CN108948421B - Epoxy plasticizer mixture and preparation method thereof - Google Patents
Epoxy plasticizer mixture and preparation method thereof Download PDFInfo
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Abstract
The invention provides an epoxy plasticizer mixture and a preparation method thereof, wherein the mixture comprises an epoxy compound of a first component and an epoxy compound of a second component, the first component comprises fatty acid triglyceride, and the second component comprises unsaturated fatty acid ester. By adding the epoxy compound containing unsaturated fatty acid ester into the epoxy compound containing fatty acid triglyceride, the melting point of the mixture is lower than that of the traditional epoxy plasticizer by utilizing intermolecular force, so that the epoxy plasticizer has good anti-freezing performance and is more beneficial to use in low-temperature environment.
Description
Technical Field
The invention relates to a fine organic chemical plasticizer, in particular to an epoxy plasticizer mixture and a preparation method thereof.
Background
Plasticizers are generally "solvent-like" substances which, when added to plastics, resins or elastomers, improve their processability, increase their plasticity, flexibility, stretchability or expandability. The addition of plasticizers reduces the melt viscosity of the plastic, the glass transition temperature and the elastic modulus of the elastomer without altering the basic chemical characteristics of the plasticized material.
In 1975 the total world production of plasticizers reached 32 million tons. By 2000, the total production capacity of plasticizers worldwide has reached 640 million tons, and more than 500 industrial varieties exist. The total sales amount of the plasticizer accounts for 60 percent of the plastic additive. Wherein, phthalate plasticizer products are taken as the main products, which account for more than 80 percent of the total production of the whole plasticizer, while DEHP (DOP) and DBP are the main products. However, a number of physiological and pathological studies have shown in recent years: the plasticizer DEHP acts like an artificial hormone, endangers male reproductive capacity and promotes female sexual precocity, and liver cancer can be caused by long-term large-amount ingestion. Since the infant is in the reproductive development stage of the endocrine system, DEHP is more potentially harmful to the infant. Thus, three phthalate compounds, DEHP, DBP and BBP, were listed as limited-use substances in rohs2.0, which was performed starting at 1 month in 2013.
Epoxy plasticizers represented by epoxidized soybean oil become a class of products which are developed rapidly among numerous environment-friendly plasticizers. Epoxidized soybean oil is prepared from soybean oil serving as a raw material by epoxidation modification, is a nontoxic, renewable and bio-based plastic plasticizer which is a plasticizer approved by the Food and Drug Administration (FDA) and can be used for food packaging materials and is widely used for PVC nontoxic products, such as: PVC transparent articles, transparent bottles, transparent boxes, food, pharmaceutical packaging materials, PVC medical "blood transfusion bags", PVC outdoor plastic articles such as: production of waterproof coiled material, plastic door and window, plastic film for sticking wall paper, etc.
However, the traditional epoxidized soybean oil product generates phenomena of flocculation, turbidity and the like when the room temperature is lower than 15 ℃, and the phenomenon that the whole product is frozen in a packaging barrel along with the prolonging of time or the reduction of temperature brings serious inconvenience to the use, even cannot be used. This patent therefore proposes a new epoxidized soybean oil product to improve the freeze resistance of conventional epoxidized soybean oil.
Disclosure of Invention
The invention provides a novel epoxy plasticizer mixture and a preparation method thereof, which have good frost resistance and are more beneficial to use in a low-temperature environment.
The invention provides an epoxy plasticizer mixture, which comprises: a first component comprising a fatty acid triglyceride and a second component comprising an unsaturated fatty acid ester.
Wherein the fatty acid triglycerides include: one or more of soybean oil, cotton seed oil, corn oil, sunflower seed oil, peanut oil, rapeseed oil and linseed oil.
Unsaturated fatty acid esters include compounds of the following structure: cmH2m+1CkHjCnH2nCOOCxHy(ii) a Wherein, the degree of unsaturation is less than or equal to 3, m is more than or equal to 2, n is more than or equal to 0, m + k + n is less than or equal to 17, k is more than or equal to j and less than 2k, x is more than or equal to 1 and less than or equal to 8, and y is more than or equal to 2x + 1.
Preferably, the unsaturated fatty acid ester is formed by esterifying a fourth component and a fifth component; the fourth component comprises unsaturated fatty acid, and the fifth component comprises one of branched fatty alcohol, cyclic fatty alcohol or aromatic alcohol.
