Technological offer: New processs for the stereoselective synth hesiss of acetylenic compounds used as additives in galvanic baths
Technological offer: New process for the acetylenic compounds baths stereoselective synthesis of used as additives inn galvanic SUMMARY The research group of Applied Electrochemistry andd Electrocatalysis of the University of Alicante has developed a stereoselective process forr the electrochemical synthesis of 3-(2-propynoxy)-2-propenoic acid and/or mixtures of acetylenic compounds (the same acid and propargyl alcohol) throughh one step. This synthesis does not use permanganate ass oxidising agent, avoids extreme conditions of reaction and minimises the residues management. The electrochemistt group is looking for companies interested in acquiring this technology for commercial purposes or for establishing projectss to adoptt this technology to their needs. TECHNICAL DESCRIPTION The research group off Applied Electrochemistry and a Electrocatalysis has developed a new process for the synthesis of 3-(2- propynoxy)-2-propenoic acid and/ /or mixture of the same acid and propargyl alcohol through one electrosynthetic step by using an electrochemical device (electrochemical reactor, electrochemical cell, electrosynthetic cell, etc.). The electrochemical device, in which the synthesis is i performed, includes a cathode, an anode of a material which contains nickel and a separator or ionic exchange membrane. The electrosynthetic process consists c of the following stages: 1. Conversionn of the nickel surface present in the anode to species of nickel (III) via a first electrolysis using aqueous solutions of alkaline metal hydroxide, where the anode of the electrolysis cell is nickel or a material containing nickel. At this stage, the anode is subjected to an electrochemical cycling pre- treatment. 2
2. Synthesis of 3-(2-propynoxy)-2-propenoic acid and/or mixtures of the same acid and propargyl alcohol byy subjecting an aqueous solution of alkaline metal hydroxide and propargyl alcohol to a second electrolysis. At this stage, it is necessary to add propargyl alcohol until an established concentration. The temperaturt re is around 25 ºC and the electrochemical device is the same as stated above at the first stage. This second electrolysiss is performed at controlled potential (potentiostatic mode) or controlled current density (galvanostatic mode). 3. Acidification of the obtained reaction mixture from the previous stage of electrolysiss with diluted mineral acids. At this stage, it is necessaryy to subject the reaction mixture from the electrolysiss to an acidificatio on processs with diluted mineral acids, i.e. sulphuric acid or hydrochloric acid to give rise to the mixture of acetylenic compounds. Additional work upp of the reaction mixture can bee performed for the isolation of Z isomer of 3-(2-propynoxy)-2-propenoic acid via liquid liquid extraction process usingg a polar organic solvent as ethyl acetate or ethyl ether. MAIN ADVANTAGES The advantages of this procedure are evident according too the following aspects: The use of permanganate as oxidising agent is discarded. The use of extreme reaction conditions is avoided. The management off residuess such as manganese dioxide or manganesee coming from a chemical oxidising agentt is avoided. It provides mixturess of 3-(2-propynoxy)-2-propenoic acid and propargyl alcohol. Electrochemical process which oxidises propargyl p alcohol to 3-(2- propynoxy) )-2-propenoic acid via one reaction step. The process is stereoselectivee giving rise to Z isomer of 3-(2- propynoxy) )-2-propenoic acid. 3
INNOVATIVE ASPECTS Regarding the existing state of the technique, the electrochemical processes have characteristics which make them very adequate to be applied for the synthesis of organic compounds with industrial application. Here, oxidation processes occurs upon electrodess named anodes where the substance which must be oxidized loses its electrons on the anode without needing conventional oxidising agents. Therefore, contaminants derived from the use of conventional oxidising agents are not generatedd and hence, no need for the management of hazardous residues is applicable. On the other hand, the electrochemical processes are developed underr soft conditions (atmospheric pressure and room temperature) and clearly facilitate further processes of separation of one of the compounds of the reaction mixture. ACTUAL STATE OF THE TECHNOLOGY The proceduree has been demonstrated at laboratory scale and is ready to t be scaled up at pilot plant and/or industrial level. The electrochemist group makes use of a pilot plant infrastructure where it could carry out the scale up under the requirements of the interested company. COPYRIGHT The developedd procedure is protected by patent: Application number: P201200496 Submission date: 11/05/2012 APPLICATION SECTORS The 3-( (2-propynoxy)-2-propenoic acid belongs to a familyy of acetylenic compounds which are used as additive in galvanic bathss for nickell and nickel-iron electroplating. Therefore this procedure could be addressable for sectors: Metal-Mechanical industry. Chemical Industry. Automotive industry. 4
SOUGHT COLLABORATION Licence agreement of know-how and patent assignement rights for the use of the manufacture orr commercialization of the technology. Project agreement off research and development ( technical cooperation) to improve the development of thee technology or applyy it to others sectors. RESEARCH GROUP PROFILE Applied Electrochemical Research Team was created in 1983, being its founder Professor Dr. Antonio Aldaz Riera Nowadays, it is formed by two professors, one lecturer, three Post Reseachers, two pilot plant electrochemists, one electronic e engineer several students at pre and post-doctoral level. Doc and From its creation, the objective off this research team has beenn the design of electrochemical processes for its application on industrial issues. Our 30 years work have given us a deep expertise in the Electrochemical Applied fields f (batteries development, electrocatalysis, synthesis and purification of pharmaceutical products, application of electrochemical technologies to wastewater, etc.). Our experience make us able to: Develop and characterise electrocatalytic materials. Design and develop electrochemical synthesis and/or wastewater treatment processes, from lab scale to 20 Tn product / dayy or 1 m3 / day. Design industrial pilot plantss according to client requiremenr nts. Technical assistance and consultancies in electochemical technologies application. Fields of Research Application of the FV solar energy to electrochem mical processes Design and development of electrochemical reactors and processes Electrocatalysis: nanoparticl les and fuel cells Electrochemical Synthesis Wastewater treatment by electrochemical methods Selective modification of biomolecules by chemical and electrochemical methods 5
Facilities Laboratory scale: Pontentiostats press reactors, sonoreactors... and several electrochemical systems, filter- Pilot plant: Pilot plant for organic and inorganic electrochemical synthesis (batches up to 20 litres). Electrodialysis pilot plant (batches up to o 20 litres). Pilot plant for wastewater treatment by direct or indirect anodic oxidation. Pre-industriafilter press electrochemical reactorss and electrodialysers at our disposal that are scale: We have a pre-industrial pilot plant fully equipped with able to work with batches up to 600 litres. We also have at our disposal a continuous flow electrocoagulator capable or working with w up to 100 litres/hour. All our facilities are computerised and we have appropriate analytic systems. Moreover we also have at our disposal the experimental systems from the Instrumental Analysis Service from the University of Alicante. CONTACT DETAILS Víctor Manuel Pérez Lozano SGITT-OTRI ( University of Alicante) Telephone number: +34 96 590 9959 Fax: +34 96 590 3803 E-Mail: areaempresas@ ua URL: http://sgitt-otri.ua/es/empresa/ofertas-tecnologicas.html 6