CN109265361B - Method for carrying out micro-reaction continuous flow preparation by applying acylamino to vegetable oil-based plasticizer - Google Patents
Method for carrying out micro-reaction continuous flow preparation by applying acylamino to vegetable oil-based plasticizer Download PDFInfo
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Abstract
The invention discloses a method for preparing a micro-reaction continuous flow by applying acylamino to a vegetable oil-based plasticizer, which comprises the steps of dissolving epoxidized soybean oil in an organic solvent to obtain a solution A, dissolving an amide ring-opening reagent and a ring-opening reaction catalyst in the organic solvent to obtain a solution B, pumping the solution A and the solution B into a first mixer of a micro-reaction device simultaneously for mixing, then feeding the solution A and the solution B into a first microreactor of the micro-reaction device for reaction to obtain an epoxidized soybean oil ring-opening product, dissolving an acetylation reagent and the acetylation reaction catalyst in the organic solvent to obtain a solution C, pumping the solution C and the epoxidized soybean oil ring-opening product into a second mixer of the micro-reaction device simultaneously for mixing, then feeding the solution C and the epoxidized soybean oil ring-opening product into. Compared with the traditional preparation process, the method utilizes the particularity of amide groups and combines a micro-reaction continuous flow device to sequentially carry out ring-opening reaction and acetylation reaction to prepare the newly added plasticizer with more excellent performance.
Description
Technical Field
The invention relates to a method for carrying out micro-reaction continuous flow preparation by applying acylamino to a vegetable oil-based plasticizer, belonging to the field of chemical synthesis.
Background
Epoxidized Soybean Oil (ESO) is a common plasticizer and stabilizer, and is mainly characterized by low price, environmental protection and better compatibility with PVC resin, so that the advantage of stability is more prominent than that of other plasticizers. However, epoxidized soybean oil also has many defects, the migration resistance and volatility of the epoxidized soybean oil have certain problems due to the unstable three-membered ring in the structure, particularly, the mutual solubility of pure epoxidized soybean oil and epoxy resin is not good, and the optimal plasticizing performance of the epoxidized soybean oil cannot be exerted, but the epoxy group and the flexible long chain of the epoxidized soybean oil make the epoxidized soybean oil have good modification conditions.
Many amide compounds are plasticizers themselves, amides are generally near-neutral compounds, and have stable structures, and many low-molecular liquid amides such as NN dimethylformamide are not only good aprotic polar solvents, but also can be used as plasticizers, lubricant additives and the like. Compared with plasticizers containing ester groups, such as erucamide, many N-sulfoalkyl substituted fatty amides have been widely used in the fields of plasticizers and lubricants.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problem that the amide group is modified on the long chain of epoxidized soybean oil through ring-opening polymerization, so that the epoxidized soybean oil has the double advantages of ester plasticizers and amide plasticizers, and a novel excellent vegetable oil-based plasticizer is developed by combining a micro-reaction continuous flow preparation process.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for carrying out micro-reaction continuous flow preparation by applying acylamino to a vegetable oil-based plasticizer comprises the following steps:
the method comprises the following steps: dissolving epoxidized soybean oil in an organic solvent to obtain a solution A, and dissolving an amide ring-opening reagent and a ring-opening reaction catalyst in the organic solvent to obtain a solution B;
step two: simultaneously pumping the solution A and the solution B obtained in the step one into a first mixer of a micro-reaction device for mixing, and then feeding the mixture into a first micro-reactor of the micro-reaction device for reaction to obtain an epoxidized soybean oil ring-opening product;
step three: and (3) dissolving an acetylation reagent and an acetylation reaction catalyst in an organic solvent to obtain a solution C, pumping the solution C and the ring-opening product of the epoxidized soybean oil obtained in the step two into a second mixer of the micro-reaction device simultaneously for mixing, then feeding the mixture into a second microreactor of the micro-reaction device for reaction, and carrying out rotary evaporation on the reaction product to obtain the epoxidized soybean oil.
