CN101186597A - Method for preparing epoxy soybean acidified oil (C1-4) without protonic acid - Google Patents
Method for preparing epoxy soybean acidified oil (C1-4) without protonic acid Download PDFInfo
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- CN101186597A CN101186597A CNA2007103024120A CN200710302412A CN101186597A CN 101186597 A CN101186597 A CN 101186597A CN A2007103024120 A CNA2007103024120 A CN A2007103024120A CN 200710302412 A CN200710302412 A CN 200710302412A CN 101186597 A CN101186597 A CN 101186597A
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Abstract
The invention relates to a preparation method of epoxy soybean acidified oil ester (C<SUB>1-4</SUB>) without protonic acid, belonging to the preparation technical field of epoxy plasticizer. The invention relates to a comprehensive utilization of waste that prepares epoxy soybean acidified oil ester (C<SUB>1-4</SUB>) in the conditions without protonic acid, solvent and stabilizer. The invention uses relative soybean acidified oil ester (C<SUB>1-4</SUB>) as material, hydrogen dioxide solution as oxygen supply, and aminic acid as oxygen carrier, via epoxidation to obtain epoxy soybean acidified oil ester (C<SUB>1-4</SUB>). Compared with prior preparation method of epoxy plasticizer, the invention is processed in the conditions without protonic acid, solvent and stabilizer, with simple process, low energy consumption, little water consumption and low cost. The inventive product can be used as plastic agent to partially replace phthalandione-2-(2-ethyl)-hexyl-ester (DOP) to be used in polymer material as PVC.
Description
Technical Field
The invention relates to a method for preparing epoxy soybean acidified oil (C) under the conditions of no protonic acid, no solvent and no stabilizer1-4) An ester method belongs to the technical field of preparation of epoxy plasticizers.
Background
Epoxy resinBean acid oil (C)1-4) The ester is an epoxy plasticizer, and the epoxy plasticizer mainly comprises epoxy vegetable oil and epoxy fatty acid ester, and epoxy soybean acidified oil (C)1-4) The esters belong to the class of epoxy fatty acid esters. With the improvement of environmental protection consciousness of various countries in the world, plastic products such as medicine, food packaging, daily necessities, toys and the like put forward higher purity and sanitary requirements on a main plasticizer di (2 ethyl) hexyl phthalate (DOP) and the like, and the epoxy plasticizer gradually becomes a hotspot of application research at home and abroad as a nontoxic environment-friendly plasticizer. The epoxy fatty acid ester has the advantages of epoxy oil and better lubricating property, compatibility and dispersibility, China is one of the countries with the most abundant vegetable oil resources in the world, and renewable vegetable oil-based raw materials are used for carrying out vegetable oil-based epoxidation to prepare fine chemical products to replace petrochemical products, so that the epoxy fatty acid ester has better economic and social benefits. In the traditional synthesis of epoxy fatty acid ester, benzene and other solvents are used as water-carrying agents under the catalysis of strong acid protonic acid, and a stabilizing agent is added for reaction. Publication No. CN 1996497A discloses a method for synthesizing epoxy fatty acid methyl ester, which is carried out under the conditions that sulfuric acid and aluminum sulfate are used as catalysts and a complex is used as a stabilizer; publication No. CN 101029177A discloses a method for preparing epoxy plasticizer from waste oil and waste animal and vegetable oil, which is carried out under the condition of adding sodium tripolyphosphate as stabilizer. These methods all have the disadvantages of complicated operation, serious corrosion to equipment, difficult wastewater treatment, low solvent recovery rate, high cost and the like.
Disclosure of Invention
The invention aims to provide a method for preparing epoxy soybean acidified oil (C) under the conditions of no protonic acid, no solvent and no stabilizer1-4) The ester method has the advantages of low energy consumption, simple process, safe operation and low production cost, and can meet the requirement of industrial mass production.
