CN110951055B - Method for preparing environment-friendly plasticizer by using biological fermentation product lactic acid and application thereof - Google Patents
Method for preparing environment-friendly plasticizer by using biological fermentation product lactic acid and application thereof Download PDFInfo
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Abstract
A method for preparing an environment-friendly plasticizer by utilizing a biological fermentation product lactic acid and application thereof belong to the field of fine chemical synthesis and plastic additive application. According to the invention, the target product, namely the environment-friendly plasticizer, is obtained by using biological fermentation lactic acid and natural vegetable oil to extract ricinoleic acid, cyclohexanol, hydrogen peroxide and acetic anhydride as main raw materials through two-step esterification, acetylation and epoxidation reactions. The environment-friendly plasticizer prepared by using the nontoxic and renewable lactic acid and ricinoleic acid as raw materials has the advantages of lower viscosity, light yellow color, higher molecular weight than that of a traditional dioctyl phthalate plasticizer DOP, high plasticizing efficiency, 46.93 percent and 42.78 percent of extraction resistance in organic solvents cyclohexane and petroleum ether respectively compared with DOP, 70.66 percent of migration resistance in activated carbon, suitability for industrial production and hopeful replacement of the traditional phthalic plasticizer.
Description
Technical Field
The invention relates to a method for preparing an environment-friendly plasticizer by using lactic acid of a biological fermentation product and application thereof, belonging to the field of fine chemical synthesis and plastic additive application.
Background
Polyvinyl chloride (PVC) is one of the most useful materials due to its excellent mechanical and thermal stability, and is widely used in the fields of medical instruments, toys for children, food packaging, infant and baby products, and the like. In order to improve the performance of PVC and reduce the processing temperature, a proper plasticizer needs to be added into PVC, and at present, the phthalate plasticizer accounts for about 80 percent of the market share in the plasticizer for commercial PVC. However, studies have shown that phthalates may increase the incidence of asthma, bronchitis and cancer. In addition, it may cause toxicity to the human reproductive system and endogenous hormones. Thus, the european union REACH act prohibits the use of phthalate plasticizers for PVC products such as children's toys, food packaging, and the like. The development of nontoxic, environment-friendly and biodegradable plasticizers to replace phthalate plasticizers has become a necessary trend.
Lactic acid is an organic acid prepared by fermenting corn starch biologically, has excellent biological melting property due to the characteristic of levorotation, has no toxic or side effect on human body, and can be metabolized directly. The lactic acid molecule contains a hydroxyl group and a carboxyl group at the same time, and the molecular structure of the lactic acid is shown as the following formula:
the self-polymerization is the result of the interaction of intermolecular groups at normal temperature, so that the plasticizer prepared by using lactic acid as a raw material contains a large amount of strong polar lactic acid groups. The plasticizer is prepared by utilizing the nontoxic and renewable lactic acid, so that the use of the traditional petroleum-based alcohols is reduced, and the problem of the current petroleum energy shortage is solved; at present, the research on the degradable plasticizer is few, the lactic acid has good biodegradability, and the lactic acid is used as the raw material to prepare the plasticizer, so that a new idea is provided for the development of the environment-friendly plasticizer in the future.
Disclosure of Invention
The invention aims to overcome the defects and provide a method for preparing an environment-friendly plasticizer by using lactic acid as a biological fermentation product and application thereof.
According to the technical scheme, the method for preparing the environment-friendly plasticizer by using the biological fermentation product lactic acid is characterized in that the biological fermentation lactic acid and natural vegetable oil are used for extracting ricinoleic acid, cyclohexanol, hydrogen peroxide and acetic anhydride as main raw materials, and the target product environment-friendly plasticizer is obtained through two steps of esterification, acetylation and epoxidation.