The invention selects a proper amide ring-opening reagent and an acetylation reagent to react with the epoxidized soybean oil, and designs and modifies the plasticizer with excellent performance. However, the plasticizing properties of the polyamide are different by using different amide ring-opening agents and different acetylating agents. Meanwhile, different catalysts are adopted, so that the ring opening efficiency and side reactions of acetylation reaction are influenced.
The invention firstly designs a reasonable plasticizer synthesis route, and the more representative structural formulas are as follows:
The traditional kettle type reaction has the disadvantages of long reaction time, more side reactions in the reaction process, unexpected product performance of the finally synthesized product, low yield and great economic loss. Even some amide ring-opening reagents and epoxidized soybean oil are difficult to react in a reaction bottle, but the micro-flow field system adopted by the invention not only improves the yield, but also solves the influence of a plurality of side reactions on the quality of the final product. Some reagents that are difficult to react in the reaction flask can also be carried out in the microreactor.
In addition, the acylation process is exothermic for a long time resulting in many side reactions. Compared with the traditional kettle type intermittent reaction, the mass and heat transfer efficiency can be greatly improved by utilizing the micro flow field system, and the method is efficient and safe. The traditional kettle type reaction can not realize the ring-opening reaction and the acetylation process in one step, and in a micro-flow field, reasonable micro-reactor assembly can be designed, so that the two-step reaction can be continuously carried out.
Compared with other types of ring-opening reagents, the final product obtained by the amide ring-opening reagent is better improved in plasticizing performance with other modifying groups. .
In the first step, the amide ring-opening reagent is any one of acetamide, caproamide, phthalimide or benzamide.
The ring-opening reaction catalyst is sodium hydrogen or sodium ethoxide, preferably sodium ethoxide.
In the second step, the mixing molar ratio of the epoxy compound in the epoxidized soybean oil to the amide ring-opening reagent and the ring-opening reaction catalyst is 1: 5-15: 0.01-0.1, preferably 1: 5-10: 0.02-0.1.
The ring-opening reaction temperature in the first microreactor is 50-90 ℃, preferably 60-80 ℃, and the reaction residence time is 5-15 min, preferably 8-12 min.
In the third step, the acetylation reagent is acetic anhydride.
The acetylation catalyst is perchloric acid or 4-Dimethylaminopyridine (DMAP), preferably perchloric acid.
The mixing molar ratio of the epoxidized soybean oil ring-opening product to the acetylation reagent to the acetylation reaction catalyst is 1: 5-20: 0.01-0.1, and preferably 1: 5-15: 0.02-0.1.
The temperature of acetylation reaction in the second microreactor is 10-30 ℃, preferably 20-30 ℃, and the reaction residence time is 5-15 min, preferably 8-12 min.
In step three, before rotary evaporation, the reaction product is treated with NaHCO3Adjusting the pH value of the reaction product to 6.5-7.5 by using an aqueous solution, and adjusting the pH value to NaHCO3The concentration of the aqueous solution was 5 wt%.
The rotary evaporated product is preferably further washed with water and dried.
In the first step and the third step, the organic solvent is Tetrahydrofuran (THF).
The microchannel in the microreactor in the micro-reaction device is a polytetrafluoroethylene tube, the tube diameter is 0.5-1 mm, and the total volume of the inner tube of each microreactor is 5-8 m L.
Has the advantages that:
1. the invention takes epoxidized soybean oil as a raw material, utilizes the particularity of amide groups and combines a micro-reaction continuous flow device to sequentially carry out ring-opening reaction and acetylation reaction to prepare the newly added plasticizer with more excellent performance. From a cost perspective, many amide ring-opening reagents are more economical; from the aspect of product effect, the epoxidized soybean oil is modified by amide groups on long chains, so that the migration resistance in the plasticizing performance is more outstanding. In addition, the whole synthesis process is further optimized and simplified by utilizing a micro-flow field system, so that the mass transfer and heat transfer efficiency is obviously greatly improved, a plurality of side reactions caused by intense heat release time in the acylation process are avoided, the problem that some ring-opening reagents cannot be carried out in a reaction bottle is solved, the two-step reaction is changed into one-step continuous flow, and the method has higher significance for the subsequent industrial production;
2. the invention selects the amide ring-opening reagent, the alkalescence of the amide group and the hybridization conjugation of the N atom in the amide ring-opening reagent, so that 4 atoms of the amide are positioned on the same plane and are easier to insert into polymer molecules.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a reaction schematic diagram of the preparation of a vegetable oil-based plasticizer using a micro-reaction device according to the present invention.
