoic acid, oleic acid, linoleic acid and linolenic acid;

the polyhydric alcohol is one or more of monopentaerythritol, dipentaerythritol, glycerol, neopentyl glycol and trimethylolpropane;

the mass ratio of the mixed straight-chain fatty acid to the polyhydric alcohol is (2-6): 1;

B) mixing the esterification product with an additive, and blending to obtain synthetic plant type hydraulic oil;

the additive comprises an extreme pressure antiwear agent, an antioxidant and a metal passivator; the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and diisooctyl diphenylamine polymer.

2. The synthetic plant-type hydraulic oil according to claim 1, wherein the catalyst is one or more of a sulfur catalyst, a metal catalyst and a solid acid catalyst;

the mass of the catalyst accounts for 0.01-0.2% of the total mass of the mixed straight-chain fatty acid, the polyalcohol and the catalyst.

3. The synthetic plant-type hydraulic oil according to claim 1, wherein the temperature of the esterification reaction is 160-225 ℃;

the esterification reaction time is 10-18 hours;

the vacuum degree of the esterification reaction is-0.04 to-0.07 MPa.

4. The synthetic vegetable-type hydraulic oil of claim 1, wherein the extreme pressure antiwear agent is sulfurized neopentyl glycol dioleate and/or acyl polysulfide.

5. The synthetic plant-type hydraulic oil of claim 1, wherein the metal deactivator is one or more of benzotriazole, thiadiazole derivatives and benzotriazole polymers.

6. The synthetic plant-type hydraulic oil according to claim 1, wherein the temperature blended in the step B) is 100-120 ℃;

the blending time in the step B) is 2-4 hours.

7. The synthetic vegetable hydraulic oil of claim 1, wherein the formulated vacuum level is no greater than-0.093 MPa.

8. The synthetic vegetable hydraulic oil of claim 1, wherein the weight ratio of the extreme pressure antiwear agent to the antioxidant to the metal passivator is (1-3): (2-7): 0.1.

9. the synthetic vegetable hydraulic oil of claim 1, wherein the mass of the additive is 0.01-3% of the total mass of the esterification product and the additive.

10. The synthetic plant-type hydraulic oil according to any one of claims 1 to 9, wherein the kinematic viscosity of the synthetic plant-type biodegradable hydraulic oil at 40 ℃ is 41.2 to 49.1mm²S; the acid value is 0.2 to 1.5mgKOH/g, and the hydroxyl value is 0.36 to 1.92 mgKOH/g.

Technical Field

The invention belongs to the technical field of hydraulic oil, and particularly relates to synthetic plant type hydraulic oil.

Background

The environment is the basis on which human beings and other lives rely to live, and along with the continuous enhancement of environmental protection consciousness, the pollution damage of the hydraulic oil to the environment arouses the attention of various countries. Thus, the development of biodegradable hydraulic oils is receiving great attention. Biodegradable hydraulic oil is also called environment-friendly hydraulic oil, namely, the oil must meet the service performance requirement of a hydraulic system, and the self and the waste products have ecological effects, including: biodegradability, ecotoxicity, renewability, and the like.

Biodegradable hydraulic oil research and application has been vigorously pursued in europe and north america over 20 years ago, and in particular in northern europe, germany, switzerland and austria, great attention is paid to biodegradable hydraulic oil, and environmental regulations are established to limit the use of some mineral oils. The yield of biodegradable hydraulic oil is increased rapidly, and the demand is increased year by year, for example, biodegradable hydraulic oil proposed by Mobil, BP and other companies accounts for 10% of the total amount of the hydraulic oil. In China, the product standard of biodegradable hydraulic oil is not established, but with the development of times, the development of biodegradable hydraulic oil is a necessary trend.

The base oil is a decisive factor of the ecological effect of the hydraulic oil. The vegetable oil is easy to biodegrade, harmless to the environment, high in viscosity index, good in viscosity-temperature performance, good in abrasion resistance and low in price, and is the preferred biodegradable base oil. But the content of unsaturated acid is high, the iodine value is large, the oxidation stability is worse, the solidification point is high, and the low-temperature performance is poor.

Disclosure of Invention

The invention aims to provide synthetic plant type hydraulic oil which has high self-height ignition point and good biodegradability, has better oxidation resistance and low-temperature performance, and is suitable for various working conditions and environments.

