Fire retardant compounds

Abstract

Compounds with fire extinguishing properties having the formula: ##STR00001##
wherein R.sup.1 is CR.sup.5R.sup.6R.sup.7 or CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10 as well as fire extinguishing units including one or more of the compounds.

Claims

1. A fire extinguishing unit comprising a container and delivery system, the container containing a fire extinguishing compound having the formula:
(F.sub.3C)C(R.sup.2)=CR.sup.3R.sup.4 wherein R.sup.2 is iodo and R.sup.3 and R.sup.4 are both fluoro or R.sup.3 is hydrogen and R.sup.4 is fluoro; R.sup.2 is bromo, R.sup.3 is bromo and R.sup.4 is iodo; or R.sup.2 is fluoro, R.sup.3 is chloro, and R.sup.4 is iodo.

2. A fire extinguishing unit according to claim 1, wherein R.sup.2 is iodo and R.sup.3 and R.sup.4 are both fluoro or R.sup.3 is hydrogen and R.sup.4 is fluoro.

3. The fire extinguishing unit of claim 1 wherein the fire extinguishing compound is 2-iodo-1,1,3,3,3-pentafluoropropene.

4. A fire extinguishing unit according to claim 1, wherein R.sup.2 is bromo, R.sup.3 is bromo and R.sup.4 is iodo.

5. A fire extinguishing according to claim 1, wherein R.sup.2 is fluoro, R.sup.3 is chloro, and R.sup.4 is iodo.

6. A fire extinguishing unit comprising a container and delivery system, the container containing a fire extinguishing compound having the formula:
(F.sub.3C)C(R.sup.5)(R.sup.6)C(R.sup.2)=CR.sup.3R.sup.4 wherein R.sup.5 and R.sup.6 are independently hydrogen or halogen; R.sup.2 is chloro, or iodo; and R.sup.3 and R.sup.4 are defined as follows: R.sup.3 is iodo and R.sup.4 is hydrogen; R.sup.3 and R.sup.4 are both fluoro; or R.sup.3 and R.sup.4 are both hydrogen.

7. A fire extinguishing unit according to claim 6 wherein R.sup.3 is iodo and R.sup.4 is hydrogen.

8. A fire extinguishing unit according to claim 6 wherein R.sup.3 and R.sup.4 are both fluoro.

9. A fire extinguishing unit according to claim 6 wherein R.sup.3 and R.sup.4 are both hydrogen.

10. The fire extinguishing unit of claim 6 wherein R.sup.5 and R.sup.6 are each halogen.

11. The fire extinguishing unit of claim 6 wherein R.sup.5 and R.sup.6 are each F.

12. A fire extinguishing unit comprising a container and delivery system, the container containing a fire extinguishing compound selected from the group consisting of 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; 1-bromo-4,4,4-trifluoro-1-butene; 2-chloro-3,3,4,4,4-pentafluoro-1-butene; and combinations thereof.

13. A method for extinguishing a fire, the method comprising directing a compound of Formula I towards a fire, wherein Formula I is
(F.sub.3C)C(R.sup.2)=CR.sup.3R.sup.4 wherein R.sup.2 is iodo and R.sup.3 and R.sup.4 are both fluoro or R.sup.3 is hydrogen and R.sup.4 is fluoro; R.sup.2 is bromo, R.sup.3 is bromo and R.sup.4 is iodo; or R.sup.2 is fluoro, R.sup.3 is chloro, and R.sup.4 is iodo.

14. A method according to claim 13 wherein the fire extinguishing compound is 2 iodo-1,1,3,3,3-pentafluoropropene.

15. A method for extinguishing a fire, the method comprising directing a compound of Formula I towards a fire, wherein Formula I is
(F.sub.3C)C(R.sup.5)(R.sup.6)C(R.sup.2)=CR.sup.3R.sup.4 wherein R.sup.5 and R.sup.6 are independently hydrogen or halogen; R.sup.2 chloro, or iodo; and R.sup.3 and R.sup.4 are defined as follows: R.sup.3 is iodo and R.sup.4 is hydrogen; R.sup.3 and R.sup.4 are both fluoro; or R.sup.3 and R.sup.4 are both hydrogen.

