WO1990007480A1 - Acid catalyzed process - Google Patents

Acid catalyzed process Download PDF

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Publication number
WO1990007480A1
WO1990007480A1 PCT/US1990/000054 US9000054W WO9007480A1 WO 1990007480 A1 WO1990007480 A1 WO 1990007480A1 US 9000054 W US9000054 W US 9000054W WO 9007480 A1 WO9007480 A1 WO 9007480A1
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Prior art keywords
reactant
reaction product
catalyst
olefin
group
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PCT/US1990/000054
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French (fr)
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David L. King
Michael D. Cooper
Ken K. Ushiba
William A. Sanderson
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Catalytica, Inc.
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Priority to KR1019900701957A priority Critical patent/KR910700214A/en
Publication of WO1990007480A1 publication Critical patent/WO1990007480A1/en

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    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
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Definitions

  • This invention relates to an improved process for the acid-catalyzed conversion of a reactant into a reaction product.
  • Reactants which may be converted into reaction products in the process of this invention include hydrocarbons and heteroatom-substituted hydrocarbons, wherein said heteroatoms may be selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and halogen atoms.
  • olefins may be isomerized, polymerized or oligomerized; olefins may be reacted with aromatics or tertiary al anes to provide alkylated products; olefins may be reacted with carboxylic acids to obtain esters; olefins may be reacted with a peroxy acid to obtain an epoxide; alcohols may be dehydrated to obtain olefins or ethers or reacted with an aromatic compound or a carboxylic acid to obtain an alkylated product or an ester, respectively; anhydrides may be reacted with an aromatic or an olefinic compound to obtain acetylated derivatives thereof; epoxides may be reacted to the corresponding glycols; aromatic compounds may be nitrated to provide nitro aromatics, etc.
  • the acidic catalyst may be used in a homogeneous or heterogeneous mode, i.e. the catalyst can be dissolved in the reactant-containing solution or the catalyst may exist in a different phase than the reactant and/or the reaction products.
  • Homogeneous acid catalysts may have certain advantages over heterogeneous acid catalysts, such as increased activity or selectivity, provided separation of the reaction products from the catalyst is easily carried out. Since such separation may be difficult, many times a heterogeneous acid catalyst is preferred, even when the activity or selectivity is less than a homogeneous catalyst in the same reaction.
  • One widely used class of heterogeneous acid catalyst is the solid polystyrene sulfonic acids.
  • the present invention provides a process for the conversion of a reactant into a reaction product in the presence of an acid catalyst which comprises contacting said reactant with an acid catalyst comprising a compound comprising one or more fluorine atoms, sulfo radicals and phosphono radicals, each such radical being bonded to the same or different carbon atom, with the proviso that at least one sulfo radical and at least one phosphono radical are bonded to such carbon atoms through the sulfur atom and the phosphorus atom, respectively.
  • These compounds are preferably non-polymeric, i.e. they have a molecular weight of about 5000 or less.
  • These acid catalysts may be represented by compounds selected from the group of compounds represented by the general formula:
  • the above fluorinated phosphonsulfonic acids may be reacted with a tetravalent metal ion according to the procedures described in U.S. Patents 4,232,146; 4,235,990; 4,235,991; 4,256,872; 4,267,308; 4,276,409; 4,276,410; 4,276,411; 4,298,723; 4,299,943; 4,373,079; 4,384,981; 4,386,013; 4,390,690; 4,429,111; and 4,435,899, which are hereby incorporated by reference, to provide a solid acid catalyst having pendant sulfonic acid groups.
  • the phosphonic acid derivative i.e. R 2 is hydrogen
  • a tetravalent metal ion is reacted with a tetravalent metal ion to yield a solid compound represented by the general formula:
  • M[(0) 2 P(0)] y R(SO r R 1 ) x ] d wherein M is the tetravalent metal and d is 2/3, 1 or 2, as y varies from 3 to 2 to 1, respectively.
  • the acid catalyst may be prepared by the sulfonation of the reaction product of a tetravalent metal ion and ((R 2 0) 2 P(0)yR7' wherein R 2 and y are as defined above, and R 7 is an organo radical having at least one covalent carbon-fluorine bond and at least one sulfonatable group, e.g.. an aryl or olefin group.
  • the acid catalyst may be prepared by sequential impregnation of the tetravalent metal ion and ((HO) 2 P(0))yR(SO r R 1 ) x onto a suitable support, e.g. a refractory inorganic oxide such as silica, and reacting the impregnated support to yield a supported M[(0) 2 P(0)] y R(SO r R 1 ) x ] d .
  • a suitable support e.g. a refractory inorganic oxide such as silica
  • the above fluorinated phosphono sulfonic acids may be prepared by reacting a first reactant represented by the general formula (R 4 0) 3 P with a second reactant represented by the general formula R 3 X Z to yield a first reaction product represented by the general formula
  • R 4 may be a lower alkyl radical having up to six carbon atoms, e.g. methyl, ethyl, n- propyl or i-propyl, and preferably i-propyl or ethyl;
  • R 3 is an organo radical having at least one covalent fluorine bond;
  • X is bromine or iodine and
  • z is an integer of 2 or 3.
  • the first reaction product may be synthesized in high yield merely by combining the first and second reactant in a sealed vessel at a temperature of from -50°C to 200°C, e.g. from 0 to 120°C, i.e. conveniently from 0°C to about 25°C.
  • Reaction time may vary from 1 to 100 hours, e.g. 48 hours. Of course, increasing the reaction temperature can lower the reaction time to 2 to 10 hours, e.g. about 3 hours.
  • the first reaction product is recovered by methods known in the art, e.g. distillation at a reduced pressure.
  • the first reaction product may be reacted with (R 5 ) 2 S 2 0 4 , wherein R 5 is an alkali metal ion, e.g. a sodium ion, to yield a second reaction product represented by the general formula
  • Suitable fluorinated organo radicals (R 3 ) for the above reaction scheme include alkylene radicals, both cyclic and acyclic radicals, which may be interrupted with hetero atoms such as nitrogen, oxygen and sulfur, alkenylene radicals, both cyclic and acyclic, which may also be interrupted with heteroatoms such as nitrogen, oxygen and sulfur, and arylene radicals, including heteroaryl, e.g. nitrogen, sulfur and oxygen-containing heteroarylene radicals, mono and poly arylene radicals, e.g. condensed arylene radicals having from 2 to 5 aryl rings, biphenyl, etc.
  • the above fluorinated organo radicals may comprise from one to about 100 carbon atoms, e.g.
  • radicals will comprise one or more covalently • bonded fluorine and may be perfluorinated, i.e. all of the carbon bonds, other than the sulfur or phosphorus bonds, may be filled by fluorine radicals.
  • the above fluorinated organo radicals may also be substituted with inert substituents such as halo, nitro, amino, oxy, hydroxy, carboxy, thio, etc.
  • the fluorinated organo radicals will be either halo substituted or unsubstituted, i.e. all the carbon bonds other than the bonds to the fluoro, sulfo or phosphono radicals, as required by the above general formula, will be filled by hydrogen radicals or halo radicals (other than fluoro radicals) .
  • fluorinated organo radicals are chloro or bromo-substituted or unsubstituted alkylene radicals having from 1 to 6 carbon atoms and chloro or bromo-substituted or unsubstituted arylene radicals having from 6 to 10 carbon atoms.
  • alkyleneoxyalkylene radicals wherein the alkylene moieties comprise from 2 to 4 carbon atoms.
  • lower alkylene radicals including alkyleneoxyalkylene radicals such as methylene, ethylene, propylene, butylene, methyleneoxymethylene, ethyleneoxyethylene, butyleneoxyethylene radicals, etc.
