Heat mitigation in cf 3ccl 3 (CFC-113a) coupling reaction

Abstract

The present invention relates to heat mitigation for processes coupling CFC compounds having a CCl3 end group in the presence of hydrogen.

Description

TITLEHEAT MITIGATION IN CF3CCL3 (CFC-113A) COUPLING REACTIONFIELD

[0001] The invention relates to mitigating heat during exothermic reactions involving trifluorotrichloroethane.BACKGROUND

[0002] Hydrofluoroolefins (HFOs) having low ozone depletion potential (ODP) and low global warming potential (GWP) have been replacing saturated CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons) in a variety of applications for several years, as well as hydrofluorocarbons which tend to have high GWP values. As a result, low ODP and GWP materials for use as refrigerants, solvents, foam expansion agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishants, and power cycle working fluids continue to be of interest.Although processes for preparing olefin compounds, such as 1,1 , 1 ,4, 4, 4 hexafluoro- 2-butene (HFO-1336mzz), have been reported, there remains a need for process improvement to facilitate scaling up these processes for commercial production.

[0003] Preparation of olefinic refrigerants, including, but not limited to 1,1 , 1 ,4, 4, 4 hexafluoro-2-butene (HFO-1336mzz) and mixtures of the Z- and E- isomers have been described in, for example, U.S. Patent Publication No. 20190248719, the disclosure of which is incorporated herein by reference. In addition, any Z-1, 1 ,1, 4, 4, 4 hexafluoro-2-butene that is prepared can be isomerized to E-1 , 1 ,1 ,4,4,4 hexafluoro- 2-butene, as disclosed in, for example, U.S. Patent No. 10,479,745, the disclosure of which is incorporated herein by reference in its entirety.

[0004] As disclosed in U.S. Patent Publication No. 20190248719, HFO-1336mzz can be prepared through a series of reactions by preparing the intermediate E / Z- CFO-1316mxx (E / Z-CFsCC CCICFs), from trifluorotrichloroethane (CFC-CF3CCI3) by contacting 1 ,1 ,1 -trifluorotrichloroethane with hydrogen in the presence of a catalyst comprising ruthenium to produce a product mixture comprising 1316mxx. The coupling reaction of CFC-113a is typically conducted at a temperature from150°C. to 300°C. Temperature control is typically provided by a recirculating hot oil system.

[0005] Exothermicity from trifluorotrichloroethane coupling using conventional hot oil recirculation is difficult and often is uncontrollable, resulting in runaway reactions. Problems associated with runaway reactions often result is destruction of catalyst and reactor components. The Applicants have unexpectedly found that regulating and providing uniform temperature in a commercial process reaction zone, and maintaining the reaction gain at a level below 2 successfully mitigated heat, avoided / reduced hot spot formation and prevented run-away reactions possible with highly exothermic reactions.SUMMARY

[0006] The present invention relates to processes for mitigating heat during coupling of 1,1 ,1-trichloro-2,2,2-trifluoroethane (HCFC-113a).

[0007] The present invention relates to processes for mitigating heat during coupling of 1,1 ,1-trichloro-2,2,2-trifluoroethane (HCFC-113a) by conducting the reaction in the presence of a diluent.

[0008] The present invention relates to processes comprising passing a reactor feed of 1,1,1-trichloro-2,2,2-trifluoroethane (HCFC-113a) through one or more catalyst filled tubes, contacting the one or more tubes with a heat exchange liquid, monitoring hot-spot formation within the one or more tubes, monitoring the temperature change in the heat exchanging liquid, calculating a steady state measure of reactor gain in the tubes defined by the formula (G)ain = ATHS / ATOH , and adding a diluent to the reactor feed.