Preferably, the weight percentage of the first component to the second component is 1: 5-50 wt%
The invention also provides a preparation method of the mixture of two epoxy plasticizers, one of which comprises the following steps: mixing the first component and the second component to obtain a mixture; the first component comprises fatty acid triglycerides and the second component comprises unsaturated fatty acid esters; and carrying out epoxidation reaction on the mixture to obtain an epoxy plasticizer mixture. The other method comprises the following steps: respectively carrying out epoxidation reaction on the first component and the second component to obtain an epoxy compound of the first component and an epoxy compound of the second component; the first component comprises fatty acid triglycerides and the second component comprises unsaturated fatty acid esters; and mixing the epoxy compound of the first component and the epoxy compound of the second component to obtain an epoxy plasticizer mixture.
Wherein the fatty acid triglycerides comprise: one or more of soybean oil, cotton seed oil, corn oil, sunflower seed oil, peanut oil, rapeseed oil and linseed oil.
Preferably, the unsaturated fatty acid ester comprises a compound of the structure: cmH2m+1CkHjCnH2nCOOCxHy(ii) a Wherein, the degree of unsaturation is less than or equal to 3, m is more than or equal to 2, n is more than or equal to 0, m + k + n is less than or equal to 17, k is more than or equal to j and less than 2k, x is more than or equal to 1 and less than or equal to 8, and y is more than or equal to 2x + 1.
Preferably, the weight percentage of the first component and the second component is 1: 5-50 wt%.
The invention has the beneficial effects that: by adding the epoxy compound containing unsaturated fatty acid ester into the epoxy compound containing fatty acid triglyceride, the melting point of the mixture is lower than that of the traditional epoxy plasticizer by utilizing intermolecular force, so that the epoxy plasticizer has good anti-freezing performance and is more beneficial to use in low-temperature environment.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments thereof, it should be emphasized that the following description is only exemplary and is not intended to limit the scope and application of the present invention.
This example provides an epoxy-based plasticizer mixture comprising a first component comprising a fatty acid triglyceride and a second component comprising an unsaturated fatty acid ester, an epoxy compound and a second component.
Wherein, the first component fatty acid triglyceride, also called triglyceride for short, is the main component of animal and vegetable oil. Fatty acid triglycerides are fatty molecules formed from 3 molecules of long chain fatty acids (third component) and glycerol, which react as follows:
wherein the third component fatty acids comprise saturated fatty acids, monounsaturated fatty acids, and polyunsaturated fatty acids, each commonly:
(1) saturated fatty acid
Lauric acid (12 carbons, 0 double bonds, abbreviated as C12:0) having a melting point of 44 ℃ to 46 ℃;
0 part of myristic acid C14, the melting point is 52-54 ℃;
palmitic acid C16:0, the melting point is 61-62.5 ℃;
stearic acid C18:0, melting point 67-72 ℃.
(2) Monounsaturated fatty acid
Palmitoleic acid (16 carbons, 1 double bond, double bond on carbon number 9, abbreviated as 9c-16:1), melting point-0.1 ℃ to 0.5 ℃;
oleic acid 9c-18:1, the melting point is 13-14 ℃;
erucic acid 13c-22:1, melting point 28-34 deg.C.
(3) Polyunsaturated fatty acids
Linoleic acid 9c,12c-18:2, melting point-5 ℃;
linolenic acid 9c,12c,15c-18:3 with a melting point of-11.3 ℃.
Wherein the unsaturated fatty acids (mainly oleic acid, linoleic acid and linolenic acid) in the first component such as soybean oil, cotton seed oil, corn oil, sunflower seed oil, peanut oil, rapeseed oil, linseed oil and other vegetable oils account for more than 80% of the total fatty acid composition. This embodiment prefers one or more of the above vegetable oils as the first component.
The epoxy compound of the first component is prepared by taking the first component as a raw material and modifying the first component through an epoxidation reaction. During the epoxidation reaction, the double bonds in the unsaturated branches are all converted to epoxy functional groups, while the saturated branch moieties are not changed at all.
