sign in sign up
<<
Home , Barium sulfide

Nov. 24, 1970 R. C. VANDER LINDEN ET AL 3,542,808 SYNTHESIS OF EPISULFIDEs Filled Jan. 4, 1966 - 2 Sheets-Sheet

FIGURE I EFFECT OF PERCENTAGE YELD AND SELECTIVITY TO PROPYLENE EPISULPHIDE AND CONVERSION OF PROPYLENE OxIDE As A FUNCTION OF REACTANT MOLE RATIO 5, 8O

to 6O. SELECTivity 50 % - 40 3OH CONVERSION 2O u-- N O u-TYIELD

W 2/ 3/ MOLE RATIO CS2/CO

RONALD C. VANDER LINDEN JUAN. M. SALMA NVENTORS PETER A. C. SMITH EY 7-a-le a. 62-4 PATENT ATTORNEY Nov. 24, 1970 R. c. vANDER LINDEN ET AL 3,542808 ...... SYNTHESIS OF EPISULFIDES Filed Jan. 4, 1966 2 Sheets-Sheet 2 - FIGURE 2 REACTION OF PROPYLENE OXIDE WITH CARBON DISULPHIDE YIELD OF PROPYLENE EPISULPHIDE AS A FUNCTION OF REACTION TEMPERATURE 30 - 45% CONVERSION Cso

25

O. -- 2 5 35-50% CONVERSION Co. O 20% CONVERSION Cso 15% CONVERSION Cso

125 15o I75 : 2OO 225 25O ' ' ' , REACTION TEMPERATURE, C.

FIGURE 3. REACTION OF PROPYLENE OXIDE WITH CARBON DISULPHIDE EXTENT OF PROPYLENE oxIDE CONVERSION AS A FUNCTION OF TEMPERATURE