[0009] The present invention relates to processes comprising passing a reactor feed of 1,1,1-trichloro-2,2,2-trifluoroethane (HCFC-113a) and a diluent through one or more catalyst filled tubes, contacting the one or more tubes with a heat exchange liquid, monitoring hot-spot formation within the one or more tubes, monitoring the temperature change of the heat exchanging liquid, maintain the a steady state measure of reactor gain in the tubes defined by the formula (G)ain = ATHS / ATOH , by the amount of the diluent to the reactor feed.

[0010] Embodiments disclosed herein relate to processes of passing a CFC having a CCI3 end group, including but not limited to CFC-113a, through one or more tubes filled with catalyst suitable for exothermic coupling reactions in indirect exchange relationship with a heat exchanging medium, including but not limited of oil, such as Dowtherm. The inventive process further involves assessing hotspot formation which could be undetected by arranging thermocouples along a length of each tube to monitor hot spots, exchanging exothermic heat generated from the coupling reaction within each said tubes, and determining the presence of the hotspot using the thermocouple. Instead, the Applicants have developed a process to determine how the hot spot changes with a change in inlet temperature. This can be assessed through modeling where sequential cases are run with an increase in inlet temperature and then observe the change in predicted hot spot temperature. Temperature sensors are at discrete locations in a catalyst bed, and sole reliance in fixed sensor location run the risk of “missing” the hot spot. Operating the system in response to the change in hotspot temperature, and keeping reactor Gain at values <2, wherein reactor gain (G) is defined as A THS / A Ton where T= temperature, ATHS = change in hotspot temperature and ATon = change of oil temperature at the inlet, should avoid the consequences of not doing so.

[0011] In one embodiment disclosed herein diluents are added to the reaction zone to mitigate heat.

[0012] In another embodiment disclosed herein inert diluents are added to the reaction medium in reaction zones to mitigate heat.

[0013] In certain embodiments the coupling of CFC-113a in the presence of hydrogen is conducted in the presence of R-143a, R-123, R-134a and CFC 113a, wherein reactant ratios of H2:113a (H2 organic ratio) is between 1-5:1 , preferably 2- 4: 1 , most preferably 3: 1.

[0014] In certain embodiments the coupling of CFC-113a in the presence of hydrogen is conducted in the presence of a CFC 113a diluent ratio, H2:113a ratio of 3:3.5 - 6 .

[0015] In certain embodiments the coupling of CFC-113a in the presence of hydrogen is conducted in the presence of a R-143a, R-123, R-134a diluent, whereinthe reactant ratio of H2:heat diluent is between 1-5:1 , preferably 1-2:1, most preferably 1 :1.5 or 1:1.

[0016] In another embodiment disclosed herein inert diluents are added to the reaction medium in large scale, e.g., commercial scale reaction zones to mitigate heat.

[0017] In certain embodiments disclosed herein, diluents inert under reaction conditions are added at temperatures between 50°C - 300°C to mitigate heat in an exothermic reaction.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.DETAIL DESCRIPTION OF THE INVENTION

[0019] The foregoing summary and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims. Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, and from the claims.

[0020] The present invention relates to heat mitigation of exothermic reactions involving perhalogenated compounds through the use of HFC and HCFC diluents generally inert under reaction conditions, including at least temperatures between 50°C - 300°C .

[0021] Before addressing details of embodiments described herein, certain terms are defined or clarified as follows.

[0022] The term “hydro(halo)alkane,” as used herein means a molecule containing hydrogen, carbon, and optionally fluorine and / or chlorine and / or bromine and / oriodine, with no carbon-carbon double bond (halo- fluoro, chloro, bromo, iodo).Examples are described throughout the instant specification. The term hydro(halo)alkane encompasses both alkanes and halogen substituted alkanes

[0023] The term “coupling” is meant to mean the addition reaction in which two molecules of the same compound react with each other, also referred to as a conjugated reaction.

