阅读说明：本技术 一种桐油超支化聚酯增塑剂及其制备方法和应用 (Tung oil hyperbranched polyester plasticizer and preparation method and application thereof ) 是由 贾普友 宋飞 周永红 刘承果 胡立红 张猛 于 2020-11-23 设计创作，主要内容包括：一种桐油超支化聚酯增塑剂及其制备方法和应用,以桐油为原料,在碱催化下与甘油经醇解反应得到桐油基超支化多元醇,然后在碱催化下与缩水甘油经环氧开环反应后合成桐油基超支化多元醇,最后直接与酸酐通过酯化反应合成得到桐油超支化聚酯增塑剂。利用溶剂浇铸、热塑共混等方法制备桐油超支化聚酯塑化的PVC材料。该方法能够将PVC制品的玻璃化转变温度降低至32.9℃。(A tung oil hyperbranched polyester plasticizer and a preparation method and application thereof are disclosed, wherein tung oil is used as a raw material, and is subjected to alcoholysis reaction with glycerol under the alkali catalysis to obtain tung oil-based hyperbranched polyol, then is subjected to epoxy ring-opening reaction with glycidol under the alkali catalysis to synthesize the tung oil-based hyperbranched polyol, and finally is directly subjected to esterification reaction with anhydride to synthesize the tung oil hyperbranched polyester plasticizer. Solvent casting, thermoplastic blending and other methods are utilized to prepare the tung oil hyperbranched polyester plasticized PVC material. The method can reduce the glass transition temperature of the PVC product to 32.9 ℃.)

1. A tung oil hyperbranched polyester plasticizer is characterized in that the structural general formula is as follows:

wherein n is 1,2,3,4,5,6, 7.

2. The preparation method of the tung oil hyperbranched polyester plasticizer according to claim 1 is characterized in that tung oil is used as a raw material, and is subjected to alcoholysis reaction with glycerol under the catalysis of alkali to obtain tung oil-based hyperbranched polyol, wherein the molar ratio of the tung oil to the glycerol is 1 (2-3), the temperature of the alcoholysis reaction is 60-120 ℃, the time of the alcoholysis reaction is 2-12 hours, then the tung oil-based hyperbranched polyol is synthesized with glycidol through an epoxy ring-opening reaction at 50-120 ℃ under the catalysis of alkali, the mass ratio of the tung oil-based hyperbranched polyol to the glycidol is 1 (50-150), and finally the tung oil-based hyperbranched polyester plasticizer is synthesized directly with acid anhydride through an esterification reaction, wherein the temperature of the esterification reaction is 80-150 ℃; the esterification reaction time is 2-8 hours.

3. The method for preparing the tung oil hyperbranched polyester plasticizer according to claim 2, characterized in that the base is any one of sodium methoxide, sodium ethoxide, sodium propoxide, potassium methoxide, potassium ethoxide, sodium hydroxide and potassium hydroxide.

4. The method for preparing the tung oil hyperbranched polyester plasticizer according to claim 2, characterized in that the molar ratio of the tung oil to the glycerin is 1: 2.3; the temperature of the alcoholysis reaction is 60 ℃; the dosage of the alkali catalyst in each step is 1 wt.% based on the mass of the tung oil; the time for the alcoholysis reaction was 4 hours.

5. The method for preparing the tung oil hyperbranched polyester plasticizer according to claim 2, characterized in that the mass ratio of the tung oil based hyperbranched polyol to glycidol is 1: 50; the temperature of the epoxy ring-opening reaction is 80 ℃; the usage amount of the alkali is 5 wt% based on the mass of the tung oil-based hyperbranched polyol.

6. The method for preparing the tung oil hyperbranched polyester plasticizer according to claim 2, characterized in that the mass ratio of the tung oil based hyperbranched polyol to the acid anhydride is 1: 10; the acid anhydride is any one of acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride and caprylic anhydride; the temperature of the esterification reaction is 140 ℃; the time for the esterification reaction was 3.5 hours.

7. The tung oil hyperbranched polyester plasticizer prepared by the preparation method of any one of claims 1 to 6.

8. Use of the tung oil hyperbranched polyester plasticizer according to claim 7 for plasticizing PVC materials.

9. The use according to claim 8, characterized in that the mass ratio of the tung oil hyperbranched polyester plasticizer to PVC is 0.5:10, 1:10, 2:10, 4:10 or 6: 10; the required solvent is one of nitrogen, dimethyl amide, tetrahydrofuran, acetone, dichloromethane and cyclohexanone.

Technical Field

The invention belongs to the technical field of chemical synthesis, and particularly relates to a tung oil hyperbranched polyester plasticizer and a preparation method and application thereof.

