CN114276240A - Preparation method of ricinoleic acid polyol ester - Google Patents
Preparation method of ricinoleic acid polyol ester Download PDFInfo
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- 229960003656 ricinoleic acid Drugs 0.000 title claims abstract description 59
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- -1 ricinoleic acid polyol ester Chemical class 0.000 title claims abstract description 37
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Abstract
The invention relates to a preparation method of ricinoleic acid polyol ester, which takes ricinoleic acid and polyol as raw materials, stannous oxide as a catalyst to enable the ricinoleic acid and the polyol to generate dehydration esterification reaction, and a water carrying agent is used to carry out water generation, so that the product ricinoleic acid polyol ester is obtained, and the catalyst has no obvious activity reduction in multiple circulation experiments. The invention uses renewable biomass as raw material, has clean and pollution-free process, simple experimental operation and post-treatment and high conversion rate. The product can be used as a process lubricating oil base oil and has potential application in the aspects of aviation lubricating oil, hydraulic oil and the like.
Description
Technical Field
The invention relates to a synthetic method of biodegradable lubricating oil base oil ricinoleic acid polyol ester, belonging to the technical field of lubricating oil base oil.
Background
Lubricating oils are liquid or semi-solid lubricants used in various types of automobiles and machinery to reduce friction and protect machinery and workpieces. The lubricating oil mainly plays roles in lubrication, auxiliary cooling, rust prevention, cleaning, sealing, buffering and the like.
At present, the traditional mineral base oil is mainly used as the base oil of the domestic lubricating oil and is processed by taking petroleum as the base, the petroleum is a non-renewable resource and is not easy to degrade, and once leakage occurs, the environmental pollution is serious. Does not meet the requirement of environmental protection and green. With the continuous development of modern science and technology, mineral oil can not meet corresponding process requirements under certain conditions such as high temperature, high radiation, high vacuum or service life. In contrast, the lubricating oil or lubricating oil additive using biomass as raw material not only meets the requirement of sustainable development chemistry, but also has better characteristics than mineral oil, including good thermal stability and oxidation stability, high flash point, low pour point and the like. Thus, the development of lubricants or lubricant additives based on biomass has attracted a great deal of interest.
The ricinoleic acid glyceride derived from castor oil has high viscosity, low volatility, good lubricating property and film forming property and non-flammability, and is an ideal biological raw material for preparing lubricating oil or lubricating oil base oil. Castor oil, however, has thermal-oxidative instability (from double bonds in the molecular structure and hydrogen atoms on the beta carbon atom of the alcoholic hydroxyl group), poor low temperature fluidity, and limited viscosity. The lubricating property of the castor oil can be improved by modifying the castor oil. The heat-oxidation stability of the product can be improved, for example, by epoxidizing or hydrogenating the double bond of the castor oil molecule; the viscosity of the product can be improved by esterifying the hydroxyl or carboxyl groups in the ricinoleic acid or hydrogenated ricinoleic acid molecule to produce long chain alcohol esters of ricinoleic acid or hydrogenated ricinoleic acid. Hydroxyl groups in ricinoleic acid molecules are beneficial to formation of intermolecular hydrogen bonds, so that the ricinoleic acid ester has higher viscosity and lubricating property compared with other hydroxyl-free vegetable oils, and after carboxyl groups in the ricinoleic acid molecules react with alcohol to generate ricinoleic acid ester, the obtained polyol ester product has good lubricating property and oxidation stability. See: (a) tengjiang, Huilong, Haemao and the like, a new synthesis process research of pentaerythritol oleate, Shandong chemical industry 2016, 45 and 19-20.
When ricinoleic acid and polyhydric alcohols (pentaerythritol, trimethylolpropane and neopentyl glycol) are used as raw materials to carry out intermolecular esterification reaction, the obtained ricinoleic acid polyhydric alcohol ester has the characteristics of good thermal stability, viscosity-temperature performance, biodegradability and the like, can be used as process lubricating oil base oil, and in addition, the product has potential application value in the aspects of cold rolling liquid, cutting fluid, hydraulic oil, antirust agents of metals or steel plates, crude oil or emulsion high-speed spinning smoothing agents and the like, and is a green chemical product with development prospect. See: (a) coke, Huwenyun, Tangshihui, etc. Synthesis and Performance Studies of pentaerythritol ricinoleate, proceedings of the Wuhan institute of Industrial science 2012, 31, 27-30.