The invention provides synthetic plant type hydraulic oil which is prepared by the following steps:

A) mixing the mixed straight-chain fatty acid, the polyol and the catalyst, and carrying out esterification reaction to obtain an esterification product;

the mixed straight chain fatty acid is two or more of n-decanoic acid, isomers of n-decanoic acid, n-tetradecanoic acid, n-hexadecanoic acid, n-octadecanoic acid, oleic acid, linoleic acid and linolenic acid;

the polyhydric alcohol is one or more of monopentaerythritol, dipentaerythritol, glycerol, neopentyl glycol and trimethylolpropane;

the mass ratio of the mixed straight-chain fatty acid to the polyhydric alcohol is (2-6): 1;

B) mixing the esterification product with an additive, and blending to obtain synthetic plant type hydraulic oil;

the additive comprises an extreme pressure antiwear agent, an antioxidant and a metal passivator; the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and diisooctyl diphenylamine polymer.

Preferably, the catalyst is one or more of a sulfur catalyst, a metal catalyst and a solid acid catalyst;

the mass of the catalyst accounts for 0.01-0.2% of the total mass of the mixed straight-chain fatty acid, the polyalcohol and the catalyst.

Preferably, the temperature of the esterification reaction is 160-225 ℃;

the esterification reaction time is 10-18 hours;

the vacuum degree of the esterification reaction is-0.04 to-0.07 MPa.

Preferably, the extreme pressure antiwear agent is sulfurized neopentyl glycol dioleate and/or acyl polysulfide.

Preferably, the metal passivator is one or more of benzotriazole, thiadiazole derivatives and benzotriazole polymers.

Preferably, the temperature blended in the step B) is 100-120 ℃;

the blending time in the step B) is 2-4 hours.

Preferably, the adjusted vacuum degree is not more than-0.093 MPa.

Preferably, the mass ratio of the extreme pressure antiwear agent to the antioxidant to the metal passivator is (1-3): (2-7): 0.1.

preferably, the mass of the additive accounts for 0.01-3% of the total mass of the esterification product and the additive.

Preferably, the kinematic viscosity of the synthetic plant type biodegradable hydraulic oil at 40 ℃ is 41.2-49.1 mm²S; the acid value is 0.2 to 1.5mgKOH/g, and the hydroxyl value is 0.36 to 1.92 mgKOH/g.

The invention provides synthetic plant type hydraulic oil which is prepared by the following steps: A) mixing the mixed straight-chain fatty acid, the polyol and the catalyst, and carrying out esterification reaction to obtain an esterification product; the mixed straight-chain fatty acid is one or more of n-decanoic acid and isomers thereof, n-tetradecanoic acid, n-hexadecanoic acid, n-octadecanoic acid, oleic acid, linoleic acid and linolenic acid; the polyhydric alcohol is one or more of monopentaerythritol, dipentaerythritol, glycerol, neopentyl glycol and trimethylolpropane; the mass ratio of the mixed straight-chain fatty acid to the polyhydric alcohol is (2-6): 1; B) mixing the esterification product, the extreme pressure antiwear agent, the antioxidant and the metal passivator, and blending to obtain synthetic vegetable hydraulic oil; the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and diisooctyl diphenylamine polymer. The invention produces the plant type hydraulic base oil by an industrial synthetic route. The high-temperature and low-temperature performance of the plant hydraulic oil is improved by improving the structure of an oil product and compounding a high-efficiency antioxidant. The oil product has high ignition point, good biodegradability, better oxidation resistance and low temperature performance, and low price. The synthetic plant type hydraulic oil conforms to the direction of green chemical engineering development and has application potential in various industries. Experimental results show that the pour point of the synthetic plant type biodegradable hydraulic oil provided by the invention is-30 to-33 ℃; kinematic viscosity (40 ℃) is not more than 50mm2/s, acid value is not more than 2.0mgKOH/g, flash point is not less than 300 ℃, and ignition point is not less than 360 ℃; the biodegradation rate is more than 80% in 28 days; the oxidation stability (SH/T0450) meets the reported requirements, the kinematic viscosity change at 40 ℃ after oxidation is less than 3%, the acid value change after oxidation is less than 0.5mgKOH/g, the emulsibility resistance at 54 ℃ is not more than 25min, the copper sheet corrosion is 1b, the viscosity index is not less than 180, and the steel sheet passes a manifold ignition test (SH/T0567).

