An esterification reaction catalyst used for PBAT synthesis and a preparation method thereof

Abstract

The application discloses an esterification reaction catalyst used for PBAT synthesis and a preparation method thereof. The catalyst is mainly used for esterification reaction, and polyester with good color and high polymerization degree can be obtained. The catalyst is mainly obtained by compounding a multi-metal layered structure substance containing a sulfonate and a metal complex compound. The sulfonate and the multi-metal layered structure substance are grafted and assembled to form an anionic layered sulfonate compound with a multi-metal center. Then, some metal complex compounds are attached to the synthetic carrier to form catalyst microparticles with high activity and stability.

Description

TECHNICAL FIELD

[0001] The present application relates to an esterification reaction catalyst for PBAT synthesis and a preparation method thereof, more particularly to an esterification reaction catalyst with high activity formed by using a multi-metal layered structure as a skeleton, combining a bisguanide trioctyl phenyl sulfonate and simultaneously loading a metal complex compound, which can be used for polyester synthesis. TECHNICAL BACKGROUND

[0002] The catalyst for polymer material synthesis is an important material in the chemical industry, especially for esterification reaction. There are many catalysts that can be widely used for esterification catalysis. The compounds of antimony and titanium are the most common catalysts in industrial manufacturing, which are mentioned in US patents 4039515, 4482700, 5302690, etc. However, when titanium or antimony is used as a catalyst, it is easy to cause the polyester to be brittle, resulting in a mechanical strength that does not meet the standard, so it is necessary to add a phosphoric acid ester heat stabilizer. However, the phosphoric acid ester and the catalyst will interfere with each other, resulting in a decrease in catalytic activity. To solve this problem, US patent 5733969 uses a zeolite-based modified catalyst, which has certain improvement on this problem, but the product will appear yellow during the later processing process. At the same time, due to the addition of zeolite, the catalyst particles are easy to gather at the material outlet, which needs to be cleaned regularly. SUMMARY

[0003] The purpose of the present application is to improve the shortcomings of the prior art and provide an esterification reaction catalyst for PBAT synthesis. Another purpose of the present application is to provide a preparation method of the above-mentioned catalyst. The esterification reaction catalyst of the present application is formed by using a multi-metal layered structure as a skeleton, combining a bisguanide trioctyl phenyl sulfonate and simultaneously loading a metal complex compound, which has high activity and can be used for producing polyester resin with high mechanical strength and good appearance.

[0004] The technical solution of the present application is as follows: an esterification reaction catalyst for PBAT synthesis, characterized by being obtained by compounding a multi-metal layered structure containing a sulfonate and a metal complex compound; wherein the structure general formula of the multi-metal layered structure containing a sulfonate is:

[0005]

[0006] Among them, is a divalent metal substance, is a trivalent metal substance, and the value of X is between 0.17 and 0.33 (M 3+ and (M 2+ + M 3+ ) molar ratio is between 0.17 and 0.33, a complete structure catalyst can be obtained); A is an anion salt compound sulfonate.

[0007] Preferably, the mass ratio of the metal coordination compound to the multi-metal layered structure containing sulfonate is 1.0% to 15%.

[0008] Preferably, the divalent metal substance is magnesium, iron, zinc or cobalt; and the trivalent metal substance is aluminum or iron.

[0009] Preferably, the anion salt compound sulfonate is bisguanide trioctyl phenyl sulfonate.

[0010] Preferably, the particle size of the multi-metal layered structure containing sulfonate is between 0.1 and 1 microns.

[0011] Preferably, the metal coordination compound is one or more of titanate or aluminate.

