United States Patent (19) [11] 3,897,508 Tkatchenko (45) July 29, 1975

54) DOLEFIN DIMERIZATION 3,436,431 4/1969 Candlin et al...... 260/666 B 3,446,86 5/1969 Menapace et al...... 260/666 B 75) Inventor: Igor Tkatchenko, Pau, France 3,446,862 5/1969 Menapace et al...... 260/666 B 73) Assignees: Union Chimique Elf-Aquitaine, 3,526,672 9/970 Boyer ------A a a - ... 260/666 B Courbevoie; Institut Francais du 3,542,887 1 1/1970 Hillegass et al...... 260/666 B Petrole desCarburants et 3,655,793 4/1972 Myers...... 260/666 B Lubrifiants, Rueil-Malmaison, both 3,660,342 5/1972 Duggan...... 260/666 B of France Primary Examiner-Veronica O'Keefe (22 Filed Oct.... 10, 1971973 Attorney, Agent, or Firm-Ostrolenk Faber Gerb & 21 Appl. No.: 404,889 Soffen

30 Foreign Application Priority Data Oct. 10, 1972 France...... 72.35765 (57) ABSTRACT 52 U.S. Cl 260/666 B; 260/666 PY; 252/438 A process for the dimerization or codimerization of 51 ) int c a 9 coic 3700 diolefins in the liquid phase in an inert solvent solution 58 Field of search a 260/666B 666 PY using a catalyst comprising a complex obtained by re a A. A. R. a- A-4. R. R. a a a a a - s 252/438 acting the alkali metal or alkaline earth metal salt of tricarbonyl nitrosyl ferrate anion with a metallic halo 56 References Cited gen or pseudohalogen or complex thereof is disclosed. UNITED STATES PATENTS 13 Claims, No Drawings 3,377,397 4/1968 Maxfield ...... 260/666 B 3,897,508 2 DOLEFN DIMERIZATION manipulation of non-toxic materials, ease in prepara tion, absence of expensive reducing agents in the sys BACKGROUND OF THE INVENTION tem, and optimum activity obtained at controllable The manufacture of 4-vinyl cyclohexene (hereinafter tempertures s between 40- 60° C. The catalyst of the called WCH) has been the object of substantial re 5 present invention also permits one to obtain VCH search for a long period of time. VCH is a material of from butadiene at practically quantitative yields. These prime interest because it can be easily dehydrogenated and other advantages of the present dimerization cata to produce styrene. lyst will be apparent to those of ordinary skill in the art It has been known for some time that the specific di from the following detailed description. merization of butadiene to VCH is possible by thermal 10 means but this procedure requires a high temperature SUMMARY OF THE INVENTION and the dimerization is slow. Additionally, a simulta This invention relates to dimerization catalysts and a neous polymerization occurs and competes with the de process of dimerization and more particularly to a pro sired Diels-Alder reaction. cess for the liquid phase dimerization or codimerization Utilization of catalysts have been recommended to 15 of diolefins with a catalyst comprising a complex ob improve the speed of the butadiene dimerization. The tained by reacting the alkali metal or alkaline earth catalytic systems comprising salts or complexes of metal salt of tricarbonyl nitrosyl ferrate anion with a nickel, iron or manganese with amine or phosphorus metallic halogen, pseudo-halogen or complex thereof. ligands and with reducing compounds, in particular or ganoaluminums, convert butadiene to a mixture of cy 20 DESCRIPTION OF THE PREFERRED clo- i.5-octadiene, VCH and 1,5,9-cyclododecatriene EMBODIMENTS in variable proportions according to operating condi The liquid phase diolefin dimerization of the present tions although the cyclo-1,5-octadiene is the predomi invention is characterized by use of a catalyst which is nant product. Thus, German Pat. No. 1,140,569 constituted by the reaction product of an alkali metal teaches that a nickel bis(acetylacetonate)-triphenyl 25 salt or alkaline earth metal salt of tricarbonyl nitrosyl phosphine - monoethoxydiethyl aluminum catalyst ferrate anion with a metallic halogen, pseudo-halogen yields VCH with only