[0024] As disclosed herein a coupling reaction of the CFC and HCFC can be conducted at temperatures between 50°C and 300°C, in reactor provided with heat control including the use of suitable diluents. A number of reactor configurations are possible and can be operated in batch, semi-batch or continuous modes. Reactors can be provided with equipment to increase contact between fluids and can be similarly operated in batch, semi-batch and continuous modes. In addition to the reactors disclosed herein, preheaters and vaporizers, heat exchangers, feed and effluent lines, units associated with mass transfer, contacting vessels (pre-mixers), distillation columns, and valving associated with reactors, heat exchangers, vessels, columns, and units that are used in the processes of various embodiments disclosed herein should be constructed of materials resistant to corrosion.

[0025] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0026] The transitional phrase "consisting of' excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of" appears in a clause of the body of a claim,rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0027] The transitional phrase "consisting essentially of" is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term “consisting essentially of’ occupies a middle ground between “comprising” and “consisting of.”

[0028] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of’ or “consisting of.”

[0029] Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0030] As used herein, the term “about” is meant to account for variations due to experimental error (e.g., plus or minus approximately 10% of the indicated value. ±1%, ± 2%, ± 3, ... ±10%). All measurements reported herein are understood to be modified by the term “about,” whether or not the term is explicitly used, unless explicitly stated otherwise.

[0031] When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and / or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, therange is intended to include the endpoints thereof, and all integers and fractions within the range.

[0032] The term “compound” as used herein is meant to include all stereoisomers, geometric isomers, tautomers, and isotopes of the structures or chemical described. Compounds herein identified by name or structure as one particular tautomeric form are intended to include other tautomeric forms unless otherwise specified.

[0033] As used herein, the term “catalyst,” refers to a substance that speeds up the chemical reaction, but is not consumed by the reaction; thus it can be recovered chemically unchanged at the end of the reaction.

[0034] As used herein by runaway reaction is meant a thermally unstable reaction system which exhibits an uncontrolled accelerating rate of reaction leading to rapid increases in temperature and pressure.

[0035] To mitigate heat for commercial production of HCFO-1316, involving perhalogenated compounds, the applicants have unexpectedly found that adding HFC and HCFC diluents generally inert under reaction condition temperatures between 50°C - 300°C and pressures up to 400 psig, uniform temperature and control are achieved, hotspot formation is reduced, and the steady state measure of reactor gain, as defined by the formula (G)ain= ATHS / ATOH is kept below a value of 2.

[0036] The applicants have unexpectedly found that HFCs such as HFC-143a, HCFC-123, HFC-134a, and CFC 113a have the benefit of being inert under the reaction condition CFC-113a conjugation conditions, e.g., a temperature of between 50°C - 300°C and pressure of between atmospheric pressure up to 400 psig. The HCFC-123, HFC-134a, and CFC 113a also have the benefit of being nonflammable. In addition, whereas HFC-143a and HCFC-123 are by-products of the conjugated reaction between CFC-113a, it is beneficial to use them as heat diluents instead of disposing them as waste.

[0037] Quantification of heat mitigation using a heat diluent has been demonstrated through modeling. A reactor model was developed using the Aspen Plus® process simulator. Process assumptions for these examples involve reaction conditions run with reactant ratios of H2: 113a of 3: 1 , and a range of heat diluents atratios of 2.5:1 , using a typical process recycle composition. Reactor temperature control is achieved using a co-current heat transfer oil, and oil inlet temperature is adjusted to achieve ~ 60% conversion of 113a to products 1316mxx(Z / E). All runs were conducted at equal total molar flow rates, so that all cases represented similar reactor space times.

[0038] The use of these heat diluents was assessed using two performance metrics. First, reactor hotspot is assessed through modeling to avoid missing hotspot detected by thermocouples, and second reactor “gain” is computed. The “gain” is a steady-state measure of how the reactor responds to small oil temperature upsets. It is defined as the change in hot spot temperature relative to change in oil temperature:Thus, determining Gain is a function of the change in oil temperature of the reactor to calculate ATO / / .

