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Tung oil-based aqueous polyurethane coating and preparation method thereof

A technology of water-based polyurethane and tung oil, which is applied in the field of polyurethane materials, can solve the problems of prone to side reactions, high reactivity of epoxy groups, and inability to use polyurethane, so as to avoid cross-linking side reactions, improve moisture resistance, and improve hydrophobicity sexual effect

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 during the preparation of polyol epoxidation makes the epoxy group highly reactive, poor in selectivity, and prone to side reactions, thereby generating macromolecular cross-links. Co-product, causing a sharp increase in viscosity, usually solid at room temperature and cannot be used for further synthesis of polyurethane products
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 tung oil with only conjugated double bonds had a crosslinking reaction during the epoxidation process, resulting in a sharp increase in viscosity, which could not be used to prepare polyurethane products

Method used

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  • Tung oil-based aqueous polyurethane coating and preparation method thereof
  • Tung oil-based aqueous polyurethane coating and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0029] Add 500g of tung oil, 80g of formic acid (85wt% solution), 0.5g of concentrated sulfuric acid, and 150g of n-hexanoic acid into a 2000mL three-neck flask, heat up to 40°C and stir well. Then, 325g of 30wt% hydrogen peroxide solution was slowly added dropwise under vigorous stirring, and the rate of addition was controlled to keep the reaction temperature at about 50°C. After standing until the reaction system was separated, the water phase was removed, the oil phase was washed with 10wt% sodium bicarbonate aqueous solution to neutrality, 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 polyol.

[0030] Add 30 g of the above-prepared tung oil polyol, 2 g of dimethylol propionic acid, and 15 g of acetone into the reaction kettle and mix evenly, then slowly add 15 g of toluene diisocyanate, and react at 60° C. for 2.5 h. After the reaction, the material was cooled to roo...

Embodiment 2

[0032] Add 500g of tung oil, 55g of formic acid (85wt% solution), 4g of concentrated sulfuric acid, and 100g of n-hexanoic acid into a 2000mL three-neck flask, heat up to 45°C and stir well. Then, 285g of 30wt% hydrogen peroxide solution was slowly added dropwise under vigorous stirring, and the dropping rate was controlled to keep the reaction temperature at about 65°C. After standing until the reaction system was separated, the water phase was removed, the oil phase was washed with 10wt% sodium bicarbonate aqueous solution to neutrality, 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 polyol.

[0033] Add 30 g of the above-prepared tung oil polyol, 2.4 g of dimethylol propionic acid, and 15 g of acetone into the reaction kettle and mix well, then slowly add 17 g of diphenylmethane diisocyanate, and react at 60° C. for 2 h. After the reaction, the material was cooled to ro...

Embodiment 3

[0035] Add 500g tung oil, 100g formic acid (85wt% solution), 0.25g concentrated sulfuric acid, and 250g n-hexanoic acid into a 2000mL three-neck flask, heat up to 35°C and stir well. Then, 380g of 30wt% hydrogen peroxide solution was slowly added dropwise under vigorous stirring, and the dropping rate was controlled to keep the reaction temperature at about 40°C. 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 polyol.

[0036] Add 30 g of the above-prepared tung oil polyol, 1.6 g of dimethylol butyric acid, and 15 g of acetone into the reaction kettle and mix evenly, then slowly add 14 g of isophorone diisocyanate, and react at 60° C. for 5 h. After the reaction, the material was cooled to room temperat...

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Abstract

The invention discloses a preparation method of a tung oil-based aqueous polyurethane coating. The preparation method comprises the following steps: mixing tung oil, carboxylic acid, an acid catalyst and a hydroxylation reagent in proportion, and heating the obtained mixture to 35-45 DEG C; dropwise adding a hydrogen peroxide solution while intense stirring, controlling the dropwise adding speed to keep the reaction carried out at 40-65 DEG C, and keeping the reaction for 3-5 h after the dropwise addition is finished; standing and layering the obtained reaction solution after the reaction ends, separating the obtained water phase, neutralizing the water phase, washing the neutralized water phase with water, and carrying out reduced pressure distillation to obtain tung oil polyol; and uniformly mixing the tung oil polyol, a hydrophilic modifier and acetone in proportion, adding diisocyanate, carrying out a reaction at 50-70 DEG C for 2-5 h, cooling the obtained reaction product to room temperature, adding a neutralizer to form a salt, adding a diamine chain extender and deionized water mixed solution, carrying out a chain extension reaction until no free isocyanate radicals exist, and carrying out reduced pressure distillation to remove the acetone in order to obtain the tung oil-based aqueous polyurethane coating. The preparation method has the advantages of effective improvement of the hydrophobicity and the moisture resistance of the aqueous polyurethane coating, and renewable and nontoxic raw materials.

Description

technical field [0001] The invention belongs to the field of polyurethane materials, and in particular relates to a tung oil-based waterborne polyurethane coating and a preparation method thereof. Background technique [0002] With the depletion of fossil resources and the increasing awareness of environmental protection, social needs have put forward new requirements for the coatings industry, namely the development of new coatings with environmental protection, high performance, water-based solvent-free, high solids, powder and radiation curing. In the current coatings, polyurethane coatings are widely used, including general coatings, special coatings, industrial coatings, and architectural coatings. Water-based polyurethane uses water as a solvent, which is non-toxic, environmentally friendly, and energy-saving. It combines the advantages of high hardness, strong adhesion, and corrosion resistance of solvent-based polyurethane with the advantages of low VOC content of wa...

Claims

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Application Information

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IPC IPC(8): C09D175/04C08G18/36C07C67/31C07C69/675
CPCC07C67/31C08G18/36C08G2230/00C09D175/04C07C69/675
Inventor 李澜鹏白富栋李政薛冬乔凯王领民
Owner CHINA PETROLEUM & CHEM CORP
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