Detailed Description
The invention will be better understood from the following examples.
The structures, proportions, and dimensions shown in the drawings and described in the specification are for understanding and reading the present disclosure, and are not intended to limit the scope of the present disclosure, which is defined in the claims, and are not essential to the skilled in the art. In addition, the terms "upper", "lower", "front", "rear" and "middle" used in the present specification are for clarity of description, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the relative positions may be changed or adjusted without substantial technical changes.
The preparation method comprises the following steps:
the method comprises the following steps: dissolving epoxidized soybean oil in an organic solvent to obtain a solution A, and dissolving an amide ring-opening reagent and a ring-opening reaction catalyst in the organic solvent to obtain a solution B;
step two: simultaneously pumping the solution A and the solution B obtained in the step one into a first mixer of a micro-reaction device for mixing, and then feeding the mixture into a first micro-reactor of the micro-reaction device for reaction to obtain an epoxidized soybean oil ring-opening product;
step three: and (3) dissolving an acetylation reagent and an acetylation reaction catalyst in an organic solvent to obtain a solution C, pumping the solution C and the ring-opening product of the epoxidized soybean oil obtained in the step two into a second mixer of the micro-reaction device simultaneously for mixing, then feeding the mixture into a second microreactor of the micro-reaction device for reaction, and carrying out rotary evaporation on the reaction product to obtain the epoxidized soybean oil.
As shown in FIG. 1, the micro-reaction device used in the present invention comprises three syringe pumps, two mixers, and two micro-reactors. The injection pump 1 is filled with a solution A, the injection pump 2 is filled with a solution B, the solution A and the solution B are pumped into the mixer 1 to be mixed at the same time, and then enter the microreactor 1 to react to obtain an epoxidized soybean oil ring-opening product; the injection pump 3 is filled with a solution C, and the solution C and the ring-opening product of the epoxidized soybean oil are pumped into the mixer 2 to be mixed at the same time and then enter the microreactor 2 to react to obtain a final product.
The micro-channel in the micro-reactor is a polytetrafluoroethylene tube with the tube diameter of 1mm, and the total volume of the tube in each micro-reactor is 8m L.
Example 1
Diluting epoxidized soybean oil with THF to serve as one phase, filling the one phase into an injection pump, dissolving acetamide in THF, adding sodium ethoxide to serve as the other phase, filling the two phases into a microreactor simultaneously, reacting at 50 ℃ for 15min, wherein the molar ratio of epoxy compounds to acetamide in the epoxidized soybean oil is 1:5, the flow rates of the two phases are 0.146 and 0.054 respectively, the molar ratio of sodium ethoxide serving as a catalyst to epoxy compounds in the epoxidized soybean oil is 0.01:1, the obtained ring-opening product of the epoxidized soybean oil is continuously filled into the other microreactor, mixed with acetic anhydride and perchloric acid serving as a catalyst to pass through the microreactor, and reacting at 10 ℃ for 15min, wherein the molar ratio of the ring-opening product of the epoxidized soybean oil to the acetic anhydride is 1:5, and the molar ratio of the perchloric acid to the ring-opening product of the epoxidized soybean oil is 0.2: 1. Adjusting the pH value of the product to about 7 by using a sodium bicarbonate aqueous solution, carrying out rotary evaporation to obtain a final product, and then carrying out plasticizer performance detection.