[0039] If the gain exceeds a value of 2, the reactor has the potential to be overly sensitive to temperature upsets and can cause a runaway reactions. Hot spot temperature is measured using thermocouples placed along and within the length of the catalyst filled reactor tubes. These metrics were evaluated for two levels of catalyst activity: a mid-range activity and a low-range activity where catalyst comprise Ru, Pt, Pd, Rh on a support, the support can be carbon, washed carbon, SiC, CaF2, alumina. The catalyst concentration is 0.1 to 5%, The catalyst was activated by flowing H2 for 2 to 10 hrs at temperature from 100 to 30°C.

[0040] Certain embodiments disclosed herein relate to processes of coupling a CFC or HCFC by passing the CFC or HFC terminating in a CCI3 group, including but not limited to CFC-113a (RCCI3, R can be linear or branched C2-C4 fluoroalkyl, fluorochloroakyl, hydrofluoroalkyl, hydrochlorofluoroalkyl, for example, (R= C2F5, C3F7, C4F9, HCF2CF2, CF3CHF, HCF2C2F4, HCF2C3F6), through one or more tubes filled with catalyst suitable for exothermic coupling reactions in indirect exchange relationship with a heat exchanging medium, including but not limited of oil, such as Dowtherm. The coupling reaction is carried out in catalyst filled tubes, wherein the number of tubes <1 , <2, up to 10, 20, 30 or 40 or more and configured as a tube-andshell reactor with heat exchange fluid entering the shell side of the reactor to cool the exterior surface of the catalyst filled tubes. The process further involved arranging thermocouples along a length of each tube to monitor hot spots, exchanging exothermic heat generated from the coupling reaction within each said tubes, and determining the presence of hotspot using the thermocouples, detecting a change in the hotspot and heat exchange fluid temperature and passing a diluent through the tubes to maintain reactor gain (G) within reaction zones defined by the tubes to be less than <2, wherein reactor gain (G) is defined as A THS / A Ton where T= temperature, ATHS =change in hotspot temperature and AToii = the change of oil inlet temperature.

[0041] In one embodiment disclosed herein diluents are added to the reaction zone to mitigate heat.

[0042] In another embodiment disclosed herein inert diluents are added to the reaction medium in reaction zones to mitigate heat.

[0043] In certain embodiments the coupling of CFC-113a in the presence of hydrogen is conducted in the presence of R-143a, R-123, R-134a and CFG 113a, wherein reactant ratios of Fhl 13a (H2 organic ratio) is between 1-5:1, preferably 2- 4: 1 , most preferably 3: 1.

[0044] Modeling experiments with and without diluent were conducted and the result for the mid-range catalyst activity case results are shown in Table 1, and low- range catalyst activity cases are shown in Table 2.TABLE 1TABLE 2

[0045] In both catalyst states, the predicted gain and hotspot for the cases using no heat diluent, or using N2 are high, indicating unstable reactor operations. In contrast, when one of the HFC’s or the reactant 113a is used as a heat diluent, the hotspot is moderated and the gain is significantly reduced. This moderating impact increases with increased fluid heat capacity.Claim Embodiments

[0046] (1) A process comprising: a. coupling a CFC or HCFC terminating in a CCI3 group in the presence of hydrogen and a catalyst in a reaction zone, b. monitoring temperature at a plurality of spaced locations in the reaction zone to detect hotspots, and c. adding diluents to the reaction zone reduce hotspot formation.

[0047] (2) The process claim embodiment 1 wherein the CFC or HCFC comprises coupling 1 ,1 ,1-trichloro-2,2,2-trifluoroethane (HCFC-113a) to form a product mixture comprising E / Z-CFO-1316mxx (E / Z-CF3CCI=CCICF3).

[0048] (3) The process of any of claim embodiments 1 or 2 wherein the diluent comprises one of 2, 2-dichloro-1, 1 ,1 -trifluoroethane (HCFC-123), 1, 1,1,2- tetrafluoroethane (HFC-134a), 1 1,1,1 -trifluoroethane (HFC-143a) or excess CFC- 113a.

