Patent Publication Number: US-11377408-B2

Title: Fire retardant compounds

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     This application is a divisional of U.S. application Ser. No. 16/126,746, filed Sep. 10, 2018, which is a divisional of U.S. application Ser. No. 14/753,760, filed Jun. 29, 2015, the disclosure of each of which is incorporated herein by reference in its entirety. 
    
    
     BACKGROUND OF THE INVENTION 
     Field of the Invention 
     This invention concerns novel halogen containing compounds and fire extinguishing units including one or more fire extinguishing compounds. 
     Description of the Art 
     Halon 1301 is the predominant fire extinguishing agent used on aircraft. Halon 1301 is currently a banned substance with few exceptions. One such exception is its use as an aircraft fire extinguishing agent. However, even with this exception, new fire extinguishing compounds are needed because Halon 1301, as a banned substance, is no longer manufactured and eventually the current supply will be depleted. There is a need, therefore, for new fire extinguishing compounds and fire extinguishing units that contain them. 
     SUMMARY OF THE INVENTION 
     A first aspect of this invention is new compounds with fire extinguishing properties having the formula: 
                         
wherein R 1  is —CR 5 R 6 R 7  or —CR 5 R 6 CR 8 R 9 R 10 ;
 
     R 2 , R 3  and R 4  are each independently selected from halogen and hydrogen; and 
     R 5 , R 6 , R 7 , R 8 , R 9  and R 10  are each independently selected from halogen and hydrogen, wherein at least one of R 5 , R 6 , R 7 , R 8 , R 9  and R 10  is halogen; 
     wherein when R 1  is —CR 5 R 6 CR 8 R 9 R 10  and R 8 , R 9  and R 10  are each F, then at least one of R 2 , R 3  and R 4  is halogen; 
     wherein when R 1  is —CR 5 R 6 CR 8 R 9 R 10  and R 8 , R 9  and R 10  are each F and when R 2  is Br then one of R 3  and R 4  is halogen, or one of R 5  and R 6  is hydrogen; 
     wherein when R 1  is —CR 5 R 6 R 7  and R 5 , R 6 , R 7  are each F and R 2  is Br, then R 3  is halogen when R 4  is selected from hydrogen or Br, or R 3  is selected from hydrogen, Cl, Br or I when R 4  is F; and 
     wherein when R 1  is —CR 5 R 6 R 7  and R 5 , R 6 , R 7  are each F and R 2  is I, then R 3  is halogen when R 4  is hydrogen, or R 3  is selected from hydrogen, F, Cl and I when R 4  is F. 
     In the above compounds: two or more substituents selected from R 2 , R 3  and R 4  may be halogen; R 2 , R 3  and R 4  may each be halogen; and/or R 2 , R 3  and R 4  may each be independently selected from hydrogen, Br, Cl and I. 
     In the above compounds, R 1  may be —CR 5 R 6 R 7  in which case R 5 , R 6  and R 7  may each be halogen or R 5 , R 6 , and R 7  may each be F. 
     In the above compounds, R 1  may be —CR 5 R 6 CR 8 R 9 R 10  in which case R 8 , R 9  and R 10  may each be halogen; or R 8 , R 9 , and R 10  may each be F. 
     In the above compounds, R 1  may be —CR 5 R 6 CR 8 R 9 R 10  in which case R 5  and R 6  may each be halogen; or R 5  and R 6  may each be F. 
     In another aspect, the above compound may be 2-iodoperfluoro-1-butene; 2,3-dibromo-4,4,4-trifluoro-1-butene; 2-iodoperfluoro-1-butene; 2-bromoperfluoro-1-butene; 3-iodo-3,4,4,4-tetrafluoro-1-butene; 1-iodo-4,4,4-trifluoro-1-butene; 2-bromo-3,3,4,4,4-pentafluoro-1-butene; 1-bromo-4,4,4-trifluoro-1-butene; 2-chloro-3,3,4,4,4-pentafluoro-1-butene; and isomers thereof. 
     Yet another aspect of this invention are fire extinguishing units comprising a container and delivery system, the container containing at least one fire extinguishing compound having the formula: 
                         
wherein R 1  is —CR 5 R 6 R 7  or —CR 5 R 6 CR 8 R 9 R 10 ;
 