The technical scheme of the invention is as follows: preparation of epoxy soybean acidified oil (C) without protonic acid, solvent and stabilizer1-4) Method of esterification with soy acidified oil (C)1-4) Ester as raw material and hydrogen peroxideAs oxygen source, formic acid as oxygen carrier, under the condition of no protonic acid, no solvent and no stabilizing agent making epoxy soybean acidified oil (C) by means of epoxidation treatment and after-treatment1-4) Ester, the weight ratio of the raw materials is: acidified soybean oil (C)1-4) Ester, hydrogen peroxide and formic acid are 1: 0.45-0.70: 0.10-0.20; the preparation steps are as follows:
the first step is as follows: acidifying soybean oil (C)1-4) Adding ester and formic acid into a reaction kettle according to a ratio, heating to 45-55 ℃ under the condition of stirring, and stopping heating;
the second step is that: dropping hydrogen peroxide according to the proportion, controlling the temperature in the kettle within the range of 50-70 ℃, reacting for 5-9 h within the range of 55-70 ℃ after dropping hydrogen peroxide, leading the epoxidation reaction in the kettle to be full and thorough,obtaining crude epoxidized soybean acidified oil (C)1-4) An ester;
the third step: acidification oil of crude epoxy soybean (C)1-4) Washing the ester with alkali, neutralizing with water, distilling under reduced pressure, and press filtering to obtain epoxy soybean acidified oil (C)1-4) And (5) ester finished product.
The raw material soybean acidified oil (C)1-4) The iodine value of the ester is 70-120g I2In the range of 100g, the acid number is from 0.5 to 4mg KOH/g.
The concentration of the hydrogen peroxide is 35 percent, and the concentration of the formic acid is 85 percent.
In the alkali washing process, the alkali is sodium carbonate, the using amount of the alkali is 2-5 times of the theoretically required amount, and 5% sodium carbonate aqueous solution is prepared and then alkali washing is carried out.
The chemical reaction mechanism is as follows: epoxidized soybean acidified oil (C)1-4) The ester is prepared from soybean acidified oil (C)1-4) The epoxidation process of carbon-carbon double bonds in ester takes hydrogen peroxide as an oxygen source and formic acid as an oxygen carrier, and the mechanism of the epoxidation process can be represented by the following equation:
the first step is as follows:
the second step is that:
in the formula R1、R2Is C6-C8Alkyl of R3Is C1-C4Alkyl group of (1).
To achieve the above object, the present invention employs soybean acidified oil (C)1-4) Ester as raw material, hydrogen peroxide as oxygen source, formic acid as oxygen carrier, and epoxidation and post-treatment to obtain epoxidized soybean acidified oil (C)1-4) An ester having the general structural formula:
in the formula R1、R2Is C6-C8Alkyl of R3Is C1-C4Alkyl group of (1).
The invention has the beneficial effects that: the invention uses soybean acidified oil (C)1-4) The method has the advantages that the ester is used as a raw material, hydrogen peroxide is used as an oxygen source, formic acid is used as an oxygen carrier, and an acid catalyst is avoided in an epoxidation stage by changing process conditions, so that the process has low corrosion to equipment, and the wastewater amount in a post-treatment stage is greatly reduced; the use of a solvent is avoided, so that the process is simple to operate, and the defect of difficult solvent recovery is avoided; the use of a stabilizer is avoided, so that the process is low in cost, the operation in the post-treatment stage is simple, and the process can meet the requirement of industrial mass production.
Detailed description of the preferred embodiments
The invention is illustrated in further detail below by means of specific examples of the synthesis of the products.