The method comprises the following steps:
(1) esterification reaction of ricinoleic acid: adding reactants ricinoleic acid and cyclohexanol into a reactor, heating and stirring to uniformly mix the two raw materials, and taking a small amount of mixed liquid to measure an acid value; then adding the catalyst 1 and a water-carrying agent; heating and stirring the mixed solution until the first drop of water in the water separator flows out, and then continuously reacting for a period of time; stopping the reaction when the acid value is no longer reduced; when the product is naturally cooled to normal temperature, removing the water-carrying agent and unreacted alcohol by reduced pressure distillation to obtain the cyclohexyl ricinoleate;
(2) and (3) lactic acid esterification reaction: adding the cyclohexyl ricinoleate prepared in the step (1) into a reactor, uniformly mixing with lactic acid, and taking a small amount of mixed solution to measure the acid value; then adding the catalyst 1 and a water-carrying agent, heating and stirring the mixed solution until the first drop of water flows out, and then continuously stirring for a period of time; measuring the acid value at intervals until the acid value is not reduced, and stopping the reaction; removing water-carrying agent and small molecular impurities by reduced pressure distillation to obtain ricinoleic acid cyclohexyl lactate;
(3) acetylation reaction: adding the product of the ricinoleic acid cyclohexyl lactate obtained in the step (2) into a reactor, slowly dropwise adding acetic anhydride into the reactor, and controlling the reaction temperature and continuously stirring; after the reaction is finished, removing unreacted acetic anhydride by reduced pressure distillation, neutralizing with sodium bicarbonate solution, washing with water, and then dehydrating by reduced pressure distillation to obtain ricinoleic acid cyclohexyl acetylation lactate;
(4) epoxidation reaction: adding the product of the cyclohexyl acetylated ricinoleate obtained in the step (3), acetic acid and the catalyst 2 into a reactor, stirring, and slowly heating; then slowly dripping hydrogen peroxide solution, and heating to continue the reaction after dripping; after the reaction is finished, neutralizing with sodium bicarbonate, washing with water, and carrying out reduced pressure distillation to remove water to obtain the final product, namely the epoxidized cyclohexyl acetylated lactate ricinoleate.
The catalyst 1 is p-toluenesulfonic acid; the catalyst 2 is phosphoric acid; the water-carrying agent is cyclohexane.
The specific process of the step (1) is as follows: ricinoleic acid in molar ratio of reactants in the reactor: adding cyclohexanol at a ratio of 1:0.8-2.0, stirring at 50 deg.C for 20min to mix the two materials uniformly, and measuring acid value with a small amount of mixed solution; then adding 0.5-1.5% of catalyst 1 by the total mass of reactants and 8-15% of water-carrying agent by the total mass of reactants; heating and stirring the mixed solution at the temperature of 120-150 ℃ until the first drop of water in the water separator flows out, and then continuously reacting for 3-6 h; stopping the reaction when the acid value is no longer reduced; and when the product is naturally cooled to the normal temperature, removing the water-carrying agent and unreacted alcohol by reduced pressure distillation at-0.1 MPa to obtain the cyclohexyl ricinoleate.
The specific process of the step (2) is as follows: adding the cyclohexyl ricinoleate prepared in the step (1) into a reactor, and uniformly mixing the cyclohexyl ricinoleate with lactic acid, wherein the weight ratio of the cyclohexyl ricinoleate: the lactic acid molar ratio is 1: 1.0-2.0, taking a small amount of mixed liquor to measure the acid value; then adding 0.6-2.0% of catalyst 1 by mass of the total mass of the reactants and 10-20% of water-carrying agent by mass of the total mass of the reactants, heating and stirring the mixed solution at the temperature of 110-; measuring the acid value every 1h until the acid value is not reduced any more, and stopping the reaction; and (4) distilling under reduced pressure of-0.1 MPa to remove water-carrying agents and small molecular impurities to obtain the ricinoleic acid cyclohexyl lactate.