[0049] (4) The process of any of claim embodiments 1-3 wherein the coupling is conducted at an H2:113a ratio is between 1-5:1.

[0050] (5)The process of any of claim embodiments 1-4 wherein the H2:113a ratio comprises about 3:1.

[0051] (6) The process of any of claim embodiments 1-5 wherein the coupling is conducted at an H2:113a ratio which comprises about 3:3.5.

[0052] (7) The process of any of claim embodiments 1-6 wherein the coupling is conducted at an H2:diluent ratio of between 1-5:1 to 1:1-5.

[0053] (8) The process comprising, a. passing a CFC or HCFC through a plurality of parallel catalyst tubes to couple the CFC or HCFC, b. exchanging exothermic heat from said tubes with a heat exchange fluid, c. determining the presence of hotspot with the thermocouples and detecting a change in the heat exchange fluid, and d. passing a diluent through the tubes to maintain reactor gain G of <2, wherein reactor gain (G) is defined as A THS / A Ton where T= temperature, ATHS =change in hotspot temperature and ATon = the change of oil at the inlet.

[0054] (9) A process comprising controlling reactor gain of a chemical reaction comprising, circulating a heat transfer oil through a reaction zone, conducting a catalytic coupling in the reaction zone, determining the reactor gain of the reaction zone, where reactor gain (G) = A THS / A Ton where T= temperature, THS = change in hotspot temperature and A Ton = the change of oil temperature of the reaction zone, and adding diluent to the reaction zone to reduce or minimize hotspot formation and the reactor gain (G) <2.

[0055] (10) The process of any of claim embodiments 8 or 9 wherein the diluent comprises one of 2, 2-dichloro-1, 1 ,1 -trifluoroethane (HCFC-123), 1, 1,1,2- tetrafluoroethane (HFC-134a), 1 1,1,1 -trifluoroethane (HFC-143a) or excess CFC- 113a.

[0056] (11) The process of any of claim embodiments 8 -10 wherein the coupling comprises the coupling of CFC- 113a conducted at an H2:113a ratio is between 1-5:1 to 1 :1-5.

[0057] (12) The process of any of claim embodiments 8 -11 wherein the H2:113a ratio comprises about 3:1.

[0058] (13) The process of any of claim embodiments 8 -12 wherein the coupling is conducted at an H2:113a ratio which comprises about 3:3.5.

[0059] (14) The process of any of claim embodiments 8 -13 wherein the diluent comprises 2,2-dichloro-1 ,1 ,1-trifluoroethane (HCFC-123).

[0060] (15) The process of any of claim embodiments 8 -13 wherein the diluent comprises 1 ,1 ,1 ,2-tetrafluoroethane (HFC-134a).

[0061] (16) The process of any of claim embodiments 8 -13 wherein the diluent comprises 1 ,1 ,1 ,2-tetrafluoroethane (HFC-143a).

[0062] (17) A composition formed by the process of any of claim embodiments 1- 16.

[0063] (18) The process of claim embodiment 1 or 8 wherein the CFC and / or HCFC bearing a CCI3 groups is defined by the formula RCCI3, where R can be a linear or a branched C2-C4 fluoroalkyl, fluorochloroakyl, hydrofluoroalkyl, hydrochlorofluoroalkyl, preferably R is selected from one of C2F5, C3F7, C4F9, HCF2CF2, CF3CHF, HCF2C2F4, HCF2C3F6.

[0064] A composition formed by the process of claim embodiment 18.

[0065] Although certain aspects, embodiments and principles have been described above, it is understood that this description is made only by way of example and not as limitation of the scope of the invention or appended claims. The foregoing various aspects, embodiments and principles can be used alone and in combinations with each other.

Claims

CLAIMSWhat is claimed is:

1. A process comprising: a. coupling one of a HCFC or a CFC in the presence of hydrogen and a catalyst in a reaction zone, b. monitoring temperature at a plurality of spaced locations in the reaction zone to detect hotspots, and c. adding diluents to the reaction zone to reduce hotspot formation.