Example 2
Diluting epoxidized soybean oil with THF to serve as one phase, filling the one phase into an injection pump, dissolving acetamide in THF, adding sodium ethoxide to serve as the other phase, filling the two phases into a microreactor simultaneously, reacting at 100 ℃ for 10min, wherein the molar ratio of epoxy compounds to acetamide in the epoxidized soybean oil is 1:10, the flow rates of the two phases are 0.176 and 0.074 respectively, the molar ratio of sodium ethoxide serving as a catalyst to epoxy compounds in the epoxidized soybean oil is 0.08:1, the obtained ring-opening product of the epoxidized soybean oil is continuously filled into the other microreactor, mixed with acetic anhydride and perchloric acid serving as a catalyst to pass through the microreactor, and reacting at 25 ℃ for 10min, wherein the molar ratio of the ring-opening product of the epoxidized soybean oil to the acetic anhydride is 1:10, and the molar ratio of the perchloric acid to the ring-opening product of the epoxidized soybean oil is 0.08: 1. Adjusting the pH value of the product to about 7 by using a sodium bicarbonate aqueous solution, carrying out rotary evaporation to obtain a final product, and then carrying out plasticizer performance detection.
Example 3
Diluting epoxidized soybean oil with THF to serve as one phase, filling the one phase into an injection pump, dissolving acetamide in THF, adding sodium ethoxide to serve as the other phase, filling the two phases into a microreactor simultaneously, reacting at 110 ℃ for 5min, wherein the molar ratio of epoxy compounds to acetamide in the epoxidized soybean oil is 1:15, the flow rates of the two phases are 0.321 and 0.117 respectively, the molar ratio of sodium ethoxide serving as a catalyst to epoxy compounds in the epoxidized soybean oil is 0.1:1, the obtained ring-opening product of the epoxidized soybean oil is continuously filled into the other section of the microreactor, is mixed with acetic anhydride and perchloric acid serving as a catalyst to pass through the microreactor, and reacts at 30 ℃ for 5min, wherein the molar ratio of the ring-opening product of the epoxidized soybean oil to acetic anhydride is 1:20, and the molar ratio of perchloric acid to the ring-opening product of the epoxidized soybean oil is 0.1: 1. Adjusting the pH value of the product to about 7 by using a sodium bicarbonate aqueous solution, carrying out rotary evaporation to obtain a final product, and then carrying out plasticizer performance detection.
Example 4
Diluting epoxidized soybean oil with THF to serve as one phase, flushing the diluted epoxidized soybean oil into an injection pump, dissolving benzamide in THF, adding sodium ethoxide to serve as the other phase, flushing the other phase into the injection pump, simultaneously injecting the two phases into a microreactor, reacting at 80 ℃ for 12min, wherein the molar ratio of an epoxy compound to the benzamide in the epoxidized soybean oil is 1:5, the flow rates of the two phases are 0.321 and 0.117 respectively, the molar ratio of sodium hydrogen as a catalyst to the epoxy compound in the epoxidized soybean oil is 0.02:1, continuously introducing the obtained ring-opened product of the epoxidized soybean oil into the other microreactor, mixing the ring-opened product of the epoxidized soybean oil with acetic anhydride and a perchloric acid as a catalyst, passing the mixture through the microreactor, and reacting at 10 ℃ for 12min, wherein the molar ratio of the ring-opened product of the epoxidized soybean oil to the acetic anhydride is 1:5, and the molar ratio of the perchloric acid. Adjusting the pH value of the product to about 7 by using a sodium bicarbonate aqueous solution, carrying out rotary evaporation to obtain a final product, and then carrying out plasticizer performance detection.
