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Tung oil-based polyol and synthesis method thereof

A synthesis method and polyol technology, applied in the field of polyurethane materials, can solve the problems of high reactivity of epoxy groups, prone to side reactions, poor selectivity, etc., achieve good biodegradability, avoid cross-linking side reactions, and make raw materials available The effect of regeneration

Active Publication Date: 2017-09-12
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, tung oil is used to prepare high-quality vegetable oil polyols. Because tung oil has a high degree of unsaturation and is the only unsaturated vegetable oil with conjugated double bonds in nature, the iodine value reaches more than 170, and more than 85% of the unsaturated bonds are Carbon-carbon conjugated triene bonds, so the presence of conjugated double bonds in tung oil in the process of preparing polyol epoxidation makes the epoxy group highly reactive, poor in selectivity, and prone to side reactions, thereby generating macromolecular cross-links. Co-product, resulting in a sharp increase in viscosity, usually solid at room temperature, cannot be used for further synthesis of polyurethane materials
Research literature (e.g. Epoxidation of Natural Triglycerides with Ethylmethyldioxirane, Journal of the American Oil Chemists' Society, 1996, 73:461-464) examines different vegetable oils such as corn oil, soybean oil, sunflower oil, cottonseed oil, tung oil During the epoxidation process of unsaturated vegetable oils, it was also found that the tung oil with only conjugated double bonds undergoes a crosslinking reaction during the epoxidation process, resulting in a sharp increase in viscosity and cannot be used to prepare polyurethane materials.

Method used

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  • Tung oil-based polyol and synthesis method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Add 500g of tung oil and 150g of n-hexanoic acid into a 2000mL three-neck flask, heat up to 40°C and stir evenly. Then slowly add 165g concentration of 30wt% hydrogen peroxide solution, 80g formic acid (85wt% solution), 0.5g concentrated sulfuric acid solution dropwise under vigorous stirring conditions, and then add 160g concentration of 30wt% hydrogen peroxide The solution was slowly dropped into the reaction system, and the rate of addition was controlled to maintain the reaction temperature at about 50°C. After the dropwise addition, the temperature was kept at 50°C for 4 hours, and the reaction ended. After the reaction system was separated into layers, the water phase was removed, and the oil phase was washed with 10 wt% sodium bicarbonate aqueous solution until neutral, and then the product was washed with hot water at 70°C for 3 times. The washed product was distilled at 2000 Pa and 80°C for 2 hours to obtain tung oil-based polyol. After testing, the hydroxyl v...

Embodiment 2

[0027] Add 500g tung oil and 130g n-hexanoic acid into a 2000mL three-neck flask, heat up to 45°C and stir evenly. Then slowly add 165g concentration of 30wt% hydrogen peroxide solution, 60g formic acid (85wt% solution), 4g concentrated sulfuric acid solution dropwise under vigorous stirring conditions, and then add 160g concentration of 30wt% hydrogen peroxide solution Slowly drop it into the reaction system, and control the rate of addition throughout the process to keep the reaction temperature at about 65°C. After the dropwise addition, keep the temperature at 65°C for 3 hours, and the reaction ends. After the reaction system was separated into layers, the water phase was removed, and the oil phase was washed with 10 wt% sodium bicarbonate aqueous solution until neutral, and then the product was washed with hot water at 70°C for 3 times. The washed product was distilled at 2000 Pa and 80°C for 2 hours to obtain tung oil-based polyol. After testing, the hydroxyl value is 1...

Embodiment 3

[0029] Add 500g tung oil and 200g n-hexanoic acid into a 2000mL three-neck flask, heat up to 35°C and stir evenly. Then slowly add 180g concentration of 30wt% hydrogen peroxide solution, 130g formic acid (85wt% solution), 0.25g concentrated sulfuric acid solution dropwise under vigorous stirring conditions, and then add 110g concentration of 30wt% hydrogen peroxide The solution was slowly dropped into the reaction system, and the dropping rate was controlled throughout the process to keep the reaction temperature at about 40°C. After the dropwise addition was completed, the temperature was kept at 40°C for 5 hours, and the reaction ended. After the reaction system was separated into layers, the water phase was removed, and the oil phase was washed with 10 wt% sodium bicarbonate aqueous solution until neutral, and then the product was washed with hot water at 70°C for 3 times. The washed product was distilled at 2000 Pa and 80°C for 2 hours to obtain tung oil-based polyol. Aft...

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Abstract

The invention discloses a tung oil-based polyol synthesis method, which comprises: mixing tung oil and a hydroxylating reagent according to a certain ratio, and heating to a temperature of 35-45 DEG C; mixing a hydrogen peroxide solution accounting for 40-60% of the total adding amount, carboxylic acid and an inorganic acid catalyst under vigorous stirring, adding the obtained mixture to the reaction system in a dropwise manner, slowly adding the remaining hydrogen peroxide solution in a dropwise manner after completing the adding of the mixture, maintaining the reaction temperature at 40-65 DEG C by controlling the adding rate, and maintaining the reaction temperature for 3-5 h after completing the adding; and carrying out standing layering after completing the reaction, separating to obtain a water phase, neutralizing, carrying out water washing, and carrying out pressure reducing distillation to obtain the tung oil-based polyol. According to the present invention, the conjugated double bond of tung oil can improve the reactivity of the epoxy group, such that the hydroxylating reagent is added while the epoxidation is performed so as to effectively avoid the occurrence of the cross-linking side reaction and efficiently synthesize the tung oil-based polyol product; and the prepared tung oil-based polyol has the hydroxyl value of 120-270 mgKOH / g, the acid value of less than 1.0 mgKOH / g, the moisture content of less than 0.1 wt% and the yield of more than 92%, and can be used for the preparation of polyurethane materials.

Description

technical field [0001] The invention belongs to the field of polyurethane materials, and in particular relates to a tung oil-based polyol and a synthesis method thereof. Background technique [0002] Polyurethane materials have been widely used in industry and people's daily life due to their good mechanical properties and easy molding. The main raw materials used to produce polyurethane include isocyanates, polyols and other additives, of which polyols account for more than 50%. In the process of industrial production, polyols are mainly used in the field of polyurethane, so the factors affecting the polyurethane industry are also the main factors affecting the polyol market. Polyols can be divided into polyether polyols and polyester polyols according to their molecular structure. Among them, polyether polyols dominate the market, accounting for more than 70% of the entire polyol demand. [0003] Typically, polyols are prepared from petroleum. As a non-renewable resourc...

Claims

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Application Information

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IPC IPC(8): C07C69/675C07C67/31C08G18/36C08G101/00
CPCC07C67/31C07D301/16C07D303/42C08G18/36C08G2110/0025C07C69/675
Inventor 李澜鹏白富栋李政乔凯王领民
Owner CHINA PETROLEUM & CHEM CORP
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