CN102432870B - Synthesis method of dendritic complex main antioxidant - Google Patents

Abstract

The invention relates to a synthesis method of a dendritic complex main antioxidant. The synthesis method comprises the following steps of: taking 1.0 substituted dendritic polyamide-amine and beta-(3,5-ditertbutyl-4-hydroxyl phenyl) propionyl chloride which adopts quadrol as a core as a raw material, taking K2CO3 as an accelerating agent, taking benzene and water as solvents, carrying out amidating condensation reaction, and by filtering under pressure, obtaining a dendritic complex main antioxidant crude product; then adding trichloromethane into the crude product, and filtering; and adding benzene into the filtrate, precipitating out white solid under the low temperature, filtering under pressure, carrying out low-temperature vacuum drying and obtaining the dendritic complex main antioxidant. In the synthesis method, the reaction condition is moderate, the purification of a product is easy, the reaction is of a basic reaction type, and the industrialization is easy to realize; and the synthesized antioxidant has the structural characteristics of two types of main antioxidants such as hindered phenol and amine, and has higher antioxygenic property.

Description

A kind of synthetic method of dendritic composite main antioxidant

technical field

The present invention relates to a synthetic method of a dendritic composite antioxidant, specifically using an organic substance as a raw material, using _K2CO3 as a promotor, and under the _condition that a mixed solvent of benzene and water exists, it is synthesized by a simple organic synthesis reaction A new class of additives for polymer materials.

Background technique

Antioxidant is an important additive that can stabilize polymers, and its application involves almost all polymer products. Phenolic antioxidants are the most non-polluting and non-discoloring antioxidants among all antioxidants. At present, phenolic antioxidants account for about 50% of the consumption in my country, and 2,6-di-tert-butylphenol (BHT), as the basic species, still occupies a dominant position. However, due to the relatively low molecular weight and high volatility of BHT, And there are shortcomings such as yellowing and discoloration, and the consumption is decreasing year by year. The consumption proportion of hindered phenol varieties with relatively high molecular weight, represented by Irganox 1010 and Irganox 1076 of Ciba-Geigy in Switzerland, has been increasing year by year, and has become the leading product in the phenolic antioxidant market. In 2002, Helena Bergenudda proposed a new type of antioxidant, that is, hyperbranched phenolic antioxidant, which is an antioxidant modification of hyperbranched macromolecules, so that it has multiple antioxidant groups, Improve its antioxidant activity, but this type of antioxidant has good antioxidant performance in high-grade lubricants with low freezing point, but in polyolefin materials due to poor compatibility, the antioxidant performance is inferior to the antioxidant Irganox 1010. 2006 In 2010, Yang Hongjun and others used 1.0-generation polyamide-amine and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride as raw materials, used chloroform as solvent, and triethylamine As an acid-binding agent, a class of dendritic phenolic antioxidants were synthesized, but due to the poor solubility of 1.0-generation dendritic polyamide-amines in chloroform, the grafting reaction was incomplete, and bifurcation and trifurcation by-products were generated, resulting in the target The yield of product is low.

Contents of the invention

In order to solve the problems existing in the background technology, the present invention adopts a simple synthetic method to synthesize the dendritic composite primary antioxidant. The method adopts _K2CO3 aqueous solution and benzene as the reaction _mixed solvent, and the purification adopts the method of washing out by low-temperature precipitation , the method has mild reaction conditions, easy product purification, high product yield, the reaction is a basic reaction type, and it is easy to realize industrialization.

The content of the technical solution adopted in the present invention is: the synthesis method of the dendritic composite primary antioxidant uses 1.0 generation dendritic polyamide-amine and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propane Acyl chloride as raw material, _K2CO3 as accelerator, benzene and water as solvent, react at 15~45° _C for 1~12h, and filter the reaction mixture under negative pressure to obtain the crude product of dendritic composite primary antioxidant; Add trichloromethane to the crude product, filter; add benzene to the filtrate, precipitate at 0~20°C for 1~5h, filter under negative pressure, and vacuum dry at 20~40°C for 2~6h to obtain the dendritic composite primary antioxidant .

In the synthesis of above-mentioned dendritic composite main antioxidant, the substance ratio of 1.0 generation dendritic polyamide-amine and β-(3,5-di-tert-butyl-4-hydroxyl phenyl) propionyl chloride is 1:( 4~12), the accelerator K ₂ CO ₃ is 20-70% of the total mass of the reaction raw materials, the volume fraction of solvent benzene is 60~90%, the volume fraction of solvent water is 10~30%, and the reaction temperature is 0~25 ℃, the reaction time is 1~12h; during the purification process of the crude product, the quality of the solvent chloroform used for the dissolution of the crude product is 8~16 times of the quality of the crude product, and the quality of the solvent benzene used for precipitation is 15~35 times of the quality of the crude product. times, the temperature for precipitation is 0~20°C, and the time is 1~3h; the temperature for solid vacuum drying is 20~40°C, and the time is 2~6h.