a 21% selectivity. or complex thereof, compound. Catalyst compositions giving VCH in a selective The alkali metal or alkaline earth metal salt of the tri manner from butadiene are known. Such systems are carbonyl nitrosyl ferrate anion is of the formula constituted by such metals as iron, ruthenium and co 30 M'Fe(CO)NO in which M is an alkali metal when balt which include a nitrosyl ligand in association with m is 1 and is an alkaline earth metal when m is 2. The a carbonyl ligand and/or 7t-allyl. Such systems are de compounds M'Fe(CO)NO) are known materials scribed in British Pat. Nos. 1,085,875 and 1,148,177 and can be prepared by methods described in the litera with iron dinitrosyl dicarbonyl, cobalt dinitrosyl dicar ture, for example, in R. D. King, Organometallic Syn bonyl and T-allyl iron nitrosyl dicarbonyl being recom 35 thesis, 1,167-168 (1965). Examples of usable salts in mended. However, these catalytic systems present a clude sodium and potassium tricarbonyl nitrosyl ferrate number of disadvantages. Their preparation requires and magnesium, calcium, strontium and barium bis(- two reaction steps starting from the metal carbonyl and tricarbonyl nitrosyl ferrate). they have a major disadvantage of being very volatile The halogen or pseudo-halogen compound is of the and having a significantly high toxicity. 40 formula MX in which M' is an element of Groups Further, when one uses these catalysts, the dimeriza I-A, II, III, IV, V, VI-B, VII-B or VIII of the Periodic tion reaction requires temperatures of at least 100° C. Table appearing on pages 60-61 of Lange's Handbook which involves a rapid deactivation of the catalyst. of Chemistry (Revised 10th Edition). The metals of Also, this catalyst can only be used after a more or less Groups II-A and VIII are particularly preferred. X is a long period of induction which decreases the economic 45 mono- or divalent anion and is a halogen such as fluo feasibility of the process. rine, chlorine, bromine and iodine or a pseudo-halogen French Pat. No. 1,502,141 describes a catalytic sys such as cyanide, sulfocyanide, isocyanate, nitrate, ni tem which has the advantage of accomplishing the di trite, sulfate, acetylacetonate, carboxylate, and the merization of butadiene at a temperature as low as like, and n is an integer from 1-6. As examples of these room temperature. This system is constituted by a hal 50 halogen and pseudo-halogen compounds there can be ide of iron dinitrosyl in association with a donor com listed: sodium chloride, magnesium chloride, calcium pound and a reducer. Butadiene is quantitatively trans chloride, strontium chloride, barium chloride, alumi formed to VCH at temperatures below 30°C. This dis num chloride, aluminum bromide, silver nitrate, fer advantage of this catalytic system is that it requires the rous acetylacetonate, and ferric acetylacetonate. use of an expensive reducer compound such as allyl 55 The complexes of MX are of the formula LMX magnesium bromide thereby decreasing industrial in in which L is a chalcogen or pnicogen and p is an inte terest in this catalytic procedure. ger of 1-6. Typical complexes include dichlorozinc bi French Pat. No. 1,535,936 teaches a catalytic system pyridine, dichlorotin bipyridine, dichloronickel bipyri using compounds such as dihalo-bis-(T-allyl dinitrosyl dine, dichloropalladium bipyridine, bis(pyridine) di iron) tin or germanium prepared in situ attemperatures 60 chloronickel, bis-(pyridine) dichloropalladium, bis(tri of the order of 40° C. for dimerizing butadiene. This phenylphosphine) dichloronickel, bis(triphenylphos catalytic system also requires the use of organometallic phine) dichloropalladium, bis(diphenylphosphino) compounds of tin or germanium which are expensive ethane) dichloronickel, bis(diphenylphosphino) eth and most often toxic. ane) dichloropalladium, and the like. The complexes The present invention remedies the disadvantages of 65 are prepared by mixing the compound MX with the the prior art. Thus, the catalyst of the present invention ligand L in an appropriate solvent, such as those de presents the following simultaneous advantages: easy scribed below. 