After epoxidation reaction, the unsaturated degree of the system is greatly reduced, and correspondingly, the melting point of the system is also greatly improved. Therefore, the traditional epoxy plasticizer has high melting point of the saturated branched triglyceride in the first component and does not change in the epoxidation reaction process, and the unsaturated degree is greatly reduced because unsaturated bonds of the unsaturated triglyceride and free unsaturated fatty acid are converted into epoxy groups in the epoxidation reaction process, so that the traditional epoxy plasticizer has poor freezing resistance because the phenomena of flocculation, turbidity and the like at room temperature below 15 ℃.
In order to solve the problem of poor freezing resistance of the existing epoxy plasticizer, the embodiment provides the epoxy compound of the second component, which is mixed with the epoxy compound of the first component to be used as the epoxy plasticizer mixture.
The second component comprises unsaturated fatty acid ester, and the structure of the unsaturated fatty acid ester is as follows:
CmH2m+1CkHjCnH2nCOOCxHy
preferably, the degree of unsaturation is less than or equal to 3, m is more than or equal to 2, n is more than or equal to 0, m + k + n is less than or equal to 17, k is less than or equal to j and less than 2k, x is more than or equal to 1 and less than or equal to 8, and y is less than or equal to 2x + 1.
The second component is directly available from the market, and is an ester obtained by esterification reaction of unsaturated fatty acid (fourth component) and low molecular alcohol (fifth component), and the reaction process is as follows:
CmH2m+1CkHjCnH2nCOOH+HOCxHy→CmH2m+1CkHjCnH2nCOOCxHy
fourth component fifth component second component
Due to the similarity of the structure, the second component has very good compatibility with the triglyceride; similarly, the epoxy compound has very good compatibility with the epoxy compound of triglyceride. In addition, the epoxy plasticizer mixture containing the epoxy compound of the second component and the epoxy compound of the triglyceride breaks the regular chain structure in the triglyceride structure through the branched chain structure of the alcohol part in the second component, inhibits crystallization and lowers the melting point, and the melting point of the mixture is lower than that of the epoxy compound of the triglyceride through intermolecular force, so that the mixture has good frost resistance.
In this embodiment, the use of unsaturated fatty acid esters is also advantageous in that: on one hand, unsaturated double bonds can participate in epoxidation reaction, and the epoxy value of the epoxy plasticizer mixture cannot be reduced; on the other hand, after the epoxidation reaction, the product also contains partial unsaturated fatty acid ester which does not participate in the reaction, and the melting point of the unsaturated fatty acid ester is lower than that of the saturated acid ester.
In this embodiment, the fifth component of the raw material for forming unsaturated fatty acid ester includes low molecular alcohol, which may be straight chain fatty alcohol, branched chain fatty alcohol, cyclic fatty alcohol, or aromatic alcohol, but this embodiment prefers one or more of branched chain fatty alcohol, cyclic fatty alcohol, or aromatic alcohol. The unsaturated fatty acid ester formed by the low molecular alcohol with a branched structure, especially a cyclic structure, has large steric hindrance, so that the regularity of the molecular structure in the whole epoxy compound system (the mixture of the epoxy compound of the fatty acid triglyceride and the epoxy compound of the unsaturated fatty acid ester) can be damaged, the crystallization is not facilitated, the crystallization rate is reduced, and the melting point of the whole system is reduced.
This example also provides a method of preparing such an epoxy-based plasticizer mixture, which can be prepared in two ways.
The epoxy plasticizer mixture is prepared by respectively carrying out epoxidation reaction on a first component and a second component to obtain an epoxy compound of the first component and an epoxy compound of the second component, and then mixing the epoxy compound of the first component and the epoxy compound of the second component.
The above methods require epoxidation reactions respectively, and the operation process is complicated, so that the operation can be further simplified, and the second method is: the first component and the second component are mixed to obtain a mixture, and then the mixture is subjected to epoxidation reaction to obtain an epoxy plasticizer mixture.
In both of the above methods, the first component and the second component are directly commercially available. The second component can also be obtained by esterification of the fourth and fifth components according to the prior art. The weight percentage of the first component and the second component is preferably 1: 5 to 50 wt%, more preferably 1: 10-20 wt%, can not only ensure the frost resistance of the final epoxy plasticizer mixture, but also can not increase the cost obviously.
In the above process, the conditions for physical mixing are: the time is 2-4h at room temperature.
