Patent Application
20070197840
The disclosure pertains to compositions, halogenated compositions, chemical production and telomerization processes.
Compositions such as surfactants, polymers, and urethanes have incorporated halogenated functional groups. These functional groups have been incorporated to affect the performance of the composition when the composition is used as a treatment for materials and when the composition is used to enhance the performance of materials. For example, surfactants incorporating halogenated functional groups can be used as fire extinguishants either alone or in formulations such as aqueous film forming foams (AFFF). Polymers and/or urethanes incorporating halogenated functional groups have also been used to treat materials. To prepare these compositions, halogenated intermediate compositions can be synthesized.
Compositions are provided that can include RF(RT)nQ and/or one or both of
Within these compositions the RF group can have at least four fluorine atoms, the RT group can include at least one C-2 group having at least one pendant —CF3 group, n can be at least 1, the R1 group can include at least one carbon atom, and the Q group can include one or more atoms of the periodic table of elements. Compositions are provided that can also include RCl(RT)nH, with the RCl group having at least one —CCl3 group.
Telomerization processes are also provided that include exposing at least one CF3-comprising taxogen to a fluorine-comprising telogen to produce a telomer, with the fluorine-comprising telogen including at least four fluorine atoms.
The FIGURE is a diagram of a system according to an exemplary embodiment of an exemplary aspect of the invention.
This disclosure of the invention is submitted in furtherance of the constitutional purposes of the U.S. Patent Laws “to promote the progress of science and useful arts” (Article 1, Section 8).
Compositions and methods of making compositions are described with reference to the FIGURE. Referring to the FIGURE, a system 10 is shown for preparing halogenated compositions that includes reagents such as a taxogen 2, a telogen 4, and an initiator 6 being provided to reactor 8 to form a product such as a telomer 9. In exemplary embodiments system 10 can perform a telomerization process. According to an embodiment, taxogen 2 can be exposed to telogen 4 to form telomer 9. In accordance with another embodiment, taxogen 2 can be exposed to telogen 4 in the presence of initiator 6. Reactor 8 can also be configured to provide heat to the reagents during the exposing.
Taxogen 2 can include at least one CF3-comprising compound. The CF3-comprising compound can have a C-2 group having at least one pendant —CF3 group. In exemplary embodiments taxogen 2 can comprise an olefin, such as 3,3,3-trifluoropropene (TFP, trifluoropropene) and/or 1,1,3,3,3-pentafluoropropene (PFP, pentafluoropropene).
Telogen 4 can include halogens such as fluorine and/or chlorine. Telogen 4 can include at least four fluorine atoms and can be represented as RFQ and/or RClQ. The RF group can include at least four fluorine atoms and the Q group can include one or more atoms of the periodic table of elements. The Q group can be H or I with the RF group being (CF3)2CF— and/or —C6F13, for example. The RCl group can include at least one —CCl3 group. Exemplary telogens can include (CF3)2CFl, C6F13I, trichloromethane, HP(O)(OEt)2, BrCFClCF2Br, R—SH (R being a group having carbon), and/or MeOH. In exemplary embodiments, taxogen 2 can include trifluoropropene and telogen 4 can include (CF3)2CFl, with a mole ratio of taxogen 2 to telogen 4 being from about 1:1 to about 1:10, 1:4 to about 4:1, and/or to about 2:1 to about 4:1.
Reactor 8 can be any lab-scale or industrial-scale reactor and, in certain embodiments, reactor 8 can be configured to control the temperature of the reagents therein. According to exemplary embodiments reactor 8 can be used to provide a temperature during the exposing of the reagents of from about 130° C. to about 150° C.
