Patent Application
20070098619
This invention relates to porous microcomposites comprising fluorinated sulfonic acid and a network of silica.
Homogeneous catalysts, such as HF, AlCl3 and H2SO4, while effective, produce highly corrosive media and chemically reactive waste streams. Thus, there has been considerable effort to replace homogeneous catalysts with cost-effective and active solid acid catalysts, which allow for simpler product purification and safer process operation. The use of solid acid catalysts has been reviewed by M. A. Harmer, Industrial Processes Using Solid Acid Catalysts (in Handbook of Green Chemistry and Technology, J. Clark and D. Macquarrie (eds.), 2002, Blackwell Science Ltd., London, Chapter 6, pages 86-119).
A. de Angelis, et al. (Catalysis Today, 2001, 65:363-371) describe the preparation of a solid acid catalyst by treating amorphous silica gel with trifluoromethanesulfonic (triflic) acid which can be used to catalyze the alkylation of isobutane with n-butenes to yield high-octane gasoline components. A disadvantage encountered in the preparation of the triflic acid/SiO2 catalyst is the loss of triflic acid from the silica during drying of the composite under vacuum. Thus, the activity of the triflic acid/SiO2 composite catalyst is reduced.
The present invention provides novel solid acid catalysts (microcomposites) comprised of fluorosulfonic acids on silica. The fluorosulfonic acids of the invention are less volatile during drying of the microcomposite; thus more of the fluorosulfonic acids are retained in the microcomposite, and the microcomposite retains higher catalytic activity compared to triflic acid microcomposites prepared under the same conditions. In addition, the fluorosulfonic acids exhibit higher catalytic activity as part of the microcomposite with silica than they do as individual acids.
The present invention relates to the preparation of a porous microcomposite comprising at least one fluorinated sulfonic acid and silica made by a process comprising the steps of:
The present invention also relates to a porous microcomposite comprising at least one fluorinated sulfonic acid and silica made by a process comprising the steps of:
The present invention relates to a porous microcomposite of fluorinated sulfonic acid catalyst and silica having high surface area and exhibiting catalytic activity.
In one embodiment of the invention, the porous microcomposite comprises at least one fluorinated sulfonic acid and silica made by a process comprising the steps of:
The term “silica precursor” refers to a silicon and oxygen-containing compound capable of forming silica in the presence of water. For example, it is well known that a range of silicon alkoxides of the Formula Si(OR)4, wherein R is —CH3, —C2H5, or C3 to C6 straight-chain or branched alkyl, can be hydrolyzed and condensed to form a silica network. A silica network is a known concept in the art and is described in Brinker, C. J. and G. W. Scherer, Sol-Gel Science (Academic Press, NY, 1990). Preferably R is methyl or ethyl. Such precursors include tetramethoxysilane (tetramethyl orthosilicate), tetraethoxysilane (tetraethyl orthosilicate), tetrapropoxysilane, tetrabutoxysilane. Also included as a silica precursor is silicon tetrachloride. Further silica precursors comprise organically modified silica, for example, CH3Si(OCH3)3, PhSi(OCH3)3 where Ph is phenyl, and (CH3)2Si(OCH3)2. Other silica precursors include metal silicates, such as potassium silicate, sodium silicate, and lithium silicate. Potassium, sodium, or lithium ions can be removed using a cation exchange resin, such as DOWEX® (Dow Chemical, Midland, Mich.), that generates polysilicic acid, which gels upon aging and drying.
The fluorinated sulfonic acids may be synthesized as described in the following references: U.S. Pat. No. 2,403,207, Rice, et al. (Inorg. Chem., 1991, 30:4635-4638), Coffman, etal. (J. Org. Chem., 1949, 14:747-753 and Koshar, et al. (J. Am. Chem. Soc. (1953) 75:4595-4596), and can be used in either hydrated or anhydrous forms.
An inorganic acid or a fluorinated sulfonic acid selected from the group consisting of 1,1,2,2-tetrafluoroethanesulfonic acid, 1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonic acid, 1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonic acid, 1,1,2,3,3,3-hexafluoropropanesulfonic acid, and 2-chloro-1,1,2-trifluoroethanesulfonic acid may be used to hydrolyze silicon alkoxides or organically modified silicon alkoxides. Suitable inorganic acids include hydrochloric acid, sulfuric acid, and nitric acid.
The non-reacting solvent may be a lower aliphatic alcohol such as methanol, 1-propanol, 2-propanol, and n-butanol. Other suitable solvents include acetonitrile, diethyl ether, dimethyl formamide, dimethylsulfoxide, nitromethane, tetrahydrofuran and acetone.
Aging of the mixture may be carried out under air. Alternatively, the mixture may be aged under a flowing, non-reactive gas such as argon, nitrogen or helium, or under a vacuum. The temperature for aging of the mixture may be from about 15° C. to about 150° C. Gelation of the mixture will be dependent on a number of factors such as the amount of water present, temperature, solvent, concentrations, and the acid or acids used. See Brinker, C. J. and G. W. Scherer, supra, pages 518-523 for a discussion of silica gel formation.
Drying of the gelled mixture to remove substantially all remaining water and/or alcohol can be carried out as described for aging. The gelled mixture is preferably dried under an inert gas such as nitrogen at a temperature from about 50° C. to about 150° C. Drying times are 5 to 10 hours, preferably 2-3 days. Longer drying times are not harmful.