Detailed Description

The invention provides synthetic plant type hydraulic oil which is prepared by the following steps:

A) mixing the mixed straight-chain fatty acid, the polyol and the catalyst, and carrying out esterification reaction to obtain an esterification product;

the mixed straight-chain fatty acid is one or more of n-decanoic acid and isomers thereof, n-tetradecanoic acid, n-hexadecanoic acid, n-octadecanoic acid, oleic acid, linoleic acid and linolenic acid;

the polyhydric alcohol is one or more of monopentaerythritol, dipentaerythritol, glycerol, neopentyl glycol and trimethylolpropane;

the mass ratio of the mixed straight-chain fatty acid to the polyhydric alcohol is (2-6): 1;

B) mixing the esterification product, the extreme pressure antiwear agent, the antioxidant and the metal passivator, and blending to obtain synthetic vegetable hydraulic oil;

the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and diisooctyl diphenylamine polymer.

In the invention, the mixed straight-chain fatty acid is preferably one or more of n-decanoic acid, isomers of n-decanoic acid, n-tetradecanoic acid, n-hexadecanoic acid, n-octadecanoic acid, oleic acid, linoleic acid and linolenic acid; specifically, in the embodiment of the present invention, there may be n-decanoic acid, n-octadecanoic acid, a mixture of oleic acid, linoleic acid and linolenic acid, n-tetradecanoic acid, n-octadecanoic acid, a mixture of oleic acid, linoleic acid and linolenic acid, decanoic acid isomers, a mixture of oleic acid, linoleic acid and linolenic acid, n-decanoic acid, n-tetradecanoic acid and n-octadecanoic acid; the polyalcohol is preferably one or more of monopentaerythritol, dipentaerythritol, glycerol, neopentyl glycol and trimethylolpropane; the mass ratio of the mixed straight-chain fatty acid to the polyhydric alcohol is preferably (2-6): 1, preferably (3-5.5): specifically, in the embodiment of the present invention, the ratio of 3.6: 1. 3.8:1, 4: 1 or 5.2: 1. More specifically, in the embodiment of the present invention, the following ratio may be adopted: the molar ratio of n-decanoic acid, n-octadecanoic acid, oleic acid, linoleic acid, linolenic acid and monopentaerythritol is 1.1: 2.9: 0.7: 0.3: 0.2: 1; the molar ratio of the n-tetradecanoic acid to the n-octadecanoic acid to the oleic acid to the linoleic acid to the linolenic acid to the trimethylolpropane is 0.5: 1.5: 1.6: 0.3: 0.1: 1; the molar ratio of n-decanoic acid isomer, oleic acid, linoleic acid, linolenic acid and glycerol is 0.7: 2.6: 0.2: 0.1: 1; the molar ratio of oleic acid, linoleic acid, linolenic acid, pentaerythritol and dipentaerythritol is 0.7: 2.6: 0.2: 0.1: 1; the molar ratio of n-decanoic acid, n-tetradecanoic acid, n-octadecanoic acid and glycerol is 2.4: 0.8: 0.6: 1.

in the invention, the catalyst is preferably one or more of a sulfur catalyst, a metal catalyst and a solid acid catalyst, and more preferably one or more of solid phosphoric acid, stannous oxalate and sodium bisulfate; the mass of the catalyst is preferably 0.01 to 0.2%, more preferably 0.1 to 0.2%, more preferably 0.15%, and particularly, in the embodiment of the present invention, 0.1%, 0.15%, or 0.2% of the total mass of the mixed straight chain fatty acid, the polyhydric alcohol, and the catalyst.

In the invention, the temperature of the esterification reaction is preferably 160-225 ℃, more preferably 80-220 ℃, and specifically, in the embodiment of the invention, the temperature can be 185 ℃, 190 ℃, 220 ℃ or 225 ℃; the time of the esterification reaction is preferably 10 to 18 hours, more preferably 12 to 16 hours, and specifically, in the embodiment of the present invention, 10 hours and 14 hours may be used. The degree of vacuum of the esterification reaction is preferably-0.04 to-0.07 MPa, more preferably-0.05 to-0.06 MPa, and specifically, in the embodiment of the present invention, may be-0.05 MPa, -0.06MPa or-0.07 MPa.