The epoxidation reaction adopts the epoxidation reaction used for modifying animal and vegetable oil in the prior art. The specific process is as follows: uniformly mixing a strong acid catalyst, formic acid or acetic acid and hydrogen peroxide, and then dropwise adding the mixture into a reactant; wherein, the temperature of the epoxidation reaction is preferably 60-90 ℃; the reaction time is 4-16 h; the catalyst is concentrated sulfuric acid or methanesulfonic acid (MSA).
Example 1
Weighing 2000g of soybean oil, adding 400 g of methyl oleate (cis-9-octadecenoate), placing the mixture into a 5L double-layer reaction kettle, uniformly stirring, then uniformly mixing 160 g of formic acid, 1600 g of hydrogen peroxide and 4.0 g of concentrated sulfuric acid, dropwise adding the mixture into the reaction product, controlling the temperature to be 70-80 ℃, stirring and reacting for 12 hours, adding 24 g of calcium carbonate and 2000L of water, uniformly stirring, standing for layering, removing the water on the lower layer, heating to 100 ℃, and carrying out vacuum distillation to obtain the finished product. The finished product was tested for specific gravity, epoxy value and results of the freezing test, and the results are shown in table 1.
Example 2
Weighing 2000g of soybean oil, adding 300 g of tert-butyl oleate (cis-9-octadecenoate), placing the mixture into a 5L double-layer reaction kettle, uniformly stirring, then uniformly mixing 160 g of formic acid, 1600 g of hydrogen peroxide and 4.0 g of concentrated sulfuric acid, dropwise adding the mixture into the reaction product, controlling the temperature to be 70-80 ℃, stirring for reacting for 12 hours, adding 24 g of calcium carbonate and 2000L of water, uniformly stirring, standing for layering, removing the water on the lower layer, and heating to 100 ℃ for vacuum distillation to obtain the finished product. The finished product was tested for specific gravity, epoxy value and results of the freezing test, and the results are shown in table 1.
Example 3
Weighing 2000g of soybean oil, adding 120 g of oleic acid (cis-9-octadecenoic acid) 4-ethyl-1-cyclohexanol ester, placing the mixture into a 5L double-layer reaction kettle, stirring uniformly, then uniformly mixing 160 g of formic acid, 1600 g of hydrogen peroxide and 4.0 g of concentrated sulfuric acid, dropwise adding the mixture into the reaction product, controlling the temperature to be 70-80 ℃, stirring for reacting for 12 hours, adding 24 g of calcium carbonate and 2000L of water, stirring uniformly, standing for layering, removing the lower layer of water, heating to 100 ℃, and carrying out vacuum distillation for moisture to obtain the finished product. The finished product was tested for specific gravity, epoxy value and results of the freezing test, and the results are shown in table 1.
Example 4
Weighing 2000g of soybean oil, adding 100 g of palmitoleic acid (cis-9-hexadecenoic acid) benzyl alcohol ester, placing the soybean oil and the benzyl alcohol ester into a 5L double-layer reaction kettle, stirring uniformly, then uniformly mixing 160 g of formic acid, 1600 g of hydrogen peroxide and 4.0 g of concentrated sulfuric acid, then dropwise adding the mixture into the reaction product, controlling the temperature to be between 70 and 80 ℃, stirring and reacting for 12 hours, adding 24 g of calcium carbonate and 2000L of water, stirring uniformly, standing and layering, removing water on the lower layer, heating to 100 ℃, and carrying out vacuum distillation and water-removing to obtain a finished product. The finished product was tested for specific gravity, epoxy value and results of the freezing test, and the results are shown in table 1.
Example 5
Weighing 2000g of cottonseed oil, adding 200 g of myrenoic acid (cis-9-dodecenoic acid) isoamyl alcohol ester, placing the mixture into a 5L double-layer reaction kettle, uniformly stirring, then uniformly mixing 160 g of formic acid, 1600 g of hydrogen peroxide and 4.0 g of concentrated sulfuric acid, dropwise adding the mixture into the reaction product, controlling the temperature to be 70-80 ℃, after stirring reaction for 12 hours, adding 24 g of calcium carbonate and 2000L of water, uniformly stirring, standing for layering, removing the water in the lower layer, and heating to 100 ℃ for vacuum distillation moisture to obtain a finished product. The finished product was tested for specific gravity, epoxy value and results of the freezing test, and the results are shown in table 1.