Drying is important for best catalytic activity of the porous microcomposite. When the microcomposite has been dried, it should be stored so as to avoid picking up moisture, such as from the atmosphere.
The microcomposite of the present invention exists as a particulate solid that is glass-like in nature, typically 0.1 to 4 millimeters in size (particles are roughly spherical and size refers to the diameter or longest dimension) and structurally hard, similar to dried silica gels. The porous nature of the material is evident from the high surface areas measured for these glass-like pieces. Typical pore diameters are in the range of about 0.5 to about 75 nanometers; preferably the pore diameters are in the range of about 0.5 to about 25 nanometers. The weight percentage of fluorinated sulfonic acid relative to silica is from about 0.1% to about 90%, that is, acid is about 0.1% to 90%, silica is about 99.9% to 10%. Optionally, the hard glass-like product can be comminuted, such as by grinding with a pestle and mortar.
It is believed that the highly porous structure of the microcomposite comprises a continuous silicon oxide phase that absorbs the highly dispersed fluorinated sulfonic acid catalyst within and throughout a connected network of porous channels. The porous nature of the material can be readily demonstrated, for example, by solvent absorption. The microcomposite can be observed to emit bubbles, which are evolved due to the displacement of the air from within the porous network.
In another embodiment of the invention, the porous microcomposite comprises at least one fluorinated sulfonic acid and silica made by a process comprising the steps of:
The preformed porous silica support may be obtained commercially from, for example, PQ Corporation (Valley Forge, Pa.), W. R. Grace (Baltimore, Md.) or Aldrich (St. Louis, Mo.). An example is Silica Gel Beads (2-3 millimeter amorphous silicon dioxide beads) from PQ Corporation.
The non-reacting solvent may be a lower aliphatic alcohol such as methanol, 1-propanol, 2-propanol, and n-butanol. Other suitable solvents include acetonitrile, diethyl ether, dimethyl formamide, dimethylsulfoxide, nitromethane, tetrahydrofuran and acetone.
Drying of the acid-impregnated porous silica may be carried out under air. Alternatively, the acid-impregnated porous silica may be aged under a flowing, non-reactive gas such as argon, nitrogen or helium, or under a vacuum. The temperature for drying is from about 15° C. to about 150° C. Preferably the acid-impregnated porous silica is dried under an inert gas such as nitrogen at a temperature from about 50° C. to about 150C.
The weight percentage of fluorinated sulfonic acid relative to silica is from about 0.1% to about 90%; the weight percent of the fluorinated sulfonic acid will depend on the pore volume of the preformed support.
Applications of the Fluorinated Sulfonic Acid/Silica Composites of the Invention
The microcomposites of the invention are useful as catalysts, for example, for alkylating aliphatic or aromatic hydrocarbons, for decomposing organic hydroperoxides, such as cumene hydroperoxide, for sulfonating or nitrating organic compounds, and for oxyalkylating hydroxylic compounds, i.e. etherification. The microcomposites of the present invention provide the benefit of reduced costs, higher catalytic activity, and improved reaction selectivity. Other commercially important applications for fluorinated sulfonic acid/silica catalysts of the present invention comprise hydrocarbon isomerizations and polymerizations; carbonylation and carboxylation reactions; hydrolysis and condensation reactions, esterifications and etherification; hydrations and oxidations; aromatic acylation, alkylation and nitration; and isomerization and metathesis reactions.
Alkylation
The fluorinated sulfonic acid on silica porous microcomposites of the invention are useful for making alkylated aromatic compounds of the Formula:
wherein:
The production of at least one alkylated aromatic compound is carried out by a process comprising reacting a C2 to C18 straight-chain monoolefin with an aromatic compound of the Formula:
wherein Q1 and Q2 are as defined above; in the presence of a dried porous microcomposite of the invention, wherein the catalyst is used at from about 0.01% to about 20% by weight of the reaction mixture comprising the aromatic compound and the monoolefin.
The aromatic compound is benzene or a benzene-derivative, such as toluene, xylene, ethyl benzene or isopropyl benzene.
The reaction is carried out at a temperature between about 25° C. and about 200° C., and a pressure between atmospheric pressure and that pressure required to maintain the reactants in a liquid state. In one embodiment of the invention, the reaction is carried out at about 25° C. and the pressure is atmospheric pressure.
At the start of the reaction the aromatic compound is in molar excess relative to the monoolefin. In one embodiment, the molar ratio of the aromatic compound to the monoolefin at the start of the reaction is about 8:1.
The aromatic alkylation reaction may be carried out in batch, sequential batch (i.e., a series of batch reactors) or in continuous mode in any of the equipment customarily employed for continuous process (see for example, H. S. Fogler, Elementary Chemical Reaction Engineering, Prentice-Hall, Inc., N.J., USA). One skilled in the art will recognize that at higher temperatures or pressures a sealed vessel or pressure vessel is required.
Isomerization
The fluorinated sulfonic acid on silica porous microcomposites of the invention are useful for making internal olefins by a process comprising forming a reaction mixture comprising (1) at least one α-olefin, and (2) at least one dried porous microcomposite of the invention.
