CN112920394B - Preparation method and application of lactic acid-based environment-friendly plasticizer - Google Patents
Preparation method and application of lactic acid-based environment-friendly plasticizer Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a lactic acid-based environment-friendly plasticizer, belonging to the fields of fine chemical synthesis, environment-friendly plastic additives and plastic additive application. Lactic acid, 2-ethylhexanoic acid and diethylene glycol monobutyl ether are used as main raw materials, and diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate is prepared through two esterification reactions, wherein excessive lactic acid is added in the first esterification reaction, and the obtained molecules contain oligomeric lactic acid chain segments, so that the compatibility of the plasticizer and PVC is further improved. The diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate plasticizer prepared by the invention has light color, low viscosity and good compatibility with PVC, and compared with di (2-ethylhexyl) terephthalate and tributyl acetylcitrate, the plasticizer can endow PVC with similar thermal stability, better tensile property and solvent resistance and ideal comprehensive performance, is a novel environment-friendly plasticizer with industrial application prospect, and is expected to replace the traditional phthalate plasticizer.
Description
Technical Field
The invention relates to a preparation method and application of a lactic acid-based environment-friendly plasticizer, belonging to the fields of fine chemical synthesis, environment-friendly plastic additives and plastic additive application.
Background
Polyvinyl chloride (PVC) is one of the most widely used engineering plastics in the world at present, and is used in the fields of packaging, pipes, cables, floors, medical instruments and the like. However, pure PVC materials have hard and brittle properties at normal temperature, which limits the range of applications, and plasticizers must be added to lower the glass transition temperature, impart flexibility to PVC materials, and improve processability during processing PVC products. The PVC plasticizer which is most commonly used up to now is phthalate plasticizer, which has the advantages of low cost and high plasticizing efficiency, but many researches show that the phthalate plasticizer is easy to migrate out of PVC materials, not only accumulates in the environment and pollutes the environment, but also poses threats to human health. Several commonly used phthalate plasticizers have been banned from use in many fields in countries and regions such as the united states, european union and japan, and at present, our country is gradually restricting the use of phthalate plasticizers. The requirements of the world on environmental protection and health are becoming stricter, so that a novel environment-friendly plasticizer with low migration and low toxicity is urgently required to replace the o-benzene plasticizer, and the application of PVC products in the fields of food packaging, medical health and the like is expanded.
Lactic acid is a carboxylic acid containing hydroxyl, has wide sources in nature, can be produced massively by fermentation laws, and is a renewable biomass raw material. Lactic acid is nontoxic and harmless to the environment and human bodies, accords with the concept of environmental protection, and is an ideal plasticizer raw material. Because the lactic acid molecules contain hydroxyl and carboxyl, the lactic acid molecules can generate self-polymerization reaction under certain conditions to obtain oligomeric lactic acid molecular chains, and the oligomeric lactic acid molecular chains contain more ester groups, which are favorable for improving the compatibility of the plasticizer and PVC, so the lactic acid is an ideal raw material for preparing the plasticizer.
Disclosure of Invention
The invention aims to overcome the defects of the traditional o-benzene plasticizer, and compared with the traditional industrial environment-friendly plasticizer, the invention discloses a preparation method and application of a non-o-benzene plasticizer taking lactic acid as a molecular framework, develops the environment-friendly plasticizer with high plasticizing efficiency and migration resistance, and is suitable for industrial production.
According to the technical scheme, lactic acid, 2-ethylhexanoic acid and diethylene glycol monobutyl ether are used as raw materials, and the lactic acid-based environment-friendly plasticizer diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate is obtained through two-step esterification reaction.
The reaction equation is as follows:
the method comprises the following specific steps:
(1) primary esterification reaction: adding diethylene glycol monobutyl ether and lactic acid into a reactor, and heating and mixing; adding catalyst 1 and cyclohexane, and raising the temperature to continue the reaction; after the reaction is finished, cooling to room temperature, washing the product to be neutral by using a sodium bicarbonate solution and deionized water, and performing vacuum distillation to remove residual water and low-boiling-point impurities to obtain a product diethylene glycol monobutyl ether lactate;
(2) and (3) secondary esterification reaction: adding the diethylene glycol monobutyl ether lactate obtained in the step (1) and 2-ethylhexanoic acid into a reactor, and heating and mixing; continuously heating, adding the catalyst 2 and cyclohexane, and then raising the temperature to continuously react; after the reaction is finished, washing the product to be neutral by using sodium bicarbonate solution and deionized water, and then removing residual water by vacuum distillation to obtain the plasticizer diethylene glycol monobutyl ether-lactic acid-2-ethyl hexanoate.