  • R-* may be CF , — CF, CHF, CFBr, - CF 2 ) 4 0(CF 27 - 2 , etc. f /
  • the second reaction product may be oxidized to yield a third reaction product having the general formula
  • H 0 2 or similar oxidizing agent may be provided in molar excess directly to the second reaction product or to an aqueous solution thereof.
  • a sufficient amount of a 30% aqueous H 2 0 2 solution may be combined with the second reaction product to provide an aqueous solution, H 2 0 2 comprising from 1.1 to 5 moles of per mole of the second reaction product, at a temperature of from 0° to 25°C and such aqueous solution allowed to react for 1 to 10 hours, e.g. about 4 to 5 hours.
  • the third reaction product is conveniently recovered by evaporation of the excess solvent.
  • (R 4 0) 2 P ( O) CFBr (S0 3 R 5 ) may be reduced to (R 4 0) 2 P(0)CHF(S0 3 R 5 ) by a reducing agent, for example metallic zinc, in a suitable inert solvent, for example tetrahydrofuran.
  • a reducing agent for example metallic zinc
  • a suitable inert solvent for example tetrahydrofuran.
  • Such reduction may be effected at an elevated temperature, e.g. about 60°C and a ratio of Zn to the bromo product of about 1 to about 2, e.g. about 1.1 and the reduced product recovered by extraction with water.
  • the third reaction product may be reacted, e.g. hydrolyzed, to yield the corresponding phosphonic acid.
  • the third reaction product may be hydrolyzed in an aqueous solution of a strong acid, e.g. concentrated hydrochloric acid, wherein said hydrolysis is effected at an elevated temperature, e.g. at reflux, in the presence of excess strong acid, e.g. from about 1.1 to 10 moles, i.e. 3 moles of strong acid per equivalent of R 4 .
  • a strong acid e.g. concentrated hydrochloric acid
  • excess strong acid e.g. from about 1.1 to 10 moles, i.e. 3 moles of strong acid per equivalent of R 4 .
  • the hydrolysis product or the fourth reaction product may be recovered by evaporation of excess solvent.
  • the fourth reaction product may be further reacted to exchange hydrogen ions for R 5 .
  • the fourth reaction product may be passed through an ion exchange column, e.g. a strong acid such as an acidified sulfonated polystyrene resin such as Amberlite 1R-120 to exchange hydrogen ions for the alkali ions.
  • a strong acid such as an acidified sulfonated polystyrene resin such as Amberlite 1R-120 to exchange hydrogen ions for the alkali ions.
  • sulfate ion contamination may be removed by reacting an aqueous solution thereof with an excess of barium ions to precipitate barium sulfate.
  • the filtrate, comprising the acid-exchanged reaction product and sodium and barium ions is then passed through the acid form of an ion exchange column, to remove such ions and a purified solution of such acid-exchanged reaction product is recovered.
  • phosphate contaminants can also be removed as an insoluble product.
  • the acid-exchanged reaction product may be converted to the corresponding phosphonylsulfonyl chloride by reaction with sufficient PCI5 to yield such phosphonylsulfonyl chloride which can be recovered by distillation.
  • Any or all of the sulfonic acid and phosphonic acid moieties of the acid-exchanged reaction product may be converted into the corresponding acid chloride by reaction with an amount of PC1 5 equivalent to from 1 to all of the acid moieties in the acid-exchanged reaction product.
  • reaction scheme utilizes a monophosphono reactant.
  • Compounds within the scope of the present invention, wherein polyphosphono functionality are desired, e.g. wherein y is 2 or 3, may be prepared by reacting supra molar amounts of (R 4 0) 3 P with R 3 X 2 wherein z is from 3 to 6 and proceeding according to the above illustrative reaction scheme.
  • An alternate method for making certain of the fluorinated phosphonosulfo compounds of the present invention comprises reacting a first reactant having the general formula
  • the first reactant may be prepared by reacting
  • CF 2 CF 2 in the presence of KF and IC1
  • anhydride Another reactant that may be used in the process of the present invention is an anhydride.
  • anhydrides such as acetic anhydride
  • acetic anhydride may be reacted with a compound having an aromatic group or an olefinic group to yield acetylated aromatics or acetylated olefins, respectively.
  • acetic anhydride may be reacted with anisole to provide p-methoxyacetophenone or with diisobutylene to provide 2,2-methyl, 6-oxo-hept-4- ene.
  • These reactions can be carried out at a temperature of from 25 to 125°C. and a pressure of from 1 to- 30 At os.
  • Aldehydes orketones may be condensed to provide the respective condensed products by means of the process of the present invention.
  • 2-ethylhexenal may be prepared by condensing two molecules of n-butyraldehyde at a temperature of from 20 to 70°C. and a pressure of from 1 to 10 Atmos.
  • methylisobutylketone may be condensed to 1-methyl, 4-methyl, 6-oxo, 9-methylnon-4-ene.
  • aldehydes and ketones, having from one to ten carbon atoms may be condensed to provide dimers thereof in the process of the present invention.
  • Fumed silica having a BET surface area of 200 M 2 /gm was impregnated with an aqueous solution of ZrOCl 2 .8H 2 0, using the incipient wetness technique, and the resulting composite was dried for 12 hours at 110°C.
  • the dried composite was impregnated with an aqueous solution of (HO) 2 P(0)CF 2 S0 3 H.H 2 0 using the incipient wetness technique and the resulting composite was dried for 12 hours at 110 o C. 49.92 gms. of the supported acid catalyst having a BET surface area of 143.99 M 2 /gm and a pore volume of 99 cc/gm. was obtained.
  • Example 7(a) The procedure of Example 7(a) was repeated except that the first drying step was carried out at 80°C to yield 47.81 gms. of supported acid catalyst having a BET surface area of 173.38 M 2 /gm and a pore volume of 1.08 cc/gm.
  • This acid catalyst may be represented by the general formula:
  • a catalyst was prepared by incipient wetness impregnation of an aqueous alcoholic solution of Nafion, equivalent weight 1000, depositing on Si0 2 to a weight loading of 12.8 wt %.
  • the catalyst was vacuum dried at 100°C. overnight and stored in a bottle under N 2 .
  • 2.29 g catalyst (5.0 ml) was loaded into the reactor and dry nitrogen was passed over the catalyst at ambient temperature for 12 hours.
  • Liquid isobutane was fed over the catalyst and the temperature raised to 60°C. Upon reaching temperture, the feed was changed to (wt %) isobutane, 92.2; butene-1, 5.5; isobutene, 1.6; n-heptane, 0.75.
  • a reaction product after removal of C 4 components, consisted of 0.68 g C 5 + (productivity 0.03 g/g catalyst-h) which comprised the following: 57.1 wt % C 8 olefin, 36.4 wt % C 12 olefin, and 6.2 wt % C 8 saturate.
  • the catalytic behavior is similar to that of the catalysts described in Examples 8 and 9, but the catalyst productivity is clearly lower with Nafion compared with the catalysts derived from the sulfodifluoromethylphosphonic acid.
  • a catalyst comprising 23.0 wt % zirconium sulfodifluoromethylphosphonate on a fumed silica support was prepared by sequential impregnation by incipient wetness of a solution of sulfodifluoromethylphosphonic acid followed by drying and then impregnation of zirconium oxychloride. (The procedure was similar to the procedure of Example 7(a) except for the reversal of the impregnation steps.) 2.08 g (5.3 ml) of catalyst was loaded into the fixed bed reactor and the catalyst was predried by passing dry N over the catalyst for 0.5 hour at 100°C.
  • the catalyst was cooled to ambient, a liquid isobutane feed was added to thecatalyst, and the catalyst was heated to 140°C. while maintaining a liquid phase at 610 psig.
  • The- feed was then switched to one comprising by weight %: isobutane, 93.1; trans-2-butene, 4.2; isobutene, 1.4; n-heptane, 1.4.
