USOO5719313A United States Patent (19) 11 Patent Number: 5,719,313 Drent et al. 45) Date of Patent: Feb. 17, 1998

54 CARBONYLATION CATALYST SYSTEMAND 5,258,546 1/1993 Klusener et al...... 560f2O7 A PROCESS FOR THE CARBONYLATON 5,350,876 9/1994 Drent et al...... 560/207 OF ACETYLENICALLY UNSATURATED 5,414,109 5/1995 Drent et al...... 560/2O7 COMPOUNDS 5,436,356 7/1995 Drent et al...... 554/129 FOREIGN PATENT DOCUMENTS I75) Inventors: Eit Drent; Willem Wabe Jager, both of Amsterdam, Netherlands 0233759 8/1987 European Pat. Off...... 560/2O7 0441446 8/1991 European Pat. Off...... 560/307 O565199 10/1993 European Pat. Off. . ... 560/207 73) Assignee: Shell Oil Company, Houston, Tex. WO95/05357 2/1995 WIPO ...... 560/2O7 (21) Appl. No.: 614,563 Primary Examiner-Floyd D. Higel Attorney, Agent, or Firm-Del S. Christensen 22 Filed: Mar 13, 1996 30 Foreign Application Priority Data 57 ABSTRACT The invention relates to a novel carbonylation catalyst Mar. 16, 1995 EP European Pat. Off...... 952OO643 system and a process for the carbonylation of acetylenically (51) Int. Cl...... C07C 67/36; CO7C 51/14; unsaturated compounds, whereby a feedstock, comprising CO7C 67/38; CO7C 69/54; B01J 31/02; an acetylenically unsaturated compound and a relatively BO 31/24 minor amount of an 1.2-alkadiene compound, is contacted (52) U.S. C...... 560/207; 560/97; 560/104; under carbonylation conditions with monoxide and a 554/129 hydroxylated co-reactant in the presence of the novel car 58) Field of Search ...... 560/207: 502/167 bonylation catalyst system that is based on: a) a source of cations of one or more metals of Group VIII (56) References Cited of the Periodic Table; b) a of the general formulae PRRR, RRM U.S. PATENT DOCUMENTS R-PRR, or RRM-R-PR'R'', wherein R repre 4,739,109 4/1988 Drent ...... 56O2O7 sents a substituted or non-substituted 6-membered het 4,739,110 4/1988 ... 560/2O7 eroaryl group having at least one imino atom 483,187 5/1989 56O107 next to the carbon atom that is attached to the phosphorus 4.940,787 7/1990 ... 536,124 atom; R represents a halogenated aryl group; R or each 5,028,576 7/1991 ... 502/167 of the R's represents a substituted or non-substituted 5,099,062 3/1992 560/2O7 (hetero)hydrocarbyl group, M is an element of Group Va, 5,103,043 4/1992 ... 560/2O7 preferably a nitrogen or phosphorus atom, R represents a 5,149,868 9/1992 ... S62497 5,158,921 10/1992 502/167 bridging (substituted) hydrocarbyl group having 1 to 4 5,166,411 11/1992 ... S6O2O7 carbon atoms in the bridge; and 5,177.253 1/1993 56O2O7 c) a source of protons. 5,179.225 1/1993 ... 56O2O7 5,189,003 2/1993 Klusener et al...... 502,167 11 Claims, No Drawings 5,719,313 1 2 CARBONYLATION CATALYST SYSTEMAND osmium, but in particular nickel, palladium and platinum. A PROCESS FOR THE CARBONYLATION Preferably, the catalyst system is based on a source of OF ACETYLENICALLY UNSATURATED palladium cations. COMPOUNDS The source of cations of metals of Group VIII may be the FIELD OF THE INVENTION metallic element or a metal compound, such as a metal salt The invention relates to a novel carbonylation catalyst or a complex of the metal with a phosphine, with carbon system and a process for the carbonylation of acetylenically monoxide or with acetylacetonate. It is advantageously a unsaturated compounds, whereby a feedstock, comprising metal compound, in particular a metal salt. Examples of an acetylenically unsaturated compound and a relatively suitable metal salts are salts of sulfuric acid, nitric acid, minor amount of an 1.2-alkadiene compound, is contacted O sulfonic acids, phosphonic acids, perhalic acids and car under carbonylation conditions with and a boxylic acids, such as carboxylic acids with 1 to 12 hydroxylated co-reactant in the presence of the novel car carbon atoms, for example and propionic acid, or bonylation catalyst system. halogenated carboxylic acids, for example trichloroacetic BACKGROUND TO THE INVENTION acid and trifluoroacetic acid. Palladium acetate has proved to 15 be a particularly suitable source of metal cations. Generally, the feedstocks available for the carbonylation of acetylenically unsaturated compounds additionally con As regards component b) of the catalyst system, R' may tain 1.2-alkadiene compounds (so-called ). Typically, for instance be a 2-pyridyl-, or the radical of any of the the presence of these 1.2 