阅读说明：本技术 一种环氧类增塑剂及其制备方法 (Epoxy plasticizer and preparation method thereof ) 是由 聂勇 刘忠会 吴振宇 梁晓江 解庆龙 卢美贞 王迪淼 李肖华 计建炳 于 2019-11-08 设计创作，主要内容包括：本发明公开了一种环氧类增塑剂及其制备方法,本发明制备环氧类增塑剂的方法为：在碱催化下,将生物柴油与甘油进行甘油解反应,反应结束后,反应液进行闪蒸,以蒸出回收过量未反应的甘油,然后过滤、水洗、减压蒸馏除去水分得到甘油酯,所得甘油酯与甲酸、双氧水进行环氧化反应,得到环氧甘油酯粗产品,环氧甘油酯粗产品再进行精制,得到环氧甘油酯,即为所述的环氧类增塑剂。本发明制得的环氧增塑剂与PVC树脂的相容性良好,替代40%DOP制得的软质塑料拉伸强度和弹性模量分别可以达到20Mpa和16Mpa,断裂伸长率可以达到397%,迁移性在0.001%左右,煤油中的抽提性在0.001%左右。利用本发明制得的增塑剂的增塑效果优于环氧脂肪酸甲酯,与环氧大豆油相近。(The invention discloses an epoxy plasticizer and a preparation method thereof, and the method for preparing the epoxy plasticizer comprises the following steps: the method comprises the following steps of carrying out glycerolysis reaction on biodiesel and glycerol under the catalysis of alkali, carrying out flash evaporation on reaction liquid after the reaction is finished so as to evaporate and recover excessive unreacted glycerol, then filtering, washing, carrying out reduced pressure distillation to remove water so as to obtain glyceride, carrying out epoxidation reaction on the obtained glyceride, formic acid and hydrogen peroxide so as to obtain a crude epoxy glyceride product, and refining the crude epoxy glyceride product so as to obtain the epoxy plasticizer. The epoxy plasticizer prepared by the invention has good compatibility with PVC resin, the tensile strength and the elastic modulus of soft plastics prepared by replacing 40% DOP can respectively reach 20Mpa and 16Mpa, the elongation at break can reach 397%, the mobility is about 0.001%, and the extractability in kerosene is about 0.001%. The plasticizing effect of the plasticizer prepared by the method is superior to that of epoxy fatty acid methyl ester and is similar to that of epoxidized soybean oil.)

1. A process method for preparing epoxy plasticizer by using biodiesel is characterized by comprising the following steps:

1) carrying out glycerolysis reaction on biodiesel and glycerol under the catalysis of alkali, carrying out flash evaporation on reaction liquid after the reaction is finished, recovering excessive unreacted glycerol, and then filtering, washing and carrying out reduced pressure distillation to remove water to obtain glyceride;

2) epoxidizing the glyceride obtained in the step 1) with formic acid and hydrogen peroxide to obtain a crude epoxy glyceride product, and refining the crude epoxy glyceride product to obtain epoxy glyceride, namely the epoxy plasticizer.

2. The process method for preparing the epoxy plasticizer by using the biodiesel according to claim 1, wherein in the glycerolysis reaction in the step 1), the molar ratio of the glycerol to the biodiesel is 0.33-10: 1.

3. The process method for preparing the epoxy plasticizer by using the biodiesel according to claim 1, wherein the base in the glycerolysis reaction of the step 1) is potassium carbonate.

4. The process method for preparing the epoxy plasticizer by using the biodiesel according to claim 1, wherein the reaction temperature in the glycerolysis reaction of the step 1) is 120-250 ℃ and the reaction time is 0.5-5 h.

5. The process method for preparing the epoxy plasticizer by using the biodiesel according to claim 1, wherein the flash evaporation temperature is 70-250 ℃ in the flash evaporation of the reaction liquid in the step 1), and the vacuum degree of the flash evaporation operation is below 1000 pa.

6. The process method for preparing the epoxy plasticizer by using the biodiesel according to claim 1, wherein the reaction temperature in the epoxidation reaction in the step 2) is 30-90 ℃ and the reaction time is 0.5-20 hours.

7. The process for preparing epoxy plasticizer by using biodiesel according to claim 1, wherein the iodine value of the epoxy glyceride prepared in step 2) is less than 10, and the epoxy value is greater than 3.