  • the reaction proceeded for 1.75 hours, during which time 1.75 g of a liquid product free of C 4 was collected (productivity, 0.19 g/g cat-hr) .
  • the liquid product had the following distribution, in wt./ %: C 8 saturates, 28.1; C 8 olefins, 31.0; C ⁇ 2 olefin, 35.1. Trimethylpentanes, indicative of alkylation activity, comprised 34.9% of the total C 8 saturates and 9.8 wt. % of the total product.

Abstract

The present invention provides a process for the conversion of a reactant into a reaction product in the presence of a solid acid catalyst comprising one or more fluorine atoms, sulfo radicals and phosphono radicals, each such radical being bonded to the same or different carbon atom, with the proviso that at least one sulfo radical and at least one phosphono radical are bonded to such carbon atoms through the sulfur atom and the phosphorus atom, respectively. These compounds are preferably non-polymeric, i.e. they have a molecular weight of about 5000 or less. The above acid catalysts may be reacted with a tetravalent metal, e.g. Zr, to provide a solid acid catalyst.

Description

ACID CATALYZED PROCESS
BACKGROUND OF THE INVENTION
1. Field of the invention
This invention relates to an improved process for the acid-catalyzed conversion of a reactant into a reaction product. Reactants which may be converted into reaction products in the process of this invention include hydrocarbons and heteroatom-substituted hydrocarbons, wherein said heteroatoms may be selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and halogen atoms. For example, in the present inventive process, olefins may be isomerized, polymerized or oligomerized; olefins may be reacted with aromatics or tertiary al anes to provide alkylated products; olefins may be reacted with carboxylic acids to obtain esters; olefins may be reacted with a peroxy acid to obtain an epoxide; alcohols may be dehydrated to obtain olefins or ethers or reacted with an aromatic compound or a carboxylic acid to obtain an alkylated product or an ester, respectively; anhydrides may be reacted with an aromatic or an olefinic compound to obtain acetylated derivatives thereof; epoxides may be reacted to the corresponding glycols; aromatic compounds may be nitrated to provide nitro aromatics, etc.
2 . Strπππa-ry of the Art
Many chemical reactions are catalyzed by acidic catalysts. The acidic catalyst may be used in a homogeneous or heterogeneous mode, i.e. the catalyst can be dissolved in the reactant-containing solution or the catalyst may exist in a different phase than the reactant and/or the reaction products. Homogeneous acid catalysts may have certain advantages over heterogeneous acid catalysts, such as increased activity or selectivity, provided separation of the reaction products from the catalyst is easily carried out. Since such separation may be difficult, many times a heterogeneous acid catalyst is preferred, even when the activity or selectivity is less than a homogeneous catalyst in the same reaction. One widely used class of heterogeneous acid catalyst is the solid polystyrene sulfonic acids. These polymers are known to be effective as acid catalysts for many reactions, but, due to the organic polymer backbone, are not always as stable as desired. Moreover, the organic nature of the polymer may hinder polar reactants from contacting the functional sulfonic acid sites. In addition, the well known high temperatures utilized to remove such organic tars and crud from inorganic acid catalysts, such as zeolites, of course, cannot be used to reactivate polystyrene sulfonic acids because of the thermal instability of the organic polymer backbone.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a process for the conversion of a reactant into a reaction product in the presence of an acid catalyst which comprises contacting said reactant with an acid catalyst comprising a compound comprising one or more fluorine atoms, sulfo radicals and phosphono radicals, each such radical being bonded to the same or different carbon atom, with the proviso that at least one sulfo radical and at least one phosphono radical are bonded to such carbon atoms through the sulfur atom and the phosphorus atom, respectively. These compounds are preferably non-polymeric, i.e. they have a molecular weight of about 5000 or less.
These acid catalysts may be represented by compounds selected from the group of compounds represented by the general formula:
Figure imgf000005_0001
wherein R is an organo radical having at least one covalent carbon-fluorine bond, R1 is hydrogen, R2 is a hydrocarbyl radical, having up to 20 carbon atoms, e.g. a lower alkyl radical or is hydrogen, r is 2 or 3, preferably 3, y is an integer of from 1 to 3 and x is an integer of from 1 to 3, with the proviso that the phosphorus and the sulfur are covalently bonded to a carbon atom.
In another embodiment of the present invention, the above fluorinated phosphonsulfonic acids may be reacted with a tetravalent metal ion according to the procedures described in U.S. Patents 4,232,146; 4,235,990; 4,235,991; 4,256,872; 4,267,308; 4,276,409; 4,276,410; 4,276,411; 4,298,723; 4,299,943; 4,373,079; 4,384,981; 4,386,013; 4,390,690; 4,429,111; and 4,435,899, which are hereby incorporated by reference, to provide a solid acid catalyst having pendant sulfonic acid groups.
In this embodiment, the phosphonic acid derivative, i.e. R2 is hydrogen, is reacted with a tetravalent metal ion to yield a solid compound represented by the general formula:
M[(0)2P(0)]yR(SOrR1)x]d wherein M is the tetravalent metal and d is 2/3, 1 or 2, as y varies from 3 to 2 to 1, respectively.
In another embodiment of the present invention, the acid catalyst may be prepared by the sulfonation of the reaction product of a tetravalent metal ion and ((R20)2P(0)yR7' wherein R2 and y are as defined above, and R7 is an organo radical having at least one covalent carbon-fluorine bond and at least one sulfonatable group, e.g.. an aryl or olefin group.
Finally, the acid catalyst may be prepared by sequential impregnation of the tetravalent metal ion and ((HO)2P(0))yR(SOrR1)x onto a suitable support, e.g. a refractory inorganic oxide such as silica, and reacting the impregnated support to yield a supported M[(0)2P(0)]yR(SOrR1)x]d.
DETAILED DESCRIPTION OF THE INVENTION
The above fluorinated phosphono sulfonic acids may be prepared by reacting a first reactant represented by the general formula (R40)3P with a second reactant represented by the general formula R3XZ to yield a first reaction product represented by the general formula
Figure imgf000006_0001
In this general scheme, R4 may be a lower alkyl radical having up to six carbon atoms, e.g. methyl, ethyl, n- propyl or i-propyl, and preferably i-propyl or ethyl; R3 is an organo radical having at least one covalent fluorine bond; X is bromine or iodine and z is an integer of 2 or 3. The first reaction product may be synthesized in high yield merely by combining the first and second reactant in a sealed vessel at a temperature of from -50°C to 200°C, e.g. from 0 to 120°C, i.e. conveniently from 0°C to about 25°C. Reaction time may vary from 1 to 100 hours, e.g. 48 hours. Of course, increasing the reaction temperature can lower the reaction time to 2 to 10 hours, e.g. about 3 hours.
The reaction can be carried out neat or in the presence of an inert solvent. Conveniently, an ether solvent may be used. In particular, diethylether is useful as a solvent for this reaction.
The first reaction product is recovered by methods known in the art, e.g. distillation at a reduced pressure.
The first reaction product may be reacted with (R5)2S204, wherein R5 is an alkali metal ion, e.g. a sodium ion, to yield a second reaction product represented by the general formula
(R40)2P(0)R3Xz„1_p(S02R5)p
wherein p is an integer of 1 or 2. This reaction is conveniently carried out by combining the first reaction product and the above dithionite in a basic aqueous solution comprising, as a cosolvent, acetonitrile or the like. The reaction may be effected at an elevated temperature of from 50 to 100°C, e.g. about 80°C, and a reaction time of from 1 to 20 hours, e.g. 2 to 12 hours. The second reaction product may be recovered by evaporation of the excess solvent and purified by extraction with acetonitrile or a like solvent.