The α-olefin starting material comprises from about four carbons to about twenty carbons. In a more specific embodiment, the α-olefin starting material may comprise from about 12 carbons to about 18 carbons. The starting material may comprise either linear or branched olefins, however preferably the starting material will comprise greater than 60 mol % linear α-olefin. The starting material may also comprise from about 10 mol % to about 35 mol % branched α-olefin, from about 0 mol % to about 10 mol % linear internal olefin, and/or from about 0 mol % to about 10 mol % branched internal olefin. The olefin starting material may also be admixed with one or more inert hydrocarbons, such as paraffins, or cycloparaffins, however preferably, the olefin starting material comprises at least 90% by weight of olefins.
The at least one porous microcomposite of fluorinated sulfonic acid on silica is used at a concentration of from about 0.1% to about 20% by weight of the weight of the α-olefin(s) at the start of the reaction. The reaction is preferably carried out at a temperature of from about 50° C. to about 175° C. In a more specific embodiment, the reaction is carried out at a temperature of from about 50° C. to about 120° C.
The reaction is preferably carried out under an inert atmosphere, such as nitrogen, argon or helium. The reaction may be performed at atmospheric pressure, or at pressures above atmospheric pressure.
The time for the reaction will depend on many factors, such as the reactants, reaction conditions and reactor. One skilled in the art will know to adjust the time for the reaction to achieve optimal isomerization of the α-olefins.
The isomerization reaction may be carried out in batch, sequential batch (i.e., a series of batch reactors) or in continuous mode in any of the equipment customarily employed for continuous process (see for example, Fogler, supra).
Acylation
The fluorinated sulfonic acid on silica porous microcomposites of the invention are useful for the acylation of aromatic compounds using acyl halides or anhydrides as the acylating agent. The acylation of an aromatic compound may be carried out by a process comprising forming a reaction mixture comprising 1) at least one aromatic compound selected from the group consisting of anisole, m-xylene, o-xylene, and toluene, 2) at least one acyl halide or acyl anhydride, and 3) at least one porous microcomposite of the invention under conditions described in A. Heidekum, et al., J. Catalysis (1999) 188:230-232. The reaction may be carried out under an inert atmosphere at a temperature from about 25° C. to about 150° C.
Fries Reaction
The fluorinated sulfonic acid on silica porous microcomposites of the invention are useful for the Fries rearrangement of phenyl acetate. The reaction may be carried out by contacting a porous microcomposite of the invention with phenol and phenyl acetate under an inert atmosphere, such as nitrogen or argon, at a temperature of from about 100° C. to about 200° C. The Fries rearrangement of phenyl acetate is described in A. Heidekum, et al., J. Catalysis (1998) 176:260-263.
The following abbreviations are used:
Milliliter is abbreviated mL; gram is abbreviated g; Centigrade is abbreviated C; meter is abbreviated m; cubic centimeter is abbreviated cc; nanometer is abbreviated nm; gas chromatography is abbreviated GC; tetramethyl orthosilicate is abbreviated TMOS, tetraethyl orthosilicate is abbreviated TEOS; weight percent is abbreviated wt %.
Acetonitrile, oleum (20% SO3), sodium sulfite (Na2SO3, 98%), phenol, anisole, acetic anhydride, phenyl acetate and acetone were obtained from Acros (Hampton, N.H.). Potassium metabisulfite (K2S2O5, 99%), was obtained from Mallinckrodt Laboratory Chemicals (Phillipsburg, N.J.). Tetramethyl orthosilicate, tetraethyl orthosilicate HCI, p-xylene, potassium sulfite hydrate (KHSO3.xH2O, 95%), sodium bisulfite (NaHSO3), diethyl ether, and 1-dodecene were obtained from Aldrich (St. Louis, Mo.). Sulfuric acid was obtained from EMD Chemicals, Inc. (Gibbstown, N.J.). Perfluoro(ethyl vinyl ether), perfluoro(methyl vinyl ether), hexafluoropropene and tetrafluoroethylene were obtained from DuPont Fluoroproducts (Wilmington, Del.). 1,1,2,2-Tetrafluoro-2-(pentafluoroethoxy)sulfonate was obtained from SynQuest Laboratories, Inc. (Alachua, Fla.).
Preparation of Fluorosulfonic Acid Precursors
A 1-gallon Hastelloy® C276 reaction vessel was charged with a solution of potassium sulfite hydrate (176 g, 1.0 mol), potassium metabisulfite (610 g, 2.8 mol) and deionized water (2000 ml). The pH of this solution was 5.8. The vessel was cooled to 18° C., evacuated to 0.10 MPa, and purged with nitrogen. The evacuate/purge cycle was repeated two more times. To the vessel was then added tetrafluoroethylene (TFE, 66 g), and it was heated to 100° C. at which time the inside pressure was 1.14 MPa. The reaction temperature was increased to 125° C. and kept there for 3 hr. As the TFE pressure decreased due to the reaction, more TFE was added in small aliquots (20-30 g each) to maintain operating pressure roughly between 1.14 and 1.48 MPa. Once 500 g (5.0 mol) of TFE had been fed after the initial 66 g precharge, the vessel was vented and cooled to 25° C. The pH of the clear light yellow reaction solution was 10-11. This solution was buffered to pH 7 through the addition of potassium metabisulfite (16 g).
