Compositions, Halogenated Compositions, Chemical Production, and Telomerization Processes

Abstract

Compositions are provided that can include RF(RT)nQ, formula I (I), formula II (II), and/or RCl(RT)nH. The RF group can have four fluorine atoms, the RT group can include a C-2 group having a pendant —CF3 group, n can be at least 1, the R1 group can include a carbon atom, the RCl group can be —CCI3, and the Q group can include one or more atoms of the periodic table of elements. Telomerization processes are also provided.

Description

TECHNICAL FIELD

The disclosure pertains to compositions, halogenated compositions, chemical production and telomerization processes.

BACKGROUND

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.

SUMMARY

Compositions are provided that can include R_F(R_T)_nQ and/or one or both of Within these compositions the R_F group can have at least four fluorine atoms, the R_T 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 R_Cl(R_T)_nH, with the R_Cl 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.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is a diagram of a system according to an exemplary embodiment of an exemplary aspect of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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).

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 R_FQ and/or R_ClQ. The R_F 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 R_F group being (CF₃)₂CF— and/or —C₆F₁₃, for example. The R_Cl 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 R_F(R_T)_nQ and/or R_Cl(R_T)_nH. The R_T 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 and with R₁ including at least one carbon atom, such as —CH₂—, 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 and

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 Table 1 below.

TABLE 1
Telomerization of Trifluoropropene Taxogen
	Yield (%) by GCc
	P (bars)	% Conv. of		MonoAdduct	DiAdduct
Runa	Init.d	R0b	C0b	T (° C.)	tr (hrs)	max	min	Taxogen	Telogen	(n = 1)	(n = 2)
1	Therm	0.50	—	160	20	22	17	79.2	27.6	51.9	20.5
2	Therm	0.25	—	160	20	39	34	36.8	52.8	26.2	21
3	Therm	0.50	—	180	22	30	11	73.4	2.4	65.9	31.2
4	Perk	0.50	0.03	62	20	7	5	79.2	23.8	35.4	40.8
5	AIBN	0.50	0.03	82	18	10	7	79.2	17.4	38.8	42
6	TRIG	0.50	0.03	134	6	16	0.6	89.6	3.7	19	63.8
7	DTBP	0.50	0.03	140	6	17	0.2	97.9	3.7	19	63.8
8	DTBP	0.50	0.03	143	4	19	0.8	94.3	9.6	21	66.6
9	DTBP	1.4	0.03	150	4	13	1.1	95.2	22.5	54.4	15.7
10	DTBP	0.75	0.03	145	4	20	3.0	93.8	6.8	34.1	49.0
11	DTBP	1.2	0.03	150	4	20	5.0	90.0	14.9	46.3	33.4
12	DTBP	1.4	0.03	150	4	21	3.5	95.0	12.6	54.1	28.6
13	DTBP	1.5	0.03	150	4	19	5.0	95.0	24.6	43.9	28.3
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.

Claims

1. A composition comprising RF(RT)nQ, wherein: the RF group comprises at least four fluorine atoms; the RT group comprises at least one C-2 group having at least one pendant —CF3 group; n is at least 1; and the Q group comprises a halogen.

2. The composition of claim 1 wherein the RF group comprises at least one —CF3 group.

3. The composition of claim 1 wherein the RF group comprises at least two —CF3 groups.

4. The composition of claim 3 wherein the RF group comprises —CF(CF3)2.

5. The composition of claim 1 wherein the RF group comprises —C6F13.

6. The composition of claim 1 wherein the RT group comprises

7. The composition of claim 1 wherein n is at least 2 and the composition comprises

8. The composition of claim 1 wherein n is at least 2 and the composition comprises

9. The composition of claim 1 wherein the Q group comprises at least one of F, Cl, Br, and I.

10. A composition comprising one or both of

11. The composition of claim 10 wherein the RF group comprises at least two —CF3 groups.

12. The composition of claim 10 wherein the R1 group consists of —CH2—.

13. The composition of claim 10 wherein n is equal to 1 and the composition comprises

14. The composition of claim 10 wherein the Q group comprises at least one halogen.

15. A composition comprising: RCl(RT)nH, wherein: the RCl group comprises at least —CCl3; the RT group comprises at least one C-2 group having at least one pendant —CF3 group; and n is at least 1.

16. The composition of claim 15 wherein n is at least 2 and the composition comprises

17. The composition of claim 15 wherein n is at least 2 and the composition comprises

18. A telomerization process comprising exposing at least one CF3-comprising taxogen to a fluorine-comprising telogen to produce a telomer, wherein the fluorine-comprising telogen comprises at least four fluorine atoms.

19. The process of claim 18 wherein the CF3-comprising taxogen is trifluoropropene.

20. The process of claim 18 wherein the fluorine-comprising telogen is (CF3)2CFl.

21. The process of claim 18 wherein the exposing the CF3-comprising taxogen to the fluorine-comprising telogen is in the presence of an initiator.

22. The process of claim 21 wherein the initiator comprises a peroxide.

23. The process of claim 22 wherein the peroxide comprises di-tert-butyl peroxide.

24. The process of claim 22 wherein the exposing occurs within a reactor and the initiator and telogen are provided to the reactor, a mole ratio of the initiator to the telogen being between about 0.001 and about 0.05.

25. The process of claim 24 wherein the mole ratio of the initiator to the telogen is between about 0.01 and about 0.03.

26. The process of claim 19 wherein the exposing occurs within a reactor, a temperature within the reactor during the exposing being from about 130° C. to about 150° C.

27. The process of claim 18 wherein: the CF3-comprising taxogen is trifluoropropene; and the telomer comprises wherein: the RF group comprises at least four fluorine atoms; n is at least 1; and the Q group comprises one or more atoms of the periodic table of elements.

28. The process of claim 18 wherein: the CF3-comprising taxogen is trifluoropropene; the fluorine-comprising telogen is (CF3)2CFl; and a mole ratio of the taxogen to the telogen is from about 2:1 to about 4:1.