3,897,508 3 4. The catyalyst of the present invention can be pre ing the recovery of VCH by a simple distillation with pared by mixing a suspension or solution of the alkali out having the need to separate solvents. metal or alkaline earth metal carbonyl nitrosyl ferrate The diolefins which can be dimerized with the de in an appropriate solvent with a solution or suspension scribed catalyst of this invention are very diversified. of MX or LMX in the same solvent. The mixture They can contain up to 10 or more carbon atoms and is heated from 30-70 C. and agitated for a time suffi can be conjugated dolefins such as butadiene, iso cient for reaction to occur, which can conveniently be prene, dimethylbutadiene and unconjugated diolefins about 1 hour. The ratio between the alkali metal or al such as norbornadiene. Codimerization can also be ac kaline earth metal ferrate and the MX compound or complished. The present catalytic system is especially one of its LMX complexes can vary over a wide 10 appropriate for the dimerization of butadiene in vinyl range of between 0.5 n/m and 5 n/m. It is preferable, cyclohexene with quantitative yield. however, that this ratio be equal to n/m which corre Another particular trait of the present invention is sponds to the stoichiometry of the reaction. that the catalyst will selectively dimerize the diolefin in The reaction which occurs to give the catalytic com a diolefin-monoolefin mixture. The monoolefin is un pound can be thought out as occurring according to the 15 changed after the dimerization process and separation following reaction scheme: of the dimer and the olefin is very easy. (m/n) M (Fe(CO)NO) -- One particularly interesting application of the pres LMX - LM'Fe(CO)NO) + (n/n) MX ent catalyst is in the treatment of hydrocarbon fractions obtained from refineries which contain mixtures of di One preferred embodiment of the invention involves 20 preparing the catalyst in situ and utilizing the catalyst olefins and monoolefins. Thus, the butadiene in the C without isolating the LPM'Fe(CO)NO) from the re fraction, which contains a mixture of butadiene and bu action mixture. tenes, can be totally converted to VCH w ... a selectiv. In the dimerization process, a catalytic amount of the ity of 100 percent. It is much easier to separate VCH catalyst, which can vary within broad limits of up to 25 from non-dimerized butenes than to separate butadiene about 10 m. Mole percent, is used. It has been found from butenes. It is apparent that this is an industrial op that a ratio of diolefin to catalyst in the order of 300, eration of economic importance. i.e., about 0.33 m. Mole percent, gives excellent results. In the following Examples, a 125 ml stainless steel au The dimerization of the instant invention is achieved toclave provided with a double lining for thermostatic by adding the liquid diolefin to the catalyst. The reac 30 control was used. In each case, the autoclave was tion is effected in a pressure vessel which is maintained cooled to -20° C. and placed under an inert atmo under sufficient pressure to maintain the reaction mix sphere such as nitrogen or argon. The ferrate and MX ture in the liquid phase. In general, a pressure of about compound or one of the complexes LMX was added 5 kg/cm, preferably about 3 kg/cm, can be used and and then the liquid diolefin was added. The C fraction the particular pressure varies according to the particu 35 utilized in the Examples contained approximately lar parameters used. The reaction temperature can 35-45% butadiene and 