Background

Polyvinyl chloride (PVC) is one of the most used plastics in the world, and is widely used in the fields of building materials, medical instruments, household appliances and the like. Because of the large interaction force among the polyvinyl chloride molecular chains, a large amount of plasticizer is required to be added in the processing process to reduce the interaction among the macromolecular chains, thereby achieving the purposes of improving the processing performance and softening the product. At present, the capacity of plasticizers in China reaches 450 million tons, wherein the yield of o-benzene plasticizers accounts for about 80 percent of the total yield of the plasticizers, and the usage amount of o-benzene plasticizers in European and American countries accounts for about 65 percent of the usage amount of all the plasticizers. In fact, the modern plasticizer industry is a diverse large-scale chemical industry based on petrochemical industries, centered on ortho-benzenes. Because the o-benzene plasticizer is easy to be extracted by the solvent, the o-benzene plasticizer can enter a human body through various ways such as oral administration, respiratory tract and intravenous infusion, has toxic effect on a plurality of systems of the organism and is considered as an environmental endocrine interference factor. Therefore, the use in medical instruments, food packaging materials and children's toys is prohibited in succession in europe, the united states, japan and korea. The raw materials for the synthesis of ortho-benzene plasticizers are all derived from petrochemical resources and this industrial model is not sustainable. Therefore, there is an urgent need to develop a novel plasticizer which is safe, non-toxic, environmentally friendly and migration resistant.

China is the largest China producing tung oil in the world, has more than thousand years of tung oil tree cultivation history, has about 184 tung oil tree varieties which are mainly distributed in Yangtze river basin and south areas thereof, and the tung oil tree planting area in history of Jiangsu province reaches 14.6 ten thousand mu once. Tung oil is an important industrial oil, the main component of which is tung oil glyceride accounting for 73-80% of the mass of tung oil. The chemical structure of the glycerol eleostearate contains functional groups such as unsaturated bonds, ester bonds and the like, and can perform reactions such as epoxidation, alcoholysis, ester exchange, Diels-Alder, Friedel-Crafts, amidation, addition and the like. Most of the series products obtained from petroleum can also be obtained from the deep processing of tung oil. The development of tung oil-based fine chemicals, the improvement of the technological content of tung oil products and the increase of the development of tung oil added value products is a main trend of the development of tung oil industry. The tung oil-based plasticizer synthesized by using the tung oil has the characteristics of good plasticizing performance, easy degradation, small pollution, no toxicity and the like, is an environment-friendly plasticizer, and is an important way for increasing the technological content of tung oil products, improving the additional value of the tung oil and increasing the diversification of the tung oil products.

Disclosure of Invention

The technical problem to be solved is as follows: the invention provides a tung oil hyperbranched polyester plasticizer, a preparation method and application thereof, and the plasticized PVC material has excellent tensile property, thermal stability, solvent extraction resistance and volatility resistance.

The technical scheme is as follows: a tung oil hyperbranched polyester plasticizer has a structural general formula as follows:

wherein n is 1,2,3,4,5,6, 7.

The preparation method of the tung oil hyperbranched polyester plasticizer comprises the steps of taking tung oil as a raw material, carrying out alcoholysis reaction on the tung oil and glycerol under the catalysis of alkali to obtain tung oil-based hyperbranched polyol, wherein the molar ratio of the tung oil to the glycerol is 1 (2-3), the temperature of the alcoholysis reaction is 60-120 ℃, the time of the alcoholysis reaction is 2-12 hours, then carrying out epoxy ring-opening reaction on the tung oil-based hyperbranched polyol and glycidol under the catalysis of alkali to synthesize the tung oil-based hyperbranched polyol, the mass ratio of the tung oil-based hyperbranched polyol to the glycidol is 1 (50-150), and finally directly carrying out esterification reaction on the tung oil-based hyperbranched polyester plasticizer and acid anhydride to obtain the tung oil-based hyperbranched polyester plasticizer; the esterification reaction time is 2-8 hours.

The alkali is any one of sodium methoxide, sodium ethoxide, sodium propoxide, potassium methoxide, potassium ethoxide, sodium hydroxide and potassium hydroxide.

The molar ratio of the tung oil to the glycerin is 1: 2.3; the temperature of the alcoholysis reaction is 60 ℃; the dosage of the alkali catalyst in each step is 1 wt.% based on the mass of the tung oil; the time for the alcoholysis reaction was 4 hours.

The mass ratio of the tung oil-based hyperbranched polyol to the glycidol is 1: 50; the temperature of the epoxy ring-opening reaction is 80 ℃;

the amount of the alkali is 5 wt% based on the mass of the tung oil-based hyperbranched polyol.

