CN110804029A - Epoxy plasticizer and preparation method thereof - Google Patents
Epoxy plasticizer and preparation method thereof Download PDFInfo
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- CN110804029A CN110804029A CN201911087222.0A CN201911087222A CN110804029A CN 110804029 A CN110804029 A CN 110804029A CN 201911087222 A CN201911087222 A CN 201911087222A CN 110804029 A CN110804029 A CN 110804029A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
- C07D301/16—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof formed in situ, e.g. from carboxylic acids and hydrogen peroxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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Abstract
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.
Description
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.
Example 1:
adding 250g of fatty acid methyl ester and 79 g of glycerol (the molar ratio of the fatty acid methyl ester to the glycerol is about 1: 1) into a 500ml four-neck flask, adding 2.5g of potassium carbonate catalyst, introducing nitrogen into the four-neck flask, wherein the nitrogen flow is 0.3L/min, arranging a condenser pipe on the four-neck flask, opening external condensate water of the condenser pipe, heating reaction liquid in the four-neck flask to 200 ℃ for continuous reaction for one hour, stopping the reaction to obtain a mixture of glyceride and glycerol, carrying out flash evaporation on the mixture under the conditions of vacuum degree of 60pa, flash evaporation temperature of 200 ℃ and overhead condensate water, continuously carrying out flash evaporation for three hours to recover the glycerol, and filtering, washing and carrying out rotary evaporation on the flash-evaporated mixture to remove water to obtain a glyceride mixture (the iodine value of the glyceride mixture is measured to be 124).
100g of the obtained glyceride mixture (with the iodine value of 124) is taken out and placed in a four-neck flask, 6g of formic acid is added after the mixture is heated to 60 ℃, 56g of hydrogen peroxide (with the mass fraction of 50%) is uniformly dripped in the mixture within 30min, and after the dripping is finished, the reaction is continued for 6h at 65 ℃ to obtain a crude product of the epoxy glyceride. The crude product of the epoxyglyceride was washed with deionized water to neutrality, and then the low boiling point components were removed by distillation under reduced pressure to obtain 95g of an epoxyglyceride product (measured as a residual iodine value of 3.21 and an epoxy value of 6.03).
And (3) plastic production: 100g of polyvinyl chloride particles, 40g of plasticizer and 3g of heat stabilizer are taken, mixed for about 8min by a two-roll open mill at 180 ℃, and then pressed into a 1mm slice by a universal sampling machine, namely the soft plastic is reserved. Wherein 40g of the plasticizer comprises 60 percent of DOP by mass and 40 percent of epoxy plasticizer by mass; 3g of heat stabilizer consisted of 1.5g of calcium stearate and 1.5g of zinc stearate.
In the above-mentioned plastic production process, the epoxidized glycerin ester, epoxidized fatty acid methyl ester (iodine value of 1.86, epoxy value of 5.93) and epoxidized soybean oil (iodine value of 1.45, epoxy value of 6.17) prepared in this example were used as the epoxy plasticizer, respectively, and the soft plastic was prepared by the above-mentioned method. Under the same plastic processing conditions, the soft plastics prepared by using the glycidyl ester prepared in example 1 (iodine value 3.21 and epoxy value 6.03), the epoxy fatty acid methyl ester (iodine value 1.86 and epoxy value 5.93) and the epoxy soybean oil (iodine value 1.45 and epoxy value 6.17) as raw materials respectively are subjected to performance tests, and the test results are shown in table 1 and the test methods are as follows:
anti-extraction property: in order to verify the anti-extraction performance of the soft plastic in water, an aqueous solution with a soap mass concentration of 1% or kerosene, the process is as follows: and (3) making the plastic sheet into a square with the side length of 5cm, putting the square into water, an aqueous solution with the soap mass concentration of 1% or kerosene, standing at room temperature for 24h, taking out, drying at 30 ℃ for 24h, weighing, and calculating the mass difference.
The determination of the migration is carried out according to the chemical industry Standard HG/T4454-2012 "determination of migration of Plastic plasticizers".
The elastic modulus, tensile strength and elongation at break are measured according to the national standard GB/T1040.2-2006 "determination of tensile Properties of plastics" second part: test conditions for molded and extruded plastics.
TABLE 1
As can be seen from Table 1, the novel epoxy plasticizer prepared by the invention has better plasticizing effect than epoxy fatty acid methyl ester and is close to epoxy soybean oil; the biodiesel is used as the main raw material, so that the production cost is greatly reduced, and the economic benefit is improved.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (8)
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.
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Cited By (2)
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| CN112961404A (en) * | 2020-12-24 | 2021-06-15 | 中国林业科学研究院林产化学工业研究所 | Epoxy oligoether glyceride plasticizer and preparation method thereof |
| CN114316460A (en) * | 2021-11-01 | 2022-04-12 | 江苏赛贝尔新材料科技有限公司 | High-strength heat-resistant PVC composite board and preparation method thereof |
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| CN114316460A (en) * | 2021-11-01 | 2022-04-12 | 江苏赛贝尔新材料科技有限公司 | High-strength heat-resistant PVC composite board and preparation method thereof |
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