Further, the catalyst 1 is p-toluenesulfonic acid.
Further, in the esterification reaction in the step (1), the raw material of diethylene glycol monobutyl ether: the molar ratio of lactic acid is 1: 1-3, the mass of the catalyst 1 is 0.4-0.8% of the total mass of the raw materials, and the volume of the cyclohexane is 5-10% of the total volume of the reactants.
Further, in the step (1), adding diethylene glycol monobutyl ether and lactic acid into a reactor, heating to 50-80 ℃, adding a catalyst 1 and cyclohexane, raising the temperature to 100-130 ℃, and continuing to react for 3-9 hours; and washing the product to be neutral by using a sodium bicarbonate solution and deionized water, and carrying out vacuum distillation for 0.5-2.5 h at the temperature of-0.1 MPa and 60-80 ℃ to remove residual water and low-boiling-point impurities to obtain the product diethylene glycol monobutyl ether lactate.
Further, in the step (2), the catalyst 2 is tetrabutyl titanate.
Further, in the step (2), the molar ratio of the diethylene glycol monobutyl ether lactate to the 2-ethylhexanoic acid is 1: 1 to 1.3; the mass of the catalyst 2 is 0.1-0.5% of the total mass of the reaction system, and the volume of the cyclohexane is 5-10% of the total volume of the reactants.
Further, in the step (2), adding the diethylene glycol monobutyl ether lactate obtained in the step (1) and 2-ethylhexanoic acid into a reactor, heating to 50-80 ℃, adding a catalyst 2 and cyclohexane, raising the temperature to 150-180 ℃, and continuing to react for 4-8 hours; after the reaction is finished, washing the product to be neutral by using a sodium bicarbonate solution and deionized water, and then carrying out vacuum distillation at-0.1 MPa and 60-80 ℃ for 0.5-2.5 h to remove residual water, thereby obtaining the plasticizer diethylene glycol monobutyl ether-lactic acid-2-ethyl hexanoate.
The application of the lactic acid-based environment-friendly plasticizer is characterized in that the prepared diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate is applied to the preparation of PVC materials as a main plasticizer or an auxiliary plasticizer.
The invention has the following beneficial effects: the invention uses lactic acid, diethylene glycol monobutyl ether and 2-ethyl caproic acid as main raw materials, and designs a novel plasticizer molecular structure by using lactic acid as a molecular link through two-step esterification reaction. The performance of the plasticizer prepared by the method is equivalent to or even superior to that of the current commonly used industrial environment-friendly plasticizer, and the plasticizer is expected to replace the traditional phthalate plasticizer.
Drawings
FIG. 1 infra-red spectra of the starting materials and products of example 3;
1. lactic acid; 2. diethylene glycol monobutyl ether lactate; 3. diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate.
FIG. 2 graph of the thermogravimetry of three samples using example 1;
1. plasticizing diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate; 2. plasticizing ATBC; 3. and (3) plasticizing by DOTP.
FIG. 3 is a graph showing migration resistance tests of three samples of application example 1;
1. diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate; 2. DOTP; 3. ATBC.
FIG. 4 DMA plots of three samples using example 1;
1. diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate; 2. DOTP; 3. ATBC.
Detailed Description
EXAMPLE 1 preparation of lactic acid-based Environment-friendly plasticizer diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate
(1) Primary esterification reaction: adding lactic acid and diethylene glycol monobutyl ether into a reactor, wherein the raw material of the diethylene glycol monobutyl ether: the molar ratio of lactic acid is 1: 1.5, heating to 70 ℃, and heating and mixing for about 0.5 h; adding catalysts of p-toluenesulfonic acid and cyclohexane, wherein the mass of the p-toluenesulfonic acid is 0.8 percent of the mass of the reaction system, the volume of the cyclohexane is 5 percent of the volume of the reaction system, raising the temperature to 110 ℃, and continuing to react for 8 hours; after the reaction is finished, cooling the system to normal temperature, washing the product to be neutral by using a sodium bicarbonate solution with the mass fraction of 10% and deionized water in sequence, and then carrying out vacuum distillation for 1h under the conditions of-0.1 MPa and 80 ℃ to remove residual water and low-boiling-point impurities to obtain the product diethylene glycol monobutyl ether lactate.