In order to improve the economy and greenness of synthesis of ricinoleic acid polyol ester, research and improvement on a catalyst of the reaction system have been conducted by various groups. The Huwenyun task group reports that the corresponding ricinoleic acid polyol ester is formed by catalyzing ricinoleic acid and pentaerythritol or trimethylolpropane by adopting p-toluenesulfonic acid, sulfuric acid and tetrabutyl titanate, the obtained product has good viscosity-temperature performance, but a catalyst used in the process is not easy to separate and recycle, and acidic wastewater is generated in the production process. Luzhimin et al developed solid catalyst SO4 2-/TiO2The catalyst has good catalytic effect for promoting the reaction of ricinoleic acid and pentaerythritol, but the preparation process is complex and not easy to obtain. See: (a) synthesis and performance research of coke, Huwenyun, Tang Shihui, etc. pentaerythritol ricinoleate, Wuhan industry academy of academic, 2012, 31, 27-30, (b) coke, Huwenyun, Tang Shihui, etc. synthesis process conditions and performance of trimethylolpropane ricinoleate, Wuhan industry academy of academic, 2012, 34, 34-38, (c) Ruizime, Baijing, and Jiapu friend, preparation and application of a novel pentaerythritol ricinoleate, Chinese plastics, 2015, 29, 96-99, (d) Song Yang, Zhang Chenghui, a synthesis method of trimethylolpropane ricinoleate [ P]201911391042.1.2020.05.15. therefore, it is inexpensiveThe development of catalysts which are efficient and easy to separate and recycle remains the key to the industrial production of ricinoleic acid polyol esters.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of ricinoleic acid polyol ester, which realizes the economical and green preparation of biodegradable lubricating oil base oil ricinoleic acid polyol ester through the development of a catalyst and the optimization of a process, and obtains a castor-based lubricating oil product with proper viscosity, acid value and pour point. The technology adopts solid Lewis acid stannous oxide as a catalyst, so that ricinoleic acid and polyol are subjected to esterification reaction, the problems of pollution and catalyst recovery in the existing preparation method are solved, the complex catalyst preparation process is avoided, the production process is clean and pollution-free, the operation is simple, the catalyst can be recycled for multiple times, and the obtained product ricinoleic acid polyol ester meets the technical indexes of lubricating oil base oil (GB/T265, GB/T1995-1998, GB/T3535 and GB/T3536), so the technology has potential commercial application prospect.
The preparation method of the ricinoleic acid polyol ester provided by the invention comprises the following specific operation steps:
the method comprises the following steps: adding ricinoleic acid, polyalcohol and their mixture (carboxylic acid and alcoholic hydroxyl functional group ratio is 1: 1), catalyst and water-carrying agent into a reaction bottle;
step two: heating to the reaction temperature under the condition of stirring, and starting the reaction;
step three: after the reaction is finished, centrifuging to remove the catalyst, washing with water to remove incompletely reacted raw materials in the reaction mixture, and removing the water-carrying agent through reduced pressure distillation to obtain the ricinoleic acid polyol ester product.
In the preparation of the ricinoleic acid polyol ester, the adopted catalyst is stannous oxide, and the dosage of the stannous oxide is 0.1-10 wt% of the dosage of the ricinoleic acid.
The water-carrying agent is toluene, cyclohexane or xylene; the dosage of the water-carrying agent is 5-50 wt%.
The reaction temperature of the dehydration esterification reaction is between 160 ℃ and 180 ℃, and the reaction time is 2-5 h.
The reaction formula of the preparation process is shown in the attached figures 1-3.