The specific process of the step (3) is as follows: adding the product of the ricinoleic acid cyclohexyl lactate obtained in the step (2) into a reactor, and slowly dropwise adding acetic anhydride and ricinoleic acid cyclohexyl lactate into the reactor: the molar ratio of acetic anhydride is 1: 1.0 to 2.0, controlling the reaction temperature to be 60 to 70 ℃, and continuously stirring for 4 to 6 hours; after the reaction is finished, unreacted acetic anhydride is removed through reduced pressure distillation at the pressure of-0.1 MPa, sodium bicarbonate solution with the mass fraction of 10% is used for neutralizing and washing, and reduced pressure distillation dehydration is carried out at the pressure of-0.1 MPa, so that the cyclohexyl acetylation lactate ricinoleic acid is obtained.
The specific process of the step (4) is as follows: adding the product of the cyclohexyl acetylated lactate ricinoleic acid obtained in the step (3), acetic acid and the catalyst 2 into a reactor for stirring; slowly heating to 48-52 ℃; then slowly dripping a hydrogen peroxide solution with the mass concentration of 50%, heating to 58-68 ℃ after dripping, and continuing to react for 4-6 h; after the reaction is finished, neutralizing the mixture by using sodium bicarbonate with the mass concentration of 10%, washing the mixture by using water, and carrying out reduced pressure distillation and dehydration at-0.1 MPa to obtain a final product, namely, epoxidized cyclohexyl acetylated lactate ricinoleate;
wherein, the ricinoleic acid cyclohexyl acetylation lactate: the molar ratio of hydrogen peroxide is 1: 1.0-3.0; based on the total mass of the cyclohexyl acetylated lactate ricinoleate and the hydrogen peroxide, the using amount of the acetic acid is 8-15% of the total mass of the reactants, and the using amount of the catalyst 2 is 0.5-3% of the total mass of the reactants.
The environment-friendly plasticizer prepared by the method is applied to PVC products as a main plasticizer to replace a common phthalate plasticizer.
The invention has the beneficial effects that: lactic acid, ricinoleic acid, cyclohexanol, acetic anhydride and 50% hydrogen peroxide obtained by corn fermentation are used as main raw materials, crude lactate is obtained through esterification, acetylation and epoxidation reactions, and a refined product is obtained after a crude product is neutralized, washed and dried, wherein the molecular structure of the refined product is long-chain ester without benzene rings. The environment-friendly plasticizer prepared by using the nontoxic and renewable lactic acid and ricinoleic acid as raw materials has the advantages of low viscosity, light yellow color, higher product molecular weight than that of a common o-phthalate plasticizer DOP, regulation and control according to different PVC application fields, high plasticizing efficiency, excellent migration resistance, suitability for industrial production and hopeful replacement of the traditional o-phthalate plasticizer.
Drawings
FIG. 1 shows the flight mass spectrum of the product.
FIG. 2 is a diagram showing the solvent extraction resistance of PVC test pieces.
FIG. 3 is a graph showing migration resistance of PVC test pieces in activated carbon.
FIG. 4 is a graph showing the weight loss of PVC test piece.
FIG. 5 is a graph of glass transition temperature of PVC test pieces.
Detailed Description
Example 1 preparation of epoxidized cyclohexylacetylated lactate ricinoleate
The reaction route is as follows:
the method comprises the following specific steps:
(1) adding 29.85g (0.10mol) of ricinoleic acid and 12.02g (0.12mol) of cyclohexanol into a reactor, stirring for 20min at 50 ℃ to uniformly mix the two raw materials, taking a small amount of mixed liquid and measuring the acid value; then 0.37g of p-toluenesulfonic acid (0.9% of the reaction mass) and 6.40g of cyclohexane (12% of the reaction mass) of a water-carrying agent were added; heating and stirring the mixed solution at 130 ℃ until the first drop of water in the water separator flows out, and stopping the reaction when the acid value is not reduced any more; and when the product is naturally cooled to the normal temperature, carrying out reduced pressure distillation at-0.1 MPa to remove the water-carrying agent and unreacted alcohol, and obtaining the cyclohexyl ricinoleate.