[0012] The present application also provides a method for preparing the above-mentioned esterification reaction catalyst for PBAT synthesis, which is obtained by compounding a multi-metal layered structure containing sulfonate with a metal coordination compound. The sulfonate is assembled with the multi-metal layered structure to form an anion layered sulfonate compound with a multi-metal center; and then the metal coordination compound is attached to the interlayer gap of the synthesized carrier to form catalyst particles with high activity and stability; the specific steps are as follows:

[0013] (a). A multi-metal layered structure containing target metals is designed by ion exchange method, and a compound containing M 2+ (such as magnesium carbonate, ferrous oxide, zinc carbonate, cobalt carbonate, etc.) and an oxide containing M3 + (such as aluminum oxide or iron oxide, etc.) are mixed to form a solution with a molar concentration of 1 to 10%, and the solution is ion exchanged with a multi-layer metal substance with a structural formula of [Mg6Al2(OH) 16 CO3] purchased from Sakai Chemical Industry Co., Ltd. of Japan at 60 to 80℃ to obtain a multi-metal layered structure with a target metal core and a ratio;

[0014] (b). Bisguanide trioctyl phenyl sulfonate is configured into a solution with a molar concentration of 5 to 15%;

[0015] (c). The multi-metal layered structure obtained in step a is mixed with the anion salt compound sulfonate according to a molar ratio of 1:(1 to 2) with the anion salt compound sulfonate solution, and reacted at a certain temperature, and then dried to obtain a solid product;

[0016] (d). The metal coordination compound is compounded with the solid product obtained in step c in a solvent, and the reaction product is filtered and dried to obtain an esterification reaction catalyst for PBAT synthesis.

[0017] The reaction temperature in step (c) is preferably 80-100 DEG C; the reaction time is 2-5 hours; the complexing reaction temperature in step (d) is 30-100 DEG C, and the complexing reaction time is 2-5 hours.

[0018] The solvent in step (d) is preferably water or ethanol.

[0019] The present application has the following advantages:

[0020] 1. The present application develops a new esterification catalyst.

[0021] 2. The present application optimizes the performance of the esterification catalyst in the field of polyester material synthesis.

[0022] 3. Compared with the conventional esterification catalyst, the present application has the advantages of high catalytic efficiency, good product performance, and good color. DETAILED DESCRIPTION

[0023] Example 1

[0024] Zinc carbonate is used as the substance containing divalent metal M2+, and iron oxide is used as the substance containing trivalent metal M3+ to mix and configure a solution with a molar concentration of 1%, wherein the molar ratio of M3+ to (M2++ M3+) is 0.2. The solution is ion-exchanged with a multi-layer metal substance with a structural formula of [Mg6Al2(OH)16CO3] purchased from Sakai Chemical Co., Ltd. in Japan at 60 DEG C to obtain a multi-metal layered structure substance with a target metal core and a ratio, the particle size of which is 0.1 microns. The substance is mixed with bis-guanide tris-octylphenyl sulfonate in a system with water as a solvent according to a molar ratio of 1:1 and is reacted at 80 DEG C for 2 hours to obtain a catalyst particle with a structural formula of [Zn 2+0.8Fe3+0.2(OH)2]0.2+[(C72H131N7O9S3)0.2*mH2O]0.2. Then, titanium acid ester is further compounded with the catalyst particle according to a proportion of 15wt% of the mass of [Zn 2+0.8Fe3+0.2(OH)2]0.2+[(C72H131N7O9S3)0.2*mH2O]0.2, and the solvent used in the compounding process is ethylene glycol, the temperature of which is set to 30 DEG C, and the reaction time is 5 hours. After the reaction is completed, the final catalyst is obtained by drying.

[0025] Example 2

[0026] Fe2O3 as the substance containing trivalent metal M3+, and the molar ratio of M3+ to (M2++ M3+) is 0.3, and the solution is ion-exchanged with a multi-layer metal substance with a structural formula of [Mg6Al2(OH)16CO3] purchased from Japan Sakai Chemical at 70℃ to obtain a multi-metal layered structure substance with a target metal core and a ratio, and the particle size is 0.5 microns, and the multi-metal layered structure substance is mixed with bisguanide tricaprylyl phenyl sulfonate in a system with water as a solvent at a molar ratio of 1 to 1.5, and the reaction is carried out at 90℃ for 4 hours to obtain a catalyst particle with a structural formula of [Fe2+0.7Al3+0.3(OH)2]0.3+[(C72H131N7O9S3)0.3*mH2O]0.3, and then the aluminum ester is further compounded at a ratio of 10wt% of the mass of [Fe2+0.7Al3+0.3(OH)2]0.3+[(C72H131N7O9S3)0.3*mH2O]0.3, and the solvent water used in the process is set to 50℃, and the reaction time is 3 hours. After the reaction is completed, the final catalyst is obtained by drying.