Example 1
Weighing 80g of soybean acidified oil methyl ester, hydrogen peroxide and formic acid according to the weight ratio of 1: 0.55: 0.15Soybean acidified oil methyl ester (iodine value of 108g I)2100g, acid value 0.5mg KOH/g) and 12g of 85% formic acid in a three-necked flask with stirrer, thermometer and dropping funnelIn the water bath system, stirring is carried out, 44g of 35% hydrogen peroxide is dropwise added after the temperature in a bottle is raised to 50 ℃, the temperature of the system is controlled within the range of 50-55 ℃, the dropwise adding time is 5min, the temperature of the system is controlled to 60 ℃ after the dropwise adding is finished, the heat preservation is started, the heat preservation time is 5h, and the epoxidation reaction is finished. Transferring the reaction mixed solution into a separating funnel, standing for a moment to remove a water layer, measuring that the acid value of a crude product is 0.72mgKOH/g according to GB/T1668, directly washing an ester layer to be neutral by using distilled water at about 70 ℃ because the acid value is lower, washing for 3 times, wherein the water consumption is about 40 percent of the volume of the ester layer each time, then distilling the product under reduced pressure for 0.5h at the vacuum degree of 0.095MPa and the temperature of 80-110 ℃, removing a low-boiling-point product, cooling to obtain a product, namely, the epoxy value of the epoxy soybean acidified oil methyl ester is 4.57 percent, and the iodine value of the epoxy soybean acidified oil methyl ester is 4.12gI2100g, and the acid value is 0.42 mgKOH/g.
Example 2
At 5m3The material loading coefficient of the stainless steel reaction kettle is 0.75, the weight ratio of the materials is 1: 0.50: 0.12 according to the weight ratio of the butyl soyate, the hydrogen peroxide and the formic acid, and the iodine value of the butyl soyate is 96g I2100g, the acid value is 2.5mg KOH/g, the concentration of hydrogen peroxide is 35 percent, and the concentration of formic acid is 85 percent. Firstly, filling the soybean acidified oil butyl ester and formic acid into a reaction kettle according to the proportion, starting to heat to 45-50 ℃ under the stirring condition, stopping heating, and starting to dropwise add hydrogen peroxide; because of the exothermic reaction, cooling water is adopted for temperature regulation, the temperature in the kettle is ensured to be between 55 and 65 ℃, the dropping time of hydrogen peroxide is 3 to 4 hours, the temperature is controlled to be between 55 and 70 ℃ after the dropping is finished, and the temperature is kept for 6 to 7 hours, so that the epoxidation reaction is fully and thoroughly carried out, and the crude epoxidized oil butyl ester is obtained; standing and layering the reacted materials, discharging a water layer at the bottom, measuring the acid value of an ester layer remained in a kettle according to GB/T1668 to be 3.64mg KOH/g, calculating the weight of sodium carbonate required for neutralization, weighing 4 times of theoretical value, preparing into a 5% sodium carbonate aqueous solution, performing alkali washing, then washing with water to be neutral, then beginning to distill and remove low-boiling-point substances in the sodium carbonate aqueous solution at the temperature of 80-110 ℃ under the vacuum degree of 0.085-0.095 MP, wherein the distilling time is 0.5-1 h, and finally performing pressure filtration on the materials to obtain a product ringThe epoxy value of the epoxidized soybean acidified oil butyl ester is 4.24 percent and the iodine value of theepoxidized soybean acidified oil butyl ester is 4.52g I through detection2100g, acid value 0.39mg KOH/g.
Example 3
According to the weight ratio of soybean acidified oil ethyl ester, hydrogen peroxide and formic acid being 1: 0.45: 0.10, the iodine value of soybean acidified oil ethyl ester is 80gI2100g, acid value of 0.61mgKOH/g, other technical parameters and operation steps are the same as example 1, and the epoxy value of the epoxy soybean acidified oil ethyl ester is 3.42 percent, and the iodine value is 5.27g I2100g, acid value 0.46mg KOH/g.
Example 4
At 8m3The weight ratio of the materials in the stainless steel reaction kettle is 1: 0.50: 0.12, the iodine value of the soybean acidified oil methyl ester is 88g I2Per 100g, acid value of 2.7mg KOH/g, other technical parameters and operating procedures were the same as in example 2 to obtain epoxidized soyate methyl ester with an epoxy value of 3.24% and an iodine value of 4.74g I2100g, acid value 0.42mg KOH/g.