(2) Adding 13.52g (0.15mol) of lactic acid, mixing uniformly, taking a small amount of mixed solution, and measuring the acid value; then 0.46g of p-toluenesulfonic acid (reaction mass: 0.9%) and 7.90mL of cyclohexane as a water-carrying agent (reaction mass: 12%) were added, the above mixed solution was heated and stirred at 130 ℃ until the first drop of water flowed out, and the reaction was stopped when the acid value was no longer reduced by measuring the acid value once every 1 hour; and (4) distilling under reduced pressure of-0.1 MPa to remove water-carrying agents and small molecular impurities to obtain the ricinoleic acid cyclohexyl lactate.
(3) Slowly dripping 11.23g (0.11mol, excess 10%) of acetic anhydride into the reactor, controlling the reaction temperature to be 70 +/-2 ℃, and continuously stirring for 4-6 h; and after the reaction is finished, carrying out reduced pressure distillation at-0.1 MPa to remove unreacted acetic anhydride, neutralizing by using a sodium bicarbonate solution with the mass fraction of 10%, washing by using water, and carrying out reduced pressure distillation and dehydration at-0.1 MPa to obtain the cyclohexyl acetylation lactate ricinoleic acid.
(4) Adding 5.70g of acetic acid (10% of the reaction mass) and 0.57g of phosphoric acid (1% of the reaction mass) into a reactor, stirring, and slowly heating to 50 +/-2 ℃; then slowly dripping 13.61g (0.2 mol) of 50% hydrogen peroxide solution, heating to 63 +/-5 ℃ after dripping, and continuing to react for 4-6h until the epoxy value is unchanged; then neutralizing with 10% sodium bicarbonate, washing with water, and distilling under reduced pressure to remove water to obtain the final product, namely the epoxidized cyclohexyl acetylated ricinoleate.
Performing flight mass spectrometry on the product, wherein the obtained mass spectrogram is shown in figure 1: as can be seen from the figure, the molecular mass peak with the same interval of 5 appears between 500-900, the interval is 72, namely one polymeric lactic acid molecule C3H4O2Relative molecular weight of (a). The molecular weights corresponding to lactate with different polymerization degrees in the product can be in one-to-one correspondence in the figure, and the difference between the measured value of the molecular weight of the product and the theoretical value is less than 0.5. The results show that the products obtained in the reaction system are mixed products with different molecular weights.
Comparative example 1 was used
Respectively mixing a commercial plasticizer DOP, a new prepared plasticizer epoxidized ricinoleic acid cyclohexyl acetylation lactate, PVC resin and a Ca/Zn heat stabilizer according to a mass ratio of 60: 100: 3, standing for a period of time, pouring the mixture on a double-roller plasticator to plasticate the mixture for 5 min at 160 ℃, selecting a type with the thickness of 1 mm according to the specification of a mould, putting the mould on a flat vulcanizing machine to carry out hot pressing at 180 ℃ for 2 min, cooling at normal temperature for 5 min to obtain a sheet-shaped PVC test piece, and carrying out solvent extraction resistance, activated carbon migration resistance, thermogravimetry and vitrification conversion temperature tests on the obtained PVC test piece.
The extraction resistance of two PVC test pieces in several solvents is tested, and the results are shown in figure 2, the mass loss rate of the epoxidized cyclohexylacetylated ricinoleate plasticized PVC test piece in cyclohexane and petroleum ether with weaker polarity is respectively reduced by 46.93 percent and 42.78 percent compared with the DOP plasticized test piece, which indicates that the newly prepared plasticizer has stronger polarity and has better extraction resistance in a weak-polarity solvent.
The migration resistance of the two PVC test pieces in the activated carbon is tested, and the results are shown in figure 3, after the activated carbon is wrapped for 24 hours, the mass loss rate of the epoxidized cyclohexylacetylated ricinoleic acid lactate plasticized PVC test piece is reduced by 70.66% compared with that of the DOP plasticized test piece, which indicates that the newly-prepared plasticizer has better migration resistance compared with that of the commercial plasticizer DOP.