(2) And (3) secondary esterification reaction: adding diethylene glycol monobutyl ether lactate and 2-ethylhexanoic acid into a reactor, wherein the raw materials are diethylene glycol monobutyl ether lactate: the molar ratio of 2-ethyl hexanoic acid is 1: 1.2, heating to 80 ℃, and heating and mixing for about 0.5 h; adding catalyst tetra-n-butyl titanate and cyclohexane, wherein the mass of the tetra-n-butyl titanate is 0.5 percent of the mass of the reaction system, the volume of the cyclohexane is 5 percent of the volume of the reaction system, raising the temperature to 170 ℃, and continuing to react for 6 hours; after the reaction is finished, cooling the system to normal temperature, washing the product to be neutral by using a sodium bicarbonate solution with the mass fraction of 10% and deionized water in sequence, and then carrying out vacuum distillation for 1h under the conditions of-0.1 MPa and 80 ℃ to remove residual water and low-boiling-point impurities to obtain the final product, namely diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate.
EXAMPLE 2 preparation of lactic acid-based Environment-friendly plasticizer diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate
(1) Primary esterification reaction: adding lactic acid and diethylene glycol monobutyl ether into a reactor, wherein the raw material of the diethylene glycol monobutyl ether: the molar ratio of lactic acid is 1: 2, heating and mixing for about 0.5h when the temperature is raised to 60 ℃; adding catalysts of p-toluenesulfonic acid and cyclohexane, wherein the mass of the p-toluenesulfonic acid is 0.5 percent of the mass of the reaction system, the volume of the cyclohexane is 10 percent of the volume of the reaction system, raising the temperature to 120 ℃, and continuing to react for 7 hours; after the reaction is finished, cooling the system to normal temperature, washing the product to be neutral by using a sodium bicarbonate solution with the mass fraction of 15% and deionized water in sequence, and then carrying out vacuum distillation for 2h under the conditions of-0.1 MPa and 60 ℃ to remove residual water and low-boiling-point impurities to obtain the product diethylene glycol monobutyl ether lactate.
(2) And (3) secondary esterification reaction: adding diethylene glycol monobutyl ether lactate and 2-ethylhexanoic acid into a reactor, wherein the raw materials are diethylene glycol monobutyl ether lactate: the molar ratio of 2-ethyl hexanoic acid is 1: 1.1, heating and mixing for about 0.5h when the temperature is raised to 70 ℃; adding catalyst tetra-n-butyl titanate and cyclohexane, wherein the mass of the tetra-n-butyl titanate is 0.4% of the mass of the reaction system, the volume of the cyclohexane is 10% of the volume of the reaction system, raising the temperature to 160 ℃, and continuing to react for 7 hours; after the reaction is finished, cooling the system to normal temperature, washing the product to be neutral by using a sodium bicarbonate solution with the mass fraction of 15% and deionized water in sequence, and then carrying out vacuum distillation for 2h under the conditions of-0.1 MPa and 60 ℃ to remove residual water and low-boiling-point impurities to obtain the final product diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate.
EXAMPLE 3 preparation of lactic acid-based Environment-friendly plasticizer diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate
(1) Primary esterification reaction: adding lactic acid and diethylene glycol monobutyl ether into a reactor, wherein the raw material of the diethylene glycol monobutyl ether: the molar ratio of lactic acid is 1: 3, heating to 50 ℃, and mixing for about 0.5 h; adding catalysts of p-toluenesulfonic acid and cyclohexane, wherein the mass of the p-toluenesulfonic acid is 0.6 percent of the mass of the reaction system, the volume of the cyclohexane is 8 percent of the volume of the reaction system, raising the temperature to 130 ℃, and continuing to react for 6 hours; after the reaction is finished, cooling the system to normal temperature, washing the product to be neutral by using a sodium bicarbonate solution with the mass fraction of 15% and deionized water in sequence, and then carrying out vacuum distillation for 1.5h under the conditions of-0.1 MPa and 70 ℃ to remove residual water and low-boiling-point impurities to obtain the product diethylene glycol monobutyl ether lactate.
(2) And (3) secondary esterification reaction: adding diethylene glycol monobutyl ether lactate and 2-ethylhexanoic acid into a reactor, wherein the raw materials are diethylene glycol monobutyl ether lactate: the molar ratio of 2-ethyl hexanoic acid is 1: 1.3, heating to 80 ℃, and heating and mixing for about 0.5 h; adding catalyst tetra-n-butyl titanate and cyclohexane, wherein the mass of the tetra-n-butyl titanate is 0.3 percent of the mass of the reaction system, the volume of the cyclohexane is 8 percent of the volume of the reaction system, raising the temperature to 180 ℃, and continuing to react for 5 hours; after the reaction is finished, cooling the system to normal temperature, washing the product to be neutral by using a sodium bicarbonate solution with the mass fraction of 10% and deionized water in sequence, and then carrying out vacuum distillation for 1.5h under the conditions of-0.1 MPa and 70 ℃ to remove residual water and low-boiling-point impurities to obtain the final product diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate.