     R 2 , R 3  and R 4  are each independently selected from halogen or hydrogen wherein at least one of R 2 , R 3  and R 4  must be halo; and 
     R 5 , R 6 , R 7 , R 8 , R 9  and R 10  are each independently selected from halogen or hydrogen wherein at least one of R 5 , R 6 , R 7 , R 8 , R 9  and R 10  must be halogen; 
     wherein when R 1  is —CR 5 R 6 CR 8 R 9 R 10  and R 8 , R 9  and R 10  are each F, then at least one of R 3  and R 4  is halogen when R 2  is hydrogen, or R 2  is Cl, F or I when R 3  and R 4  are both hydrogen; and 
     wherein when R 1  is —CR 5 R 6 R 7  and R 5 , R 6 , R 7  are each F then R 2 , R 3  and R 4  are each hydrogen or halogen, or when R 2  is Br then R 3  is selected from halogen and R 4  is selected from hydrogen, Cl, F and I. 
     In the above fire extinguishing unit, the fire extinguishing compound may include substituents R 2 , R 3  and R 4  wherein two or more of the substituents are halogen; or where each substituent is halogen; or where each substituent is selected from hydrogen, Br, Cl and I. 
     In the above fire extinguishing unit, the fire extinguishing compound includes substituent R 1  that may be —CR 5 R 6 R 7  in which case R 5 , R 6 , and R 7  may each be halogen; or R 5 , R 6 , and R 7  may each be F. 
     In the above fire extinguishing unit, the fire extinguishing compound includes substituent R 1  that may be —CR 5 R 6 CR 8 R 9 R 10  in which case R 8 , R 9 , and R 10  may each be halogen; or R 8 , R 9 , and R 19  may each be F; or in which case R 5  and R 6  may each be halogen or may each be F. 
     In the above fire extinguishing unit, the fire extinguishing compound may be selected from 2-iodoperfluoro-1-butene; 2,3-dibromo-4,4,4-trifluoro-1-butene; 2-iodoperfluoro-1-butene; 2-bromoperfluoro-1-butene; 3-iodo-3,4,4,4-tetrafluoro-1-butene; 1-iodo-4,4,4-trifluoro-1-butene; 2-bromo-3,3,4,4,4-pentafluoro-1-butene; 1-bromo-4,4,4-trifluoro-1-butene; 2-chloro-3,3,4,4,4-pentafluoro-1-butene; 2-bromo-1,1,3,3,3-pentafluoropropene; 2-iodo-1,1,3,3,3-pentafluoropropene; 2-iodo-3,3,3-trifluoropropene, isomers thereof and combinations thereof. 
    
    
     DESCRIPTION OF CURRENT EMBODIMENTS 
     The present invention relates to novel compounds that have fire retarding properties as well as fire extinguishing units that include one or more fire retarding compounds. The compounds discussed below are all expected to have acceptable to very good abilities to extinguish a heptane flame—Heptane Cap Burner Value. 
     Useful fire extinguishing compounds have the general formula: 
                         
wherein R 1  is —CR 5 R 6 R 7  or —CR 5 R 6 CR 8 R 9 R 10 ;
 
     R 2 , R 3  and R 4  are each independently selected from halogen or hydrogen wherein at least one of R 2 , R 3  and R 4  must be halo; and 
     R 5 , R 6 , R 7 , R 8 , R 9  and R 10  are each independently selected from halogen or hydrogen wherein at least one of R 5 , R 6 , R 7 , R 8 , R 9  and R 10  must be halogen; 
     wherein when R 1  is —CR 5 R 6 CR 8 R 9 R 10  and R 8 , R 9  and R 10  are each F, then at least one of R 3  and R 4  is halogen when R 2  is hydrogen, or R 2  is Cl, F or I when R 3  and R 4  are both hydrogen; and 
     wherein when R 1  is —CR 5 R 6 R 7  and R 5 , R 6 , R 7  are each F then R 2 , R 3  and R 4  are each hydrogen or halogen, or when R 2  is Br then R 3  is selected from halogen and R 4  is selected from hydrogen, Cl, F and I. 
     In this aspect, when R 1  is —CR 5 R 6 R 7  or —CR 5 R 6 CR 8 R 9 R 10  then two or more substituents selected from R 2 , R 3  and R 4  may be halogen; or R 2 , R 3  and R 4  may each be halogen; or R 2 , R 3  and R 4  may each be independently selected from hydrogen, Br, Cl and I. 
     Alternatively, in this aspect, when R 1  is —CR 5 R 6 R 7  then R 5 , R 6 , and R 7  may each be halogen and more narrowly R 5 , R 6 , and R 7  may each be F. Moreover, when R 1  is —CR 5 R 6 R 7  then the fire extinguishing compound of this invention may be selected from 2-bromo-1,1,3,3,3-pentafluoropropene; 2-iodo-1,1,3,3,3-pentafluoropropene; 2-iodo-3,3,3-trifluoropropene and combinations thereof identified in Table 1 below. 
     In the aspect above, when R 1  is —CR 5 R 6 CR 8 R 9 R 10  then R 8 , R 9 , and R 10  may each be halogen and more narrowly, R 8 , R 9 , and R 10  may each be F. Alternatively or in addition, when R 1  is —CR 5 R 6 CR 8 R 9 R 10  then R 5  and R 6  may each be halogen and more narrowly R 5  and R 6  may each be F. Finally, when R 1  is —CR 5 R 6 CR 8 R 9 R 10  then the fire extinguishing compound of this invention may be selected from 2-iodoperfluoro-1-butene; 2,3-dibromo-4,4,4-trifluoro-1-butene; 2-iodoperfluoro-1-butene; 2-bromoperfluoro-1-butene; 3-iodo-3,4,4,4-tetrafluoro-1-butene; 1-iodo-4,4,4-trifluoro-1-butene; 2-bromo-3,3,4,4,4-pentafluorobutene; 2-chloro-3,3,4,4,4-pentafluoro-1-butene; isomers thereof and combinations thereof as identified in Table 1 below. 
     