alkadiene compounds, even in diazines, triazines or tetrazines. Moreover, the 6-membered relatively small amounts (say up to 0.4%), unfavorably ring system may be part of a larger, fused ring system (e.g., affects the activity of the catalyst system. Therefore, special 20 (iso)quinolinyl-, a radical of any of the benzodiazines or measures to purify the feedstocks need to be taken, before benzotriazines). Preferably, the phosphine is substituted they can be used for the carbonylation process. with a 2-pyridyl group. Suitable substituents on the In International application WO95/05357, a carbonyla 6-membered heteroaryl group include alkyl groups, for tion catalyst system is disclosed, that comprises a certain example methyl and ethyl groups, amino and (di)alkylamino (mono or bidentate) (di)phosphine bearing for instance 25 groups and halogen atoms. 6-halo-2-pyridyl groups on the phosphorus atomas ligand to R’ is a phenyl group or a larger aryl group having at least the transition metal, that easily outperforms the already fine one or more halogen atoms substituted thereon. Suitably, the catalyst system disclosed in EP-A-0.441.446 and even per halogen atoms are chlorine or bromine atoms. More suitably, forms satisfactorily in the presence of 7.0% v of 12 R’ is a phenyl group having one or more chlorine atoms alkadiene impurities. However, it remains desirable to be 30 substituted thereon. The location of the or each halogen able to use alternative catalyst systems of at least similar atom is not very important, i.e., excellent results have been competence. Moreover, as the carbonylation reaction pro achieved with meta-chlorine substituents. duces heat, a carbonylation catalyst system is looked for that R or each of the R's preferably represents a substituted on the one hand can feed on feedstocks comprising an or unsubstituted pyridyl, alkyl or aryl group, and-more acetylenically unsaturated compound and a relatively minor 35 preferably-is identical to either R' or R. Examples of amount of an 1.2-alkadienes, and on the other hand is stable suitable R groups are 2-pyridyl, phenyl, tolyi, xylyl, and at temperatures in the range of 70 to 100° C. cyclohexyl groups and alkyl groups having from 3 to 7 SUMMARY OF THE INVENTION carbon atoms. wherein both RandR represent The invention may be defined as relating to a novel a halogenated phenyl group are preferred. carbonylation catalyst system and to a process for the Preferably, the phosphine is a monophosphine of the carbonylation of acetylenically unsaturated compounds, general formula PR'R'R''. whereby a feedstock comprising an acetylenically unsatur As regards component c) of the catalyst system, the ated compound and a relatively minor amount of an 1.2- source of protons may be provided by a protonic acid or alkadiene compound is contacted under carbonylation con even traces . Indeed, the protonic acid may be gener ditions with carbon monoxide and a hydroxylated ated in situ, for instance, upon addition of a Lewis acid to the co-reactant, in the presence of the novel catalyst system. The hydroxylated co-reactant, or by carbonylation of the acety novel catalyst system is based on: lenically unsaturated compound with water into the corre a) a source of cations of one or more metals of Group VIII sponding acid. Lewis acids that are suitably used include of the Periodic Table; 50 halogenated arylborates, BF, AIC, Snf Sn(CFSO) b) a phosphine of the general formulae PR'R'R'', SnCl2, Gecl and PFs. RRM-R-PRR, or RRM-R-PR'R'', wherein R Preferably, the protonic acid has a substantially non represents a substituted or non-substituted 6-membered het coordinating anion, i.e. an anion which does not, or only to eroaryl group having at least one imino nitrogen aton next a very minor extent, coordinate with the metal of Group to the carbon atom that is attached to the phosphorus atom; 55 VIII. Preferred acids in this respect include: sulfuric acid; R’ represents a halogenated aryl group; R or each of the sulfonic acids; halogenated carboxylic acids such as trifluo R's represents a substituted or non-substituted (hetero) roacetic acid; perhalic acids such as perchloric acid, and hydrocarbyl group, M is an element of Group Va, preferably acidic ion exchange resins such as a sulphonated ion a nitrogen or phosphorus atom, R represents a bridging exchange resin. Optionally substituted