O.25-O.32 V/V/HOUR O

3.o

2 OO O49-0.53 V/V/HOUR

O 5O 2OO 25o REACTION TEMPERATURE, C. RONALD C. VANDER LINDEN JUAN. M. SAVA NVENTORS PETER A. C. SMITH SY 7-4. 4. .. -04-ree PATENT ATTORNEY 3,542,808 United States Patent Office Patented Nov. 24, 1970 1. 2 3,542,808 Suitable feedstocks for use in the present invention are SYNTHESS OF EPSULFIDES unsaturated organic epoxide feeds, preferably gaseous Ronald C. Vander Linden and Juan M. Salva, Sarnia, feeds or feeds capable of being converted to a gas with Ontario, and Peter A. C. Smith, Petrolia, Ontario, out decomposition as follows: Canada, assignors to Esso Research and Engineering (a) Ca to C12, preferably C2 to C9, branched and Company, a corporation of Delaware straight chain monoolefin epoxides including epoxides con Filed Jan. 4, 1966, Ser. No. 518,591 taining other functional groups such as aryl groups, car nt. C. C07d 95/00 boxyl groups, chlorine, fluorine, etc., e.g. epoxides of the U.S. C. 260-327 14 Claims following: ethylene, propylene, isobutylene, 1-butene, 2 IO butene, 2-methyl-1-butene, pentenes, hexenes, heptenes, dodecenes, styrene, oleic acid, etc. ABSTRACT OF THE DISCLOSURE (b) Same range for epoxides of cyclic monoolefins and Episulfide compounds are synthesized by reacting either substituted cyclic monoolefins, and alkyl, aryl, carboxyl, a Saturated or unsaturated epoxide with chlorine and fluorine substituted cyclic monoolefins, be or carbonyl in the presence of a magnesium oxide, 5 ginning with the C ring, e.g. epoxides of cyclobutene, magnesium hydroxide, or sulfide catalysts. Con cyclopentene, cyclohexene, cyclohepten, cyclooctene, alkyl ventionally the reaction is conducted in the vapor phase substituted derivatives thereof, cyclopentenecarboxylic at temperatures ranging from 30 to 400° C. acid, cyclohexenecarboxylic acid, cinnamic acid, etc. (c) Same range for branched and straight chain uncon 20 jugated diolefin epoxides and alkyl, aryl, carboxyl, chlo The present invention relates to an improved process rine and fluorine substituted unconjugated diolefin epox for the economic synthesis of episulfides by reacting satu ides beginning with C3 (allene), e.g. epoxides of 1-4 rated or unsaturated epoxides in the vapor phase with pentadiene, 1-5 hexadiene, etc. , COS, or carbon disulfide, CS More (d) Same range for conjugated diolefin epoxides, particularly, this invention relates to obtaining high initial 25 branched and straight chain, and alkyl, aryl, carboxyl, selectivities, e.g. up to 70%, along with good conversions, chlorine and fluorine substituted conjugated diolefin epox e.g. up to 45%, specifically by conducting the reaction ides beginning with CA, e.g. epoxides of 1-3 butadiene, in the presence of magnesium oxide or hydroxide or isoprene, chloroprene, etc. barium sulfide. Most particularly, in a preferred embodi (e) Same range for conjugated and unconjugated cyclic ment this invention relates to carrying out the reaction 30 diolefin epoxides and alkyl, aryl, carboxyl, chlorine and at temperatures of 30-400 C. in the presence of the fol fluorine substituted cyclic diolefin epoxides beginning with lowing solid catalysts: MgO, Mg(OH) or BaS. the C ring, e.g. epoxides of cyclobutadienes, cyclopen Highly reactive olefin episulfides of the type of ethylene tadienes, cyclohexadienes, cyclohexadienecarboxylic acids, episulfide and propylene episulfide are clearly recognized cycloheptadienes and cyclooctadienes. to be potentially valuable chemical monomers useful for 35 (f) Same range for noncyclic and cyclic triolefin epox the preparation of various polymers and a variety of other ides and substituted triolefin epoxides including as sub uses. However, volume use of these materials has to the stituents alkyl groups, aryl groups, carboxyl groups, chlo present awaited an economic method for their synthesis. rine, fluorine, etc., beginning with Ce, e.g. epoxides of Such an economic synthesis is provided by the present cycloheptatrienes, cyclooctatrienes, 1,3,5 - hexatriene, process. 40 heptatrienes, etc. The catalysts of the present invention may be used alone (g) Same range for epoxides of other nonhydrocarbon or supported on standard supports such as asbestos, alumi feeds including fatty acids, furan, , 1,4-pyrone, nas, activated carbon, etc. Preferably, the supports, if alkyl- and aryl-substituted , unsaturated alco used, are nonacidic or treated, e.g. with an aqueous base, hols, e.g. epoxides of allyl alcohol, etc. to be nonacidic since cyclic dimerize to dithiane 45 The -containing compound with which the epoxide derivatives when heated with acidic catalysts. The form is reacted may be carbonyl sulfide or carbon disulfide; of the catalyst is preferably granular or pellets. both of which have been found to yield similar results The catalyst is normally used in an anhydrous condi in the synthesis of episulfides in accordance with this in tion. However, it has been found that small additions of vention. water tend to increase the resultant yield of episulfide 50 The present invention may be carried out under the fol due to increased conversion of the epoxide at similar levels lowing preferred conditions: of episulfide selectivity. Therefore, it is preferable to add (1) Temperatures in the range of 0 to 500 C., pref water in amounts of about 0.5-2.5 mole percent based on erably 30 to 400° C., more preferably 100-250° C., the reactants; about 1.0 mole percent being particularly still more preferably 100-200° C., e.g. 150° C. preferred. 55 (2) Pressures in the range of 0.1 to 50 atmospheres, The catalysts may be used as is or they may be pre preferably 1 to 5 atmospheres, e.g. 1 atmosphere. treated by calcining at temperatures ranging from 150 (3) Mole ratios of COS or CS2 to epoxide in the range 450° C. for about 0.5-3.5 hours in a helium atmosphere. of 1/10 to 1000/1, preferably 0.5/1 to 100/1, more pref Calcining results in the removal of moisture from the erably 1/1 to 10/1, still more preferably 1/1 to 3/1, e.g. catalyst. In the examples set forth below calcined catalysts 60 2/1. were utilized in order to limit catalyst hydration, and . (4) Reaction times in the range of 0.1 second to 1 therefore maintain reproducible surface areas and repro hour, preferably 0.1 minute to 0.25 hour, more preferably ducible results. Calcining, if used, is preferably carried 10 seconds to 5 minutes. out under the following conditions: (5) Flow rates of 0.05 to 1.0 volumes of feed per volume of catalyst bed per hour, preferably 0.1 to 1.0, MgO-about 0.5-2.5 hrs. at about 400-450 C. and more preferably 0.1 to 0.5, e.g. 0.25. Mg(OH)-about 0.5-1.0 hrs. at about 150–200° C. In a preferred embodiment, the reaction is carried out BaS-about 0.5-2 hrs. at about 200–250° C. in a flow reactor having an L/D of 3:1 to 25:1 at re It should be noted that in a continuous reaction an un O action times of 3 seconds to 10 minutes. Also, in a pre treated catalyst will usually have its moisture driven off ferred embodiment conditions are utilized to obtain high as a result of the reaction temperatures. conversions per pass of 50 to 95% and the desired prod 3,542,808 3 4. ucts, e.g. episulfides, are removed from the product by ratio of 1:1, with a throughput of 1.0 LHSV. The re absorption, extraction, etc. The remaining reaction prod sults shown below indicate the relative activity of ucts are recycled to extinction to thereby obtain high Mg(OH)2 overall conversions and yields. The present invention will be more clearly under as a catalyst for promoting episulfide formation: stood from a consideration of the following examples. EXAMPLE 1. Selectivity, mols episulfide Yield, mols per mol propyl- episulfide per Reaction of CO with CS over various oxide catalysts ene oxide reacted, mol propylene Propylene oxide and carbon disulfide were introduced O percent oxide, percent through rotameters into a vertically mounted pyrex glass Catalyst: Mg(OH)2------65 6.8 reactor (12% inches long by 1 inch ID) contained in a Sr(OB) 2-8HO- - - - Nil 0.6 furnace. The laboratory equipment was valved so as to Ba(OH)2.8H2O------Nil 0.9 permit mass chromatographic sampling of both the en tering and product gases from the reactor. The flow rates 5 of carbon disulfide and propylene oxide were about 12 EXAMPLE 4 15 cc./hr, and the reactor was packed with catalyst and Reaction of COS and CO at various temperatures over maintained at 280 C. and atmospheric pressure. The MgO molar ratio of carbon disulfide to propylene oxide was 1:1. The following results were obtained with various 20 In equipment similar to that used in Example 1, car metal oxide catalysts: bonyl sulfide was reacted with propylene oxide over a high purity MgO catalyst (Fisher Certified Reagent). The molar ratio of COS/CO was 1.5/1, pressure was atmospheric and the throughput, calculated on a weight Selectivity, 25 hourly space velocity basis, was 0.41-0.47 w./w./hour. mols episulfide Yield, mols per mol propyl- episulfide per The following results indicate that temperatures of about ene oxide reacted, mol propylene 150° C. produce the best results for this reaction: percent oxide, percent

