University of Central Florida STARS Retrospective Theses and Dissertations 1978 Synthesis and Flame Retardant Studies of Bromoester of 2,4-Pentadienoic Acid Hessam Ghane University of Central Florida Part of the Chemistry Commons Find similar works at: https://stars.library.ucf.edu/rtd University of Central Florida Libraries http://library.ucf.edu This Masters Thesis (Open Access) is brought to you for free and open access by STARS. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of STARS. For more information, please contact [email protected]. STARS Citation Ghane, Hessam, "Synthesis and Flame Retardant Studies of Bromoester of 2,4-Pentadienoic Acid" (1978). Retrospective Theses and Dissertations. 288. https://stars.library.ucf.edu/rtd/288 3YNTHESIS AND FLAME RETARDANT STUDIES OF BROIDESTER OF 2,4- ?ENTADIENOIC ACID BY HESS.4M GHANE B.S., National University of Iran, 1974 RESEARCH REPORT Submitted in partial fulfillment of the requirements for the degree of Master of SCience: Industrial Chemistr,y in the Graduate Studies Program of the College of Natural Sciences of Florida Technological University . Sunmer QUarter 1978 ABSTRACT The synthesis and fire retardancy of several bromoeste~ of 2,4-pentadienoic acid were investigated. The synthesis of 2,4 entadienoic acid was accomplished by liquid phase re- action of acrolein and malonic acid in the presence of pyridine. The conversion of the acid to bromoesters was performed by two different procedures. In the first procedure, the corres- ponding acid chloride was prepared from the acid via reaction 0 with 30Cl2 in the presence of powdered (3A ) molecular sieves. The molecular sieves serve as an internal trap for by-product HCl and inhibit the competing polymerization reaction of the acid chloride. Reaction o! the acid chloride with various alcohols provided the unsaturated esters. The final step in the first procedure is total bromination of the unsaturated esters. The second procedure involved bromination of 2,4 entadienoic acid followed by reaction of the bromo acid with SOC12 to produce the corresponding bromo acid chloride. Reaction of the bromi- nated acid chloride with alcohol provided the corresponding bro- minated esters. A simple laboratory test was developed to mea- sure and compare the flame retardancy of the bromoesters. iii ACK~D ~·JL EOO EMENTS The author is sincerely grateful to Dr. John P. Idoux for the unlimited patience shown to me while he directed this re­ search project. I also idsh to thank him for his friendly personal assistance during the difficult areas of this project. The author also vdshes to express his thanks to other mem­ bers of the chemistry staff who contributed to the success of this project through their instruction and expressions of in­ terest. ;t'inally, the author wants to particularly thank his parents for the sacrifices which were made by them so that this goal could be attained. i:v CONTENTS Page / Introduction 1 Background Information 1 History 3 General History 3 History of Halogenated Fire Retardants 4 Production of Fire Retardant Chemicals 7 Definitions 11 Discussion of Some Terms 11 Definition of Flame 12 Burning Velocity 12 1echanism of Flame Retardant Chemicals in Combustion Process 14 Process Involved :Jhen a Hydrocarbon Burns 14 How Flame Retardants J\brk 15 Synergism 24 Fire Retardant Chemicals Classification 26 Nondurable Fire Retardants 26 Semidurable Flame Retardant 26 Durable Flame Retardant 27 Polymer Flammability 27 Solid Phase Inhibition 28 Vapor Phase Inhibition 28 Fire Retardancy Tests 32 General Fire Retardancy Tests 3~ Fire Retardancy Test for Halons 42 Fire Retardant Chemical Product 45 Additive Fire Retardants 51 Reactive Fire Retardants 54 Purpose of This Project 57 Experimental 58 Synthesis of 2,4-Pentadienoic Acid 58 v sYnthesis of 1,2,3,4-Tetrabromo Esters of 2,4- Pentadienoic Acid 60 s,ynthesis of Acid Chloride of 2,4-Pentadienoic Acid 61 Synthesis of Esters of 2,4-Pentadienoic -~id 62 Bromoester Production 67 Flame Retardancy Evaluation of 1,2,3,4-Tetrabromo Esters of 2,4-Pentadienoic Acid 67 References 74 vi LIST OF TABLES TABLE TITLE PAGE I Demand of Fire Retardant Chemicals for Different Purposes 8 II Production of Different Fire Retardant Chemicals in Plastic Industries 9 III Fire Retardant Halogenated Compounds 21 IV Percentage of Phosphorus and Nitrogen Needed in 3ynergism for Effective Fire Retardancy 24 v Synergism of Phosphorus-Bromine and Anti- mony romine Compounds in Different Haterials 25 TI Evaluation of Portable Fire Extinguishing Agents by Army Corp of Engineers 43 VII .Ansul Portable Evaluations 46 VIII Some Conmon Commercial Fire Retardant Additives 53 IX Flame Retardant Ivbnomers for Incorporation into Po~er Chain 56 Flammability of Untreated Cotton Samples 70 XI Flammability of Unsaturated Esters of 2,4- Pentadienoic Acid (C~=CH-GH=CH-GOOR) 71 XII Flame Retardancy Evaluation of Different Bromoesters of 