The water was removed in vacuo on a rotary evaporator to produce a wet solid. The solid was then placed in a freeze dryer (Virtis Freezemobile 35xl; Gardiner, N.Y.) for 72 hr to reduce the water content to approximately 1.5 wt % (1387 g crude material). The theoretical mass of total solids was 1351 g. The mass balance was very close to ideal and the isolated solid had slightly higher mass due to moisture. This added freeze drying step had the advantage of producing a free-flowing white powder whereas treatment in a vacuum oven resulted in a soapy solid cake that was very difficult to remove and had to be chipped and broken out of the flask.
The crude TFES-K can be further purified and isolated by extraction with reagent grade acetone, filtration, and drying.
19F NMR (D2O) δ−122.0 (dt, JFH=6 Hz, JFF=6 Hz, 2F); -136.1 (dt, JFH =53 Hz, 2F).
1H NMR (D2O) 67 6.4 (tt, JFH=53 Hz, JFH=6 Hz, 1H).
% Water by Karl-Fisher titration: 580 ppm.
Analytical calculation for C2HO3F4SK: C, 10.9: H, 0.5: N, 0.0
Experimental results: C, 11.1: H, 0.7: N, 0.2.
Mp (DSC): 242° C.
TGA (air): 10% wt. loss @ 367° C., 50% wt. loss @ 375° C.
TGA (N2): 10% wt. loss @ 363° C., 50% wt. loss @ 375° C.
A 1-gallon Hastelloy® C276 reaction vessel was charged with a solution of potassium sulfite hydrate (88 g, 0.56 mol), potassium metabisulfite (340 g, 1.53 mol) and deionized water (2000 ml). The vessel was cooled to 7° C., evacuated to 0.05 MPa, and purged with nitrogen. The evacuate/purge cycle was repeated two more times. To the vessel was then added perfluoro(ethyl vinyl ether) (PEVE, 600 g, 2.78 mol), and it was heated to 125° C. at which time the inside pressure was 2.31 MPa. The reaction temperature was maintained at 125° C. for 10 hr. The pressure dropped to 0.26 MPa at which point the vessel was vented and cooled to 25° C. The crude reaction product was a white crystalline precipitate with a colorless aqueous layer (pH=7) above it.
The 19F NMR spectrum of the white solid showed pure desired product, while the spectrum of the aqueous layer showed a small but detectable amount of a fluorinated impurity. The desired product is less soluble in water so it precipitated in pure form.
The product slurry was suction filtered through a fritted glass funnel, and the wet cake was dried in a vacuum oven (60° C., 0.01 MPa) for 48 hr. The product was obtained as off-white crystals (904 g, 97% yield).
19F NMR (D2O) δ −86.5 (s, 3F); −89.2, −91.3 (subsplit ABq, JFF=147 Hz, 2F);
−119.3, −121.2 (subsplit ABq, JFF=258 Hz, 2F); −144.3 (dm, JFH=53 Hz, 1F).
1H NMR (D2O) 67 6.7 (dm, JFH=53 Hz, 1H).
Mp (DSC) 263° C.
Analytical calculation for C4HO4F8SK: C, 14.3: H, 0.3 Experimental results: C, 14.1: H, 0.3.
TGA (air): 10% wt. loss @ 359° C., 50% wt. loss @ 367° C.
TGA (N2): 10% wt. loss @ 362° C., 50% wt. loss @ 374° C.
A 1-gallon Hastelloy® C276 reaction vessel was charged with a solution of potassium sulfite hydrate (114 g, 0.72 mol), potassium metabisulfite (440 g, 1.98 mol) and deionized water (2000 ml). The pH of this solution was 5.8. The vessel was cooled to −35° C., evacuated to 0.08 MPa, and purged with nitrogen. The evacuate/purge cycle was repeated two more times. To the vessel was then added perfluoro(methyl vinyl ether) (PMVE, 600 g, 3.61 mol) and it was heated to 125° C. at which time the inside pressure was 3.29 MPa. The reaction temperature was maintained at 125° C. for 6 hr. The pressure dropped to 0.27 MPa at which point the vessel was vented and cooled to 25° C. Once cooled, a white crystalline precipitate of the desired product formed leaving a colorless clear aqueous solution above it (pH=7).
The 19F NMR spectrum of the white solid showed pure desired product, while the spectrum of the aqueous layer showed a small but detectable amount of a fluorinated impurity.
The solution was suction filtered through a fritted glass funnel for 6 hr to remove most of the water. The wet cake was then dried in a vacuum oven at 0.01 MPa and 50° C. for 48 hr. This gave 854 g (83% yield) of a white powder. The final product was pure (by 19F and 1H NMR) since the undesired product remained in the water during filtration.
19F NMR (D2O) 67 −59.9 (d, JFH=4 Hz, 3F); −119.6, −120.2 (subsplit ABq, J=260 Hz, 2F); −144.9 (dm, JFH=53 Hz, 1F).
1H NMR (D2O) 67 6.6 (dm, JFH=53 Hz, 1H).
% Water by Karl-Fisher titration: 71 ppm.
Analytical calculation for C3HF6SO4K: C, 12.6: H, 0.4: N, 0.0
Experimental results: C, 12.6: H, 0.0: N, 0.1.
Mp (DSC) 257° C.
TGA (air): 10% wt. loss @ 343° C., 50% wt. loss @ 358° C.
TGA (N2): 10% wt. loss @ 341° C., 50% wt. loss @ 357° C.