43 16 C3O con- C3S selec 9 1. 30 verted, tivity, C3S yield, Nil Nil percent percent percent ( () Temperature, C.: Nil Nil 100------48 48 23 Nil 150------49 56 27 200------38 33 13 35 This reaction indicates that carbonyl sulfide and carbon These results show that only MgO is a satisfactory disulfide may be used interchangeably in the process of catalyst for promoting episulfide synthesis according to this invention. Comparison of these results with those of this invention. Example 7, below, indicate that carbonyl sulfide will re 40 act more readily than carbon disulfide to form the desired EXAMPLE 2 episulfides. However, CS2, the less expensive reactant, was Reaction of CS and CO over various hydroxide catalysts utilized to determine catalyst activity. . EXAMPLE 5 In equipment similar to that used in Example 1 and 45 at temperatures of 250-280 C. at atmospheric pressure, Life test of MgO in reaction of CS2 with CO CS and propylene oxide in a molar ratio of 1:1 and a In equipment similar to that used in Example 1, a life throughput of 0.11-0.44 v./v./hr. were reacted over sev study of MgO catalyst was conducted. Carbon disulfide eral sulfide catalysts. The results shown below indicate and propylene oxide in a molar ratio of 2:1, and a space the relative activity of BaS as a catalyst for promoting 50 velocity of 0.5 LHSV, were reacted at 200° C. and episulfide formation as compared with other sulfides: atmospheric pressure. Fisher Certified Reagent grade MgO (8-16 mesh) was used as the catalyst.