Thermogravimetric analysis is carried out on the two PVC test pieces, and the results are shown in FIG. 4, the initial weight loss temperature of the epoxidized cyclohexylacetylated ricinoleic acid lactate plasticized PVC test piece is 164 ℃ and is lower than the initial weight loss temperature of the DOP plasticized test piece by 190 ℃, which is probably because the fresh plasticizer contains a small amount of low-molecular impurities, and the mass retention rate of the epoxidized cyclohexylacetylated ricinoleic acid lactate plasticized test piece is obviously higher than that of the DOP plasticized test piece at the middle and later stages of the thermal weight loss by 300-.
The two PVC test pieces are subjected to a glass transition temperature test, the result is shown in figure 5, and a group of peaks appear in the two test pieces, which shows that the two plasticizers are uniformly mixed with the PVC resin and have good compatibility; the glass transition temperature of the epoxidized cyclohexylacetylated ricinoleate plasticized PVC test piece is 17.5 ℃, the glass transition temperature of the DOP plasticized test piece is 30.9 ℃, and the glass transition temperature of the epoxidized cyclohexylacetylated ricinoleate plasticized PVC test piece is obviously lower than that of the DOP plasticized PVC test piece, so that the new-prepared plasticizer has higher plasticizing efficiency compared with DOP for PVC products.
Claims (6)
1. A method for preparing an environment-friendly plasticizer by using lactic acid of a biological fermentation product is characterized by comprising the following steps: extracting ricinoleic acid, cyclohexanol, hydrogen peroxide and acetic anhydride from biological fermentation lactic acid and natural vegetable oil as main raw materials, and performing two-step esterification, acetylation and epoxidation to obtain a target product, namely an environment-friendly plasticizer;
the method comprises the following steps:
(1) esterification reaction of ricinoleic acid: adding reactants ricinoleic acid and cyclohexanol into a reactor, heating and stirring to uniformly mix the two raw materials, and taking a small amount of mixed liquid to measure an acid value; then adding the catalyst 1 and a water-carrying agent; heating and stirring the mixed solution until the first drop of water in the water separator flows out, and then continuously reacting for a period of time; stopping the reaction when the acid value is no longer reduced; when the product is naturally cooled to normal temperature, removing the water-carrying agent and unreacted alcohol by reduced pressure distillation to obtain the cyclohexyl ricinoleate;
(2) and (3) lactic acid esterification reaction: adding the cyclohexyl ricinoleate prepared in the step (1) into a reactor, uniformly mixing with lactic acid, and taking a small amount of mixed solution to measure the acid value; then adding the catalyst 1 and a water-carrying agent, heating and stirring the mixed solution until the first drop of water flows out, and then continuously stirring for a period of time; measuring the acid value at intervals until the acid value is not reduced, and stopping the reaction; removing water-carrying agent and small molecular impurities by reduced pressure distillation to obtain ricinoleic acid cyclohexyl lactate;
(3) acetylation reaction: adding the product of the ricinoleic acid cyclohexyl lactate obtained in the step (2) into a reactor, slowly dropwise adding acetic anhydride into the reactor, and controlling the reaction temperature and continuously stirring; after the reaction is finished, removing unreacted acetic anhydride by reduced pressure distillation, neutralizing with sodium bicarbonate solution, washing with water, and then dehydrating by reduced pressure distillation to obtain ricinoleic acid cyclohexyl acetylation lactate;
(4) epoxidation reaction: adding the product of the cyclohexyl acetylated ricinoleate obtained in the step (3), acetic acid and the catalyst 2 into a reactor, stirring, and slowly heating; then slowly dripping hydrogen peroxide solution, and heating to continue the reaction after dripping; after the reaction is finished, neutralizing with sodium bicarbonate, washing with water, and carrying out reduced pressure distillation to remove water to obtain the final product, namely the epoxidized cyclohexyl acetylated lactate ricinoleate.
2. The method for preparing the environmentally friendly plasticizer using lactic acid, which is a biofermentation product, according to claim 1, wherein: the catalyst 1 is p-toluenesulfonic acid; the catalyst 2 is phosphoric acid; the water-carrying agent is cyclohexane.