A 1-gallon Hastelloy® C reaction vessel was charged with a solution of anhydrous sodium sulfite (25 g, 0.20 mol), sodium bisulfite 73 g, (0.70 mol) and of deionized water (400 ml). The pH of this solution was 5.7. The vessel was cooled to 4° C., evacuated to 0.08 MPa, and then charged with hexafluoropropene (HFP, 120 g, 0.8 mol, 0.43 MPa). The vessel was heated with agitation to 120° C. and kept there for 3 hr. The pressure rose to a maximum of 1.83 MPa and then dropped down to 0.27 MPa within 30 minutes. At the end, the vessel was cooled and the remaining HFP was vented, and the reactor was purged with nitrogen. The final solution had a pH of 7.3.
The water was removed in vacuo on a rotary evaporator to produce a wet solid. The solid was then placed in a vacuum oven (0.02 MPa, 140° C., 48 hr) to produce 219 g of white solid which contained approximately 1 wt % water. The theoretical mass of total solids was 217 g.
The crude HFPS-Na can be further purified and isolated by extraction with reagent grade acetone, filtration, and drying.
19F NMR (D2O) 67 −74.5 (m, 3F); −113.1, −120.4 (ABq, J=264 Hz, 2F); −211.6 (dm, 1F).
1H NMR (D2O) 67 5.8 (dm, JFH=43 Hz, 1H).
Mp (DSC) 126° C.
TGA (air): 10% wt. loss @ 326° C., 50% wt. loss @ 446° C.
TGA (N2): 10% wt. loss @ 322° C., 50% wt. loss @ 449° C.
Preparation of Catalysts From the Corresponding Anions
A 100 mL round bottomed flask with a sidearm and equipped with a digital thermometer and magnetic stirr bar was placed in an ice bath under positive nitrogen pressure. To the flask was added 50 g crude TFES-K (from Synthesis (A) above), 30 g of concentrated sulfuric acid (95-98%) and 78 g oleum (20 wt % SO3) while stirring. The amount of oleum was chosen such that there would be a slight excess of SO3 after the SO3 reacted with and removed the water in the sulfuric acid and the crude TFES-K. The mixing caused a small exotherm, which was controlled by the ice bath. Once the exotherm was over, a distillation head with a water condenser was placed on the flask, and the flask was heated under nitrogen behind a safety shield. The pressure was slowly reduced using a PTFE membrane vacuum pump (Buchi V-500) in steps of 100 Torr (13 kPa) in order to avoid foaming. A dry-ice trap was placed between the distillation apparatus and the pump to collect any excess SO3. When the pot temperature reached 120° C. and the pressure was held at 20-30 Torr (2.7-4.0 kPa) a colorless liquid started to reflux which distilled at 110° C. and 31 Torr (4.1 kPa). A forerun of lower-boiling impurity (2.0 g) was obtained before collecting 28 g of the desired colorless acid, TFESA.
It was calculated that approximately 39.8 g TFES-K was present in the 50 g of impure TFES-K. Thus, the 28 g of product is an 85% yield of TFESA from TFES-K, as well as an 85% overall yield from TFE. Analysis gave the following results: 19F NMR (CD3OD) −125.2 (dt, 3JFH=6 Hz, 3JFF=8 Hz, 2F); −137.6 (dt, 2JFH=53 Hz, 2F). 1H NMR (CD3OD). 6.3 (tt, 3JFH=6 Hz, 2JFH=53 Hz, 1H).
A 100 mL round bottomed flask with a sidearm and equipped with a digital thermometer and magnetic stirr bar was placed in an ice bath under positive nitrogen pressure. To the flask was added 50 g crude sodium hexafluoropropanesulfonate (HFPS-Na) (from Synthesis (D) above), 30 g of concentrated sulfuric acid (95-98%) and 58.5 g oleum (20 wt % SO3) while stirring.
The amount of oleum was chosen such that there would be a slight excess of SO3 after the SO3 reacted with and removed the water in the sulfuric acid and the crude HFPSA. The mixing caused a small exotherm, which was controlled by the ice bath. Once the exotherm was over, a distillation head with a water condenser was placed on the flask, and the flask was heated under nitrogen behind a safety shield. The pressure was slowly reduced using a PTFE membrane vacuum pump in steps of 100 Torr (13 kPa) in order to avoid foaming. A dry-ice trap was placed between the distillation apparatus and the pump to collect any excess S3. When the pot temperature reached 100° C. and the pressure was held at 20-30 Torr (2.7-4 kPa) a colorless liquid started to reflux and later distilled at 118° C. and 23 Torr (3.1 kPa). A forerun of lower-boiling impurity (1.5 g) was obtained before collecting 36.0 g of the desired acid, hexafluoropropanesulfonic acid (HFPSA).
It was calculated that approximately 44 g HFPS-Na was present in 50 g of impure HFPS-Na. Thus, the 36.0 g of HFPSA product was an 89% yield from HFPS-Na, as well as an 84% overall yield from HFP. 19F NMR (D2O) −74.5 m, 3F); −113.1, −120.4 (ABq, J=264 Hz, 2F); −211.6 (dm, 1F). 1 H NMR (D2O) 5.8 (dm, 2JFH=43 Hz, 1H).