The raw material lactic acid, the intermediate diethylene glycol monobutyl ether lactate, and the final product diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate in example 3 were subjected to an infrared spectroscopic test, and the test results are shown in fig. 1.
In the figure 1, 2 and 3 are respectively lactic acid, diethylene glycol monobutyl ether lactate and diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate from top to bottom. 2400 + 3400cm in the process of primary esterification reaction-1The broad diffraction peak of (A) is the peak of stretching vibration of the free hydroxyl group of lactic acid and the hydroxyl group on the carboxyl group, and the peak is attenuated and 1721cm-1A red shift of C ═ O, indicating successful esterification of the carboxyl group on lactic acid, 3437cm in Curve 2-1The peaks indicate that the first esterification product retains the free hydroxyl group on lactic acid, resulting in diethylene glycol monobutyl ether lactate. 3437cm in the second esterification reaction-1The stretching vibration peak of the hydroxyl disappears, which indicates the successful esterification of the free hydroxyl on the diethylene glycol monobutyl ether lactate, and also proves the successful synthesis of the final product diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate.
Application example 1
12g of PVC powder, 6g of diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate prepared in example 2 and 200mL of tetrahydrofuran are added into a beaker, magnetons are added, the mixture is stirred for 12-24 hours on a magnetic stirrer after being sealed, the solution is poured into a culture dish with the diameter of 15cm after being stirred uniformly, the culture dish is kept stand and volatilized in the air for 3 days and then is placed in an oven at 50 ℃ for 2 days, and the obtained PVC film sample is used for carrying out a thermal stability test, a migration resistance test and a DMA test.
A comparative PVC sample was prepared by DOTP and ATBC using the same procedure.
Thermogravimetric analysis is carried out on three PVC samples, the results are shown in figure 2, 1, 2 and 3 are respectively thermal weight loss curves of PVC samples plasticized by diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate, ATBC and DOTP, and two weight loss stages of the three PVC samples can be seen from the thermal weight loss curves. Stage a is mainly loss of plasticizer and decomposition of PVC chain to remove HCl; and the stage b is the further decomposition of the PVC carbon chain skeleton. From the three curves in the figure, it can be seen that at 10% and 50% mass loss, the temperature corresponding to PVC plasticized with diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate is higher than ATBC and slightly lower than DOTP, indicating that the PVC sample plasticized with diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate shows good thermal stability.
The specific results of comparative tests on migration resistance and volatility resistance of three PVC samples in different solvents are shown in fig. 3, wherein 1, 2 and 3 are mass loss rates of PVC films plasticized by diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate, DOTP and ATBC in different media, three solvents are selected for testing migration resistance, an activated carbon environment is selected for testing volatility resistance, and the solvents are distilled water, a non-polar solvent petroleum ether and a polar solvent absolute ethyl alcohol. And respectively putting the PVC test piece into the three solvents for soaking for 24 hours, putting the PVC test piece into activated carbon, and similarly standing for 24 hours at 70 ℃. As can be seen from the figure, the ATBC plasticized PVC sample was easily volatilized in activated carbon; the DOTP plasticized sample is easy to migrate out in a nonpolar solvent petroleum ether and has better stability in other solvents and activated carbon; the diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate plasticized PVC sample keeps good stability in the environments, basically does not migrate in distilled water, absolute ethyl alcohol and petroleum ether, and therefore has good migration resistance and volatility resistance.
DMA analysis of the three PVC samples as shown in figure 4, curves 1, 2 and 3 are plots of Tan delta versus temperature for the diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate, DOTP and ATBC plasticized PVC samples, respectively. The three curves have only one peak, which shows that the three plasticizers have good compatibility with PVC, and the temperature corresponding to the peak of the curve represents the glass transition temperature of the PVC sample. As can be seen, the glass transition temperature of PVC plasticized by DOTP is the lowest, 29.7 ℃; the glass transition temperature of PVC plasticized by ATBC is 33.8 ℃; the glass transition temperature of a PVC sample plasticized by the diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate is 38.2 ℃, and the size of the PVC sample is not much different from that of PVC plasticized by ATBC, which shows that the capability of reducing the glass transition temperature of the PVC by the diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate is similar to that of ATBC and DOTP, so that the diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate can be completely used as a main plasticizer, has the plasticizing performance similar to that of a commercial environment-friendly plasticizer, and can replace ATBC, DOTP and even traditional phthalate plasticizers.