65-55% butenes. The autoclave vary between 20°–120° C. but is preferably between was then heated to the dimerization temperature and 40°-80° C. In the dimerization of butadiene, tempera maintained at that temperature, with agitation, for a tures of the order of about 60° C. give excellent yields given amount of time. Thereafter the catalyst was deac of VCH. 40 tivated by adding hydrochloric acid with air bubbling A particular trait of the invention is that the reaction through the reaction mixture. The reaction product speed is increased by the addition to the catalytic sys thus obtained was distilled to separate out the solvent tem of a small, well-defined, amount of water of from and the different products were examined and identi 1-8 moles, preferably from 2-4 moles, of water per fied by vapor phase chromatography. mole of catalytic complex. Outside these limits, the wa 45 ter, and, in general, all proton solvents exert an injuri EXAMPLE 1-44 ous action, blocking the catalytic activity of the system. Dimerization of Butadiene With NaFe(CO)NO) -- This particular trait of the invention is advantageous MX because it allows the utilization of hydrated MX con pounds without being obliged to use anhydrous salts. A suspension or solution of 1/n mmole of MX in 5 Thus, in compounds M'Xq HO, q can be 0-6. If anhy ml toluene was added to a suspension of 193 mg (l drous complexes are initially formed, water can be mmole) of sodium tricarbonyl nitrosyl ferrate in 5 ml added to the reaction medium in the proportion indi toluene. The mixture was then agitated at 40 C. for 1 cated above. hour and a partial dissolution of the products in suspen Solvents which are of particular convenience for the 55 sion and appearance of a brick-red color was noted. dimerization of diolefins should, of course, be inert The resulting mixture was placed in the autoclave (pre with respect to the catalyst. Typical solvents include cooled to -20°C.), and 16.2 g (300 mmoles) of liquid saturated aliphatic and cycloaliphatic hydrocarbons butadiene was added. The molar ratio between the bu such as hexane, cyclohexane and dichloroethane, aro tadiene and the initial sodium ferrate was 300. The au matic or haloaromatic hydrocarbons such as benzene, 60 toclave was brought to 60° C. and maintained at that toluene and chlorobenzene, as well as aliphatic, aro temperature for 5 hours. Thereafter the catalyst was matic or cyclic ethers such as tetrahydrofuran. The last deactivated with dilute hydrochloric acid and the reac named solvent is interesting because it solubilizes the tion mixture distilled to obtain VCH. starting compounds while in most of the other noted The conversion and selectivity to VCH is shown in solvents, the catalyst remains in suspension. VCH, and 65 the following Table I. It will be observed that the cata in general the dimerization products, can conveniently lyst using zinc chloride and ferric chloride as MX be used; its utilization presents the advantage of allow gave the best results. 3,897,508 S 6 after 22 hours it is 93%. In each case, the selectivity of TABLE I VCH is complete. This Example indicates the im provement achieved when the MX or LMX, is em Example No. MX Conversion% Selectivity VCH% ployed. NaCl 56 00 NaNO 10.5 100 EXAMPLES 53-54 s MgCl, 84 100 CaCl, 91.5 100 Examples 1-44 were repeated to illustrate the influ 5 SrCl 58 100 ence of water. The results are shown in Table III below 5 BaCl 68.0 100 7 B Cl 82.0 100 and it will be observed that for the same amount of AlCl 95.0 100 10 time, the conversion of butadiene is greater with the ABI 34.0 00 O GaCl 97.5 97 hydrated material. 