Example 5
Diluting epoxidized soybean oil with THF to serve as one phase, flushing the diluted epoxidized soybean oil into an injection pump, dissolving benzamide in THF, adding sodium ethoxide to serve as the other phase, flushing the other phase into the injection pump, simultaneously injecting the two phases into a microreactor, reacting at 100 ℃ for 10min, wherein the molar ratio of an epoxy compound to the benzamide in the epoxidized soybean oil is 1:10, the flow rates of the two phases are 0.153 and 0.097 respectively, the molar ratio of sodium ethoxide as a catalyst to an epoxy compound in the epoxidized soybean oil is 0.08:1, continuously introducing the obtained epoxidized soybean oil ring-opening product into the other microreactor, mixing the epoxidized soybean oil ring-opening product with acetic anhydride and a perchloric acid as a catalyst, reacting for 10min at 25 ℃ through the microreactor, wherein the molar ratio of the epoxidized soybean oil ring-opening product to the acetic anhydride is 1:10, and the molar ratio of the perchloric acid to the epoxidized soybean oil ring-opening product is 0. Adjusting the pH value of the product to about 7 by using a sodium bicarbonate aqueous solution, carrying out rotary evaporation to obtain a final product, and then carrying out plasticizer performance detection.
Example 6
Diluting epoxidized soybean oil with THF to serve as one phase, flushing the diluted epoxidized soybean oil into an injection pump, dissolving benzamide in THF, adding sodium ethoxide to serve as the other phase, flushing the other phase into the injection pump, simultaneously injecting the two phases into a microreactor, reacting at 110 ℃ for 8min, wherein the molar ratio of an epoxy compound to the benzamide in the epoxidized soybean oil is 1:15, the flow rates of the two phases are 0.176 and 0.104 respectively, the molar ratio of sodium ethoxide serving as a catalyst to an epoxy compound in the epoxidized soybean oil is 0.01:1, continuously introducing the obtained ring-opened product of the epoxidized soybean oil into the other microreactor, mixing the ring-opened product of the epoxidized soybean oil with acetic anhydride serving as a catalyst and 4-dimethylaminopyridine, reacting for 5min at 30 ℃ through the microreactor, wherein the molar ratio of the product of the epoxidized soybean oil to the acetic anhydride is 1:15, and the molar ratio of perchloric acid to the ring-opened product of the. Adjusting the pH value of the product to about 7 by using a sodium bicarbonate aqueous solution, carrying out rotary evaporation to obtain a final product, and then carrying out plasticizer performance detection.
Example 7
Diluting epoxidized soybean oil with THF to serve as one phase, flushing the one phase into an injection pump, dissolving phthalimide in THF, adding sodium ethoxide to serve as the other phase, flushing the other phase into the injection pump, simultaneously injecting the two phases into a microreactor, reacting at 100 ℃ for 10min, wherein the molar ratio of an epoxy compound to phthalimide in the epoxidized soybean oil is 1:10, the flow rates of the two phases are 0.47 and 0.23 respectively, the molar ratio of sodium ethoxide as a catalyst to an epoxy compound in the epoxidized soybean oil is 0.08:1, continuously introducing the obtained ring-opening product of the epoxidized soybean oil into the other microreactor, mixing the ring-opening product of the epoxidized soybean oil with acetic anhydride as a catalyst, reacting at 25 ℃ for 10min through the microreactor, wherein the molar ratio of the product of the epoxidized soybean oil to the acetic anhydride is 1:10, and the molar ratio of perchloric acid to the ring-opening product of the epoxidized soybean oil is 0.08: 1. Adjusting the pH value of the product to about 7 by using a sodium bicarbonate aqueous solution, carrying out rotary evaporation to obtain a final product, and then carrying out plasticizer performance detection.
Example 8
Diluting epoxidized soybean oil with THF to serve as one phase, filling the one phase into an injection pump, dissolving caproamide in THF, adding sodium ethoxide to serve as the other phase, filling the two phases into a microreactor simultaneously, reacting at 100 ℃ for 10min, wherein the molar ratio of epoxy compounds to caproamide in the epoxidized soybean oil is 1:10, the flow rates of the two phases are 0.47 and 0.23 respectively, the molar ratio of sodium ethoxide serving as a catalyst to epoxy compounds in the epoxidized soybean oil is 0.08:1, the obtained ring-opening product of the epoxidized soybean oil is continuously filled into the other microreactor, mixed with acetic anhydride and perchloric acid serving as a catalyst to pass through the microreactor, and reacting at 25 ℃ for 10min, wherein the molar ratio of the ring-opening product of the epoxidized soybean oil to the acetic anhydride is 1:10, and the molar ratio of the perchloric acid to the ring-opening product of the epoxidized soybean oil is 0.08: 1. Adjusting the pH value of the product to about 7 by using a sodium bicarbonate aqueous solution, carrying out rotary evaporation to obtain a final product, and then carrying out plasticizer performance detection.