       
         
           
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Compound Name 
                 Formula 
               
               
                   
               
             
            
               
                 2-bromo-1,1,3,3,3-pentafluoropropene 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 2-iodo-1,1,3,3,3-pentafluoropropene 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 2-iodo-3,3,3-trifluoropropene 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 1-bromo-4,4,4-trifluoro-1-butene 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 2,3-dibromo-4,4,4-trifluoro-1-butene 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 2-iodoperfluoro-1-butene 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 2-bromoperfluoro-1-butene 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 3-iodo-3,4,4,4-tetrafluoro-1-butene 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 1-iodo-4,4,4-trifluoro-1-butene 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 2-bromo-3,3,4,4,4-pentafluorobutene 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 2-chloro-3,3,4,4,4-pentafluoro-1-butene 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
            
           
         
       
     
     In an alternative aspect, the fire extinguishing compounds have the general Formula I above wherein R 1  is —CR 5 R 6 R 7  or —CR 5 R 6 CR 8 R 9 R 10 ; 
     R 2 , R 3  and R 4  are each independently selected from halogen and hydrogen; and 
     R 5 , R 6 , R 7 , R 8 , R 9  and R 10  are each independently selected from halogen and hydrogen, wherein at least one of R 5 , R 6 , R 7 , R 8 , R 9  and R 10  is halogen, and 
     wherein when R 1  is —CR 5 R 6 CR 8 R 9 R 10  and R 8 , R 9  and R 10  are each F, then at least one of R 2 , R 3  and R 4  is halogen; 
     wherein when R 1  is —CR 5 R 6 CR 8 R 9 R 10  and R 8 , R 9  and R 10  are each F and when R 2  is Br then one of R 3  and R 4  is halogen, or one of R 5  and R 6  is hydrogen; 
     wherein when R 1  is —CR 5 R 6 R 7  and R 5 , R 6 , R 7  are each F and R 2  is Br, then R 3  is halogen when R 4  is selected from hydrogen or Br, or R 3  is selected from hydrogen, Cl, Br or I when R 4  is F; and 
     wherein when R 1  is —CR 5 R 6 R 7  and R 5 , R 6 , R 7  are each F and R 2  is I, then R 3  is halogen when R 4  is hydrogen, or R 3  is selected from hydrogen, F, Cl and I when R 4  is F. 
     In this alternative aspect, when R 1  is —CR 5 R 6 R 7  or —CR 5 R 6 CR 8 R 9 R 10  then R 2 , R 3  and R 4  may each be halogen or R 2 , R 3  and R 4  may each be independently selected from hydrogen, Br, Cl and I. In another alternative, when R 1  is —CR 5 R 6 R 7  then R 5 , R 6 , and R 7  may each be halogen or R 5 , R 6 , and R 7  may each be F. 
     Also in this alternative aspect, when R 1  is —CR 5 R 6 CR 8 R 9 R 10  then R 8 , R 9 , and R 10  may each be halogen or more narrowly R 8 , R 9 , and R 10  may each be F. Moreover, when R 1  is —CR 5 R 6 CR 8 R 9 R 10  then R 5  and R 6  may each be halogen and more narrowly R 5  and R 6  may each be each F. 
     Further in this alternative aspect, the compound is selected from 2-iodo perfluoro-1-butene; 2,3-dibromo-4,4,4-trifluoro-1-butene; 2-bromoperfiuoro-1-butene; 3-iodo-3,4,4,4-tetrafluoro-1-butene; 1-iodo-4,4,4-trifluoro-1-butene; 2-bromo-3,3,4,4,4-pentafluorobutene; 1-bromo-4,4,4-trifluoro-1-butene; 2-chloro-3,3,4,4,4-pentafluoro-1-butene; and isomers thereof as identified in Table 1 above. 
     As used herein the term halogen is used in its normal and customary manner to refer to chloro (Cl), fluoro (F), bromo (Br) and iodo (I). 
     The fire extinguishing compounds identified above are useful alone or combined with other fire extinguishing composition ingredients when used in a fire extinguishing unit to suppress or extinguish fires. Fire suppression refers to a use of agents such as gases, liquids, solids, chemicals and mixtures thereof to extinguish combustion. 
     The fire extinguishing compounds discussed above are useful in fire extinguishing units that include various containers and delivery systems that may in turn be used in a variety of fire extinguishing applications. Such units and delivery systems include, but are not limited to hand-held fire extinguishing units, permanent fire extinguishing systems, modular fire extinguishing systems and the like which may be used in the home, computer rooms, kitchens, factories warehouse facilities, airplanes, cars, trucks, heavy-equipment, etc. The fire extinguishing compound(s) may be used in units that are used in flood and streaming-type fire extinguishing applications. The compounds may be placed in any known container that is used to hold fire extinguishing compounds and compositions such as hand-held extinguishing containers, tanker trucks such as those associated with fire trucks, wheeled containers and the like. 
     Some fire suppression units or systems use a “total flooding” or a “non-total flooding” methods to apply an extinguishing agent in an enclosed volume. The total flooding or the non-total flooding method may achieve a concentration of the extinguishing agent as a volume percent to air of the extinguishing agent sufficient to suppress or extinguish a fire. 