The beneficial effects of the present invention are: the present invention adopts the 1.0th generation dendritic polyamide-amine with multi-active functional groups on the surface and symmetrical structure, and utilizes the characteristic that its terminal amine group can carry out functional group conversion, and synthesizes it through a simple organic reaction. A class of dendritic composite primary antioxidants. Since 1.0 generations of dendritic polyamidoamines with amine-terminated groups and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride were used as raw materials, K ₂ CO ₃ was used as an accelerator, and benzene With water as the reaction solvent, the reaction temperature is relatively low, and the operation is relatively easy; and the properties of the target product are quite different from those of the reaction raw materials, and the problem of difficult product purification is overcome by adopting the method of precipitation. This type of antioxidant has a symmetrical structure, contains multiple phenolic hydroxyl antioxidant groups, and the molecule contains amine antioxidant groups. Insufficient oxygen agent, can be widely used in various synthetic resins such as polyethylene, polypropylene, polystyrene, ABS, etc.

Description of drawings:

Fig. 1 is the synthesis reaction equation of dendritic composite primary antioxidant;

Fig. 2 is the yield of dendritic composite main antioxidant with the change curve of reaction raw material mol ratio;

Fig. 3 is the variation curve of the yield of dendritic composite primary antioxidant with reaction temperature;

Fig. 4 is the variation curve of the yield of dendritic composite primary antioxidant with reaction time;

Fig. 5 is the change curve of the yield of the dendritic composite primary antioxidant with the mass fraction of the accelerator.

Detailed ways:

The present invention will be further described below in conjunction with embodiment:

Example 1: Accurately weigh 1.0 g of 1.0 dendritic polyamidoamine and 2 g of K ₂ CO ₃ and dissolve it in 7 ml of distilled water, slowly add 3 g of β-(3,5-di-tert-butyl- 35ml of benzene solution of 4-hydroxyphenyl)propionyl chloride, reacted at 25°C for 15h, and filtered under negative pressure to obtain the crude product of dendritic composite primary antioxidant; then add 50ml of chloroform to the crude product, stir for 30min, and filter Add 150ml of benzene to the filtrate, precipitate at 5°C for 1h, filter under negative pressure, and dry in vacuum at 30°C for 3h to obtain a dendritic composite primary antioxidant. The influence of the molar ratio of the reaction raw materials on the yield of the dendritic composite primary antioxidant is shown in Figure 2. When the substance ratio of 1.0 generation dendritic polyamido-amine and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride was 1:6, the yield of dendritic composite primary antioxidant The rate reached 70.1%.

Example 2: Accurately weigh 1.0 g of 1.0 dendritic polyamidoamine and 2 g of K ₂ CO ₃ and dissolve in 7 ml of distilled water, slowly add and dissolve 3 g of β-(3,5-di-tert-butyl- 35ml of benzene solution of 4-hydroxyphenyl)propionyl chloride, reacted at 15~45°C for 15h, and filtered under negative pressure to obtain the crude product of dendritic composite primary antioxidant; then add 50ml of chloroform to the crude product, and stir for 30min , filtered; 150ml of benzene was added to the filtrate, precipitated at 5°C for 1h, filtered under negative pressure, and vacuum-dried at 30°C for 3h to obtain a dendritic composite primary antioxidant. The influence of reaction temperature on the yield of dendritic composite primary antioxidant is shown in Figure 3. When the reaction temperature is 25℃, the yield of dendritic composite primary antioxidant reaches 70.5%.

Example 3: Accurately weigh 1.0 g of 1.0 dendritic polyamido-amine and 2 g of K ₂ CO ₃ and dissolve in 7 ml of distilled water, slowly add and dissolve 3 g of β-(3,5-di-tert-butyl- 35ml of benzene solution of 4-hydroxyphenyl)propionyl chloride, reacted at 25°C for 1~12h, and filtered under negative pressure to obtain the crude product of dendritic composite primary antioxidant; then add 50ml of chloroform to the crude product, and stir for 30min , filtered; 150ml of benzene was added to the filtrate, precipitated at 5°C for 1h, filtered under negative pressure, and vacuum-dried at 30°C for 3h to obtain a dendritic composite primary antioxidant. The influence of reaction temperature on the yield of dendritic composite primary antioxidant is shown in Figure 4. When the reaction time is 5h, the yield of dendritic composite primary antioxidant reaches 70.5%.