According to the invention, by adjusting the acid-alcohol ratio, the biodegradable oil product which can ensure the low-temperature fluidity of the oil product and the high-temperature safety of the oil product is obtained.

After the esterification product is obtained, the esterification product is mixed with the additive and blended to obtain the synthetic plant type hydraulic oil.

In the invention, the additives are preferably an extreme pressure antiwear agent, an antioxidant and a metal passivator, and the oxidation stability of the hydraulic oil is improved by selecting the type of the antioxidant and compounding the antioxidant and other two additives.

In the invention, the mass of the additive is preferably 1-4%, more preferably 2-3% of the total mass of the esterification product and the additive.

In the invention, the extreme pressure antiwear agent is preferably sulfurized neopentyl glycol dioleate and/or acyl polysulfide; the metal passivator is one or more of benzotriazole (T706), thiadiazole derivatives (T561) and benzotriazole polymers (KF 110); the antioxidant is preferably one or more of 2, 6-di-tert-butyl-p-cresol (T501), tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester (L101) and diisooctyl diphenylamine polymer (KY 200); the mass ratio of the extreme pressure antiwear agent to the metal passivator to the antioxidant is preferably (1-3): (2-7): 0.1, specifically, in the embodiment of the present invention, may be 1:2:0.1,1:3:0.1 or 2:7: 0.1.

In the invention, the blending temperature is preferably 100-120 ℃, and more preferably 110-115 ℃; the blending time is preferably 2-4 hours, and more preferably 3 hours; the vacuum degree of the blending is preferably not more than-0.093 MPa, and preferably-0.094 MPa.

The synthetic plant-type hydraulic oil prepared by the preparation method has the kinematic viscosity of 41.2-49.1 mm2/s at 40 ℃; the acid value is 0.2 to 1.5mgKOH/g, and the hydroxyl value is 0.36 to 1.92 mgKOH/g.

The invention provides synthetic plant type hydraulic oil which is prepared by the following steps: A) mixing the mixed straight-chain fatty acid, the polyol and the catalyst, and carrying out esterification reaction to obtain an esterification product; the mixed straight-chain fatty acid is one or more of n-decanoic acid and isomers thereof, n-tetradecanoic acid, n-hexadecanoic acid, n-octadecanoic acid, oleic acid, linoleic acid and linolenic acid; the polyhydric alcohol is one or more of monopentaerythritol, dipentaerythritol, glycerol, neopentyl glycol and trimethylolpropane; the mass ratio of the mixed straight-chain fatty acid to the polyhydric alcohol is (2-6): 1; B) mixing the esterification product, the extreme pressure antiwear agent, the antioxidant and the metal passivator, and blending to obtain synthetic vegetable hydraulic oil; the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and diisooctyl diphenylamine polymer. The invention produces the plant type hydraulic base oil by an industrial synthetic route. The high-temperature and low-temperature performance of the plant hydraulic oil is improved by improving the structure of an oil product and compounding a high-efficiency antioxidant. The oil product has high ignition point, good biodegradability, better oxidation resistance and low temperature performance, and low price. The synthetic plant type hydraulic oil conforms to the direction of green chemical engineering development and has application potential in various industries. Experimental results show that the pour point of the synthetic plant type biodegradable hydraulic oil provided by the invention is-30 to-33 ℃; kinematic viscosity (40 ℃) is not more than 50mm2/s, acid value is not more than 2.0mgKOH/g, flash point is not less than 300 ℃, and ignition point is not less than 360 ℃; the biodegradation rate is more than 80% in 28 days; the oxidation stability (SH/T0450) meets the reported requirements, the kinematic viscosity change at 40 ℃ after oxidation is less than 3%, the acid value change after oxidation is less than 0.5mgKOH/g, the emulsibility resistance at 54 ℃ is not more than 25min, the copper sheet corrosion is 1b, the viscosity index is not less than 180, and the steel sheet passes a manifold ignition test (SH/T0567).

In order to further illustrate the present invention, the following examples are provided to describe the synthetic plant-type hydraulic oil of the present invention in detail, but should not be construed as limiting the scope of the present invention.