Comparative example 1
Diluting epoxidized soybean oil with THF to serve as one phase, filling the diluted epoxidized soybean oil into an injection pump, dissolving benzoic acid in THF, adding fluoboric acid to serve as the other phase, filling the two phases into a microreactor simultaneously, reacting at 100 ℃ for 10min, wherein the molar ratio of epoxy compounds to benzoic acid in the epoxidized soybean oil is 1:10, the flow rates of the two phases are 0.138 and 0.145 respectively, the molar ratio of fluoroboric acid as a catalyst to epoxy compounds in the epoxidized soybean oil is 0.08:1, continuously filling the obtained ring-opened product of the epoxidized soybean oil into the other microreactor, mixing the ring-opened product of the epoxidized soybean oil with acetic anhydride and perchloric acid as a catalyst, reacting for 10min at 25 ℃ by the microreactor, wherein the molar ratio of the ring-opened product of the epoxidized soybean oil to acetic anhydride is 1:10, and the molar ratio of perchloric acid to the ring-opened product of the epoxidized soybean oil is 0.08: 1. Adjusting the pH value of the product to about 7 by using a sodium bicarbonate aqueous solution, carrying out rotary evaporation to obtain a final product, and then carrying out plasticizer performance detection.
Comparative example 2
Diluting epoxidized soybean oil with THF to serve as one phase, flushing the diluted epoxidized soybean oil into an injection pump, dissolving furoic acid in THF, adding fluoboric acid to serve as the other phase, flushing the other phase into the injection pump, simultaneously injecting the two phases into a microreactor, reacting at 100 ℃ for 10min, wherein the molar ratio of epoxy compounds to furoic acid in the epoxidized soybean oil is 1:10, the flow rates of the two phases are 0.13 and 0.153 respectively, the molar ratio of fluoroboric acid serving as a catalyst to epoxy compounds in the epoxidized soybean oil is 0.08:1, continuously introducing the obtained ring-opened product of the epoxidized soybean oil into the other microreactor, mixing the ring-opened product of the epoxidized soybean oil with acetic anhydride serving as a catalyst, and reacting at 25 ℃ for 10min through the microreactor, wherein the molar ratio of the ring-opened product of the epoxidized soybean oil to the acetic anhydride is 1:10, and the molar ratio of perchloric acid to the ring-opened product of. Adjusting the pH value of the product to about 7 by using a sodium bicarbonate aqueous solution, carrying out rotary evaporation to obtain a final product, and then carrying out plasticizer performance detection.
Comparative example 3
Diluting epoxidized soybean oil with THF to serve as one phase to be flushed into an injection pump, dissolving acetic acid in THF, adding fluoboric acid to serve as the other phase to be flushed into the injection pump, simultaneously injecting the two phases into a microreactor, reacting at 100 ℃ for 10min, wherein the molar ratio of epoxy compounds to acetic acid in the epoxidized soybean oil is 1:10, the flow rates of the two phases are 0.209 and 0.191 respectively, the molar ratio of fluoroboric acid serving as a catalyst to epoxy compounds in the epoxidized soybean oil is 0.08:1, the obtained ring-opening product of the epoxidized soybean oil is continuously introduced into the other microreactor, is mixed with acetic anhydride and perchloric acid serving as a catalyst to pass through the microreactor, and reacting at 25 ℃ for 10min, wherein the molar ratio of the ring-opening product of the epoxidized soybean oil to the acetic anhydride is 1:10, and the molar ratio of the perchloric acid to the ring-opening product of the epoxidized soybean oil is 0.. Adjusting the pH value of the product to about 7 by using a sodium bicarbonate aqueous solution, carrying out rotary evaporation to obtain a final product, and then carrying out plasticizer performance detection.