The mass ratio of the tung oil-based hyperbranched polyol to the acid anhydride is 1: 10; the acid anhydride is any one of acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride and caprylic anhydride; the temperature of the esterification reaction is 140 ℃; the time for the esterification reaction was 3.5 hours.

The tung oil hyperbranched polyester plasticizer prepared by the preparation method.

The tung oil hyperbranched polyester plasticizer is applied to plasticizing PVC materials.

The mass ratio of the tung oil hyperbranched polyester plasticizer to PVC is 0.5:10, 1:10, 2:10, 4:10 or 6: 10; the required solvent is one of nitrogen, dimethyl amide, tetrahydrofuran, acetone, dichloromethane and cyclohexanone.

The chemical reaction mechanism is as follows: the reaction mechanism can be represented by the following synthetic pathway diagram:

the first step is as follows: synthesis of tung oil polyalcohol

The second step is that: synthesis of tung oil-based hyperbranched polyol

The third step: synthesis of tung oil based hyperbranched polyester

Has the advantages that: compared with the prior art, no synthesis method report of tung oil-based hyperbranched polyol ester exists at present in China, and the invention is the first initiative. The invention takes natural renewable tung oil as raw material, has rich raw material sources, simple synthesis process, low production cost and good product quality. The product obtained by the invention has small toxic and side effects, and the tung oil-based hyperbranched polyester plasticized PVC material has the advantages of solvent extraction resistance, strong stability and better heat resistance. The method can reduce the glass transition temperature of the PVC material to 32.9 ℃.

Drawings

Figure 1 DMA curves for pure PVC and 60 wt.% tung oil hyperbranched polyester plasticized PVC material.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the embodiments are only some embodiments of the present invention, and not all embodiments.

Example 1

And (3) synthesis of tung oil polyol:

in the embodiment of the invention, the synthesis method of the tung oil-based hyperbranched polyol needs to pass through the following processes: adding 0.3mol of tung oil and 0.75mol of glycerol into a 500mL three-neck round-bottom flask provided with a reflux condenser, introducing nitrogen, heating to 100 ℃, continuously stirring for 0.5 hour, then cooling to 80 ℃, adding 0.1 wt.% of sodium methoxide (based on the mass of the tung oil), continuously stirring for reacting for 6 hours, stopping reaction, cooling to room temperature, dissolving by using dichloromethane, washing for 3 times by using distilled water, drying by using anhydrous sodium sulfate, and removing the dichloromethane by rotary evaporation to obtain the tung oil-based hyperbranched polyol.

Synthesizing tung oil-based hyperbranched polyol:

to a 500mL three-necked round bottom flask equipped with a reflux condenser was added 0.2mol of tung oil-based hyperbranched polyol and 0.03mol of potassium methoxide, the mixture was heated to 100 ℃ under mechanical stirring, then 1.35mol of glycidol was added dropwise over 4 hours under a nitrogen atmosphere using a syringe pump, the polymerization reaction was further continued for 0.5 hour, then 100mL of methanol was added to quench the reaction, and the resulting polymer solution was concentrated, washed with acetone, and dried in a vacuum oven at 85 ℃ for 12 hours to obtain pale yellow viscous tung oil-based hyperbranched polyol.

Synthesis of tung oil-based super-esterified polyester (1):

in the embodiment of the invention, the synthesis method of the tung oil-based hyperbranched polyester needs to pass through the following processes: adding 50g of tung oil-based hyperbranched polyol into a 500mL three-neck round-bottom flask provided with a reflux condenser, heating to 130 ℃ under a nitrogen atmosphere, dripping 0.6mol of acetic anhydride within 0.5 hour, continuously stirring for reaction for 3 hours, stopping the reaction, cooling to room temperature, dissolving by using dichloromethane, washing by using saturated sodium bicarbonate solution and distilled water for 3 times respectively, drying by using anhydrous sodium sulfate, and removing the dichloromethane by rotary evaporation to obtain the tung oil-based hyperbranched polyester (1).

Example 2

And (3) synthesis of tung oil polyol:

in the embodiment of the invention, the synthesis method of the tung oil-based hyperbranched polyol needs to pass through the following processes: adding 0.3mol of tung oil and 0.9mol of glycerol into a 500mL three-neck round-bottom flask provided with a reflux condenser, introducing nitrogen, heating to 100 ℃, continuously stirring for 0.5 hour, then cooling to 60 ℃, adding 1 wt.% of sodium methoxide (based on the mass of the tung oil), continuously stirring for reacting for 12 hours, stopping the reaction, cooling to room temperature, dissolving by using dichloromethane, washing for 3 times by using distilled water, drying by using anhydrous sodium sulfate, and removing the dichloromethane by rotary evaporation to obtain the tung oil-based hyperbranched polyol.