     In aircraft applications, each cargo compartment may have its own dedicated distribution system comprising tubes routed to nozzles in a cargo bay. The nozzles may be mounted in pans down a centerline of a cargo bay ceiling liner. An extinguishing agent including one or more of the fire extinguishing compounds disclosed above may also be released directly into a compartment where there are no tubes or nozzles, as the agent container(s) is/are plugged directly into the compartment. Fire suppression systems may be operated automatically by an automatic detection and control mechanism, and/or manually by manual activation of an actuator via a local and/or remote switch, a combination thereof, and the like. 
     Fire suppression units and delivery systems are generally sized for worst case scenarios that may occur during descent when an aircraft begins to re-pressurize. Therefore, additional equipment and suppressant chemicals required during descent may determine a size of an overall system with resulting added weight and volume. 
     The useful fire extinguishing units include one or more of the above fire extinguishing compounds and optionally include additional active and inert fire suppression or extinguishing ingredients, Active ingredients might include, for example, oxygen depleting agents, heat removing (endothermic) agents such as carbon dioxide, additional flame retarding or extinguishing agents and the like. 
     Fire suppression units, delivery systems and methods that can employ one or more fire extinguishing compounds of this invention are well known. For example, U.S. Pat. No. 8,925,642 discloses a scalable cargo fire suppression agent distribution system. The system includes a plurality of fire suppression agent supply source units. During use, a supply source unit subset of the total source units is/are selected based on an operation condition, and a fire suppression agent from the supply source unit subset is distributed during the operation condition. In this manner, significantly less storage space and supply source container weight is required to store fire suppression agents. 
     In another example, U.S. Pat. No. 7,510,022 is directed to fire suppression systems for aircraft cargo compartments. The fire suppression systems can include at least one fire-suppressant vessel, at least one discharge conduit coupled to the at least one fire-suppressant vessel, and a valve arrangement coupled to the fire-suppressant vessel and the discharge conduit. The valve arrangement has multiple settings that allows for the control of the discharge rate of a fire suppressant held in the vessels. 
     In yet another example, U.S. Pat. No. 4,726,426 discloses a fire suppression system for extinguishing fires in an aircraft passenger cabin. The system uses the passenger cabin environmental control system ductwork to direct a fire suppression agent from a vessel or container in the cargo hold into the passenger cabin. Other examples of fire suppression systems are within the knowledge of one skilled in the art. 
     Example—Compound Synthesis Methods 
     Fire retardant compounds of this invention can be prepared by the synthesis methods detailed in this example. Moreover, the skilled person would understand that there are other synthesis methods that can be used to prepare the fire retardant compounds identified above. 
     Method A 
     These synthesis procedures use a (C 3 HF 5 O) aldehyde that is prepared by esterifying pentafluoropropionic acid with methanol and trace amount of sulfuric acid. The ester, methyl pentafluoropropionate, is purified by distillation. Next, the methyl pentafluoropropionate is reduced to 2,2,3,3,3-pentafluoropropionaldehyde (C 3 HF 5 O) with a slight excess of di-isobutylaluminum hydride and purified by distillation.
         (1) 2-iodoheptafluorobutene and 2-bromoheptafluorobutene are synthesized using the (C 3 HF 5 O) aldehyde made above as follows:
           (a) Perform a one-pot reaction using one equivalent of the (C 3 HF 5 O) aldehyde, three equivalents of (chlorodifluoromethyl)trimethyl silane and three equivalents of triphenylphosphine in Tetrahydrofuran (“THF”) at 70° C. for 10 hours. The “CF 2 ” equivalent converts the R(H)C═O from the aldehyde to an R(H)C═CF 2  and the product is purified by distillation.   i. 2-iodoheptafluorobutene is derived by abstracting aldehyde hydrogen with one equivalent of n-butyl lithium in THF at −78° C., warm, and quenching with iodine.   ii. 2-bromoheptafluorobutene is derived by abstracting aldehyde hydrogen with one equivalent of n-butyl lithium in THF at −78° C., warm, and quenching with bromine.   
           (2) 2-Chloro-3,3,4,4,4-pentafluorobutene is synthesized using the (C 3 HF 5 O) aldehyde made above as follows:
           a. Perform a one-pot reaction using one equivalent of the (C 3 HF 5 O) aldehyde, three equivalents of (chloromethyl)trimethyl silane and three equivalents of triphenylphosphine in THF at 70° C. for 10 hours. The “CH 2 ” equivalent converts the R(H)C═O from the aldehyde to an alkene, e.g. R(H)C═CH 2 . The resulting product is 3,3,4,4,4-pentafluoro-1-butene and it is purified by distillation.   b. 2-Chloro-3,3,4,4,4-pentafluorobutene is derived by abstracting aldehyde hydrogen with one equivalent of n-butyl lithium in THE at −78° C., warming and then quenching with aqueous chlorine.   
               