Telomer 9, produced upon exposing taxogen 2 to telogen 4, can include RF(RT)nQ and/or RCl(RT)nH. The RT group can include at least one C-2 group having a pendant —CF3 group, such as
Exemplary products include
and/or one or both of
with R1 including at least one carbon atom, such as —CH2— and/or —CF2—, for example. In exemplary embodiments, n can be at least 1 and in other embodiments n can be at least 2 and the product can include one or more of
In an exemplary embodiment, the taxogen trifluoropropene can be exposed to the telogen (CF3)2CFl to form the telomer
and, by way of another example, trifluoropropene can be exposed to the telogen C6F13I to form the telomer
In accordance with another embodiment, the taxogen trifluoropropene can also be exposed to the telogen CCl3Z, (Z═H, Br, and/or Cl, for example) to form the telomer
Products having n being at least 2 can be formed when utilizing an excess of the taxogen as compared to the telogen. For example, at least a 2:1 mole ratio of the taxogen to the telogen can be utilized to obtain products having n being at least 2. For example and by way of example only, at least two moles of the taxogen trifluoropropene can be exposed to at least one mole of the telogen (CF3)2CFl to form one or both of the telomers
In additional embodiments initiator 6 may be provided to reactor 8 during the exposing of the reagents. Initiator 6 can include thermal, photochemical (UV), radical, and/or metal complexes, for example, including a peroxide such as di-tert-butyl peroxide. Initiator 6 can also include catalysts, such as Cu. Initiator 6 and telogen 4 can be provided to reactor 8 at a mole ratio of initiator 6 to taxogen 2 of from between about 0.001 to about 0.05 and/or from between about 0.01 to about 0.03, for example.
According to exemplary embodiments, various initiators 6 and telogens 4 can be used to telomerize taxogen 2 as referenced in Table 1 below. Telomerizations utilizing photochemical and/or metal-complex initiators 6 can be carried out in batch conditions using Carius tube reactors 8. Telomerizations utilizing thermal and/or peroxide initiators 6 can be carried out in 160 and/or 500 cm3 Hastelloy reactors 8. Telogen 4 (neat and/or as a peroxide solution) can be provided as a gas at a temperature from about 60° C. to about 180° C. and a telogen 4 [T]0/taxogen 2 [Tx]0 initial molar ratio R0 can be varied from 0.25 to 1.5 and the reaction time from 4 to 24 hrs as dictated in Table 1 below. The product mixture can be analyzed by gas chromatography and/or the product can be distilled into different fractions and analyzed by 1H and 19F NMR and/or 13C NMR. MonoAdduct (n=1) and DiAdduct (n=2) products can be recognized as shown in the Tables below.
aTelogen can be C6F13I in Runs Nos 1-9 and (CF3)2CFI in Runs No 10-13
bR0 = [T]0/[Tx]0; C0 = [In]0/[Tx]
cHeavy TFP telomers (n > 2) can make up remainder of product
dInitiators can be Perk. 16s(t-butyl cyclohexyl dicarbonate); AIBN; Trig.101 (2,5-bis-(t-butyl peroxy)-2,5-dimethylhexane); and DTBP
fTelomerization of PFP with Rfl telogens at different reaction conditions (Hastelloy 160 cc reactor for runs 1-5 and 8 cc Carius tube for runs 6-15)
gRf is C6F15 except for run 2 where it is C3F7.
hDTBP-di = tert-butyl peroxide; TRIG.101-2,5-bis(tert-butylperoxy)2,5-dimethylhexane; TRIG A80-tert-butyl hydroxyperoxide; DIAD - diisopropyl azodicoarboxylate
iR0 = [T]0/[Tx]0; C0 = [In]0/[Tx],
jThe remaining part is I2 and/or heavy PFP telomers.
kinitiator can be DTBP; solvent CH3CN at 50% (wt./wt.); Temperature 143° C.;
lruns 1-4 in 8 cc Carious tube, run 5 in Hatelloy reactor
mR0 = [T]0/[Tx]0; C0 = [In]0/[Tx]
nfor run No. 5, (% wt by distillation): HSR-18.2; n = 150.1, n = 2-28.3
oRuns performed in 160 cc Hastelloy reactor with DTBP initiator (3 mol %); RlI = C6F13I; R0 = 1.0; T = 145° C.; TR = 5 hours
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11192832 | Jul 2005 | US |
| Child | 11784447 | Apr 2007 | US |