Suitable fluorinated organo radicals (R3) for the above reaction scheme include alkylene radicals, both cyclic and acyclic radicals, which may be interrupted with hetero atoms such as nitrogen, oxygen and sulfur, alkenylene radicals, both cyclic and acyclic, which may also be interrupted with heteroatoms such as nitrogen, oxygen and sulfur, and arylene radicals, including heteroaryl, e.g. nitrogen, sulfur and oxygen-containing heteroarylene radicals, mono and poly arylene radicals, e.g. condensed arylene radicals having from 2 to 5 aryl rings, biphenyl, etc. The above fluorinated organo radicals may comprise from one to about 100 carbon atoms, e.g. from 1 to about 20 carbon atoms and preferably from 1 to about 10 carbon atoms. Such radicals will comprise one or more covalently • bonded fluorine and may be perfluorinated, i.e. all of the carbon bonds, other than the sulfur or phosphorus bonds, may be filled by fluorine radicals.
The above fluorinated organo radicals may also be substituted with inert substituents such as halo, nitro, amino, oxy, hydroxy, carboxy, thio, etc. Preferably, the fluorinated organo radicals will be either halo substituted or unsubstituted, i.e. all the carbon bonds other than the bonds to the fluoro, sulfo or phosphono radicals, as required by the above general formula, will be filled by hydrogen radicals or halo radicals (other than fluoro radicals) .
One class of suitable fluorinated organo radicals are chloro or bromo-substituted or unsubstituted alkylene radicals having from 1 to 6 carbon atoms and chloro or bromo-substituted or unsubstituted arylene radicals having from 6 to 10 carbon atoms.
Another class of suitable fluorinated organo radicals are alkyleneoxyalkylene radicals, wherein the alkylene moieties comprise from 2 to 4 carbon atoms.
Particularly preferred are lower alkylene radicals, including alkyleneoxyalkylene radicals such as methylene, ethylene, propylene, butylene, methyleneoxymethylene, ethyleneoxyethylene, butyleneoxyethylene radicals, etc.
Specifically, R-* may be CF , — CF, CHF, CFBr, - CF2)40(CF27-2, etc. f /
The second reaction product may be oxidized to yield a third reaction product having the general formula
(R40)2P(0)R3X2_1_p(S03R5)p
by contacting said second reaction product with an oxidizing agent at oxidizing conditions. For example, H 02 or similar oxidizing agent may be provided in molar excess directly to the second reaction product or to an aqueous solution thereof. For example, a sufficient amount of a 30% aqueous H202 solution may be combined with the second reaction product to provide an aqueous solution, H202 comprising from 1.1 to 5 moles of per mole of the second reaction product, at a temperature of from 0° to 25°C and such aqueous solution allowed to react for 1 to 10 hours, e.g. about 4 to 5 hours. The third reaction product is conveniently recovered by evaporation of the excess solvent.
In this manner
(R40) 2P(0) CF2 (S02R5) is reacted to (R40)2P(0)CF2(S03R5),
( R4 O ) 2 P ( O ) CFBr ( S02R5 ) is reacted to (R40)2P(0)CFBr(S03R5) , and
( R4 O ) 2 P ( O ) CHF ( S θ2 R5 ) is reacted to (R40)2P(0)CHF(S03R5) .
As an alternate route to one of the novel fluorinated phosphonosulfo compounds of the present invention, (R40) 2P ( O) CFBr (S03R5 ) may be reduced to (R40)2P(0)CHF(S03R5) by a reducing agent, for example metallic zinc, in a suitable inert solvent, for example tetrahydrofuran. Such reduction may be effected at an elevated temperature, e.g. about 60°C and a ratio of Zn to the bromo product of about 1 to about 2, e.g. about 1.1 and the reduced product recovered by extraction with water.
The third reaction product may be reacted, e.g. hydrolyzed, to yield the corresponding phosphonic acid. For example, the third reaction product may be hydrolyzed in an aqueous solution of a strong acid, e.g. concentrated hydrochloric acid, wherein said hydrolysis is effected at an elevated temperature, e.g. at reflux, in the presence of excess strong acid, e.g. from about 1.1 to 10 moles, i.e. 3 moles of strong acid per equivalent of R4. Again, the hydrolysis product or the fourth reaction product may be recovered by evaporation of excess solvent.
The fourth reaction product may be further reacted to exchange hydrogen ions for R5. In particular, the fourth reaction product may be passed through an ion exchange column, e.g. a strong acid such as an acidified sulfonated polystyrene resin such as Amberlite 1R-120 to exchange hydrogen ions for the alkali ions.
If it is desirable to further purify the hydrogen ion-exchanged reaction product, i.e.
(HO)2P(O)R3Xz_1_p(S03H)p
sulfate ion contamination may be removed by reacting an aqueous solution thereof with an excess of barium ions to precipitate barium sulfate. The filtrate, comprising the acid-exchanged reaction product and sodium and barium ions is then passed through the acid form of an ion exchange column, to remove such ions and a purified solution of such acid-exchanged reaction product is recovered. In addition, if the above precipitation is effected at a sufficiently high pH, e.g. at 11 or greater, phosphate contaminants can also be removed as an insoluble product.
Finally, the acid-exchanged reaction product may be converted to the corresponding phosphonylsulfonyl chloride by reaction with sufficient PCI5 to yield such phosphonylsulfonyl chloride which can be recovered by distillation. Any or all of the sulfonic acid and phosphonic acid moieties of the acid-exchanged reaction product may be converted into the corresponding acid chloride by reaction with an amount of PC15 equivalent to from 1 to all of the acid moieties in the acid-exchanged reaction product. When the conversion of the acid- exchanged reaction product is for the purpose of recovering a purified product, sufficient PCI5 to convert all of the acid moieties to the acid halide will be provided and the resulting acid halide recovered, by distillation, and hydrolyzed to yield a further purified fluorinated phosphonicsulfonic acid.
It is noted that the above reaction scheme utilizes a monophosphono reactant. Compounds within the scope of the present invention, wherein polyphosphono functionality are desired, e.g. wherein y is 2 or 3, may be prepared by reacting supra molar amounts of (R40)3P with R3X2 wherein z is from 3 to 6 and proceeding according to the above illustrative reaction scheme.
An alternate method for making certain of the fluorinated phosphonosulfo compounds of the present invention comprises reacting a first reactant having the general formula
IR6S02F
with a second reactant represented by the general formula
(R 0)2POP(OR4)2
in the presence of a peroxide and a solvent, CF2C1CFC12, to yield a first reaction product represented by the general formula
(R40)2P(0)R6S02F
and reacting said second reaction product with a third reactant represented by the general formula
R25s2°4
to yield a second reaction product represented by the general formula
(R40)2P(0)R6S02R5
wherein R4 is a lower alkyl radical, R6 is a fluorinated polyalkylene oxide radical, and R5 is an alkali metal ion. The first reactant may be prepared by reacting
CF2 CF2
^ with S02
CF2 = CF2 in the presence of KF and IC1
according to the method disclosed in SCIENTIA SINICA, 1978, 21, 773.
The second reaction product may be treated as described above to yield the corresponding third and fourth reaction product, as well as the hydrogen ion- exchanged reaction product.
Finally, certain of the fluorinated phosphonosulfo compounds of this invention may be prepared according to the following scheme:
(R20)2P(0)CF2Br + Na2S03 >
(R20)2P(0)CF2S03Na + NaBr
wherein R2 is defined above. Note that CF2 may be any other fluorinated organo radical disclosed herein. That is, CF2 may be R as defined above. This reaction is effected in water or aqueous ethanol at reflux and provides a third reaction product which can be subsequently treated as described above.
This invention provides an improved process for converting reactants, especially organic reactants, to reaction products in the presence of an acid catalyst. The improvement in said process is found in the choice of compounds which function as the acid catalyst and are defined below. In particular, these compounds increase the rate of reaction, as compared to other well known acid catalysts, e.g. polystyrene sulfonic acids, (which comprises sulfonic acid groups pendant from a polystyrene polymer backbone) and are more stable with time and temperature, as compared to said polystyrene sulfonic acid catalysts.
