Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Hydroxyl polyether functionalized heteropolyacid polyionic liquid and application thereof in synthesis of epoxy methyl oleate by one-pot process

A technology of hydroxyl polyether functional and epoxy methyl oleate, which is applied in the direction of catalytic reaction, chemical instruments and methods, organic compound/hydride/coordination complex catalyst, etc., which can solve the problems of unstable product quality, equipment corrosion, Poor thermal stability and other problems, to achieve good surface amphiphilic activity, easy to recycle, and mild reaction conditions

Active Publication Date: 2019-10-15
MINJIANG UNIV
View PDF8 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This synthesis method has many problems such as complex production process, long process flow, high production cost, equipment corrosion, large amount of three wastes, potential safety hazards, unstable product quality, low epoxy value (about 5%), and the use of organic solvents. It has been basically eliminated
[0005] 2. In-situ oxidation method: Use organic carboxylic acids such as formic acid, acetic acid, and benzoic acid as precursors, and use concentrated sulfuric acid as a catalyst to convert organic carboxylic acids into organic peroxyacids in situ to realize unsaturated double bonds in oleic acid. The epoxidation of this method avoids the shortage of direct use of organic peroxyacids, but there are disadvantages such as low reaction activity of the catalytic system, poor selectivity, deep color of the product, low epoxy value, and poor thermal stability.
This method has the advantages of mild reaction conditions, direct use of molecular oxygen as an oxidant, and high selectivity. However, due to a series of problems such as domestication, directed evolution, engineering, and compatibility with organic solvents, there is no industrial application at present. (Siegfried W, Mark R.K. Chemo enzymatic oxidation of unsaturated carboxylic acids [J]. Journal of Molecular Catalysis B: Enzymatic, 1995.)

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Hydroxyl polyether functionalized heteropolyacid polyionic liquid and application thereof in synthesis of epoxy methyl oleate by one-pot process
  • Hydroxyl polyether functionalized heteropolyacid polyionic liquid and application thereof in synthesis of epoxy methyl oleate by one-pot process
  • Hydroxyl polyether functionalized heteropolyacid polyionic liquid and application thereof in synthesis of epoxy methyl oleate by one-pot process

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Embodiment 1: the synthesis of hydroxyl polyether

[0034] In a reaction flask equipped with magnetic stirring, add 10mL 1,2-dichloroethane, 3.5mL ethylene glycol, 1.5mL boron trifluoride ether, cool to 0-5°C and stir for 0.5 h, dropwise add 25ml epoxy Chloropropane, add 15ml 1,2-dichloroethane three times in the middle and keep it warm for 6 hours. Water was added to terminate the reaction, the organic phase was separated, washed with water until neutral, dried, and rotary evaporated to obtain 25.7 g of a colorless viscous liquid target product with a yield of 90.7%.

[0035] FT-IR (KBr), ν / cm -1 : 3460, 2918, 1430, 1121, 748.

Embodiment 2

[0036] Embodiment 2: the synthesis of quaternary ammonium salt L1-3

[0037] A. Under the protection of nitrogen, add 30 mL of acetone and 6.0 g of hydroxypolyether to the reaction bottle, raise the temperature to 45 °C, add 0.2 g of trimethylamine dropwise, and keep the reaction for 12 h after the addition, and vacuum dry to constant weight after rotary evaporation to obtain Hydroxy polyether quaternary ammonium salt L1, yield 93%.

[0038] FT-IR (KBr), ν / cm -1 : 3376, 2923, 1438, 1125, 744.

[0039] B. Replace 0.2g of trimethylamine in A with 0.3g of triethylamine, and the others are the same as in A to obtain hydroxy polyether quaternary ammonium salt L2 with a yield of 95%.

[0040] FT-IR (KBr), ν / cm -1 : 3457, 2924, 1438, 1124, 752.

[0041] C. Replace 0.2g of trimethylamine in A with 0.5g of triethanolamine, and the others are the same as in A to obtain hydroxy polyether quaternary ammonium salt L3 with a yield of 96%.

[0042] FT-IR (KBr), ν / cm -1 : 3434, 2930, 14...

Embodiment 3

[0043] Embodiment 3 [C 8 h 20 o 3 N + ] 3n [PW 12 o 40 -3 ] n (Cat-1), [C 8 h 20 o 3 N + ] 4n [SiW 12 o 40 -4 ] n (Cat-2) synthesis

[0044] After fully dissolving 0.7g of hydroxy polyether quaternary ammonium salt L1 in deionized water, slowly add an aqueous solution containing 2.0g of silicotungstic acid or 1.92g of phosphotungstic acid dropwise in 3 times, react at room temperature for 24 hours, and centrifuge The crude product of Cat-1 or Cat-2 was obtained, and the crude product was vacuum-dried at 80-85°C to constant weight. The quality of the obtained product was 1.9 g or 2.1 g, and the yields were 82% and 84%, respectively.

[0045] FT-IR (KBr) (Cat-1), ν / cm -1 : 3358, 2965, 1018, 970, 789, 535.

[0046]FT-IR (KBr) (Cat-2), ν / cm -1 : 3348, 2980, 1085, 971, 877.

[0047] There is no characteristic peak of phosphotungstic acid or silicotungstic acid in polyionic liquid XRD, indicating that polyionic liquid exists in an amorphous form.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a hydroxyl polyether functionalized heteropolyacid polyionic liquid which is a three-dimensional structure supermolecular system taking linear hydroxyl polyether functionalizedquaternary ammonium organic cations as a network and heteropolyacid anions as nodes, wherein the linear hydroxyl polyether functionalized quaternary ammonium organic cations and the Keggin type heteropolyacid anions as structural units are self-assembled in water. The synthesized polyionic liquid combines oxidizing catalytic activity, Br-nsted acidity and amphiphilic activity organically and canserve as a heterogeneous catalyst to synthesize epoxy methyl oleate through continuous esterification and epoxidation in a one-pot process in a solvent-free reaction condition. The synthetic method has the characteristics of being high in catalytic system activity, good in selectivity, high in yield, mild in reaction condition, convenient for post-treatment, easy to generate and recycle catalyticsystem and the like.

Description

technical field [0001] The invention belongs to the technical field of chemical products and their preparation, and in particular relates to a class of hydroxyl polyether functionalized heteropolyacid polyionic liquid and the use of the hydroxyl polyether functionalized heteropolyacid polyionic liquid as a heterogeneous catalyst, hydrogen peroxide as Oxidant, methanol as reaction medium and substrate, under solvent-free reaction conditions, the application of one-pot continuous esterification and epoxidation of oleic acid to synthesize epoxymethyl oleate. Background technique [0002] Epoxy methyl oleate, as a renewable green plasticizer, has developed rapidly in recent years and has been allowed to be used in food and pharmaceutical packaging materials in many countries. Compared with traditional phthalic acid plasticizers, epoxy methyl oleate has excellent biocompatibility, water resistance, oil resistance and weather resistance, and is also a good co-stabilizer, which can...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
IPC IPC(8): B01J31/02B01J27/188C07D303/42C07D301/12C08G83/00C08G65/333C08G65/28
CPCB01J31/0279B01J27/188C07D303/42C07D301/12C08G83/008C08G65/33306C08G65/33396C08G65/2609B01J2231/72B01J2231/49
Inventor 李心忠薛涵与林棋
Owner MINJIANG UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com