The above description is intended to be illustrative and not restrictive, and the scope of the invention is defined by the appended claims, which may be modified in any manner within the scope of the invention.
Claims (9)
1. A preparation method of a lactic acid-based environment-friendly plasticizer is characterized by comprising the following steps: lactic acid, 2-ethylhexanoic acid and diethylene glycol monobutyl ether are used as raw materials, and a lactic acid-based environment-friendly plasticizer diethylene glycol monobutyl ether-lactic acid-2-ethylhexanoate is obtained through two-step esterification reaction; the method comprises the following specific steps:
(1) primary esterification reaction: adding diethylene glycol monobutyl ether and lactic acid into a reactor, and heating and mixing; adding catalyst 1 and cyclohexane, and raising the temperature to continue the reaction; after the reaction is finished, cooling to room temperature, washing the product to be neutral by using a sodium bicarbonate solution and deionized water, and performing vacuum distillation to remove residual water and low-boiling-point impurities to obtain a product diethylene glycol monobutyl ether lactate;
(2) and (3) secondary esterification reaction: adding the diethylene glycol monobutyl ether lactate obtained in the step (1) and 2-ethylhexanoic acid into a reactor, and heating and mixing; continuously heating, adding the catalyst 2 and cyclohexane, and then raising the temperature to continuously react; after the reaction is finished, washing the product to be neutral by using sodium bicarbonate solution and deionized water, and then removing residual water by vacuum distillation to obtain the plasticizer diethylene glycol monobutyl ether-lactic acid-2-ethyl hexanoate.
2. The method for preparing a lactic acid-based environmentally friendly plasticizer according to claim 1, wherein: the catalyst 1 is p-toluenesulfonic acid.
3. The method for preparing a lactic acid-based environmentally friendly plasticizer according to claim 1, wherein: in the esterification reaction in the step (1), the raw material diethylene glycol monobutyl ether: the molar ratio of lactic acid is 1: 1-3, the mass of the catalyst 1 is 0.4-0.8% of the total mass of the raw materials, and the volume of the cyclohexane is 5-10% of the total volume of the reactants.
4. The method for preparing a lactic acid-based environmentally friendly plasticizer according to claim 1, wherein: in the step (1), adding diethylene glycol monobutyl ether and lactic acid into a reactor, heating to 50-80 ℃, adding a catalyst 1 and cyclohexane, raising the temperature to 100-130 ℃, and continuing to react for 3-9 hours; and washing the product to be neutral by using a sodium bicarbonate solution and deionized water, and carrying out vacuum distillation for 0.5-2.5 h at the temperature of-0.1 MPa and 60-80 ℃ to remove residual water and low-boiling-point impurities to obtain the product diethylene glycol monobutyl ether lactate.
5. The method for preparing a lactic acid-based environmentally friendly plasticizer according to claim 1, wherein: in the step (2), the catalyst 2 is tetrabutyl titanate.
6. The method for preparing a lactic acid-based environmentally friendly plasticizer according to claim 1, wherein: in the step (2), the molar ratio of the diethylene glycol monobutyl ether lactate to the 2-ethylhexanoic acid is 1: 1 to 1.3; the mass of the catalyst 2 is 0.1-0.5% of the total mass of the reaction system, and the volume of the cyclohexane is 5-10% of the total volume of the reactants.
7. The method for preparing a lactic acid-based environmentally friendly plasticizer according to claim 1, wherein: adding the diethylene glycol monobutyl ether lactate obtained in the step (1) and 2-ethylhexanoic acid into a reactor, heating to 50-80 ℃, adding a catalyst 2 and cyclohexane, raising the temperature to 150-180 ℃, and continuing to react for 4-8 hours; after the reaction is finished, washing the product to be neutral by using a sodium bicarbonate solution and deionized water, and then carrying out vacuum distillation at-0.1 MPa and 60-80 ℃ for 0.5-2.5 h to remove residual water, thereby obtaining the plasticizer diethylene glycol monobutyl ether-lactic acid-2-ethyl hexanoate.
8. Use of a lactic acid-based environmentally friendly plasticizer prepared by one of the methods of claims 1 to 7, characterized in that: the prepared diethylene glycol monobutyl ether-lactic acid-2-ethyl hexanoate is applied to the preparation of PVC materials.
9. Use of a lactic acid-based environmentally friendly plasticizer prepared by one of the methods of claims 1 to 7, characterized in that: the prepared diethylene glycol monobutyl ether-lactic acid-2-ethyl hexanoate is used as a primary plasticizer or an auxiliary plasticizer to be applied to the preparation of PVC materials.
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