3. The method for preparing the environment-friendly plasticizer by using the lactic acid as the biological fermentation product according to claim 1, wherein the specific process of the step (1) is as follows: ricinoleic acid in molar ratio of reactants in the reactor: adding cyclohexanol at a ratio of 1:0.8-2.0, stirring at 50 deg.C for 20min to mix the two materials uniformly, and measuring acid value with a small amount of mixed solution; then adding 0.5-1.5% of catalyst 1 by the total mass of reactants and 8-15% of water-carrying agent by the total mass of reactants; heating and stirring the mixed solution at the temperature of 120-150 ℃ until the first drop of water in the water separator flows out, and then continuously reacting for 3-6 h; stopping the reaction when the acid value is no longer reduced; and when the product is naturally cooled to the normal temperature, removing the water-carrying agent and unreacted alcohol by reduced pressure distillation at-0.1 MPa to obtain the cyclohexyl ricinoleate.
4. The method for preparing the environment-friendly plasticizer by using the lactic acid as the biological fermentation product according to claim 1, wherein the specific process of the step (2) is as follows: adding the cyclohexyl ricinoleate prepared in the step (1) into a reactor, and uniformly mixing the cyclohexyl ricinoleate with lactic acid, wherein the weight ratio of the cyclohexyl ricinoleate: the lactic acid molar ratio is 1: 1.0-2.0, taking a small amount of mixed liquor to measure the acid value; then adding 0.6-2.0% of catalyst 1 by mass of the total mass of the reactants and 10-20% of water-carrying agent by mass of the total mass of the reactants, heating and stirring the mixed solution at the temperature of 110-; measuring the acid value every 1h until the acid value is not reduced any more, and stopping the reaction; and (4) distilling under reduced pressure of-0.1 MPa to remove water-carrying agents and small molecular impurities to obtain the ricinoleic acid cyclohexyl lactate.
5. The method for preparing the environment-friendly plasticizer by using the lactic acid as the biological fermentation product according to claim 1, wherein the specific process of the step (3) is as follows: adding the product of the ricinoleic acid cyclohexyl lactate obtained in the step (2) into a reactor, and slowly dropwise adding acetic anhydride and ricinoleic acid cyclohexyl lactate into the reactor: the molar ratio of acetic anhydride is 1: 1.0 to 2.0, controlling the reaction temperature to be 68 to 72 ℃, and continuously stirring for 4 to 6 hours; after the reaction is finished, unreacted acetic anhydride is removed through reduced pressure distillation at the pressure of-0.1 MPa, sodium bicarbonate solution with the mass fraction of 10% is used for neutralizing and washing, and reduced pressure distillation dehydration is carried out at the pressure of-0.1 MPa, so that the cyclohexyl acetylation lactate ricinoleic acid is obtained.
6. The method for preparing the environment-friendly plasticizer by using the lactic acid as the biological fermentation product according to claim 1, wherein the specific process of the step (4) is as follows: adding the product of the cyclohexyl acetylated lactate ricinoleic acid obtained in the step (3), acetic acid and the catalyst 2 into a reactor for stirring; slowly heating to 48-52 ℃; then slowly dripping a hydrogen peroxide solution with the mass concentration of 50%, heating to 58-68 ℃ after dripping, and continuing to react for 4-6 h; after the reaction is finished, neutralizing the mixture by using sodium bicarbonate with the mass concentration of 10%, washing the mixture by using water, and carrying out reduced pressure distillation and dehydration at-0.1 MPa to obtain a final product, namely, epoxidized cyclohexyl acetylated lactate ricinoleate;
wherein, the ricinoleic acid cyclohexyl acetylation lactate: the molar ratio of hydrogen peroxide is 1: 1.0-3.0; based on the total mass of the cyclohexyl acetylated lactate ricinoleate and the hydrogen peroxide, the using amount of the acetic acid is 8-15% of the total mass of the reactants, and the using amount of the catalyst 2 is 0.5-3% of the total mass of the reactants.
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