[0027] Example 3:

[0028] Fe2O3 as the substance containing trivalent metal M3+, and the molar ratio of M3+ to (M2++ M3+) is 0.3, and the solution is ion-exchanged with a multi-layer metal substance with a structural formula of [Mg6Al2(OH)16CO3] purchased from Japan Sakai Chemical at 70℃ to obtain a multi-metal layered structure substance with a target metal core and a ratio, and the particle size is 0.5 microns, and the multi-metal layered structure substance is mixed with bisguanide tricaprylyl phenyl sulfonate in a system with water as a solvent at a molar ratio of 1 to 1.5, and the reaction is carried out at 90℃ for 4 hours to obtain a catalyst particle with a structural formula of [Fe2+0.7Al3+0.3(OH)2]0.3+[(C72H131N7O9S3)0.3*mH2O]0.3, and then the aluminum ester is further compounded at a ratio of 10wt% of the mass of [Fe2+0.7Al3+0.3(OH)2]0.3+[(C72H131N7O9S3)0.3*mH2O]0.3, and the solvent water used in the process is set to 50℃, and the reaction time is 3 hours. After the reaction is completed, the final catalyst is obtained by drying.

[0029] The catalytic efficiency of the examples and the comparative examples of the present application is shown in Table 1:

[0030] Table 1

[0031]

[0032] Note: Comparative experiments were carried out under the same conditions, the specific conditions for the reaction temperature 200 ℃, reaction time 180 min, the pressure is normal pressure.

Claims

1. An esterification reaction catalyst that can be used for PBAT synthesis, characterized by The esterification reaction catalyst for PBAT synthesis is prepared by compounding a metal coordination compound with a multi-metal layered structure containing sulfonate. wherein is a divalent metal species, is a trivalent metal species, X has a value between 0.17 and 0.33; and A is a bisguanidinium trioctylphenylsulfonate.

2. The esterification reaction catalyst according to claim 1, wherein The mass ratio of the metal coordination compound to the multi-metal layered structure containing sulfonate is 1.0% to 15%.

3. The esterification reaction catalyst according to claim 1, wherein The divalent metal is magnesium, iron, zinc or cobalt; the trivalent metal is aluminum or iron.

4. The esterification reaction catalyst according to claim 1, wherein The particle size of the multi-metal layered structure is between 0.1 and 1 microns.

5. The esterification reaction catalyst according to claim 1, wherein The metal coordination compound is one or more of titanium acid ester or aluminum acid ester.

6. A method for preparing the esterification reaction catalyst for PBAT synthesis according to claim 1, comprising the following steps: (a). The compound containing M 2+ and the oxide containing M3 + are mixed to form a solution with a molar concentration of 1-10%, and the solution is ion-exchanged with a multi-layer metal material with a structure of [Mg6Al2(OH) 16 CO3] at 60-80°C to obtain a multi-metal layered structure material with a target metal core and a proportion. (b). The biguanide trioctylphenyl sulfonate is configured into a solution with a molar concentration of 5 to 15%; (c). The multi-metal layered structure obtained in step a is mixed with the anion salt compound sulfonate according to a molar ratio of 1:(1 to 2) to the anion salt compound sulfonate solution, and reacted at a certain temperature, and then dried to obtain the multi-metal layered structure containing sulfonate; (d). The metal coordination compound is compounded with the multi-metal layered structure containing sulfonate obtained in step c in a solvent, and the reaction product is filtered and dried to obtain the esterification reaction catalyst for PBAT synthesis.

7. The method of claim 6, wherein The reaction temperature in step (c) is 80 to 100°C, and the reaction time is 2 to 5 hours; the compounding reaction temperature in step (d) is 30 to 100°C, and the compounding reaction time is 2 to 5 hours.

8. The method of claim 6, wherein The solvent in step (d) is water or ethanol.

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