8. An epoxy plasticizer prepared by the method according to any one of claims 1 to 7.

Technical Field

The invention relates to a fine organic chemical plasticizer, in particular to an epoxy plasticizer and a preparation method thereof.

Background

The plasticizer (also called plasticizer) is a polymer material additive widely used in industry, and is a substance which can improve the plasticity of a product without influencing the polymer per se after being added. The plasticizer is added to increase the flexibility, the flexure, the cold resistance and the elongation of the plastic, reduce the hardness, the modulus, the glass transition temperature, the melting point, the softening temperature or the flowing temperature of the plastic, reduce the viscosity of the plastic, increase the fluidity and improve the processability. Thus, plasticizers can be used legally in plastic processing.

The plasticizer product can be more than hundreds of types, and the most common type is phthalate (or phthalate) compounds. However, this compound is potentially harmful and has been banned from use in food, infant toys and food packaging. Today, with increasing environmental awareness, there is an increasing need for a new family of bio-based plasticizers for practical use.

As a novel plasticizer which is nontoxic, sufficient in raw materials and biodegradable, the epoxy plasticizer is regarded as a product which can partially or even completely replace the traditional phthalate plasticizer, so that the research and development of the plasticizer are gradually increased.

Currently, the epoxy plasticizer mainly takes epoxidized soybean oil as a main raw material, and the epoxidized soybean oil is a bio-based plasticizer prepared by taking soybean oil as a raw material through epoxy modification, and is widely applied to PVC non-toxic products. In addition, the epoxidized soybean oil can also be used as an auxiliary heat stabilizer of PVC, and can generate a synergistic effect with a metal salt heat stabilizer to play a heat stabilizing effect and reduce the dosage of an expensive organic metal salt heat stabilizer.

The existing production methods and researches mostly use natural vegetable oil or certain components of the oil as raw materials, and the side reactions are reduced by methods such as modification, ester exchange and the like to obtain the epoxy plasticizer with high epoxy value or improve the compatibility of the plasticizer and PVC resin.

The Chinese patent CN106519081A, an epoxy plasticizer and a preparation method thereof, discloses a method for producing an epoxy plasticizer with a high epoxy value by carrying out ester exchange on fatty acid esters and HTPB to obtain an intermediate product and then carrying out a solvent-free epoxidation method. Similar patent applications for invention also include: CN105722906A, CN105153462A, CN103703069A, CN104059032A, CN105085442A, CN106753811A, CN101367958A, and CN 106398236A.

Chinese patent CN105175362A, a preparation method of a high-compatibility modified epoxy plasticizer, discloses a method for improving compatibility with PVC by epoxidizing unsaturated fatty acid ester with organic acid and hydrogen peroxide and then chlorinating unreacted double bonds in the fatty acid ester with chlorine gas, and simultaneously, the residual iodine value of epoxy grease is reduced through chlorination, and the stability of the plasticizer is improved.

In addition, studies have been made on mixing different plasticizers to achieve a high epoxy value and good compatibility with PVC, for example, chinese patent CN101914219A, "a method for preparing a composite epoxy plasticizer", discloses a method for preparing a composite epoxy plasticizer by mixing soybean oil and fatty acid methyl ester in a certain ratio, and then performing an epoxidation reaction using an organic acid as an oxygen carrier and hydrogen peroxide as an oxygen donor.

The natural vegetable oil is used as a production raw material, so that the production cost is high on one hand, and the production cost is easily influenced by the market of agricultural products on the other hand, which brings great pressure to the sale of products such as epoxidized soybean oil and the like, and directly influences the economic benefit of enterprises. The green environment-friendly plasticizer which is low in price, stable and capable of replacing epoxidized soybean oil and similar to the physical and chemical properties of the epoxidized soybean oil is found out, and the condition is greatly improved.

The biodiesel (fatty acid methyl ester) produced by using the waste oil is large in quantity, cheap and easy to obtain, and the research of preparing epoxy glyceride by using the biodiesel as the raw material is only reported, so that the development and production of the plasticizer can meet the requirement of China on a large amount of environment-friendly plasticizers and has positive influence on the environment and the society.

Disclosure of Invention

In view of the above technical problems in the prior art, the present invention aims to provide an epoxy plasticizer and a preparation method thereof.