1 nCl 98.8 00 2 TIC 96.5 00 TABLE II 3 Gec 96.5 100 4 SnCl 98 100 L5 SnCl 97.5 100 15 Ex. No. MXch,O Conversion% Selectivity VCH % 6 CuCl 99.5 100 7 CuCl 80.5 OO 53 CoCl2.6HO 99.5 100 8 AgNO3 90 00 37 CoCl 35.5 100 9 AuCla 98.5 100 54 NiCl6HO OO 100 20 ZnCl2 99.5 00 41 NiCl, 4.5 100 21 CodCl 99 100 22 HgCl, 38 100 20 3 TiCl 8 100 4 2rCl 81 99 EXAMPLES 55-59 HfCl 97 OO 6 ThCl 95 99 7 W Cl 62 100 Inflfuence of Water on the Catalyst 8 CrCl 97.5 100 These Examples show the influence of different 29 MoCls 68 OO 25 30 W Cl 97 100 quantities of water present in the catalyst (NaFe(- 3. MnCl 80 99.7 CO)NO) -- ZnCl2. The procedure of Examples 1-44 32 ReCl 98.5 100 33 FeCl 37 100 was followed except that in Example 55, the sodium tri 34 FeCl 98.5 00 35 RuCl 00 100 carbonyl nitrosyl ferrate was used in aqueous solution. 36 OsCl 99 100 37 CoCl 35.5 100 38 CoCl 98.5 100 TABLE IV 39 RhCl 96.5 100 O IrCl3 97 OO mM HO/mN 4. NiCl 4.5 100 Example Complex Conversion a Selectivity VCH 76 42 PdCl 81 100 43 PtCl 90 00 35 55 pure HO 11 100 4 PtCl 81.5 OO 56 98 99.5 57 2 99 99.5 58 4. 99.5 99.5 59 8 98 99.5 EXAMPLES 45-51 The procedure of Examples 1-44 was repeated ex 40 cept that the MX was replaced with LM'X. The di In Example 55, the catalyst converted only small merization time was 5 hours except in Example 48 quantities of the butadiene with concurrent total selec where a period of 16 hours was used. The results are tivity to VCH. This Example shows that too much shown in the following Table II and it will be noted that water should be avoided. Quantities of water between the zinc complex gave the best results while the tin and 45 1 and 8, and preferably between 2 and 4, moles per palladium complexes also gave convenient results. mole of the complex gives the best results. TABLE II EXAMPLES 60-63 Influence of Iron Anion Conver- Selectivity 50 These Examples show the influence on the conver Ex. LMX sion 6 VCH% sion by the kind of iron anion in the valence states 2 45 dichlorozinc bipyridine 100 100 and 3. All other conditions were the same as described 46 dichlorotin bipyridine 98 00 47 dichloronickel bipyridine 76 100 in Examples 1-44. 48 dichloropalladium bipyridine 96.5 100 49 dichloronickel bis pyridine 94.5 95 55 TABLE V 50 dichloronickel-bis(tri phenylphosphine) 2O OO 51 dichloronickel-bis(diphenyl MX phosphino)ethane 47 100 Example Iron Salt Conversion 96 Selectivity VCH% 33 FeCl 37 100 60 FeBr 99.5 100 60 6 Fel OO 100 EXAMPLE 52 62 Fe(acetyl acetonate) 100 00 34 FeCl 98.5 100 A suspension of 193 mg (1 mmole) of sodium tricar 63 Fe(acetyl bonyl nitrosyl ferrate in 5 ml of toluene was placed in acetonate) 98.0 100 the autoclave and 16.2 g (300 mmole) of liquid butadi 65 ene was added at -20 C. The reaction mixture was brought to 60° C. and agitated for 5 hours. At the end Iron acetylacetonate (Example 62) gives the best re of this period, the conversion of butadiene is 37% and sults with conversion and selectivity being 100%. Addi 3,897,508 7 8 tionally, the catalyst system is soluble in the toluene. Various changes and modifications can be made in From a practical point of view, however, the use offer the catalyst and process of the present invention with ric chloride appears particularly advantageous. out departing from the spirit and the scope thereof. The various embodiments set forth herein were for the pur EXAMPLES 64-71 pose of further illustrating the invention but were not Influence of Solvent intended to limit it. These Examples show the influence of different sol What is claimed is: vents on the reactivity of the NaFe(CO)NO) -- ZnCl2 1. A process for the dimerization of diolefins of up to catalyst system. The procedure of Examples 1-44 was 10 carbon atoms in the liquid phase comprising con repeated except for the solvent used. The results are 10 tacting the diolefin in solution in an inert solvent at a shown in the following Table. It will be noted that the temperature between 20-120° C. with a dimerization utility of tetrahydrofuran is very advantageous because catalytic amount of up to iO mmole percent of a cata it