Sample period, hr------3rd 10th Selectivity, 55 mois episulfide Yield, mols Conversion of propylene oxide, percent-- 25 2 per mol propyl- episulfide per Conversion of CS2, percent------9 5 ene oxide reacted, mol propylene Selectivity to propylene episulfide, percent.------60 68 percent Oxide, percent Yield of propylene episulfide------15 8

() (1) Ni 60 These results indicate that catalyst activity with re 32 4.2 spect to CS2 and CO decreased with time; however, se Nil Ni lectivity increased slightly. This example shows the feasi bility of conducting relatively long-time continuous re actions. 65 EXAMPLE 6 Optimization of reaction conditions would increase the Reaction condition parameters with MgO catalyst episulfide yield over a BaS catalyst. The same equipment as used in Example 1 was em EXAMPLE 3 ployed to determine the influence of certain reaction 70 parameters, i.e. temperature, mole ratio, and space velocity Reaction of CS2 and CO over various hydroxide catalysts at atmospheric pressure, on the conversion (oxide reacted/ oxide feed), selectivity (sulfide formed/oxide reacted) In equipment similar to that used in Example 1, and at and yield of episulfide obtained with MgO as the catalyst. a temperature of 150 C. at atmospheric pressure, carbon Results obtained are shown in the accompanying drawings. disulfide was reacted with propylene oxide in a molar FIG. 1 shows the yield, episulfide selectivity, and propylene 3,542,808 5 6 oxide conversion as a function of molar ratio of CS2/ At 150 C. and atmospheric pressure, CS and CO in propylene oxide, at 200 C., atmospheric pressure and a a molar ratio of 1/1 were fed to the reactor at a through space velocity of 0.5 v./v./hr. FIG. 2 shows the episulfide put of 1.0 LHSV. The results are as shown below: yield as a function of reaction temperature, and FIG. 3 shows the propylene oxide conversion at two different space velocities as a function of temperature. , Referring to FIG. 1, it can be seen that yield and se Conversion, Selectivity, Yield, lectivity increase with increasing molar ratios of carbon Pretreatment percent percent percent disulfide to propylene oxide. Conversion of propylene None------26 34 9.2 oxide increases with increasing mole ratio to a maximum 0.75 hrs. at 150-170 C------1. 65 6.8 between a ratio of 2/1 to 3/1 of CS2/CO. It is interest 10 ing to note that although the conversion drops off slightly at a ratio of 3/1, the yield increases because of increasing selectivity. FIG. 2 indicates that greater episulfide yields Again, conversion is increased with no catalyst pre and propylene oxide conversions are obtained at reaction 5 treatment, probably due to increased moisture content. temperatures in the lower end of the preferred range. Similarly, in FIG. 3, greater conversions of propylene EXAMPLE 10 oxide are shown at lower temperatures and also at lower space velocities. Reaction of CS2 with butadiene oxide EXAMPLE 7 20 In equipment similar to that used in Example 1, butadi ene oxide is used as the epoxide, CS2 as the source of sul Addition of water to reaction between CS and CO fur, and magnesium oxide as the catalyst. Butadiene epi sulfide, i.e. the unsaturated episulfide, is obtained with In equipment similar to that used in Example 1, carbon good selectivity and yield. disulfide and propylene oxide in a molar ratio of 1:1, were 25 reacted at 280 C. and atmospheric pressure over a 4-10 EXAMPLE 11 mesh Fisher Certified Reagent grade MgO catalyst. The throughput of the reactants was 0.11 v./v./hr. The fol Reaction of CS with propylene oxide over 98% lowing results indicate the effect of adding water to the MgO catalyst feed for increasing episulfide yield: m 30 This example shows the versatility of the preferred MgO catalyst. The catalyst was ball milled to 4-10 mesh with 2% graphite added to the mixture. CS2 and CO ofConversion propylene Selectivity,. Yield, Water added oxide, percent percent percent in a 1/1 mole ratio were reacted at 250 C. in equip 35 ment similar to that used in Example 1. Conversion of None------46 33 15.2 CO was 12%, selectivity to episulfide was 44% and the imole percent (0.36 g/hr.).----- 72 33 24 episulfide yield was 5.5%. In a similar experiment a 98% MgO containing 2% graphite was obtained initially. Under the same reaction conditions the CO conversion It should be noted that the selectivity remained con 40 was 22%, the episulfide selectivity was 23%, and the epi stant, but the conversion increased considerably, thereby sulfide yield was 5%. The episulfide yield is normally resulting in greater yields of episulfide. Consequently, it lower at temperatures of about 250 C. and over. is not necessary to completely dry the catalysts before What is claimed is: conducting the reaction. Y 1. A process for the synthesis of episulfides which com EXAMPLE 8 prises reacting a C-C2 straight chain or branched chain 45 epoxide with a sulfur compound selected from the group Effect of catalyst calcination on MgO consisting of carbon disulfide and carbonyl sulfide in the In equipment similar to that used in Example 1, an vapor phase at a temperature varying from 100 to 250 episulfide synthesis was conducted with an MgO catalyst C. in the presence of from about 0.5 to 2.5 mol percent (4-10 mesh Fisher Certified Reagent) to determine the 50 water, based upon sulfur compound and epoxide, and a effect of calcination prior to conducting the episulfide solid catalyst selected from the group consisting of mag synthesis. nesium oxide, magnesium hydroxide and barium sulfide At 280° C. and atmospheric pressure, CS, and CO in and thereafter recovering an episulfide product. a molar ratio of 1/1 were fed to the reactor at a through 2. The process of claim 1 wherein said epoxide is put of 0.10 v./v./hr. The results are as shown below: 55 propylene oxide. 3. The process of claim 1 in which said reaction is conducted within a reaction zone containing a fixed bed Conversion, Selectivity, Yield, of catalyst and the flow rate of sulfur compound and Pretreatment percent percent percent epoxide feed to said reaction zone is from 0.5 to 1.0 None------94 20 9