The invention has the advantages and positive effects that:
the preparation process of the method is simple to operate, the raw materials are cheap and easy to obtain, and the storage and the transportation are easy. The reaction temperature is relatively low, the reaction time is short, the requirement on equipment is low, high-pressure equipment is not needed, the investment cost is reduced, the energy consumption is saved, and meanwhile, the whole process flow has the characteristic of environmental friendliness;
2, the stannous oxide catalyst used in the method can be recycled and reused, and the catalyst used repeatedly still has high catalytic activity, so that the production cost is greatly reduced, and considerable economic benefit is achieved;
3 the ricinoleic acid polyol ester prepared by the invention has good lubricating property and low-temperature flow property, can be used as lubricating oil base oil, and belongs to a clean and environment-friendly product;
4 the ricinoleic acid polyol ester prepared by the method has the esterification rate of over 99 percent, and the waste material of the product after use is biodegradable, meets the environmental protection requirement and has industrial production prospect.
Drawings
FIG. 1 is a reaction equation for the synthesis of pentaerythritol ricinoleate.
FIG. 2 is a reaction equation for synthesizing trimethylolpropane ricinoleate.
FIG. 3 is a reaction equation for the synthesis of neopentyl glycol ricinoleate.
FIG. 4 is a FT-IR spectrum of the product RA-PE.
FIG. 5 is a drawing of the product RA-PE1H NMR spectrum.
FIG. 6 is a drawing of the product RA-PE13C NMR spectrum.
FIG. 7 is an ESI-MS spectrum of the product RA-PE.
FIG. 8 is a FT-IR spectrum of the product RA-TMP.
FIG. 9 is a drawing of the product RA-TMP1H NMR spectrum.
FIG. 10 is a graph of the product RA-TMP13C NMR spectrum.
FIG. 11 is an ESI-MS spectrum of the product RA-TMP.
FIG. 12 is an FT-IR spectrum of the product RA-NPG.
FIG. 13 is a graph of the product RA-NPG1H NMR spectrum.
FIG. 14 is a graph of the product RA-NPG13C NMR spectrum.
FIG. 15 is an ESI-MS spectrum of the product RA-NPG.
FIG. 16 shows catalyst recycle experiments and acid number measurements.
Detailed Description
The invention relates to a preparation method of ricinoleic acid polyol ester, aiming at meeting the industrial requirement, stannous oxide is found to be capable of effectively catalyzing esterification reaction of ricinoleic acid and polyol through experimental screening, and the process is environment-friendly, economic and convenient to operate and high in product yield. Ricinoleic acid is an easily available renewable resource and can be applied to industrial production in large quantities. When the polyhydric alcohol is pentaerythritol, trimethylolpropane and neopentyl glycol, the specific reaction is shown in attached figures 1-3.
EXAMPLE 1 Performance Studies of the reaction of various polyols with ricinoleic acid to prepare a polyol ricinoleate
8g of ricinoleic acid, polyol (pentaerythritol, trimethylolpropane, neopentyl glycol, alcohol and carboxylic acid functions in a ratio of 1: 1), 10mg of stannous oxide and 5mL of xylene are placed in a reaction flask and the temperature is raised to 170 ℃ with stirring. Water is continuously carried out by the dimethylbenzene along with the reaction, and after the water is separated by the water separator, the dimethylbenzene flows back to the flask to continuously carry out the generated water. The reaction was stopped after 4h and about 0.5mL of water was observed to be carried over. Then removing the catalyst by centrifugation, washing with water, evaporating out water-carrying agent to obtain the product ricinoleic acid polyol ester (RA-PE, RA-TMP, RA-NPG respectively, and the specific characterization result is shown in figures 5-16).
The acid value of the product is determined by the GB/T4945-2002 method, the kinematic viscosity is determined by the GB/T265 method, the viscosity index is determined by the GB/T1995-1998 method, the pour point is determined by the GB/T3535 method, and the flash point is determined by the GB/T3536 method.
TABLE 1 lubricating Properties test data for polyol ricinoleate
TABLE 2 Experimental data for four ball machine
The performance of the product, including acid value, kinematic viscosity, viscosity index, flash point, pour point and the like, is measured and compared with the standard limit of the polyol ester compound used as the lubricating oil base oil (table 1), and the product meets the index requirement of the lubricating oil base oil. The results of the test using a four-ball machine for the diameter of the wear marks, and the comparison with 150BS base oil (mineral oil base oil), castor oil and tetrapolyricinoleate show that the ricinoleic acid polyol ester has good wear resistance and friction reducing properties (table 2). The above results indicate that the ricinoleic acid polyol ester meets the index requirements of the industrial lubricant base oil.
