Method for synthesizing lactide by means of catalysis of lactid acid

Abstract

The present invention relates to a method for the catalytic synthesis of lactide from lactic acid. The method relates to the synthesis of lactide from lactic acid under the catalysis of a zinc oxide nanoparticle aqueous dispersion as a catalyst. The present invention has four technical characteristics: I. the zinc oxide nanoparticle aqueous dispersion catalyst has a sufficient surface area, and the size of nanoparticles is merely 30-40 nm, providing a sufficient contact area between the substrate (lactic acid) and the catalyst; II. the new catalyst has a milder catalytic effect on polymerization, allowing the molecular weight distribution of a prepolymer within a range of 400-1500 g/mol, which is advantageous for depolymerization to proceed; III. the new catalyst is stable, thus avoiding oxidation or carbonization in a high temperature reaction; and IV. the new catalyst has a low toxicity and a small threat to human health.

Claims

1. A method for the catalytic synthesis of lactide from lactic acid, characterized in that the synthesis of lactide from lactic acid is catalyzed solely by a zinc oxide aqueous nanoparticle dispersion.

2. The method for the catalytic synthesis of lactide from lactic acid according to claim 1, characterized in that said zinc oxide nanoparticle aqueous dispersion is a dispersion of zinc oxide nanoparticles in water; and in said zinc oxide nanoparticle aqueous dispersion, the particle size of the zinc oxide nanoparticles is 30-40 nm, and the mass percentage of the zinc oxide nanoparticles is 20%.

3. The method for the catalytic synthesis of lactide from lactic acid according to claim 1, characterized in that the method comprises the following steps: a. Dehydration: lactic acid and a catalyst are mixed at a ratio under the conditions of 60-80 C. and 60 kPa, and subjected to a dehydration reaction for 2 hours to remove free water from the lactic acid to obtain a dehydration product; b. Polymerization: said dehydration product is subjected to a polymerization reaction for 3 hours under the conditions of 120-150 C. and 10 kPa to obtain an oligomer; and c. Depolymerization: said oligomer is subjected to a depolymerization reaction for 3-5 hours under the conditions of 170-220 C. and 1-3 kPa.

4. The method for the catalytic synthesis of lactide from lactic acid according to claim 3, characterized in that the amount of said catalyst in dehydration step a. is 0.3-0.6% by weight of said lactic acid.

5. A method for the catalytic synthesis of lactide from lactic acid, characterized in that the catalytic synthesis of lactide from lactic acid occurs by operation of a catalyst consisting of a zinc oxide aqueous nanoparticle dispersion.

6. The method for the catalytic synthesis of lactide from lactic acid according to claim 5, characterized in that said zinc oxide nanoparticle aqueous dispersion is a dispersion of zinc oxide nanoparticles in water; and in said zinc oxide nanoparticle aqueous dispersion, the particle size of the zinc oxide nanoparticles is 30-40 nm, and the mass percentage of the zinc oxide nanoparticles is 20%.

7. The method for the catalytic synthesis of lactide from lactic acid according to claim 5, characterized in that the method comprises the following steps: a. Dehydration: lactic acid and a catalyst are mixed at a ratio under the conditions of 60-80 C. and 60 kPa, and subjected to a dehydration reaction for 2 hours to remove free water from the lactic acid to obtain a dehydration product; b. Polymerization: said dehydration product is subjected to a polymerization reaction for 3 hours under the conditions of 120-150 C. and 10 kPa to obtain an oligomer; and c. Depolymerization: said oligomer is subjected to a depolymerization reaction for 3-5 hours under the conditions of 170-220 C. and 1-3 kPa.

8. The method for the catalytic synthesis of lactide from lactic acid according to claim 5, characterized in that the amount of said catalyst in said dehydration step a. is 0.3-0.6% by weight of said lactic acid.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) In order to more clearly illustrate the technical solutions in the embodiments of the present invention or in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. Obviously, the drawings in the following description are merely for some embodiments of the present invention, and a person skilled in the art would be able to obtain other drawings according to these drawings without involving any inventive effort.