Comparative example 4
The reference product, namely the pure epoxidized soybean oil plasticizer (ESO), is a plasticizer, and the ESO is directly used as the plasticizer to prepare the plastic for detecting the plasticizing performance.
Comparative example 5
Weighing 0.03mol of epoxidized soybean oil into a 50ml three-necked bottle, dissolving 0.3mol of benzamide in 20m of L THF, adding the dissolved benzamide into the three-necked bottle, adding 0.0024mol of sodium ethoxide, stirring and heating in a 100 ℃ oil bath for 48 hours, adjusting the ph of the product to about 7.0 by using sodium bicarbonate, extracting and rotationally steaming the product by using ethyl acetate, placing the obtained product into another three-necked bottle, adjusting the ph value to about 7.0, extracting and rotationally steaming the product by using ethyl acetate to obtain a final product, and detecting the plasticizing performance.
Comparative example 6
Weighing 0.03mol of epoxidized soybean oil into a 50ml three-necked bottle, dissolving 0.15mol of benzamide in 20m of THF (tetrahydrofuran) L, adding the dissolved benzamide into the three-necked bottle, adding 0.0024mol of sodium ethoxide, stirring and heating the mixture in a 100 ℃ oil bath for 48 hours, adjusting the pH of the product to about 7.0 by using sodium bicarbonate, extracting and rotationally steaming the product by using ethyl acetate, adding the obtained product into another three-necked bottle, adding 0.0024mol of perchloric acid into 0.15mol of acetic anhydride, putting the mixture into a dropping funnel at constant pressure, dropwise adding the mixture into the three-necked bottle to continuously react with a ring-opening product, reacting the mixture at 10 ℃ for 48 hours, adjusting the pH value to 7, extracting and rotationally steaming the mixture by using ethyl acetate to obtain a final product, and detecting the acceleration performance.
Mixing the prepared plasticizer with PVC, an auxiliary agent, a lubricant and the like in a proper proportion, frying, vulcanizing and pressing, finally cutting, and detecting indexes such as tearing strength, strain stretching force and the like. Wherein, the tearing strength is detected by a tensile machine according to the standard of GB/T528-2009; wherein the tensile strength is detected by an extensometer and is detected according to the standard of DB 37/T2263-2012; the water absorption test method comprises the steps of shearing each sample into a shape with small difference, recording each mass, soaking in water for 48 hours, weighing the mass, and calculating the difference value before and after soaking.
Table 1 shows the tear strength parameters of the plasticizers prepared in examples 1-8 and comparative examples 1-6, respectively:
TABLE 1
As can be seen from table 1: compared with epoxidized soybean oil and the ring-opening product containing ester groups, the amide-group-containing product subjected to ring-opening treatment is greatly improved in tear strength, and the three amide-group-containing ring-opening products have almost the same advantages in comparison of the index. And the product produced in the micro flow field has better product performance than the obtained product of the kettle type reaction. And the best effect is achieved when the molar ratio of the epoxidized soybean oil to the ring-opening product is 1 to 10 and the reaction temperature is 100 ℃.
Table 2 shows the tensile test parameters of the plasticizers prepared in examples 1 to 8 and comparative examples 1 to 6, respectively:
TABLE 2
As can be seen from the data in Table 2, the respective modified products showed an improvement in both the strain-stretching force and the tensile strength, compared with epoxidized soybean oil, wherein the effect of using benzamide as the ring-opening agent was the most excellent. And the optimal reaction molar ratio in a micro-flow field is 1:10, wherein the catalyst is preferably fluoroboric acid and perchloric acid, and the optimal reaction temperature is 100 ℃.