16. A method for extinguishing a fire, the method comprising directing a fire extinguishing compound towards a fire, wherein the fire extinguishing compound is selected from the group consisting of 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; 1-bromo-4,4,4-trifluoro-1-butene; 2-chloro-3,3,4,4,4-pentafluoro-1-butene; and combinations thereof.

Description

DESCRIPTION OF CURRENT EMBODIMENTS

(1) 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 flameHeptane Cap Burner Value.

(2) Useful fire extinguishing compounds have the general formula:

(3) ##STR00004##
wherein R.sup.1 is CR.sup.5R.sup.6R.sup.7 or CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10;

(4) R.sup.2, R.sup.3 and R.sup.4 are each independently selected from halogen or hydrogen wherein at least one of R.sup.2, R.sup.3 and R.sup.4 must be halo; and

(5) R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are each independently selected from halogen or hydrogen wherein at least one of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10 must be halogen;

(6) wherein when R.sup.1 is CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10 and R.sup.8, R.sup.9 and R.sup.10 are each F, then at least one of R.sup.3 and R.sup.4 is halogen when R.sup.2 is hydrogen, or R.sup.2 is Cl, F or I when R.sup.3 and R.sup.4 are both hydrogen; and

(7) wherein when R.sup.1 is CR.sup.5R.sup.6R.sup.7 and R.sup.5, R.sup.6, R.sup.7 are each F then R.sup.2, R.sup.3 and R.sup.4 are each hydrogen or halogen, or when R.sup.2 is Br then R.sup.3 is selected from halogen and R.sup.4 is selected from hydrogen, Cl, F and I.

(8) In this aspect, when R.sup.1 is CR.sup.5R.sup.6R.sup.7 or CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10 then two or more substituents selected from R.sup.2, R.sup.3 and R.sup.4 may be halogen; or R.sup.2, R.sup.3 and R.sup.4 may each be halogen; or R.sup.2, R.sup.3 and R.sup.4 may each be independently selected from hydrogen, Br, Cl and I.

(9) Alternatively, in this aspect, when R.sup.1 is CR.sup.5R.sup.6R.sup.7 then R.sup.5, R.sup.6, and R.sup.7 may each be halogen and more narrowly R.sup.5, R.sup.6, and R.sup.7 may each be F. Moreover, when R.sup.1 is CR.sup.5R.sup.6R.sup.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.

(10) In the aspect above, when R.sup.1 is CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10 then R.sup.8, R.sup.9, and R.sup.10 may each be halogen and more narrowly, R.sup.8, R.sup.9, and R.sup.10 may each be F. Alternatively or in addition, when R.sup.1 is CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10 then R.sup.5 and R.sup.6 may each be halogen and more narrowly R.sup.5 and R.sup.6 may each be F. Finally, when R.sup.1 is CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.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.

(11) TABLE-US-00001 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 0 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

(12) In an alternative aspect, the fire extinguishing compounds have the general Formula I above wherein R.sup.1 is CR.sup.5R.sup.6R.sup.7 or CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10;

(13) R.sup.2, R.sup.3 and R.sup.4 are each independently selected from halogen and hydrogen; and

(14) R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are each independently selected from halogen and hydrogen, wherein at least one of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10 is halogen, and

(15) wherein when R.sup.1 is CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10 and R.sup.8, R.sup.9 and R.sup.10 are each F, then at least one of R.sup.2, R.sup.3 and R.sup.4 is halogen;

(16) wherein when R.sup.1 is CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10 and R.sup.8, R.sup.9 and R.sup.10 are each F and when R.sup.2 is Br then one of R.sup.3 and R.sup.4 is halogen, or one of R.sup.5 and R.sup.6 is hydrogen;