60 volumes of sulfur compound and epoxide feed per volume 2 hrs. at 400-450° C. 46 33 15.2 of catalyst per hour. 4. The process of claim 1 wherein said epoxide is an This example shows higher conversions with an un unsaturated epoxide. treated catalyst, confirming the result of Example 7 where 5. The process of claim 1 wherein said epoxide is a 65 saturated epoxide. the addition of water to the feed increases the conversion 6. The process of claim 1 in which the catalyst is MgO. of propylene oxide (since calcination serves to remove 7. The process of claim 1 in which the catalyst is the Water)...... Mg(OH)2. w EXAMPLE 9 8. The process of claim 1 in which the catalyst is BaS. Effect of catalyst calcination on Mg(OH)2 70 9. The process of claim 1 in which the mole ratio of the sulfur compound to the epoxide is from 1/1 to 10/1. In equipment similar to that used in Example 1, an 10. The process for the synthesis of episulfides which episulfide synthesis was conducted with an Mg(OH)2 comprises reacting a C-C2 straight chain or branched catalyst to determine the effect of catalyst calcination chain epoxide with a sulfur compound selected from the prior to conducting the episulfide synthesis. 75 group consisting of carbon disulfide and carbonyl sul 3,542,808 7 8 fide in the vapor phase at a temperature varying from 100 to 250 C. in the presence of a solid catalyst se References Cited lected from the group consisting of magnesium hydroxide UNITED STATES PATENTS and barium sulfide and thereafter recovering an episulfide 3,073,846 1/1963 Millikan ------260-327 product. 5 3,213,108 10/1965 Osborn et al. ------260-327 11. The process of claim 14 wherein said epoxide is 3,426,039 2/1969 Osborn et al. ... 260-327 propylene oxide. 12. The process of claim 10 wherein said epoxide is OTHER REFERENCES propylene oxide. Durden et al.: Jour. Amer. Chem. Soc., vol. 82, 1960, 13. The process of claim 10 wherein said catalyst is 10 pp. 3032-4. barium sulfide. 14. The process of claim 10 wherein said reaction is JAMES A. PATTEN, Primary Examiner conducted in the presence of from 0.5 to 2.5 mol percent - . - U.S. C. X.R. water, based on said sulfur compound and epoxide. 260-329