Example 2 the reaction of ricinoleic acid with pentaerythritol was taken as an example to examine the effect of different reaction temperatures on the product properties.
Adding 8g of ricinoleic acid, 0.912g of pentaerythritol, 10mg of stannous oxide and 5mL of xylene into a reaction bottle, starting stirring, and heating to a certain temperature. And (3) continuously carrying out water with xylene along with the reaction, and refluxing the xylene to the flask to continuously carry out generated water after the xylene is separated by a water separator. The reaction was stopped after 4h and about 0.5mL of water was observed to be carried over. Then removing the catalyst by centrifugation, washing with water, and evaporating the water-carrying agent to obtain the product.
TABLE 3 Effect of temperature on the Properties of the reaction products
TABLE 4 Effect of temperature on product scrub Spot diameter and Friction coefficient
From the results in tables 3 and 4, it can be seen that when ricinoleic acid is reacted with pentaerythritol at different temperatures, the lubricating properties of the resulting products will be slightly different, but all meet the standards for industrial lubricant base oils.
Example 3 the reaction of ricinoleic acid with pentaerythritol was taken as an example to examine the effect of the amount of catalyst on the product properties.
Adding 8g of ricinoleic acid, 0.912g of pentaerythritol, different amounts of stannous oxide and 5mL of xylene into a reaction bottle, starting stirring, and heating to 170 ℃. And (3) continuously carrying out water with xylene along with the reaction, and refluxing the xylene to the flask to continuously carry out generated water after the xylene is separated by a water separator. The reaction was stopped after 4h and about 0.5mL of water was observed to be carried over. Then removing the catalyst by centrifugation, washing with water, and evaporating the water-carrying agent to obtain the product.
TABLE 5 influence of the amount of catalyst on the Properties of the reaction products
TABLE 6 influence of catalyst dosage on product scrub spot diameter and coefficient of friction
From the results in tables 5 and 6, it can be seen that when ricinoleic acid is reacted with pentaerythritol at different temperatures, the lubricating properties of the resulting products will be slightly different, but all meet the standards for industrial lubricant base oils.
Example 4 the reaction of ricinoleic acid with pentaerythritol was taken as an example to examine the effect of time on the properties of the reaction product.
8g of ricinoleic acid, 0.912g of pentaerythritol, 10mg of stannous oxide and 5mL of xylene are added to a reaction flask, and stirring is started and the temperature is raised to 170 ℃. Water is continuously carried out by the dimethylbenzene along with the reaction, and after the water is separated by the water separator, the dimethylbenzene flows back to the flask to continuously carry out the generated water. The reaction was stopped after a certain time and about 0.5mL of water was observed to be carried over. Then removing the catalyst by centrifugation, washing with water, and evaporating the water-carrying agent to obtain the product.
TABLE 7 Effect of time on the Properties of the reaction products
TABLE 8 Effect of time on product scrub Spot diameter and Friction coefficient
From the results in tables 7 and 8, it can be seen that when ricinoleic acid is reacted with pentaerythritol at different times, the lubricating properties of the resulting products will be slightly different, but all meet the standards for industrial lubricant base oils.
Example 5 the reaction of ricinoleic acid with pentaerythritol was taken as an example to examine the effect of catalyst recycling on product properties.
8g of ricinoleic acid, 0.912g of pentaerythritol, 10mg of stannous oxide and 5mL of xylene are added into a reaction flask, stirring is started, and the temperature is raised to 170 ℃. And (3) continuously carrying out water with xylene along with the reaction, and refluxing the xylene to the flask to continuously carry out generated water after the xylene is separated by a water separator. The reaction was stopped after 4h and about 0.5mL of water was observed to be carried over. Then removing the catalyst by centrifugation, washing with water, and evaporating the water-carrying agent to obtain the product. And washing the catalyst with dichloromethane, drying to constant weight, taking the recovered stannous oxide as the catalyst, keeping the operation flow unchanged, and repeating the experiment for five times.