Claims (4)
1. Epoxidized soybean acidified oil (C)1-4) A process for the preparation of esters, characterized in that it consists in preparing a soy acidified oil (C)1-4) Ester as raw material, hydrogen peroxide as oxygen source, formic acid as oxygen carrier, and epoxy soybean acidified oil (C) prepared by epoxidation and post-treatment under the conditions of no protonic acid, no solvent and no stabilizer1-4) Ester, the weight ratio of the raw materials is: acidified soybean oil (C)1-4) Ester, hydrogen peroxide and formic acid are 1: 0.45-0.70: 0.10-0.20; the preparation steps are as follows:
the first step is as follows: acidifying soybean oil (C)1-4) Adding ester and formic acid into a reaction kettle according to a ratio, heating to 45-55 ℃ under the condition of stirring, and stopping heating;
the second step is that: beginning to drop hydrogen peroxide according to the proportion, controlling the temperature in the kettle within the range of 50-70 ℃, and reacting for 5-9 h within the range of 55-70 ℃ after the hydrogen peroxide is dropped, so that the epoxidation reaction in the kettle is full and thorough, and a coarse ring is obtainedOxygenated soybean acidified oil (C)1-4) An ester;
the third step: acidification oil of crude epoxy soybean (C)1-4) Washing the ester with alkali, neutralizing with water, distilling under reduced pressure, and press filtering to obtain epoxy soybean acidified oil (C)1-4) And (5) ester finished product.
2. Epoxidized soybean acidified oil (C) according to claim 11-4) A process for the preparation of an ester, characterized in that: the raw material soybean acidified oil (C)1-4) The iodine value of the ester is 70-120g I2In the range of 100g, the acid number is from 0.5 to 4mg KOH/g.
3. Epoxidized soybean acidified oil (C) according to claim 11-4) A process for the preparation of an ester, characterized in that: the concentration of hydrogen peroxide is 35 percent, and the concentration of formic acid is 85 percent.
4. Epoxidized soybean acidified oil (C) according to claim 11-4) The preparation method of ester is characterized in that in the alkali washing process, the alkali is sodium carbonate, the dosage of the alkali is 2-5 times of the theoretically required amount, and 5%sodium carbonate aqueous solution is prepared and then alkali washing is carried out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007103024120A CN101186597A (en) | 2007-12-20 | 2007-12-20 | Method for preparing epoxy soybean acidified oil (C1-4) without protonic acid |
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| CNA2007103024120A CN101186597A (en) | 2007-12-20 | 2007-12-20 | Method for preparing epoxy soybean acidified oil (C1-4) without protonic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921248A (en) * | 2010-08-04 | 2010-12-22 | 湖北巨源油业有限公司 | Preparation method of epoxidation biodiesel plasticizer |
| CN101624386B (en) * | 2009-08-13 | 2011-02-09 | 江苏卡特新能源有限公司 | Method for preparing epoxy fatty acid ethylester plasticizer |
| CN114735651A (en) * | 2021-01-07 | 2022-07-12 | 中国石油化工股份有限公司 | Oxygen carrier for chemical ring hydrogen production and preparation method and application thereof |
-
2007
- 2007-12-20 CN CNA2007103024120A patent/CN101186597A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624386B (en) * | 2009-08-13 | 2011-02-09 | 江苏卡特新能源有限公司 | Method for preparing epoxy fatty acid ethylester plasticizer |
| CN101921248A (en) * | 2010-08-04 | 2010-12-22 | 湖北巨源油业有限公司 | Preparation method of epoxidation biodiesel plasticizer |
| CN114735651A (en) * | 2021-01-07 | 2022-07-12 | 中国石油化工股份有限公司 | Oxygen carrier for chemical ring hydrogen production and preparation method and application thereof |
| CN114735651B (en) * | 2021-01-07 | 2024-01-05 | 中国石油化工股份有限公司 | Oxygen carrier for chemical looping hydrogen production and preparation method and application thereof |
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Open date: 20080528 |