Example 6
Weighing 2000g of corn oil, adding 1000g of tert-butyl carnosote (cis-9-tetradecenoic acid) into the corn oil, placing the corn oil and the tert-butyl carnosote into a 5L double-layer reaction kettle, uniformly stirring, then uniformly mixing 220 g of formic acid, 2240 g of hydrogen peroxide and 5.6 g of concentrated sulfuric acid, dropwise adding the mixture into the reaction product, controlling the temperature to be 70-80 ℃, stirring for reaction for 12 hours, adding 24 g of calcium carbonate and 2000L of water, uniformly stirring, standing for layering, removing the water on the lower layer, and heating to 100 ℃ for vacuum distillation to obtain the finished product. The finished product was tested for specific gravity, epoxy value and results of the freezing test, and the results are shown in table 1.
Example 7
Weighing 2000g of peanut oil, adding 400 g of palmitoleic acid (cis-9-hexadecenoic acid) isoamyl alcohol ester, placing the mixture into a 5L double-layer reaction kettle, stirring uniformly, then uniformly mixing 180 g of formic acid, 1760 g of hydrogen peroxide and 4.5 g of concentrated sulfuric acid, then dropwise adding the mixture into the reaction product, controlling the temperature to be 70-80 ℃, stirring for reacting for 12 hours, adding 24 g of calcium carbonate and 2000L of water, stirring uniformly, standing for layering, removing the water on the lower layer, and heating to 100 ℃ for vacuum distillation to obtain the finished product. The finished product was tested for specific gravity, epoxy value and results of the freezing test, and the results are shown in table 1.
Example 8
Weighing 2000g of soybean oil, adding 400 g of cis-2, cis-4-dodecadienoic acid isopropyl ester, placing the mixture into a 5L double-layer reaction kettle, uniformly stirring, then uniformly mixing 180 g of formic acid, 1760 g of hydrogen peroxide and 4.5 g of concentrated sulfuric acid, dropwise adding the mixture into the reaction product, controlling the temperature to be 70-80 ℃, stirring for reacting for 12 hours, adding 24 g of calcium carbonate and 2000L of water, uniformly stirring, standing for layering, removing the water at the lower layer, and heating to 100 ℃ for vacuum distillation to obtain the finished product. The finished product was tested for specific gravity, epoxy value and results of the freezing test, and the results are shown in table 1.
Example 9
Weighing 2000g of soybean oil, adding 300 g of isobutyl linolenate (cis-9, cis-12, cis-15-octadecatrienoic acid), placing the mixture into a 5L double-layer reaction kettle, stirring uniformly, then uniformly mixing 180 g of formic acid, 1760 g of hydrogen peroxide and 4.5 g of concentrated sulfuric acid, dropwise adding the mixture into the reaction product, controlling the temperature to be 70-80 ℃, stirring for reacting for 12 hours, adding 24 g of calcium carbonate and 2000L of water, stirring uniformly, standing for layering, removing the water on the lower layer, heating to 100 ℃, and carrying out vacuum distillation for moisture to obtain the finished product. The finished product was tested for specific gravity, epoxy value and results of the freezing test, and the results are shown in table 1.
Comparative example 1
Weighing 2000g of soybean oil, placing the soybean oil in a 5L double-layer reaction kettle, stirring uniformly, then uniformly mixing 160 g of formic acid, 1600 g of hydrogen peroxide and 4.0 g of concentrated sulfuric acid, then dropwise adding the mixture into the reaction product, controlling the temperature to be 70-80 ℃, stirring for reacting for 12 hours, then adding 24 g of calcium carbonate and 2000L of water, stirring uniformly, standing for layering, removing the water at the lower layer, and heating to 100 ℃ for vacuum distillation to obtain a finished product. The finished product was tested for specific gravity, epoxy value and results of the freezing test, and the results are shown in table 1.
The specific gravity, epoxy value and freezing test analysis were carried out on the products obtained in the above examples, and the results are shown in Table 1 below.