2. The process of claim 1 wherein the CFC comprises coupling 1 , 1 , 1 -trichloro- 2,2,2-trifluoroethane (HCFC-113a) to form a product mixture comprising E / Z- CFO-1316mxx (E / Z-CF3CCI=CCICF3).

3. The process of any of claims 1 or 2 wherein the diluent comprises one of 2,2- dichloro-1,1,1-trifluoroethane (HCFC-123), 1 ,1 ,1 ,2-tetrafluoroethane (HFC- 134a), 1 1 ,1 ,1 -trifluoroethane (HFC-143a) or excess CFC-113a.

4. The process of claim 2 wherein the coupling is conducted at an H2:113a ratio is between 1-5:1.

5. The process of claim 4 wherein the H2:113a ratio comprises about 3:1.

6. The process of claim 4 wherein the coupling is conducted at an H2:113a ratio which comprises about 3:3.5.

7. The process of claim 3 wherein the coupling is conducted at an H2:diluent ratio of between 1-5:1 to 1:1-5.

8. The process comprising, d. passing a CFC through a plurality of parallel catalyst tubes to couple the CFC, e. arranging thermocouples along a length of each tube to monitor hot spots, f. exchanging exothermic heat from said tubes with a heat exchange fluid,g. determining the presence of hotspot with the thermocouples and detecting a change in the heat exchange fluid, and h. passing a diluent through the tubes to maintain reactor gain G of <2, wherein reactor gain (G) is defined as A THS / A To, / where T= temperature, ATHS =change in hotspot temperature and ATou = the change of oil temperature of the reaction zone.

9. A process comprising controlling reactor gain of a chemical reaction comprising, circulating a heat transfer oil through a reaction zone, conducting a catalytic coupling in the reaction zone, determining the reactor gain of the reaction zone, where reactor gain (G) = ATHS / ATO, / where T= temperature, ATHS = change in hotspot temperature and Toii = the change of oil temperature at the inlet, and adding diluent to the reaction zone to reduce or minimize hotspot formation and the reactor gain (G) < 2.

10. The process of any of claims 8 or 9 wherein the diluent comprises one of 2,2- dichloro-1,1,1-trifluoroethane (HCFC-123), 1 ,1 ,1 ,2-tetrafluoroethane (HFC- 134a), 1 1 ,1 ,1 -trifluoroethane (HFC-143a) or excess CFC-113a.

11. The process of claim 10 wherein the coupling comprises the coupling of CFC- 113a conducted at an FLU 3a ratio is between 1-5:1 to 1:1-5.

12. The process of claim 11 wherein the H2:113a ratio comprises about 3:1.

13. The process of claim 11 wherein the coupling is conducted at an H2:113a ratio which comprises about 3:3.5.

14. The process of any of claim 10 wherein the diluent comprises 2,2-dichloro- 1 ,1 ,1 -trifluoroethane (HCFC-123).

15. The process of any of claim 10 wherein the diluent comprises 1 , 1 , 1 ,2- tetrafluoroethane (HFC-134a).

16. The process of any of claim 10 wherein the diluent comprises 1 , 1 , 1 ,2- tetrafluoroethane (HFC-143a).

17. A composition formed by the process of any of claims 1-16.

18. The process of any of claims 1 or 8 wherein the CFC and / or HCFC bearing a CCb groups is defined by the formula RCCI3, where R can be a linear or a branched C2-C4 fluoroalkyl, fluorochloroakyl, hydrofluoroalkyl, hydrochlorofluoroalkyl, preferably R is selected from one of C2F5, C3F7, C4F9, HCF2CF2, CF3CHF, HCF2C2F4, HCF2C3F6.

19. A composition formed by the process of claim 18.

20. The process of claim 9 wherein the inlet temperature is changed to assess hotspot formation.