Synthesizing tung oil-based hyperbranched polyol:

to a 500mL three-necked round bottom flask equipped with a reflux condenser was added 0.2mol of tung oil-based hyperbranched polyol and 0.04mol of potassium methoxide, the mixture was heated to 80 ℃ under mechanical stirring, then 1mol of glycidol was added dropwise over 10 hours under a nitrogen atmosphere using a syringe pump, the polymerization reaction was further continued for 0.5 hour, then 100mL of methanol was added to quench the reaction, and the resulting polymer solution was concentrated, washed with acetone, and dried in a vacuum oven at 85 ℃ for 12 hours to obtain pale yellow viscous tung oil-based hyperbranched polyol.

Synthesis of tung oil-based hyperbranched ester (2):

in the embodiment of the invention, the synthesis method of the tung oil-based hyperbranched polyol ester needs to pass through the following processes: adding 50g of tung oil-based hyperbranched polyol into a 500mL three-neck round-bottom flask provided with a reflux condenser, heating to 100 ℃ under the nitrogen atmosphere, dripping 0.5mol of propionic anhydride within 0.5 hour, continuously stirring for reaction for 5 hours, stopping the reaction, cooling to room temperature, dissolving by using dichloromethane, washing by using saturated sodium bicarbonate solution and distilled water for 3 times respectively, drying by using anhydrous sodium sulfate, and removing the dichloromethane by rotary evaporation to obtain the tung oil-based hyperbranched polyester (2).

Example 3

And (3) synthesis of tung oil polyol:

in the embodiment of the invention, the synthesis method of the tung oil-based hyperbranched polyol needs to pass through the following processes: adding 0.3mol of tung oil and 0.9mol of glycerol into a 500mL three-neck round-bottom flask provided with a reflux condenser, introducing nitrogen, heating to 100 ℃, continuously stirring for 0.5 hour, then cooling to 60 ℃, adding 1 wt.% of sodium methoxide (based on the mass of the tung oil), continuously stirring for reacting for 12 hours, stopping the reaction, cooling to room temperature, dissolving by using dichloromethane, washing for 3 times by using distilled water, drying by using anhydrous sodium sulfate, and removing the dichloromethane by rotary evaporation to obtain the tung oil-based hyperbranched polyol.

Synthesizing tung oil-based hyperbranched polyol:

to a 500mL three-necked round bottom flask equipped with a reflux condenser was added 0.2mol of tung oil-based hyperbranched polyol and 0.04mol of potassium methoxide, the mixture was heated to 80 ℃ under mechanical stirring, then 1mol of glycidol was added dropwise over 10 hours under a nitrogen atmosphere using a syringe pump, the polymerization reaction was further continued for 0.5 hour, then 100mL of methanol was added to quench the reaction, and the resulting polymer solution was concentrated, washed with acetone, and dried in a vacuum oven at 85 ℃ for 12 hours to obtain pale yellow viscous tung oil-based hyperbranched polyol.

Synthesis of tung oil-based hyperbranched ester (3):

in the embodiment of the invention, the synthesis method of the tung oil-based hyperbranched polyol ester needs to pass through the following processes: adding 50g of tung oil-based hyperbranched polyol into a 500mL three-neck round-bottom flask provided with a reflux condenser, heating to 100 ℃ under the nitrogen atmosphere, dripping 0.5mol of butyric anhydride within 0.5 hour, continuously stirring for reaction for 5 hours, stopping the reaction, cooling to room temperature, dissolving by using dichloromethane, washing by using saturated sodium bicarbonate solution and distilled water for 3 times respectively, drying by using anhydrous sodium sulfate, and removing the dichloromethane by rotary evaporation to obtain the tung oil-based hyperbranched polyester (3).

Example 4

Preparing tung oil hyperbranched polyester (1), (2) and (3) plasticized PVC materials:

in the embodiment of the invention, the preparation of the tung oil hyperbranched polyester plasticized PVC material needs to pass through the following processes: weighing 5 parts of 3g of PVC powder, dissolving the PVC powder with 30mL of tetrahydrofuran respectively, adding 1.8g of tung oil hyperbranched polyester (1), (2) and (3) into the PVC solution after the PVC is completely dissolved, uniformly mixing by stirring, pouring the mixture into a mold, standing at room temperature overnight, and then drying in vacuum at 40 ℃ for 24 hours to obtain the tung oil hyperbranched polyester (1), (2) and (3) plasticized PVC material. Wherein the glass transition temperature of the PVC was decreased from 81 ℃ to 32.9 ℃ (60 wt.% tung oil hyperbranched polyester (3)), as shown in fig. 1.