Preferably, the reactants utilized in the process of this invention are hydrocarbons or hydrocarbons substituted with heteroatoms such as nitrogen, oxygen, sulfur, phosphorus and halogen atoms, and especially oxygen atoms.
Certain of the preferred reactants are unsaturated hydrocarbons such as olefins and aromatics. That is, olefins may be isomerized or oligomerized or polymerized in one embodiment of the process of this invention. (Isomerization of olefins will include skeletal isomerization as well as migration of the double bond.) For example, mono olefins having from four to ten carbon atoms may be isomerized or oligomerized or polymerized to reaction products in accordance with the present invention. A mixture of nonenes comprising predominantly 1-n-nonene is reacted to nonene dimer by heating at 130°C. for two hours in the presence of an acid catalyst comprising the acid catalysts disclosed herein. Propylene is heated for 1 hour, or more, at a temperature of from 50 to 175°C. and a pressure of from 1 to 50 atmospheres, in the presence of any of the acid catalysts disclosed herein, to yield a mixture including as the predominant fraction monoolefins having from nine to twelve carbon atoms and useful as a polymer gasoline.
In another embodiment of this invention, the olefin is contacted with the acid catalyst, described herein, in the presence of another reactant to yield reaction products of said olefin and said other reactant. Thus, said second reactant may include a hydroxyl group to yield an ether or an alcohol. For example, alkanols having from one to four carbon atoms may be reacted with olefins having from two to seven carbon atoms in the presence of the acid catalysts described below to yield ethers. Particularly preferred is the reaction of ethanol and isobutylene, isoamylene or propylene to yield methyl- tertiary butyl ether, methyl-tertiary amyl ether or methyl isopropyl ether, respectively. Such reactions may take place at a temperature of from 15 to 100°C. and a pressure of from 1 to 10 atmospheres.
Olefins may also be contacted with a carboxylic acid in the process of this invention to yield esters. Thus, straight chain olefins, having from two to ten carbon atoms, isobutylene or cyclohexene may be reacted in the presence of carboxylic acids having from one to eight carbon atoms at a temperature within the range of 0°C. to 100°C. to yield the corresponding esters as the reaction product. U.S. Patent 3,037,052 to Bortnick gives the details on this general reaction and is hereby incorporated by reference to show specific reactants and reaction conditions. Particularly preferred reactions, within this embodiment of the present process, include the reaction of monoolefins having from one to eight carbon atoms, more preferably from two to four carbon atoms, with methacrylic acid, acrylic acid, acetic acid or phthalic acid to obtain the corresponding esters. These esters of acrylic acid and methacrylic acid are useful monomers for the preparation of acrylic plastics and rubbers. The acetate esters, of course, are useful as solvents. The phthalic esters are useful as plasticizers.
The olefin may also be reacted in the presence of an aromatic compound to provide alkylated aromatics. For example, propylene may be reacted with benzene to provide cumene. 1-n-olefins, having from six to twelve carbon atoms, may be reacted with phenol to provide alkylated phenols which may be subsequently reacted with ethylene oxide to provide nonionic surfactants such as nonophenylethyleneoxide adducts. (Other alkylations of olefins with isoparaffins, such as with tertiary alkanes, e.g. 1-n-butene and isobutane, to yield isoctane may be carried out in the present process.)
The olefin may be carbonylated by reaction with carbon monoxide using known Koch chemistry.
Finally, the above olefins may be reacted in the presence of a peroxy acid compound to obtain an epoxide. In this manner, ethylene and propylene may be converted to ethylene oxide and propylene oxide, respectively. (Unsaturated oils and esters, such as soybean oil, oleic acid esters, tall oil esters may be epoxidized, similarly, in the presence of hydrogen peroxide.)
Aromatics having from 6 carbon atoms to about 14 to about may be alkylated by alkylhalides, alcohols, ethers or esters of up to about 10 carbon atoms, e.g. from one to four carbon atoms, byuse of the acid catalysts disclosed herein. Similarly, such aromatics maybe acylated or transalkylated.
Other reactants useful in the process of the present invention include alcohols. Thus, in one embodiment of the invention, alcohols, having from one to eight carbon atoms, more preferably from one to four carbon atoms, are reacted, in the presence of the acid catalyst described below, to yield either ethers or olefins (by dehydration) . For example, methanol or ethanol may be reacted at a temperature of from 25 to 150°C. and a pressure of from 1 to 20 At os. to yield dimethyl ether or diethylether, respectively. Tertiary butanol may be dehydrated to isobutene at a temperature of from 50 to 175°C. Similarly, butanediol may be dehydrated to tetahydrofuran.
Like the olefin, alcohols may be reacted in the presence of a second reactant to provide reaction products of said alcohol and said second reactant. In particular. said second reactant may comprise a carboxylic acid group or an aromatic group to yield an ester or an alkylated aromatic, respectively. The reactants and the conditions for these reactions have been described above.
Another reactant that may be used in the process of the present invention is an anhydride. For example, anhydrides, such as acetic anhydride, may be reacted with a compound having an aromatic group or an olefinic group to yield acetylated aromatics or acetylated olefins, respectively. In particular, acetic anhydride may be reacted with anisole to provide p-methoxyacetophenone or with diisobutylene to provide 2,2-methyl, 6-oxo-hept-4- ene. These reactions can be carried out at a temperature of from 25 to 125°C. and a pressure of from 1 to- 30 At os. Aldehydes orketones may be condensed to provide the respective condensed products by means of the process of the present invention. For example, 2-ethylhexenal may be prepared by condensing two molecules of n-butyraldehyde at a temperature of from 20 to 70°C. and a pressure of from 1 to 10 Atmos. Similarly, methylisobutylketone may be condensed to 1-methyl, 4-methyl, 6-oxo, 9-methylnon-4-ene. In general, aldehydes and ketones, having from one to ten carbon atoms may be condensed to provide dimers thereof in the process of the present invention.
In addition, the above aldehydes and ketones may be reacted in the presence of an aromatic compound to obtain the resulting reaction products. In particular, acetone may be reacted with phenol to yield bisphenol A and formaldehyde may be reacted with aniline to yield diaminodiphenylmethane.
Peroxides or hydroperoxides may be decomposed to the corresponding decomposition products by the process of this invention. For example, cumene hydroperoxide may be decomposed to acetone and phenol at low temperatures as compared to the non-acid catalyzed decomposition. Moreover, unlike the prior art polystyrene sulfonic acid catalysts, which are sensitive to heat (and thus the reactor must be designed to remove heat and avoid catalyst degradation) , the acid catalysts of this invention are not heat sensitive.
Glycols may be prepared by utilizing an epoxide as the reactant in the process of the present invention. In particular, ethylene oxide and propylene oxide may be converted to ethylene glycol and propylene glycol, respectively.
Esters may be converted, efficiently, to carboxylic acid and alcohol in the present inventive process. For example, sucrose may be hydrolyzed to fructose and glucose.
The present process may also be utilized to provide nitroaromatics by utilizing as a reactant a mixture of an aromatic compound, e.g. benzene or toluene, and nitric acid. The reaction conditions for these reactions are well known in the art.
It is important to note that all of the above examples of reactants, reaction products and reaction conditions are known in the art.
The invention is further illustrated by the following examples which are illustrative of various aspects of the invention, and are not intended as limiting the scope of the invention as defined by the appended claims.
EXAMPLE 1
Preparation of (HO)2P(0)CF2S03H:
(a) 12.4 mmols of (C2H50)3P was combined with 13.1 mmoles of CF2Br2 in a 75 cc. steel bomb, which was sealed and allowed to react at room temperature for 48 hours. A 100% yield of (C2H50)2P(0) CF2Br(I) was obtained by distilling the resultant reaction product at 10-20 microns.