A 1-gallon Hastelloy® C276 reaction vessel was charged with a solution of 240 g sodium bisulfite hydrate (NaHSO3.H2O, 95%), 128 g sodium metabisulfite (Na2S2O5, 99%) and 800 mL of deionized water. The vessel was cooled to 18° C., evacuated to 0 kPa, and purged with nitrogen. The evacuate/purge cycle was repeated two more times. To the vessel was then added 233 g of chlorotrifluoroethylene in 50 g amounts until the last 33 g at a temperature of 125° C. which time the inside pressure is 250 psi (1830 kPa). The reaction temperature was maintained at 125° C. for 3 hr., and then cooled to room temperature. The water was removed in vacuo on a rotary evaporator to produce a yellow/white solid which contained in part the sodium salt, CCIHFCF2SO3H. To 160 g of the yellow/white solid was added 250 mLs of 98% sulfuric acid in a round bottomed flask. The mixture was heated and the acid monohydrate was distilled undervacuum at 119-120° C. (0.8 mm Hg). Thionyl chloride (70 mLs) was then added to the acid monohydrate under a nitrogen atmosphere; the mixture was heated at 50° C. for one hour, and the excess thionyl chloride was removed under vacuum. The acid was removed by distillation under vacuum to give pure HCICFCF2SO3H, as shown by NMR.
Examples 1 to 12 illustrate the synthesis of microcomposites of the invention.
Tetramethyl orthosilicate (4 g), water (4.7 g), and 0.04 M HCI (0.05 g) were stirred together for 15 minutes to hydrolyze the tetraalkoxide. HCF2CF2SO3H (0.5 g) was then added, and the mixture was stirred for several hours. The resulting gel was left to dry in air in an uncovered beaker at room temperature for four days. Drying of the composite was completed in a 100° C. vacuum oven for 48 hours. The surface area, pore volume and pore diameter were determined by the Brunauer-Emmett-Teller (BET; see C. N. Satterfield, Heterogeneous Catalysis in Industrial Practice, 2nd Edition,1991, McGraw-Hill, Inc., NY, pages 134-139) method to be 565 m2/g, 0.32 cc/g and 2.3 nm.
Tetramethyl orthosilicate (16 g), water (18.8 g) and 0.04 M HCI (0.2 g) were stirred together for 15 minutes to hydrolyze the tetraalkoxide. HCF2CF2SO3H (2 g) was then added, and the mixture was stirred in a loosely capped jar for 72 hours to gel. The resulting gel was dried slowly in a 75° C. nitrogen oven (still in a loosely capped jar) for 7 days. Drying of the composite was completed in a 100° C. vacuum oven for 48 hours. The surface area, pore volume and pore diameter were determined to be 584 m2/g, 0.39 cc/g and 2.7 nm, respectively.
Tetramethyl orthosilicate (8 g), water (9.4 g) and 0.04 M HCI (0.1 g) were stirred together for 15 minutes to hydrolyze the tetraalkoxide. HCF2CF2SO3H (1 g) was then added; the mixture was stirred for 1 minute to mix and then placed immediately in a 90° C. oven, in an open beaker under a nitrogen stream for 48 hours. Drying of the composite was completed in a 100° C. vacuum oven for 72 hours. The surface area, pore volume and pore diameter were determined by BET to be 506 m2/g, 0.29 cc/g and 2.3 nm respectively.
Tetramethyl orthosilicate (4 g), water (4.7 g) and 0.04 M HCI (0.05 g) were stirred together for 15 minutes to hydrolyze the tetraalkoxide. HCF2CF2SO3H (1.59 g) was then added, and the mixture was stirred to gel (less than about two hours). The resulting gel was left to dry in air in an uncovered beaker at room temperature for four days. Drying of the composite was completed in a 100° C. vacuum oven for 48 hours. The composite comprised approximately 50% by weight of the acid relative to the weight of the silica. The surface area, pore volume and pore diameter were determined by BET to be 597 m2/g, 0.42 cc/g and 2.8 nm, respectively.
Tetramethyl orthosilicate (8 g), water (9.4 g) and 0.04 M HCI (0.1 g) were stirred together for 15 minutes to hydrolyze the tetraalkoxide. HCF2CF2SO3H (0.45 g) was then added, and the mixture was stirred to gel (less than about two hours). The resulting gel was left to dry in air in an uncovered beaker at room temperature for four days. Drying of the composite was completed in a 100° C. vacuum oven for 48 hours. The composite comprised approximately 12.5% by weight of the acid relative to the weight of the silica. The surface area, pore volume and pore diameter were determined by BET to be 576 m2/g, 0.25 cc/g and 1.4 nm, respectively.
Tetramethyl orthosilicate (16 g), water (18.8 g) and 0.04 M HCI (0.2 g) were stirred together for 15 minutes to hydrolyze the tetraalkoxide. HCF2CF2SO3H (0.33 g) was then added, and the mixture was stirred to gel (less than about two hours). The resulting gel was left to dry in air in an uncovered beaker at room temperature for four days. Drying of the composite was completed in a 1 00° C. vacuum oven for 48 hours. The composite comprised approximately 5% by weight of the acid relative to the weight of the silica. The surface area, pore volume and pore diameter were determined by BET to be 571 m2/g, 0.24 cc/g and 1.4 nm, respectively.
