Vegetable oil polyol and the preparation method and the application thereof

Patent metadata

Field	Value
Publication number	US-10259771-B2
Application number	US-201615506686-A
Country	US
Kind code	B2
Filing date	Jan 28, 2016
Priority date	Nov 11, 2015
Publication date	Apr 16, 2019
Grant date	Apr 16, 2019

Abstract

A preparation method of vegetable oil polyol, which is obtains by carrying out allylic oxidation treatment of vegetable oil, increasing the content of hydroxyl group in the product and then one step reaction between epoxidation and ring-opening. At the same time, the present invention also discloses novel vegetable oil polyol made by the preparation method and the application of the vegetable oil polyol in preparation of polyurethane foam material. Compared with the prior art, the method has the advantages of simple operation, low energy consumption and low side reaction occurrence rate.

First claim

What is claimed is:

1. A preparation method of vegetable oil polyol, characterized in that, it comprises the steps of:
(1) oxidating an allyl group of a vegetable oil with an allylic oxidant for introducing a secondary hydroxyl group into the vegetable oil; wherein the allylic oxidant is a selenium dioxide, or a tert-Butyl hydroperoxide, or a combination of selenium dioxide and tert-Butyl hydroperoxide;
(2) simultaneously pumping the product obtained in the step (1) and an epoxy-hydroxylation reagent into a micro flow reactor for reaction;
(3) collecting an organic phase in the product obtained in step (2), washing and drying to obtain vegetable oil polyol.

2. The preparation method according to claim 1 , characterized in that, in the step (1), the vegetable oils are any one or combination of olive oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, coconut oil, palm oil, sesame oil, sunflower oil, linseed oil, castor oil, tung oil, rice bran oil and corn oil.

3. The preparation method according to claim 2 , characterized in that, in the step (1), the method of oxidating the allyl group of vegetable oil and introducing the secondary hydroxyl group is dissolving the vegetable oil into an organic solvent, adding the allylic oxidant, uniformly mixing, stirring at 35-55° C. for 25-45 h, adding Na 2 CO 3 saturated aqueous solution, cooling, adding Na 2 SO 3 and stirring, separating organic phase, and then the organic phase was washed and dried.

4. The preparation method according to claim 3 , characterized in that, in the step (1), the molar ratio of the vegetable oil and the organic solvent is 1:50-70, and the volume ratio of the organic solvent and Na 2 CO 3 saturated aqueous solution is 3˜1:1; wherein, the organic solvent is ethyl acetate or tetrahydrofuran, the allylic oxidant is selenium dioxide or tert-Butyl hydroperoxide or a mixture of selenium dioxide and tert-Butyl hydroperoxide.

5. The preparation method according to claim 4 , characterized in that, in the step (1), when the allylic oxidant is selenium dioxide, the molar ratio of selenium dioxide to vegetable oil double bond is 0.3˜0.6:1; when the allylic oxidant is tert-Butyl hydroperoxide, the molar ratio of the tert-Butyl hydroperoxide to vegetable oil double bond is 0.8˜2.8:1; when the allylic oxidant is the mixture of selenium dioxide and tert-Butyl hydroperoxide, the molar ratio of selenium dioxide to tert-Butyl hydroperoxide is 0.2˜0.5:1, and the molar ratio of selenium dioxide to the vegetable oil double bond is 0.1˜0.2:1.

6. The preparation method according to claim 1 , characterized in that, in the step (2), the epoxy-hydroxylation reagent includes hydrogen peroxide, formic acid, sulfuric acid and ethylenediamine tetraacetic acid disodium; wherein, the molar ratio of hydrogen peroxide to formic acid is 1:1, the molar ratio of formic acid, sulfuric acid and ethylenediamine tetraacetic acid disodium to the vegetable oil is 7˜16:0.02˜0.2:0.01˜0.2:1.

7. The preparation method according to claim 1 , characterized in that, in the step (2), the reaction temperature in the micro flow reactor is 60˜120° C., and the duration of stay for material is 4˜13 min.

8. The preparation method according to claim 1 , characterized in that, in the step (2), the micro flow field reactor is a micro channel modular reaction apparatus, which comprises a micro mixer, a microstructure heat exchanger and a microstructure reactor are pipeline connected in turn; wherein, the micro mixer is pipeline connected with two feed pumps.

Assignees

• Nanjing University Of Technology

Inventors

• Guo Kai
• Fang Zheng
• Ji Dong
• Tao Junjie
• Li Xin
• Wan Li
• Zhu Ning
• Zhang Kai
• Ouyang Pingkai

Classifications

• C08G18/67

  Unsaturated compounds having active hydrogen · CPC title

• C08G2101/0025

  Chemistry & Metallurgy · mapped topic

• C08G18/36 Primary

  Hydroxylated esters of higher fatty acids · CPC title

• C07C67/31 Primary

  by introduction of functional groups containing oxygen only in singly bound form · CPC title

• C08G2110/0025

  rigid · CPC title