(b) 39.9 mmoles of I was combined with 79.8 mmoles of Na2S 0 in 100 L of a 50/50, by volume, solution of water and acetonitrile. (79.8 mmols. of NaHC03 had been previously dissolved in such aqueous acetonitrile solution.) After heating at 80°C for 12 hours (C2H5θ)2P(0)CF2S02Na(II) was recovered by evaporation of the filtered solution at 80% yield.
(c) An aqueous solution of 30% H202 was added to II, dropwise with stirring, at 0°C until the molar ratio of H202 to II was about 1.75. The resulting solution was allowed to react for 4 hours. (C2H50)2-P(0)CF2SD3Na (III) was recovered after evaporation of the solvent at 56.3% yield.
(d) The product from (c) was refluxed with concentrated hydrochloric acid (mole ratio 1:6) for 12 hours. (H0)2P(0)CF2S03Na (IV) was recovered at 78.9% yield by evaporating the solvent, extracting with acetonitrile and evaporation.
(e) An aqueous solution of IV was passed through a packed column of Amberlite IR-120 (an acidic sulfonated polystyrene resin) having the dimensions 3cm x 35 cm. , at a flow rate of about 0.3 ml/min. The effluent was evaporated and the residue was distilled at about 10-20 microns to recover (HO)2P(0)CF2S03H.
EXAMPLE 2
Preparation of (HO)2P(0)CFHS03H:
(a) 50 mmols of (C2H5θ)3P and 50 mmols of CFBr3 were reacted in accordance with the method of Example 1(a) (except that the reaction was carried out at 0°C for 4 hours in a 40ml vessel) to yield 76.9% of (C2H50)2P(0)CFBr2 (VI).
(b) 12 mmols of VI were reacted with 14.4 mmols of Na2S204 in a solution comprising 14.4 mmols of NaHC03 dissolved in 5 mL of water and 5 mL of acetonitrile. After 4 hours at room temperature (C2H50)2P(0)CFBrS02Na
(VII) was recovered in 64.4% yield by evaporating the solvent under vacuum, extracting the residue with acetonitrile and drying under vacuum to recover the product.
(c) 14.9 mmoles of VII was reacted with 26 mmoles of H202 which was added dropwise, with stirring, as a 30% aqueous solution. After 5 hours, at room temperature, (C2H50)2P(0)CFBrS03Na (VIII) was recovered at 74.8% yield after evaporation of the solvent.
(d) 11.1 mmoles of VIII was reduced with excess Zn at 60°C, for 6 hours in 10ml. of tetrahydrofuran (THF) . (The molar ratio of Zn to VIII was about 1.1) The resulting mixture was combined with 20 ml. of water and stirred to yield (C2H50)2P(0)CFHS03Na (IX) at 61.2% yield.
(e) IX was hydrolyzed in accordance with the method of Example 1(d) to yield (HO)2P(0)CFHS03Na (X) in 53.5% yield.
(f) X was passed through a packed column, according to the method of Example 1(e) to yield (HO)2P(0)CFHS03H in 80% yield after evaporating the solvent under vacuum and drying the resulting product, under vacuum for 4 hours at 80°C. EXAMPLE 3
Preparation of (HO)2P(0) (CF2)40(CF2)2S03H:
(a) 38 mmol. of I (CF2) 40(CF2) 2S02F, 57 m ol. (C2H50)2POP(OC2H5)2 and 19 mmol. of (CH3)3C00C(CH3)3 were dissolved in 80 ml. of CF2C1CFC12 and reacted in a 150cc steel bomb at 120°C for 3 hours. To the resulting reaction product, 45 ml. of (CH3)3COOH and 45 ml. of CH OH were added, dropwise, over 1 hour at from -10°C to 0°C to o b t a i n 18 mmo l s ( 48 % y i e l d ) o f (C2H50)2P(0) [(CF2)40(CF2)2S02F]. (XVI) The product was recovered by distilling under vacuum. (The boiling point of XVI is 133°C at l.lmm.
(b) 9.3 mmol of XVI were reacted with 18.6 mmol of Na2S204 and 18.6 mmol of NaHC03 in a solution of 8 ml. of water and 4 ml. of acetonitrile. The reaction temperature was 85°C and the reaction time was 2 hours. (C2H50)2P(0) [(CF2)40(CF2)2S02Na] (XVII) was recovered in 89% yield by repeated extraction of the solid from the evaporated solution with acetonitrile and evaporation of the acetonitrile solvent.
(c) 8.3 mmol of XVII were oxidized by 40 mmol of H202, added dropwise as a 30% aqueous solution. After stirring for 10 hours at room temperature (C2H50)2P(0) [(CF2)40(CF2)2S03Na] (XVIII) was recovered at a yield of 92% after evaporation to dryness under vacuum.
(d) 7.7 mmol. of XVIII were hydrolyzed in accordance with the method of Example 1(d) to yield (HO)2P(0) [(CF2)40(CF2)2S03Na] (XIX) at a yield of 88%.
(e) XIX was reacted according to the method of Example 1(e) to yield (HO)2P(0) [(CF2)40(CF2)2S03H] . H20 (XX) at a yield of 78%.
EXAMPLE 4 Removal of Sulfate and Phosphate Ion
The product of Example 1(e), containing sulfate ions, was dissolved in water and an aqueous BaCl2 solution was added thereto with stirring, until an excess was present, i.e. until additions caused no further precipitation of BaS04. After centrifugation, a supernatant was decanted, concentrated, and passed through a 4.5cm by 50 cm packed column of DOWEX M-31 (Dow Chemical Company) , a styrenesulfonic acid resin, to recover an eluate containing no detectable sulfate.
Alternatively, Ba(OH)2 may be used in place of BaCl2 to obtain a similarly purified solution. Moreover, if the pH of said purification was adjusted to 11 or greater, by addition of Ba(OH)2, the inorganic phosphate ion was reduced to a level undetectable by 31P NMR.
EXAMPLE 5 Preparation of Acid Halide
(a) 11.1 gms of the product of Example 1(e) dissolved in 10 ml of P0C13 were combined with 35 gms of PC15 in a 100 ml flask and heated to 120°C. After holding at such temperature for one hour, the corresponding triacidhalide was recovered by distillation at 0.1mm. (At this pressure, the triacid halide - C12P(0)CF2S02C1 - had a boiling point of 76°C.
(b) A portion of the distillate was combined with water at 0°C to regenerate the product of Example 1(e) in a more purified condition, as evidenced by 31p and 13C NMR. EXAMPLE 6 Preparation of Unsupported Zr(03PCF2S03H)2
4.52 gms of (HO)2P(0)CF2S03H.H20 were added to 100 gms of H20 in a 500 ml. flask. 3.16 gms. of ZrOCl2.8H20 were added to 100 gms. of H20 in a second 500 ml. flask. The contents of the first flask were added to the second flask, with stirring, and the solution refluxed. Upon cooling and removal of the water 5.06 gms. of Zr(03PCF2S03H)2 were recovered.
EXAMPLE 7 Preparation of Supported Acid Catalysts
(a) A 15% w/w Zr(03PCF2S03H)2 on fumed silica was prepared as follows:
Fumed silica having a BET surface area of 200 M2/gm was impregnated with an aqueous solution of ZrOCl2.8H20, using the incipient wetness technique, and the resulting composite was dried for 12 hours at 110°C. The dried composite was impregnated with an aqueous solution of (HO)2P(0)CF2S03H.H20 using the incipient wetness technique and the resulting composite was dried for 12 hours at 110oC. 49.92 gms. of the supported acid catalyst having a BET surface area of 143.99 M2/gm and a pore volume of 99 cc/gm. was obtained.