     Method B 
     1-Iodo-4,4,4-trifluoro-1-butene and 1-bromo-4,4,4-trifluoro-1-butene are synthesized as follows: 
     React propargyl chloride with one equivalent of tris(triphenylphosphine)copper trifluoromethane, (Ph 3 P) 3 CuCF 3  to give 4,4,4-trifluoro-1-butyne. Next, react 4,4,4-trifluoro-1-butyne with dibutylaluminum hydride in n-heptane solution at &lt;40° C.) and then warm the solution to 50° C. 
     a. 1-lodo-4,4,4-trifluorobutene is derived from the reaction product above by cooling the solution to −50° C., and quenching with iodine to give a mixture of cis- and trans-1 -iodo-4,4,4-trifluoro-1-butene.
         1-Bromo-4,4,4-trifluoro-1-butene is derived from the reaction product above by using bromine instead of iodine in reaction step (a) above to form a cold quench mixture of cis- and trans-1-bromo-4,4,4-trifluoro-1-butene.       

     Method C 
     2,3-dibromo-4,4,4-trifluoro-1-butene is prepared by reacting 2-bromo-4,4,4-trifluoro-1-butene with one equivalent of sodium t-butoxide in t-butanol at low temperature (−78° C. to −40° C.) and then quenching the solution slowly with bromine to yield the above-mentioned dibromo product. 
     2-bromo-4,4,4-trifluoro-1-butene is prepared by reacting 2,3-dibromo-1-propene with one equivalent of (1,10-phenanthroline)(trifluoromethyl) copper 
     Method D 
     3,4,4,4-tetrafluoro-1-butene is prepared by reacting 3-bromo-3-fluoro-1-propene with (1,10-phenanthroline)(trifluoromethyl) copper(I). 
     3,4,4,4-tetrafluoro-3-iodo-1-butene is prepared by reacting sodium t-butoxide with 3,4,4,4-tetrafluoro-1-butene, followed by quenching with iodine. 
     The foregoing description of the specific embodiments will reveal the general nature of the disclosure so others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and therefore such adaptations and modifications are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology herein is for the purpose of description and not of limitation.