Tetramethyl orthosilicate (2 g), water (2.35 g) and 0.04 M HCI (0.025 g) were stirred together for 15 minutes to hydrolyze the tetraalkoxide. HCF2CF2SO3H (2.37 g) was then added, and the mixture was stirred to gel (less than about 20 seconds). The resulting gel was left to dry in air in an uncovered beaker at room temperature for three days and then in a 70° C. oven under nitrogen for 24 hours. Drying of the composite was completed in a 100° C. vacuum oven for 24 hours. The composite comprised approximately 75% by weight of the acid relative to the weight of the silica.
Tetraethyl orthosilicate (14 g), water (12 g) and 1 M HCI (0.1 g) were stirred together for 2 hours to hydrolyze the tetraalkoxide. HCF2CF2SO3H (1 g) was then added, and the mixture was stirred in an open beaker to gel (less than about two hours). The resulting gel was left to dry in air in an uncovered beaker at room temperature for 48 hours. Drying of the composite was completed in a 100° C. vacuum oven for 24 hours. The surface area, pore volume and pore diameter were determined by BET to be 342 m2/g, 0.16 cc/g and 1.9 nm, respectively.
Tetramethyl orthosilicate (8 g), water (9.4 g) and 0.04 M HCI (0.1 g) were stirred together for 15 minutes to hydrolyze the tetraalkoxide. CF3HCFCF2SO3H (1 g) was then added, and the mixture was stirred to gel (less than about two hours). The resulting gel was left to dry in air in an uncovered beaker at room temperature. Drying of the composite was completed in a 100° C. vacuum oven.
Tetramethyl orthosilicate (8 g), water (9.4 g) and 0.04 M HCI (0.1 g) were stirred together for 15 minutes to hydrolyze the tetraalkoxide. HCFCICF2SO3H (1 g) was then added, and the mixture was stirred to gel (less than about two hours). The resulting gel was left to dry in air in an uncovered beaker at room temperature. Drying of the composite was completed in a 100° C. vacuum oven.
HCF2CF2SO3H H2O (50 g) was added to 125 mLs of diethyl ether. This mixture was added to 140 g of a spherical silica support (Silica Gel beads, 2-3 mm amorphous silicon dioxide beads, PQ Corporation, Valley Forge, Pa.) in a larger glass bottle. The bottle and contents were gently shaken for twenty minutes. The material was dried using a roto-vap at 35° C. under vacuum for 2 hours.
CF3SO3H (5.1 g) was added to 16.7 g of diethyl ether. This mixture was added to 16 g of a spherical silica support (Silica Gel beads, 2-3 mm amorphous silicon dioxide beads, PQ Corporation) in a larger glass bottle. The bottle and contents were gently shaken for twenty minutes. The material was dried using a roto-vap at 35° C. under vacuum for 2 hours.
Examples 13 to 18 illustrate the use of microcomposites of the invention in alkylation reactions.
The catalytic activity of HCF2CF2SO3H H2O on silica versus CF3SO3H (triflic acid) on silica were compared using an alkylation reaction.
HCF2CF2SO3H H2O on silica from Example 11 (1 g) was placed in an oven at 150° C., and dried overnight under vacuum. The dried material was rapidly added to a round bottomed flask containing 15 mLs of p-xylene and 5 mLs of dodecene under nitrogen. The flask and contents were heated at 100° C. with stirring. GC analysis at 2 hours showed that >95% of the dodecene had reacted to form the alkylated product.
CF3SO3H (triflic acid) on silica from Example 12 (1 g) was placed in an oven at 150° C., and dried overnight under vacuum. The dried material was rapidly added to a round bottomed flask containing 15 mLs of p-xylene and 5 mLs of dodecene under nitrogen. The flask and contents were heated at 100° C. with stirring. GC analysis at 2 hours showed that <1% of the dodecene had reacted to form the alkylated product.
The acid catalyst HCF2CF2SO3H supported on silica (24 wt % acid) was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded into a dried Schlenk flask, followed by the addition of anhydrous p-xylene (15 mL) and anhydrous 1-dodecene (5 mL). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis (see
The acid catalyst HCF2CF2SO3H (0.125) was loaded into a dried Schlenk flask under a nitrogen atmosphere, followed by the addition of anhydrous p-xylene (15 mL) and anhydrous 1-dodecene (5 mL). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis (see
The microcomposite HCF2CF2SO3H supported on silica was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded to a dried Schlenk flask, followed by the addition of anhydrous p-xylene (15 mL) and anhydrous 1-dodecene (5 mL). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. Samples were withdrawn at 15 minutes, 1 hour and 2 hours, and diluted 1 to 20 in diethyl ether for GC analysis.
The mixture was cooled and transferred back to a nitrogen box. The solvent comprising unreacted p-xylene and 1-dodecene and the alkylated product was decanted and the solid was rinsed with fresh solvent mixture (15 mL p-xylene and 5 mL 1-dodecene). This was decanted and replaced with fresh solvent mixture. The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 2 hours showed that >96% of the 1-dodecene was converted to the alkylated product.