In addition, the action mechanism of the plasticizer is that plasticizing molecules are inserted among polymer molecular chains, so that the stress of the polymer molecular chains is weakened, and the crystallinity of the polymer molecular chains is reduced, thereby achieving the plasticizing effect. The weak basicity of the amide group, and the hybrid conjugation of the N atom therein, makes the 4 atoms of the amide in the same plane easier to insert into the polymer molecule than the lipid group and amide group ring-opening agents. Many amide group-containing substances are good plasticizers themselves, and for example, NN dimethylformamide has been reported to have a good plasticizing effect on starch pulp films in Liwei, Xuzhen and other people's journal of the university of Anmi engineering. In addition, some plasticizers containing lipids do not have good migration resistance. Thus, epoxidized soybean oil modified with amide groups may have superior properties to products plasticized with epoxidized soybean oil modified with lipid groups alone.
Table 3 shows the water absorption test data of the plasticizers prepared in examples 1 to 8 and comparative examples 1 to 6:
TABLE 3
Table 3 (continuation)
As can be seen from the data in Table 3, the improved product also has improved migration resistance, and the advantages are more pronounced compared to the epoxidized soybean oil control, including compared to the ester-based plasticizer alone.
The present invention provides a method and a method for applying amide group to plant oil-based plasticizer for micro-reaction continuous flow preparation, and a method and a way for implementing the technical scheme are many, the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of modifications and embellishments can be made without departing from the principle of the present invention, and the modifications and embellishments should be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (8)
1. The method for preparing the vegetable oil-based plasticizer by the micro-reaction continuous flow is characterized by comprising the following steps of:
the method comprises the following steps: dissolving epoxidized soybean oil in an organic solvent to obtain a solution A, and dissolving an amide ring-opening reagent and a ring-opening reaction catalyst in the organic solvent to obtain a solution B;
step two: simultaneously pumping the solution A and the solution B obtained in the step one into a first mixer of a micro-reaction device for mixing, and then feeding the mixture into a first micro-reactor of the micro-reaction device for reaction to obtain an epoxidized soybean oil ring-opening product;
step three: dissolving an acetylation reagent and an acetylation reaction catalyst in an organic solvent to obtain a solution C, pumping the solution C and the ring-opening product of the epoxidized soybean oil obtained in the step two into a second mixer of the micro-reaction device for mixing, then feeding the mixture into a second microreactor of the micro-reaction device for reaction, and carrying out rotary evaporation on the reaction product to obtain the epoxidized soybean oil;
in the first step, the amide ring-opening reagent is any one of acetamide, phthalimide or benzamide;
the ring-opening reaction catalyst is sodium hydrogen or sodium ethoxide.
2. The method for preparing the vegetable oil-based plasticizer according to the micro-reaction continuous flow of claim 1, wherein in the second step, the mixing molar ratio of the epoxy compound in the epoxidized soybean oil to the amide-based ring-opening reagent and the ring-opening reaction catalyst is 1: 5-15: 0.01-0.1.
3. The method of claim 1, wherein in step two, the temperature of the ring-opening reaction in the first microreactor is 50-90 ℃ and the reaction residence time is 5-15 min.
4. The method of micro-reactive continuous flow for the preparation of vegetable oil-based plasticizers according to claim 1, wherein the acetylating agent is acetic anhydride in step three.
5. The method of microreaction continuous flow for making a vegetable oil-based plasticizer according to claim 1 wherein in step three, said acetylation catalyst is perchloric acid or 4-dimethylaminopyridine.
6. The method for preparing the vegetable oil-based plasticizer according to the micro-reaction continuous flow of claim 1, wherein in the third step, the mixing molar ratio of the ring-opening product of the epoxidized soybean oil to the acetylation reagent and the acetylation reaction catalyst is 1: 5-20: 0.01-0.1.
7. The method of micro-reactive continuous flow for preparing a vegetable oil-based plasticizer according to claim 1, wherein in step three, the temperature of acetylation reaction in the second micro-reactor is 10-30 ℃ and the reaction residence time is 5-15 min.
8. According to the rightThe method of micro-reaction continuous flow for preparing a vegetable oil-based plasticizer according to claim 1, wherein in step three, the reaction product is treated with NaHCO before rotary evaporation3Adjusting the pH value of the reaction product to 6.5-7.5 by using an aqueous solution.
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