(b) The procedure of Example 7(a) was repeated except that the first drying step was carried out at 80°C to yield 47.81 gms. of supported acid catalyst having a BET surface area of 173.38 M2/gm and a pore volume of 1.08 cc/gm. This acid catalyst may be represented by the general formula:
Zr(03PCF2S03H) #97(03POH) η..09 (c) 10%, 15% and 20% W/W (H02P(0)CF2S03H.H20 was prepared by impregnating an aqueous solution of said acid catalyst onto fumed silica and drying the resulting composite at 110°C. for twelve hours.
EXAMPLE 8 Isomerization of Olefins
1.51 g (4.7 ml) of a catalyst comprising 23.0 wt. % zirconium sulfodifluoromethylphosphonate on fumed silica prepared according to the procedure of Example 7(a) was loaded into the fixed bed reactor. The catalyst was dried by passing dry N2 at 100°C. for 2 hours, followed by initiating flow of liquie isobutane over the catalyst. The catalyst temperature was raised to 80oC. and after the catalyst reached temperature, the feed mixture comprising (in wt. %) 88.6 isobutane, 9.7 butene-1, 1.14 isobutene, and 0./6 n-heptane. After 7 1/2 hours on stream, the reactor effluent was weathered to remove C4*s and the C5+ product was analyzed by GLC. A total of 1.2 g of product were collected, and was analyzed to contain 58.3% C8 olefin, 33.2% Cg+ (predominantly C^2) , with the remainder mostly C8 saturate. The catalyst can be seen as an effective olefin oligomerization catalyst at the 80oC. temperature, with a productivity 0.09 g product per gram catalyst-hour.•
EXAMPLE 9 Olefin Dime-rination and Oliσomerization
1.78 g (5.0 al) of a catalyst comprising 8.4 wt % sulfodifluoromethyl phosphonic acid was loaded into the fixed bed reactor and dried by passing dry N2 at 100oC. for one hour. The catalyst was then fed a pure mixture of isobutane while the reactor temperature was raised to 3 0C., at which time the feed was changed to (in wt %) 92.6 isobutane, 2.2 trans-2-butene, 3.9 isobutene, and 1.4 n-heptane as internal standard. After 2 1/2 hours on stream, 0.35 g of product was collected (productivity 0.06 g/g catalyst hour), purged of C4 components, and was analyzed as follows: 86.9 wt % C8 olefin, 7.1 wt % C1 olefin and 6.0 wt % C8 saturate. The temperature was then raised to 60°C. and a new sample of effluent was collected from the reactor. Over the course of 3 hours, 2.15 g effluent (not including C4's, productivity 0.32 g/g catalyst-hour) was collected, and had the following composition: 49.9 wt % C8 olefin, 42.0 wt % C12 olefin, and 8.0 wt % Cg saturate. Thus, the catalyst can be seen tobe a selective C4 olefin dimerization catalyst at low temperatures (34°C.) and an active olefin oligomerization catalyst at 60°C.
EXAMPLE 10
Process Usinσ Nafion " Fluorinated Sulfonic
Acid Polymer Available From duPont
A catalyst was prepared by incipient wetness impregnation of an aqueous alcoholic solution of Nafion, equivalent weight 1000, depositing on Si02 to a weight loading of 12.8 wt %. The catalyst was vacuum dried at 100°C. overnight and stored in a bottle under N2. 2.29 g catalyst (5.0 ml) was loaded into the reactor and dry nitrogen was passed over the catalyst at ambient temperature for 12 hours. Liquid isobutane was fed over the catalyst and the temperature raised to 60°C. Upon reaching temperture, the feed was changed to (wt %) isobutane, 92.2; butene-1, 5.5; isobutene, 1.6; n-heptane, 0.75. The experiment continued for three hours, following which the temperature was raised to 80°C. for an additional 4 1/2 hours. A reaction product, after removal of C4 components, consisted of 0.68 g C5+ (productivity 0.03 g/g catalyst-h) which comprised the following: 57.1 wt % C8 olefin, 36.4 wt % C12 olefin, and 6.2 wt % C8 saturate. The catalytic behavior is similar to that of the catalysts described in Examples 8 and 9, but the catalyst productivity is clearly lower with Nafion compared with the catalysts derived from the sulfodifluoromethylphosphonic acid.
EXAMPLE 11 Isobutane Allviation
A catalyst comprising 23.0 wt % zirconium sulfodifluoromethylphosphonate on a fumed silica support was prepared by sequential impregnation by incipient wetness of a solution of sulfodifluoromethylphosphonic acid followed by drying and then impregnation of zirconium oxychloride. (The procedure was similar to the procedure of Example 7(a) except for the reversal of the impregnation steps.) 2.08 g (5.3 ml) of catalyst was loaded into the fixed bed reactor and the catalyst was predried by passing dry N over the catalyst for 0.5 hour at 100°C. The catalyst was cooled to ambient, a liquid isobutane feed was added to thecatalyst, and the catalyst was heated to 140°C. while maintaining a liquid phase at 610 psig. The- feed was then switched to one comprising by weight %: isobutane, 93.1; trans-2-butene, 4.2; isobutene, 1.4; n-heptane, 1.4. The reaction proceeded for 1.75 hours, during which time 1.75 g of a liquid product free of C4 was collected (productivity, 0.19 g/g cat-hr) . The liquid product had the following distribution, in wt./ %: C8 saturates, 28.1; C8 olefins, 31.0; C^2 olefin, 35.1. Trimethylpentanes, indicative of alkylation activity, comprised 34.9% of the total C8 saturates and 9.8 wt. % of the total product. These data indicate that at the higher temperatures than described in the previous examples, the zirconium sulfodifluoromethylphosphonate catalyst has sufficient acidity to promote isobutane alkylation.
EXAMPLE 12 Isobutane Alkylation
The same catalyst and loading as was described in Example 9 was again employed, comprising 8.4 wt % of sulfodifluoromethylphosponic acid on a fumed silica support. After predrying thecatalyst at 100°C. in flowing N2 for 1 hour, liquid isobutane was introduced to the catalyst and the temperature was raised to 130°C. The feed was then switched to one comprising the following in wt %: isobutane, 93.5; trans-2-butene, 3.7; isobutene, 1.8; n-heptane, 1.0. The reaction proceeded for 4.85 hours, during which time 1.6 g of C4-free product was collected (productivity 0.19 g/g cat-h) . The product was analyzed as follows in wt %: C8 saturates, 14.8; C8 olefins, 26.6; C^2 olefins, 51.0. Of the C saturates, 62.7 wt % were trimethyl pentanes. As in Example 11, the data shows that the catalyst prepared from sulfodifluoromethylphosphonic acid has sufficient acidity to catalyze alkylation of isobutane provided that the reaction temperature is sufficiently high.

Claims

WHAT IS CLAIMED IS:
1. A process for the conversion of a reactant into a reaction product in the presence of an acid catalyst comprising one or more fluorine atoms, sulfo radicals and phosphono radicals, each such radical being bonded to the same or different carbon atom, with the proviso that at least one sulfo radical and at least one phosphono radical are bonded to such carbon atom through the sulfur atom and the phosphorus atom, respectively.
2. The process of claim 1 wherein said reactant is an organic reactant.
3. The process of claim 2 wherein said reactant is an olefin.
4. The process of claim 3 wherein said reaction product is an iso er of said olefin.
5. The process of claim 3 wherein said reaction product is an oligomer or a polymer of said olefin.
6. The process of claim 3 further comprising contacting said olefin with said catalyst in the presence of a second reactant having a hydroxyl group to obtain a reaction product comprising an ether or an alcohol.
7. The process of claim 3 further comprising contacting said olefin with said catalyst in the presence of a second reactant comprising a carboxylic acid group to obtain a reaction product comprising an ester.
8. The process of claim 3 further comprisin contacting said olefin with said catalyst in the presenc of a second reactant comprising an aromatic group t obtain a reaction product comprising an alkylated aromati compound.