2,4-Pentadienoic Acid 73 LIST OF FIGURES FIGURE TITLE -PAGE 1 Rapid Increase in Additive Fire Retardant Sale 10 2 Schematic Diagram of Burning Velocity 13 3 Continuous Cycle of Polymer Combustion Process 29 4 Solid Phase Flame Extinguishment of Polymers 30 5 Vapor Phase Flame Extinguishment of Polymers 31 6 Geometrical Test of Fire Retardancy and Anal- ysis of Penetrating The Flame 38 7 Oxygen Index Apparatus for Fire Retardancy Evaluation of Polymers 40 8 Fire Pan and Discharge Nozzle Arrangement Ansul Co. Portable Evaluation - 1955 45 9 Performance Curves for Halons 1301, 12~1, 1202, and 2402 . Ansul Co. Portable Evalua- tion - 195.5 45 10 Schematic of Total Flooding Fire SUppression System 48 11 Sample of Cotton Used for Flame Retardancy Evaluation of Bromoesters 68 12 Apparatus Used for Flame Retardancy Evalua- tion of Bromoesters. 69 1 TI'iTRODUCTION Background Information The United States has the largest number of fires in the world. Each year there are 2. 6 million fires resulting in 7500 deaths and more than four billion dollars in direct property damage •1 Since the late 18th centur.y, there have been a large number of industries involved in the production of flame retardants. These materials are both natural and synthetic in origin and have found a variety of applications in helping to reduce different types of fire hazardso Today much is known about the way flame retardants work and researchers are using this information to improve the flame retar­ dancy of various materials. However, in many cases, solutions are based on limited experience and assumptions, thus, there is still the need for more research on extinguishing agents in order to improve their effectiveness.~ Anyone who has been near a roaring fire or who has known burn victims are aware of the need of rapid, effective fire suppressants. In the area of building construction, especi~ modern buildings, there are regulations concerning the use of firetrucks and sprinkler systems to extinguish fires, but in many cases, '\ihe water damage can match or even exceed the direct fire damage. Even with these problems, water is still the most deliverable, often the most available suppressant for a f~ developed conflagra­ tion. However, in some situations, particularly indoors, using water is not the best choice as a fire extinguishant, and in these 2 areas, a less massive agent is desirable. In many cases of fire, people need to remain in the area to secure valuables or expensive and heavy equipment which are pre­ sent. Or perhaps, the fire is too small to warrent calling the fire department. In any event, a convenient, local, non- destruc­ tive, and physiologically tolerable fire suppressant is desirable.3 An early alternative candidate to water was carbon tetra­ chloride. It is an effective flame quenching agent but is too toxic to use indoors. However, the application of halogenated flame retardants to extinguish a flame was so effective that co­ pious testing was performed on a wide variety of these compounds. These agents are commonly lmown as halons.4 Most of these sub- stances were found effective, but some were found to present unac­ ceptable health hazards. The major halon agents in commercial use tod~ are CF3Br halon(lJOl), CF2C1Br halon(l211), and C2F4Br2 halon (2402). In 1972, a National Acad~ of Science Committee and a National Research Council Committee held a s.ymposium to evaluate the toxi­ cology and usage of these major halons. Some of these agents dis­ play variable degrees of effectiveness in f~re suppression as well as potential p~siological hazards.J There were several complementary approaches to improve knowledge in this direction in the symposium. Investigations on the basic pro­ cess occurring in inhibited flames and deducing the mechanistic ele­ ments for suppressing fires by halons were the main interests. These approaches would be helpful for other researchers in the area of fire protection. History 3 I. General History Research into what causes a substance to burn and ho"'"r the com­ bustion process m~ be altered or stopped has been conducted for many lears. For example, attempts to make fabrics flame retardant can be traced back to the early seventeenth century. The major aspect of fire problems is not only based on life hazards and property damages, but on the pollution of the air, the "Nater, and the ground. In this context, fire safety is considered to be more important than ever. As a consequence, there has been an increase in the regulations, security, and safety of fire retar- dant materials. Similarly, the proof of safety of many products such as pesticides and phar.maceuticals are being firmly placed on their manufacturers. The fire safety of these materials in many different areas are the main concern. Thus, there are a large num­ ber of private industries and goverrunent laboratories searching for better ways of controlling the flammability of chemical products.