The process method for preparing the epoxy plasticizer by using the biodiesel is characterized by comprising the following steps of:

1) carrying out glycerolysis reaction on biodiesel and glycerol under the catalysis of alkali, carrying out flash evaporation on reaction liquid after the reaction is finished, recovering excessive unreacted glycerol, and then filtering, washing and carrying out reduced pressure distillation to remove water to obtain glyceride;

2) epoxidizing the glyceride obtained in the step 1) with formic acid and hydrogen peroxide to obtain a crude epoxy glyceride product, and refining the crude epoxy glyceride product to obtain epoxy glyceride, namely the epoxy plasticizer.

The process method for preparing the epoxy plasticizer by using the biodiesel is characterized in that in the step 1) of glycerolysis reaction, the molar ratio of glycerol to the biodiesel is 0.33-10: 1.

The process method for preparing the epoxy plasticizer by using the biodiesel is characterized in that in the glycerolysis reaction in the step 1), the alkali is potassium carbonate.

The process method for preparing the epoxy plasticizer by using the biodiesel is characterized in that in the step 1) of the glycerolysis reaction, the reaction temperature is 120-250 ℃, and the reaction time is 0.5-5 h.

The process method for preparing the epoxy plasticizer by using the biodiesel is characterized in that in the step 1), the reaction liquid is subjected to flash evaporation, the flash evaporation operation vacuum degree is below 1000pa, and the flash evaporation temperature is 70-250 ℃.

The process method for preparing the epoxy plasticizer by using the biodiesel is characterized in that in the epoxidation reaction in the step 2), the reaction temperature is 30-90 ℃, and the reaction time is 0.5-20 hours.

The process method for preparing the epoxy plasticizer by using the biodiesel is characterized in that the iodine value of the epoxy glyceride prepared in the step 2) is less than 10, and the epoxy value is greater than 3.

An epoxy plasticizer prepared by any of the above methods.

Compared with the prior art, the invention has the following beneficial effects:

(1) according to statistics, about 300 million tons of illegal cooking oil are produced every year in China, wherein less than one third of illegal cooking oil is prepared into biodiesel (namely fatty acid methyl ester), and more than two thirds of illegal cooking oil is not treated by a good method temporarily. The method takes the biodiesel and the byproduct glycerol in the biodiesel production process as raw materials, and prepares the fatty glyceride after the glycerolysis, which can be used as the raw material of the epoxy plasticizer, thereby indirectly improving the demand of the biodiesel. Meanwhile, the biodiesel is used as a main raw material to produce the epoxy plasticizer, so that the saving concept of waste recycling which is always advocated by China is realized.

(2) According to the invention, the biodiesel is used as a raw material, and the biodiesel and the glycerol can be subjected to glycerolysis reaction with the glycerol under normal pressure, so that the reaction is simple; at high temperature, the reaction rate of the glycerolysis reaction is high, the reaction is thorough, and the conversion rate of the biodiesel can reach 100% in a short time; in the glycerolysis reaction, the glycerol which does not participate in the reaction can be recovered in a flash evaporation mode and can be reused; the invention can adjust the proportion of monoglyceride, diglyceride and triglyceride generated by the glycerolysis reaction by adjusting the amount of the added glycerol, and the reaction is more flexible; the epoxy value of the epoxy plasticizer prepared by the invention can reach more than 4.5, and the epoxy plasticizer has good plasticizing performance; the invention has simple process, low energy consumption and safe operation, greatly reduces the manufacturing cost of the epoxy plasticizer because of using the biodiesel as the raw material, and can be used as the plasticizer for packaging materials and decorative materials.

(3) The method utilizes the biodiesel and the glycerol to prepare the epoxy plasticizer with high added value, has low production cost and is environment-friendly; the prepared epoxy plasticizer has good compatibility with PVC resin, the tensile strength and the elastic modulus of soft plastics prepared by replacing 40% of DOP can respectively reach 20Mpa and 16Mpa, the elongation at break can reach 397%, the mobility is about 0.001%, and the extractability in kerosene is about 0.001%. The plasticizing effect of the plasticizer prepared by the method is superior to that of epoxy fatty acid methyl ester and is similar to that of epoxidized soybean oil.

Detailed Description

The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.