(17) wherein when R.sup.1 is CR.sup.5R.sup.6R.sup.7 and R.sup.5, R.sup.6, R.sup.7 are each F and R.sup.2 is Br, then R.sup.3 is halogen when R.sup.4 is selected from hydrogen or Br, or R.sup.3 is selected from hydrogen, Cl, Br or I when R.sup.4 is F; and

(18) wherein when R.sup.1 is CR.sup.5R.sup.6R.sup.7 and R.sup.5, R.sup.6, R.sup.7 are each F and R.sup.2 is I, then R.sup.3 is halogen when R.sup.4 is hydrogen, or R.sup.3 is selected from hydrogen, F, Cl and I when R.sup.4 is F.

(19) In this alternative aspect, when R.sup.1 is CR.sup.5R.sup.6R.sup.7 or CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10 then R.sup.2, R.sup.3 and R.sup.4 may each be halogen or R.sup.2, R.sup.3 and R.sup.4 may each be independently selected from hydrogen, Br, Cl and I. In another alternative, when R.sup.1 is CR.sup.5R.sup.6R.sup.7 then R.sup.5, R.sup.6, and R.sup.7 may each be halogen or R.sup.5, R.sup.6, and R.sup.7 may each be F.

(20) Also in this alternative aspect, when R.sup.1 is CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10 then R.sup.8, R.sup.9, and R.sup.10 may each be halogen or more narrowly R.sup.8, R.sup.9, and R.sup.10 may each be F. Moreover, when R.sup.1 is CR.sup.5R.sup.6CR.sup.8R.sup.9R.sup.10 then R.sup.5 and R.sup.6 may each be halogen and more narrowly R.sup.5 and R.sup.6 may each be each F.

(21) 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-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; 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.

(22) 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).

(23) 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.

(24) 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.

(25) 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.

(26) 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.

(27) 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.

(28) 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.

(29) 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.

(30) 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.

(31) 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.

EXAMPLECOMPOUND SYNTHESIS METHODS

(32) 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.

(33) Method A

(34) These synthesis procedures use a (C.sub.3HF.sub.5O) 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.sub.3HF.sub.5O) with a slight excess of di-isobutylaluminum hydride and purified by distillation. (1) 2-iodoheptafluorobutene and 2-bromoheptafluorobutene are synthesized using the (C.sub.3HF.sub.5O) aldehyde made above as follows: (a) Perform a one-pot reaction using one equivalent of the (C.sub.3HF.sub.5O) aldehyde, three equivalents of (chlorodifluoromethyl)trimethyl silane and three equivalents of triphenylphosphine in Tetrahydrofuran (THF) at 70 C. for 10 hours. The CF.sub.2 equivalent converts the R(H)C=O from the aldehyde to an R(H)C=CF.sub.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.sub.3HF.sub.5O) aldehyde made above as follows: a. Perform a one-pot reaction using one equivalent of the (C.sub.3HF.sub.5O) aldehyde, three equivalents of (chloromethyl)trimethyl silane and three equivalents of triphenylphosphine in THF at 70 C. for 10 hours. The CH.sub.2 equivalent converts the R(H)C=O from the aldehyde to an alkene, e.g. R(H)C=CH.sub.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 THF at 78 C., warming and then quenching with aqueous chlorine.

(35) Method B

(36) 1-Iodo-4,4,4-trifluoro-1-butene and 1-bromo-4,4,4-trifluoro-1-butene are synthesized as follows:

(37) React propargyl chloride with one equivalent of tris(triphenylphosphine)copper trifluoromethane, (Ph.sub.3P).sub.3CuCF.sub.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 <40 C.) and then warm the solution to 50 C.

(38) a. 1-Iodo-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.

(39) Method C

(40) 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.

(41) 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

(42) Method D

(43) 3,4,4,4-tetrafluoro-1-butene is prepared by reacting 3-bromo-3-fluoro-1-propene with (1,10-phenanthroline)(trifluoromethyl) copper(I).

(44) 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.

(45) 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.