TABLE 1
| Scheme(s) | Specific gravity of | Epoxy value | Results of freezing experiments |
| Example 1 | 0.986 | 6.30 | Turbidity appeared at 0 deg.C for 30min |
| Example 2 | 0.982 | 6.28 | Turbidity appeared at 0 deg.C for 45min |
| Example 3 | 0.984 | 6.25 | Turbidity appeared at 0 deg.C for 60min |
| Example 4 | 0.984 | 6.22 | Turbidity appeared at 0 deg.C for 80min |
| Example 5 | 0.976 | 6.02 | Turbidity appeared at 0 deg.C for 20min |
| Example 6 | 0.972 | 6.20 | Turbidity appeared at 0 deg.C for 90min |
| Example 7 | 0.982 | 6.23 | Turbidity appeared at 0 deg.C for 60min |
| Example 8 | 0.985 | 6.36 | Turbidity appeared at 0 deg.C for 75min |
| Example 9 | 0.986 | 6.42 | Turbidity appeared at 0 deg.C for 60min |
| Comparative example 1 | 0.985 | 6.12 | Turbidity appeared at 0 deg.C for 10min |
The raw materials in the embodiment are cheap and easy to obtain, the whole reaction preparation method is simple, and the obtained epoxy plasticizer mixture has better frost resistance than the traditional epoxy plasticizer, and is more favorable for being used in a low-temperature environment. Meanwhile, the PVC resin has high compatibility with PVC resin and can be used as a PVC main plasticizer; in addition, the epoxy value is not reduced in the modification process, and the heat stabilizer function of the epoxy plasticizer can be fully exerted.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and these substitutions and modifications should be considered to fall within the scope of the invention.
Claims (9)
1. An epoxy-based plasticizer mixture comprising: a first component of an epoxy compound and a second component of an epoxy compound, the first component comprising a fatty acid triglyceride and the second component comprising an unsaturated fatty acid ester; the unsaturated fatty acid ester is formed by esterifying a fourth component and a fifth component; the fourth component comprises unsaturated fatty acid, and the fifth component is one of cycloaliphatic alcohol or aromatic alcohol.
2. The epoxy-based plasticizer mixture according to claim 1, wherein the fatty acid triglyceride comprises: one or more of soybean oil, cotton seed oil, corn oil, sunflower seed oil, peanut oil, rapeseed oil and linseed oil.
3. The epoxy-based plasticizer mixture according to claim 1, wherein the unsaturated fatty acid ester comprises a compound of the structure:
CmH2m+1CkHjCnH2nCOOCxHy；
wherein, the degree of unsaturation is less than or equal to 3, m is more than or equal to 2, n is more than or equal to 0, m + k + n is less than or equal to 17, k is more than or equal to j and less than 2k, x is more than or equal to 1 and less than or equal to 8, and y is more than or equal to 2x + 1.
4. The epoxy plasticizer mixture according to claim 1 wherein the weight percent of said first component to said second component is from 1: 5-50 wt%.
5. The preparation method of the epoxy plasticizer mixture is characterized by comprising the following steps of:
mixing the first component and the second component to obtain a mixture; the first component comprises fatty acid triglycerides and the second component comprises unsaturated fatty acid esters; the unsaturated fatty acid ester is formed by esterifying a fourth component and a fifth component; the fourth component comprises unsaturated fatty acid, and the fifth component is one of cycloaliphatic alcohol or aromatic alcohol; and carrying out epoxidation reaction on the mixture to obtain an epoxy plasticizer mixture.
6. The preparation method of the epoxy plasticizer mixture is characterized by comprising the following steps of:
respectively carrying out epoxidation reaction on the first component and the second component to obtain an epoxy compound of the first component and an epoxy compound of the second component; the first component comprises fatty acid triglycerides and the second component comprises unsaturated fatty acid esters; the unsaturated fatty acid ester is formed by esterifying a fourth component and a fifth component; the fourth component comprises unsaturated fatty acid, and the fifth component is one of cycloaliphatic alcohol or aromatic alcohol;
and mixing the epoxy compound of the first component and the epoxy compound of the second component to obtain an epoxy plasticizer mixture.
7. The method of claim 5 or 6, wherein the fatty acid triglyceride comprises: one or more of soybean oil, cotton seed oil, corn oil, sunflower seed oil, peanut oil, rapeseed oil and linseed oil.
8. The method of claim 5 or 6, wherein the unsaturated fatty acid ester comprises a compound of the structure:
CmH2m+1CkHjCnH2nCOOCxHy；
wherein, the degree of unsaturation is less than or equal to 3, m is more than or equal to 2, n is more than or equal to 0, m + k + n is less than or equal to 17, k is more than or equal to j and less than 2k, x is more than or equal to 1 and less than or equal to 8, and y is more than or equal to 2x + 1.
9. The method according to claim 5 or 6, wherein the weight percentages of the first component and the second component are 1: 5-50 wt%.
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