TABLE 9 Effect of catalyst recycle on reaction product Properties
TABLE 10 influence of catalyst recycle on product scrub spot diameter and coefficient of friction
From the results in tables 9 and 10, it can be seen that the acid value of the product is slightly increased during the recycling of the catalyst, and the lubricating properties of the product obtained after 5 times of recycling meet the standards of the industrial lubricant base oil. The stannous oxide has good stability and can be recycled in industry. In connection with the fact that the acid value of the product increases slightly with the increase in the number of catalyst cycles and the catalyst quality decreases slightly during the cycle in FIG. 16, it is presumed that the slight increase in the acid value of the product may be attributed to the loss of the catalyst during the cycle, and thus the product performance can be maintained by the addition of a small amount of the catalyst in the industrial production.
Several examples of the invention were detailed above and the products were tested for their relative lubricity under different experimental conditions. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (8)
1. A preparation method of ricinoleic acid polyol ester is characterized in that: ricinoleic acid and polyalcohol are used as raw materials, stannous oxide is used as a catalyst to enable the ricinoleic acid and the polyalcohol to generate a dehydration esterification reaction, and a water carrying agent is used to carry out generated water, so that the product ricinoleic acid polyalcohol ester can be obtained.
2. A process for the preparation of a polyol ricinoleate according to claim 1, wherein: the method comprises the following steps:
the method comprises the following steps: ricinoleic acid, polyol (the ratio of alcohol to carboxylic acid functional groups is 1: 1), a catalyst and a water-carrying agent are put into a reaction bottle;
step two: heating to the reaction temperature under the condition of stirring, and starting the reaction;
step three: after the reaction is finished, centrifuging to remove the catalyst, washing with water to remove incompletely reacted raw materials, and removing the water-carrying agent by reduced pressure distillation to obtain the ricinoleic acid polyol ester product.
3. A process for the preparation of a polyol ricinoleate according to claims 1, 2, wherein: the acid value of the used raw material ricinoleic acid is 150-180 mg KOH/g.
4. A process for the preparation of a polyol ricinoleate according to claims 1, 2, wherein: the polyhydric alcohol is one or a mixture of several polyhydric alcohols, and comprises one or a combination of several of pentaerythritol, trimethylolpropane and octapentanediol.
5. A process for the preparation of a polyol ricinoleate according to claims 1, 2, wherein: the dosage of the catalyst stannous oxide is 0.1-10 wt%.
6. A process for the preparation of a polyol ricinoleate according to claims 1, 2, wherein: the water-carrying agent is toluene, cyclohexane or xylene; the dosage of the water-carrying agent is 5-50 wt%.
7. A process for the preparation of a polyol ricinoleate according to claims 1, 2, wherein: the reaction temperature of the dehydration esterification reaction is 160-180 ℃, and the reaction time is 2-5 h.
8. A process for the preparation of a polyol ricinoleate according to claims 1, 2, wherein: the acid value of the prepared ricinoleic acid polyol ester is 0.2-1 mg KOH/g; at 40 ℃, the kinematic viscosity is more than or equal to 190mm2S; the kinematic viscosity is more than or equal to 20mm at 100 DEG C2And s. When the polyhydric alcohols are pentaerythritol respectivelyTrimethylolpropane and octapentanediol, the final product has the following structural formulas:
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| CN109761804A (en) * | 2018-11-29 | 2019-05-17 | 南开大学 | A kind of preparation method of oligomeric ricinoleate ester |
| CN109810736A (en) * | 2019-02-25 | 2019-05-28 | 山东大学 | Application of a kind of compound as gasoline lubricant on gasoline |
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| CN109761804A (en) * | 2018-11-29 | 2019-05-17 | 南开大学 | A kind of preparation method of oligomeric ricinoleate ester |
| CN109810736A (en) * | 2019-02-25 | 2019-05-28 | 山东大学 | Application of a kind of compound as gasoline lubricant on gasoline |
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