9. The process of claim 3 further comprisin contacting said olefin with said catalyst in the presenc of a second reactant comprising a peroxyacid group t obtain a reaction product comprising an epoxide.
10. The process of claim 2 wherein said reactant i an alcohol.
11. The process of claim 10 wherein said reactio product is an olefin.
12. The process of claim 10 further comprisin contacting said alcohol with said catalyst in the presence of a second reactant comprising a carboxylic acid group to obtain a reaction product comprising an ester.
13. The process of claim 10 further comprising contacting said alcohol with said catalyst in the presence of a second reactant comprising an aromatic group to obtain a reaction product .comprising an alkylated aromatic.
14. The process of claim 2 wherein said reactant is an anhydride^
15. The process of claim 14 further comprising contacting said anhydride with said catalyst in the presence of a second reactant comprising an aromatic or olefinic group to obtain a reaction product comprising an acetylated aromatic or an acetylated olefin.
16. The process of claim 2 wherein said reactant is an aldehyde or ketone and said reaction product comprises condensed aldehydes or ketones.
17. The process of claim 2 wherein said reactant is a hydroperoxide or a peroxide.
18. The process of claim 7 wherein said first reactant is selected from the group consisting of C2 to C8 straight and branched chain olefins and C5 to C8 cyclic olefins and said second reactant is selected from the group consisting of saturated and unsaturated carboxylic acids having from 1 to 8 carbons.
19. The process of claim 18 wherein said first reactant is isobutylene and said second reactant is selected from the group consisting of methacrylic acid and acetic acid.
20. The • process of claim 8 wherein said first reactant comprises propylene, said second reactant comprises benzene and said reaction product comprises cumene.
21. The process of claim 4 wherein said olefin is a C4 to C10 mono olefin.
22. The process of claim 21 wherein said olefin is selected from the group consisting of nonene, 1-butene and 1-octene.
23. The process of claim 17 wherein said first reactant is cumene hydroperoxide and said reaction product is a mixture of acetone and phenol.
24. The process of claim 2 wherein said reactant is an epoxide and said reaction product is a glycol.
25. The process of claim 24 wherein said epoxide is selected from the group consisting of ethylene oxide and propylene oxide.
26. The process of claim 2 wherein said reactant is an ester and said reaction product comprises a carboxylic acid and an alcohol.
27. The process of claim 2 wherein said reactant comprises a mixtures of an aromatic compound and HN0 and said reaction product is nitroaromatic compound.
28. The process of claim 27 wherein said aromatic compound is selected from the group consisting of benzene and toluene.
29. The process of claim 3 further comprising contacting said olefin with said catalyst in the presence of a tertiary alkane and said reaction product comprises an alkylation product.
30. The process of claim 29 wherein said olefin is n-butene, said tertiary alkane is isobutane and said reaction product comprises iso-octane.
31. The process of claim 2 wherein said reaction product is a linear alkane and said reaction product is a branched isomer of said linear alkane.
32. The process of claim 10 wherein said reaction product is an ether.
33. The process of claim 32 wherein said alcohol is selected fromt he group consisting of methanol and ethanol and said reaction product is dimethylether and diethylether, respectively.
34. The process of claim 17 further comprising contacting said peroxide with said catalyst in the presence of a carboxylic acid and said reaction product is a percarboxylic acid.
35. The process of claim 34 wherein said peroxide is hydrogen peroxide, said carboxylic acid is acetic acid and said percarboxylic acid is peracetic acid.
36. The process of claim 26 wherein said ester is sucrose and said reaction product comprises fructose and glucose.
37. The .process of claim 2 wherein said reactant comprises an aldehyde or a ketone and said reaction is carried out in the presence of an aromatic compound.
38. The process of claim 37 wherein said reactant comprises acetone and said aromatic compound is phenol.
39. The process of claim 37 wherein said reactant comprises formaldehyde and said aromatic compound is aniline.
40. The process of claim 5 wherein said olefin is C to C^o monoolefin.
41. The process of claim 1 wherein said conversio is effected at a temperature of from 25°C. to 175°C. and pressure of from 1 Atmos. to 50 Atmos.
42. The process of claim .1 wherein said reactant i contacted with said solid acid catalyst in the liqui phase.
43. The process of claim 1 wherein said acid catalyst is a compound selected from the group of compounds represented by the general formula:
(R20)2P(θ RfSOj-R1).
wherein R is an organo radical having at least one covalent carbon-fluorine bond, R1 is hydrogen, R2 is a lower alkyl radical or is hydrogen, r is 2 or 3, y is an integer of from 1 to 3 and x is an integer of from 1 to 3, with the proviso that the phosphorus and the sulfur are covalently bonded to a carbon atom.
44. The compound of claim 43 wherein R1 and R2 are hydrogen.
45. The compound of claim 44 wherein y is 1.
46. The compound of claim 45 wherein R is selected from the group comprising fluorinated alkylene and fluorinated alkyleneoxyalkylene radicals.
47. The compound of claim 46 wherein R is a radical selected from the group consisting of "^ CF2, ^.CFH, CFBr, "^ CF and —fCF2) 0(CF2 j" •
48. The compound of claim 43 wherein R1 and R2 are hydrogen, R is CF2, 1 is 2, r is 3 and x is 1.
49. The compound of claim 43 wherein R1 and R2 are hydrogen, R is CFH, y is 1, r is 3 and x is 1.
50. The compound of claim 43 wherein R1 and R2 are hydrogen, R is CFBr, y is 1, r is 3 and x is 1.
51. The compound of claim 43 wherein R1 and R2 are hydrogen, R is (CF2)40(CF2)2, y is 1, r is 3 and x is l.
52. The process of claim 43 wherein said acid catalyst is provided as a solid acid catalyst by reaction with a tetravalent metal ion.
53. The process of claim 52 wherein said tetravalent metal ion is selected from the group consisting of Zr, W, U, Ti, Th, Te, Sn, Si, Ru, Fu, V, Pr, Pb, Os, Nb, No, Mn, Ir, H , Ge, Ce and mixtures thereof.
54. The process of claim 53 wherein said tetravalent metal ion is Zr. I. Classification of Subject Matter
41/02
41/04, 41/14; C07D: 301/14; B01J: 31/00
II. Fields Search
562/607;549/523,524,525;536/124; 127/36,46.1
PCT/US1990/000054 1989-01-03 1990-01-03 Acid catalyzed process WO1990007480A1 (en)

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EP0580735A1 (en) * 1991-04-09 1994-02-02 Catalytica Inc. Preparation of trialkylacetic acids, particularly of pivalic acid, using solid acid catalysis
US5731299A (en) * 1992-05-29 1998-03-24 The Procter & Gamble Company Phosphonosulfonate compounds, pharmaceutical compositions, and methods for treating abnormal calcium and phosphate metabolism
CN105152936A (en) * 2015-09-14 2015-12-16 江苏隆昌化工有限公司 Method for nitrifying paradichlorobenzene by using solid acid catalyst

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0580735A1 (en) * 1991-04-09 1994-02-02 Catalytica Inc. Preparation of trialkylacetic acids, particularly of pivalic acid, using solid acid catalysis
EP0580735A4 (en) * 1991-04-09 1994-03-30 Catalytica Inc.
US5731299A (en) * 1992-05-29 1998-03-24 The Procter & Gamble Company Phosphonosulfonate compounds, pharmaceutical compositions, and methods for treating abnormal calcium and phosphate metabolism
CN105152936A (en) * 2015-09-14 2015-12-16 江苏隆昌化工有限公司 Method for nitrifying paradichlorobenzene by using solid acid catalyst
CN105152936B (en) * 2015-09-14 2017-10-10 江苏隆昌化工有限公司 A kind of method that solid acid catalysis nitrifies paracide

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