(2) FIG. 1 is a structural schematic diagram of a reaction apparatus for implementing the present invention; (1) oil bath, (2) round-bottom flask reactor, (3) condenser, (4) collector, (5) cold trap, (6) oil pump, (7) thermo-controller, (8) heating plate, (9) thermometer, (10) pressure detector, and (11) gas valve;

(3) FIG. 2 is a flow chart of an optimized reaction process for the catalytic synthesis lactide from lactic acid of the present invention;

(4) FIG. 3 is a set of photographs of Examples 3 and 5 recorded during depolymerization; FIG. 3(A) is the case where the reaction temperature of Example 3 is 200 C., and FIG. 3(B) is the case where the reaction temperature of Example 3 is 250 C.; and FIG. 3(C) is the case where the reaction temperature of Example 5 is 200 C., and FIG. 3(D) is the case where the reaction temperature of Example 5 is 220 C.;

(5) FIG. 4 is a nuclear magnetic resonance spectrum of crude lactide synthesized using the novel catalysis method in Example 5 as detected using a 1H-NMR method;

(6) and FIG. 5 is a nuclear magnetic resonance spectrum of the lactide product purified by recrystallization in ethyl acetate in Example 1 as detected using a 1H-NMR method.

DETAILED DESCRIPTION OF EMBODIMENTS

(7) The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with examples.

EXAMPLE

(8) 1. Raw Material

(9) In this example, commercial lactic acid (86%, 50 ml per group) supplied by Sigma is used as a raw material.

(10) 2. Catalyst

(11) The catalyst used in each example is shown in Table 1. In Example 1, a group without a catalyst is set as a control group. The addition amounts of tin(II) 2-ethylhexanoate (also known as stannous octoate) in Examples 2 and 3 are respectively 0.3 wt % and 0.6 wt % of the weight of the raw material. 0.3 wt % and 0.6 wt % of a zinc oxide nanoparticle (30-40 nm) aqueous dispersion (20 wt %, US Research Nanomaterials) are respectively used as catalysts in Examples 4 and 5.

(12) All chemicals are used directly without pretreatment.

(13) TABLE-US-00001 TABLE 1 Catalysts used in Examples 1-5 Example No. Catalyst Catalyst amount A (wt %) 1 None 2 Tin(II) 2-ethylhexanoate 0.3 3 0.6 4 zinc oxide nanoparticle 0.3 aqueous dispersion 5 (30-40 nm, 20 wt %) 0.6

(14) 3. Reaction Process

(15) FIG. 2 shows a process flow chart of the process for the catalytic synthesis lactide from lactic acid of the present invention. As shown in FIG. 2, lactic acid and a catalyst are firstly added to a round-bottom flask (250 ml), and the lactic acid and the catalyst are uniformly mixed by means of a magnetic stirrer under the conditions of 60-80 C. and 60 kPa, and reacted for 2 hours to remove free water therefrom. Then, the heating temperature is gradually adjusted to 120-150 C., and the reactants are subjected to a polymerization reaction for 3 hours under 10 kPa conditions to obtain an oligomer. Finally, depolymerization is performed at 170 C. for a period of time (about 20-30 minutes), the temperature is then increased and the pressure reduced gradually, and under the conditions of 1-3 kPa and 170-220 C., lactide is continuously distilled out until no more product is formed.

(16) The weights of the products collected in the condenser and collector are measured by an electronic balance. Equation 1 and Equation 2 are used to calculate the conversion yield and production yield of the product.
Conversion yield=(Mass of lactide produced)/(Mass of lactide added)*100% Equation 1
Production yield=(Mass of lactide produced in reality)/(Mass of lactide produced in theory)*100% Equation 2

(17) The molecular weight of the oligomer/prepolymer is detected by a GPC method (Gel Permeation Chromatography, Waters, USA). The purity of lactide is determined by 1H-NMR.

(18) 4. Results

(19) 1) Molecular Weight of Oligomer/Prepolymer and Polymer

(20) TABLE-US-00002 TABLE 2 The molecular weight of prepolymer and polymer in Examples 1-5 Molecular Molecular weight weight of of prepolymer polymer Example (g (g No. Catalyst mol.sup.1) mol.sup.1) 1 None 1169 1719 2 Tin(II) 2-ethylhexanoate (0.3 wt %) 1877 8839 3 Tin(II) 2-ethylhexanoate (0.6 wt %) 2354 11875 4 Zinc oxide nanoparticle aqueous 877 3352 dispersion (30-40 nm, 0.3 wt %) 5 Zinc oxide nanoparticle aqueous 684 3066 dispersion (30-40 nm, 0.6 wt %)