The acid catalyst HCF2CF2SO3H supported on silica was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded to a dried Schlenk flask, followed by the addition of anhydrous p-xylene (150 mL) and anhydrous 1-dodecene (50 mL). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. Samples were withdrawn at 2 hours, 4 hours and 6.5 hours, and diluted 1 to 20 in diethyl ether for GC analysis. The reaction was stopped and left at room temperature for 3 days, restarted stirring at 100° C. for 7 hours, GC samples being drawn at 4.5 hours and 7 hours. GC analysis of the products at 2 hours showed that >90% of the 1-dodecene was converted to the alkylated product.
The acid catalyst CF3HCFCF2SO3H supported on silica was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded into a dried Schlenk flask, followed by the addition of anhydrous p-xylene (15 mL) and anhydrous 1-dodecene (5 mL). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. Samples were withdrawn at 15 minutes, 1 hour and 2 hours, and diluted 1 to 20 in diethyl ether for GC analysis. GC analysis of the products at 2 hours showed that >95% of the 1-dodecene was converted to the alkylated product.
The acid catalyst HCFCICF2SO3H supported on silica was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded into a dried Schlenk flask, followed by the addition of anhydrous p-xylene (15 mL) and anhydrous 1-dodecene (5 mL). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 2 hours showed that >95% of the 1-dodecene was converted to the alkylated product.
Examples 20 to 24 illustrate the use of microcomposites of the invention in isomerization reactions.
In a nitrogen atmosphere, the acid catalyst HCF2CF2SO3H (0.5 g) was loaded into a dried Schlenk flask, followed by the addition of anhydrous 1-dodecene (15 mL). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 2 hours showed that <5% of the 1-dodecene was isomerized (see
The acid catalyst HCF2CF2SO3H supported on silica (24 wt % acid) was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded into a dried Schlenk flask, followed by the addition of anhydrous 1-dodecene (15 mL). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 2 hours showed that >80% of the 1-dodecene was isomerized (see
The acid catalyst CF3HCFCF2SO3H supported on silica was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded into a dried Schlenk flask, followed by the addition of anhydrous 1-dodecene (15 mL). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 2 hours showed that >80% of the 1-dodecene was isomerized.
The acid catalyst HCFCICF2SO3H supported on silica was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded into a dried Schlenk flask, followed by the addition of anhydrous 1 -dodecene (15 mL). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 2 hours showed that >80% of the 1-dodecene was isomerized.
The acid catalyst HCF2CF2SO3H on silica was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded into a dried Schlenk flask, followed by the addition of anhydrous 1-dodecene (150 mL). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 7 hours showed that >95% of the 1-dodecene was isomerized.
Examples 25 to 31 illustrate the use of microcomposites of the invention in acylation reactions.
In a nitrogen atmosphere the acid catalyst HCF2CF2SO3H (0.125 g) was loaded into a dried Schlenk flask, followed by the addition of anhydrous anisole (9.36 g) and anhydrous acetic anhydride (9.4 g). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 2 hours showed that 60% of the anisole was converted to acetylated product.
The acid catalyst HCF2CF2SO3H supported on silica (24 wt % acid) was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded into a dried Schlenk flask, followed by the addition of anhydrous anisole (9.36 g) and anhydrous acetic anhydride (9.4 g). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 2 hours showed that 65% of the anisole was converted to acetylated product.
In a nitrogen atmosphere the acid catalyst HCFCICF2SO3H (0.5 g) was loaded into a dried Schlenk flask, followed by the addition of anhydrous anisole (9.36 g) and anhydrous acetic anhydride (9.4 g). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 2 hours showed that 56% of the anisole was converted to acetylated product.
The acid catalyst CF3HCFCF2SO3H supported on silica was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded into a dried Schlenk flask, followed by the addition of anhydrous anisole (9.36 g) and anhydrous acetic anhydride (9.4 g). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 2 hours showed that 68% of the anisole was converted to acetylated 1 5 product.
The acid catalyst HCFCICF2SO3H supported on silica was ground 20 to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded into a dried Schlenk flask, followed by the addition of anhydrous anisole (9.36 g) and anhydrous acetic anhydride (9.4 g). The flask was set up under a nitrogen blanket and stirred vigorously at 100° C. for 2 hours. GC analysis of the products at 2 hours showed that 71% of the anisole was converted to acetylated product.
Examples 30 to 31 illustrate the use of supported catalysts of the invention in Fries reactions.
The acid catalyst HCF2CF2SO3H supported on silica (24 wt % acid) was ground to a fine powder with a pestle and mortar. The finely ground powder (0.5 g) was then weighed into a vial, dried at 150° C. under vacuum for at least four hours, and cooled under vacuum before transfer into a nitrogen atmosphere. The catalyst was loaded into a dried Schlenk flask, followed by the addition of anhydrous phenol (20 g) and anhydrous phenyl acetate (5 g). The flask was set up under a nitrogen blanket and stirred vigorously at 150° C. for 2 hours. GC analysis at 2 hours showed that 71% of the phenyl acetate had been converted to product.
In a nitrogen atmosphere the acid catalyst HCF2CF2SO3H (0.5 g) was loaded into a dried Schlenk flask, followed by the addition of anhydrous phenol (20 g) and anhydrous phenyl acetate (5 g). The flask was set up under a nitrogen blanket and stirred vigorously at 150° C. for 24 hours. GC analysis at 2 hours showed that 36% of the phenyl acetate had been converted to product hydroxyacetophenone.
| Number | Date | Country | |
|---|---|---|---|
| 60730801 | Oct 2005 | US |