facilitates the solubilization of sodium tricarbonyl ni lyst which is the reaction product of an alkali metal or trosyl ferrate. alkaline earth metal salt of a tricarbonyl nitrosyl ferrate 15 TABLE VI anion and a metal halogen or pseudo-halogen com pound or complex, wherein said alkali metal or alkaline Select earth metal salt is of the formula M'Fe(CO)3(NO), Example Solvent Conversion 96 ivity VCH 96 in which m is 1 when M is an alkali metal and m is 2 64 hexane 99.0 99.5 when M is an alkaline earth metal, and wherein said 65 ether 98.5 100 metal halogen or pseudo-halogen compound or com 66 tetrahydrofuran 100 100 67 acetce 98.5 100 plex thereof is of the formula LMX in which M' is a 68 chlorobenzene 99.5 100 metal of Groups IA, II, III, IV, V, VIB, VIIB or VIII of 69 dichloroethane 98 100 the Periodic Table, X is halogen, cyanide, sulfocyanide, 70(id 20) toluene 99.5 100 7 vinylcyclohexene 83 OO isocyanate, nitrate, nitrite, sulfate, acetylacetonate, or 25 carboxylate, L is a chalcogen or pnicogen ligand, p is an integer of 0-6 and n is an integer of 1-6. EXAMPLE 72 2. The process of claim 1 wherein said catalytic amount is about 0.33 mmole percent. Dimerization of Isoprene 30 3. The process of claim 1 wherein said temperature The catalyst was prepared according to the proce is 40-80 C. dure in Examples 1-44 using sodium tricarbonyl nitro 4. The process of claim 1 wherein said alkali metal or syl ferrate and zinc chloride. In place of the butadiene, alkaline earth metal salt is sodium tricarbonyl nitrosyl 20.4 g (300 mmoles) of isoprene was used. After deac ferrate. tivation of the catalyst with dilute hydrochloric acid 35 5. The process of claim 4 wherein said LMX is se and distillation of the solvent, the dimers of isoprene lected from the group consisting of stannous chloride, are recovered. The conversion of isoprene was found stannic chloride, zinc chloride and ferric chloride. to be 98% and selectivity to dimers was 100%. 6. The process of claim 4 wherein said LMX is se lected from the group consisting of dichlorozinc bipyri EXAMPLE 73 40 dine and dichlorotin bipyridine. Example 72 was repeated precisely except that the 7. The process of claim 1 wherein the ratio of diolefin introduced into the autoclave was 300 mmoles M'Fe(CO)3(NO) to LMX is between 0.5 n/m and of an equimolar mixture of butadiene and isoprene. 5 n/m. The resulting conversion was 98% for butadiene and 8. The process of claim wherein the ratio of 98% for isoprene. 45 M(Fe(CO)3(NO) to LMX is equal to n/m and the EXAMPLE 74 dimerization process temperature is between 40°-90° C. Dimerization of a C Fraction 9. The process of claim 1 wherein the reaction me Example 72 was repeated except that the diolefin re dium contains between 1 and 8 moles of water per mole actant used was 20 g of a steam cracked CA fraction 50 of catalyst. containing 38% butadiene. At the termination of the 10. The process of claim 9 wherein the reaction me reaction, 35% of the butadiene was found to have been dium contains between 2 and 4 moles of water per mole converted to VCH. of catalytic complex. 11. The process of claim 1 wherein the inert solvent EXAMPLE 75 55 is selected from the group consisting of toluene, hex Dimerization of Norbornadiene ane, tetrahydrofuran and vinylcyclohexene. The catalyst of Example 72 was placed in a Schlenk 12. The process of claim 1 wherein the diolefin is se tube and then 15 g of bicyclo-2,2,1)-heptadiene (nor lected from the group consisting of butadiene, iso bornadiene) was added. The mixture was heated at 85 60 prene, norbornadiene and mixtures thereof. C. for 3 hours, the catalyst inactivated with dilute hy 13. The process of claim 1 wherein said diolefin is a drochloric acid and the solvent distilled. 98% of the refinery C4 fraction containing butadiene and butenes. norbornadiene was converted to dimers. sk k is k :