(21) From the above results, it can be seen that as compared with zinc oxide nanoparticles, tin (II) 2-ethylhexanoate is more conducive in increasing the molecular weights of the prepolymer and polymer under the conditions of a reaction temperature of 150-220 C. Where zinc oxide nanoparticle are used as a catalyst, the molecular weight of the synthesized prepolymer is less than 900 g/mol, and the prepolymer easier to depolymerize into lactide than the prepolymers with molecular weights exceeding 1800 g/mol as obtained in Examples 2 and 3. After rising the temperature to 220 C. in the depolymerization reaction, the molecular weight of the polymer obtained under the catalysis of tin(II) 2-ethylhexanoate is greater than 8000 g/mol; however, if zinc oxide nanoparticles are used as a catalyst, the molecular weight of the resulting polymer can still be limited within 4000 g/mol. Therefore, the new catalyst can better control the molecular weights of the prepolymer and polymer, and shift the reaction equilibrium to the depolymerization reaction, thereby significantly improving the efficiency of the production of lactide.

(22) 2) Synthesis of Lactide

(23) TABLE-US-00003 TABLE 3 The results of lactide synthesis in Examples 1-5 Cleavage Lactide Conversion Production Example temperature Reaction produced yield yield No. Catalyst ( C.) time (h) (g) (%) (%) 1 none 180-250 13 25.27 48.97 60.77 2 Tin (II) 180-245 12 31.09 60.25 74.77 2-ethylhexanoate (0.3 wt %) 3 Tin (II) 180-245 10.5 33.13 64.21 79.68 2-ethylhexanoate (0.6 wt %) 4 Zinc oxide aqueous 170-220 13.5 37.84 73.33 91.01 nanoparticle dispersion (30-40 nm, 0.3 wt %) 5 Zinc oxide nanoparticle 170-220 10 38.36 74.34 92.26 aqueous dispersion (30-40 nm, 0.6 wt %)

(24) According to the above-mentioned results, both the tin (II) 2-ethylhexanoate and the zinc oxide nanoparticles can catalyse the production of lactide from lactic acid. The new catalyst of zinc oxide nanoparticles has a higher catalytic efficiency than the traditional tin-based catalysts, and increases the production yield of lactide to 90% or more. Moreover, when zinc oxide nanoparticles are used as a catalyst, the required product distillation temperature is lower and the reaction time is shorter. Therefore, it can be concluded that the new catalyst (0.6 wt %) in this patent has a better catalytic effect on the synthesis of lactide and is able to increase the production yield to 92%.

(25) 3) Stability of Catalyst

(26) The changes in the appearances of the reactants during depolymerization in Examples 3 and 5 are shown in FIG. 3. When a tin-based catalyst is used in Example 3, a very significant colour change occurs to the reactants. FIG. 3(A) shows the reaction temperature at 200 C., and FIG. 3(B) shows the reaction temperature at 250 C.; this is caused by the severe oxidation reaction of the reactants at high temperatures. However, where a zinc oxide nanoparticle aqueous dispersion as a catalyst in Example 5, only a slight oxidation phenomenon occurs. FIG. 3(C) is the case where the reaction temperature is 200 C., and FIG. 3(D) is the case where the reaction temperature is 220 C. The results show that the catalyst proposed in this patent is more stable than the traditional tin-based catalysts under high temperature conditions (180 C.).

(27) 4) Purification of Lactide Product

(28) FIG. 4 is a nuclear magnetic resonance spectrum of crude lactide synthesized using the novel catalysis method in Example 5 as detected using a 1H-NMR method. In the figure, the peaks of (a) CH and (b) CH3 indicate that the resulting product is lactide, and the peak of (c) CH represents solvent chloroform. The purity of crude lactide is about 85-88%;

(29) and FIG. 5 is a curve chart of the result of the lactide purified by recrystallization in ethyl acetate in Example 5 as detected using a 1H-NMR method. In the figure, the peaks of (a) CH and (b) CH3 indicate that the resulting product is lactide, and the peak of (c) CH represents solvent chloroform. The purity of the purified lactide exceeds 99%.

(30) It should be specially stated that the above technical solutions are only used to illustrate the present invention but are not used to limit the scope of the present invention. In addition, after reading the contents of the present invention, a person skilled in the art would be able to change or modify the present invention, and the equivalent forms are also within the scope defined by the appended claims of the present application.