Example 4: Accurately weigh 1.0 g of 1.0 dendritic polyamidoamine and 0.8~2.8 g of K ₂ CO ₃ and dissolve in 7 ml of distilled water, slowly add and dissolve 3 g of β-(3,5-ditertiary 35ml of benzene solution of butyl-4-hydroxyphenyl)propionyl chloride, reacted at 25°C for 15h, and filtered under negative pressure to obtain the crude product of dendritic composite primary antioxidant; then add 50ml of chloroform to the crude product, stir After 30 minutes, filter; add 150ml of benzene to the filtrate, precipitate at 5°C for 1h, filter under negative pressure, and dry in vacuum at 30°C for 3h to obtain a dendritic composite primary antioxidant. The influence of the mass fraction of the accelerator K ₂ CO ₃ in the raw material on the yield of the dendritic composite primary antioxidant is shown in Figure 5. When the amount of the accelerator K ₂ CO ₃ is 2.0g, which accounts for 50% of the weight of the raw material, the yield of the dendritic composite primary antioxidant reaches 70.6%.

Example 5: Accurately weigh 1.0 g of 1.0 dendritic polyamidoamine and 2 g of K ₂ CO ₃ and dissolve in 7 ml of distilled water, slowly add and dissolve 3 g of β-(3,5-di-tert-butyl- 35ml of benzene solution of 4-hydroxyphenyl)propionyl chloride, reacted at 25°C for 15h, and filtered under negative pressure to obtain the crude product of dendritic composite primary antioxidant; then add 50ml of chloroform to the crude product, stir for 30min, and filter Add 150ml of benzene to the filtrate, precipitate at 5°C for 1h, filter under negative pressure, and dry in vacuum at 30°C for 3h to obtain a dendritic composite primary antioxidant with a yield of 70.2%.

Embodiment 6: According to the data of accompanying drawing 2～5, when the substance molar ratio of 1.0 generation dendritic polyamide-amine and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is 1 : 5, accelerator K ₂ CO ₃ is 50% of the reaction raw material quality, the volume fraction of solvent benzene is 83.3%, the volume fraction of solvent water is 16.7%, the reaction temperature is 25 ℃, and the reaction time is 5h; The consumption of solvent trichloromethane is 50ml, the consumption of solvent benzene used for precipitation is 150ml, the temperature during precipitation is 5°C, the time is 1h, the temperature during solid vacuum drying is 30°C, and the time is 3h. The yield of composite primary antioxidant was 70.8%. The antioxidant is applied to polyolefin resin. When the addition amount is 0.2%, the oxidation induction period of polyethylene resin is 34.0 min, and the oxidation induction period of polypropylene resin is 3.3 min, which is much higher than that without antioxidant. Polyolefin resins (1.9 min for polyethylene, 0.5 min for polypropylene).

Claims (2)

1. a synthetic method of dendritic composite primary antioxidant, is characterized in that: 1.0 generations of dendritic polyamide-amine and β-(3,5-di-tert-butyl-4-hydroxyl group) are cored with ethylenediamine Phenyl) propionyl chloride is raw material, K ₂ CO ₃ is promotor, benzene and water are solvent, carry out amidation condensation reaction, through negative pressure filtration, promptly obtain dendritic composite primary antioxidant crude product; Then add to crude product Add chloroform and filter; add benzene to the filtrate, precipitate a white solid at low temperature, filter under negative pressure, and dry in vacuum at low temperature to obtain a dendritic composite primary antioxidant; Among them, the molar ratio of 1.0 generation dendritic polyamide-amine to β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride is 1:(4-12), and the accelerator K ₂ CO ₃ is the reaction 20-70% of the total mass of raw materials; The volume fraction of the solvent benzene used in the amidation condensation reaction in the whole system is 60-90%, and the volume fraction of the solvent water used in the whole system is 10-30%; the temperature of the amidation condensation reaction is 0-25°C, The reaction time is 1~12h; during the purification process of the crude product, the quality of the solvent chloroform used for the dissolution of the crude product is 8~16 times of the quality of the crude product, and the quality of the solvent benzene used for the precipitation is 15~35 times of the quality of the crude product; During the purification process of the crude product, the precipitation temperature is 0-20°C, and the time is 1-3h; during the purification process of the crude product, the temperature of the solid vacuum drying is 20-40°C, and the time is 2-6h. 2. according to the synthetic method of dendritic composite primary antioxidant as claimed in claim 1, it is characterized in that: 1.0 generations of dendritic polyamide-amine and β-(3,5-di-tert-butyl-4-hydroxyl phenyl ) the molar ratio of propionyl chloride is 1:6, the accelerator K ₂ CO ₃ is 50% of the total mass of the reaction raw materials; the temperature of the amidation condensation reaction is 25°C, and the reaction time is 5h; during the purification process of the crude product, when the precipitation The temperature is 5°C, and the time is 1h; during the purification process of the crude product, the temperature when the solid is vacuum-dried is 30°C, and the time is 3h.

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