alkylsulfonic acids, such as methanesulfonic acid, trifluoromethanesulfonic acid (substituted) hydrocarbyl group having 1 to 4 carbon atoms and tert-butylsulfonic acid are examples of very preferred in the bridge; and protonic acids. c) a source of protons. The number of moles of phosphine and of moles of DESCRIPTION OF THE PREFERRED protonic acid permole (of atoms) of the metal of Group VII EMBODMENT 65 may vary considerably. Recommended phosphine amounts The metals as regards componenta) of the catalyst system are in the range of 10 to 100 moles of phosphine per mole include iron, cobalt, ruthenium, rhodium, iridium, and of the metal of Group VIII and in particular in the range of 5,719,313 3 4 20 to 80. The amount of protonic acid is preferably selected As soon as the falling pressure remained constant such that per mole of the metal of Group VIII, 2 to 500 moles (marking the completion of the reaction), the contents of the of protonic acid are present. autoclave were cooled and a sample was withdrawn and The catalyst system of the invention may be homoge analyzed by gas liquid chromatography. neous or heterogeneous. Preferably, it is homogeneous. The amount in which the catalyst is applied in the process of the Example I invention is suitably selected such that per mole of acety a) An experiment was carried out in the manner as lenically unsaturated compound to be converted, from 10 outlined above, whereby as phosphine 2 mmol (0.53 g) of to 10' mole of the Group VIII metal is present, preferably bisphenyl(2-pyridyl)phosphine and as protonic acid 2 mmol from 107 to 10° on the same basis. 10 (130 l) of methanesulfonic acid was used. The feed was Suitable acetylenically unsaturated compounds, to be propyne, containing 1.9% of . The reaction tem used as starting material in the process of the invention, perature was 90 C. include optionally substituted with 2 to 20 carbon The reaction time (completion) was 1 hour. Analysis atoms per . Examples are , propyne, 1-, 2-butyne, 1-, phenyl acetylene and benzyl showed that methyl methacrylate (MMA) had been formed ethyne. Preferably, unsubstituted alkynes with 3 to 10 car 15 with a selectivity of 98.7% at a propyne conversion of about bon atoms are used. 100%. The average reaction rate was calculated to be 25,800 In view of the industrial outlets for the carbonylated moles of product per mole of palladium and per hour products, propyne is a preferred starting material. (mol/mol.hr). As has been stated above, a major advantage of the b) The experiment described under a) was repeated at 80° catalyst systems of the invention consists in their tolerance 20 C. with the difference that as phosphine 2 mmol (0.66 g) of towards 12-alkadiene compounds in the acetylenic feed bis(3-chlorophenyl)(2-pyridyl)phosphine was used. stocks. Accordingly, commercially available feedstocks may The reaction time was 1 hour. Analysis showed that MMA be used that containing small amounts of 1,2-alkadiene had been formed with a selectivity of about 98.5% at a compounds, such as propadiene, in addition to the acety propyne conversion of about 100%. The average reaction lenically unsaturated compounds. In general, a 12-alkadiene rate was calculated to be 50,000 mol/mol.hr, content of at most 0.1 mole per mole (e.g., 10%), based on Example II acetylenically unsaturated compound, can be tolerated. It is a) An experiment was carried out in the manner as recommended to use feedstocks in which the amount of outlined above, whereby as phosphine 1 mmol (0.26 g) of 1.2alkadiene compounds is lower, suitably in the range of 30 bisphenyl(2-pyridyl)phosphine and as protonic acid 2 mmol 0.002 to 0.05 moles per mole of acetylenically unsaturated (130 ul) of methanesulfonic acid were used. The feed was compound. propyne, containing 2.3% of propadiene. The reaction tem The hydroxylated co-reactant may be any hydroxyl perature was 90° C. containing compound such as a monohydric, dihydric or The reaction time (completion) was 5 hours. Analysis polyhydric alkanol, a phenol, or water. 35 showed that MMA had been formed with a selectivity of Monohydric alkanols are preferred, in particular those 98.6% at a propyne conversion of about 84%. The average having from 1 to 4 carbon atoms. Among these, is reaction rate was calculated to be 5,000 mol/mol.hr, most preferred. b) The experiment described under a) was repeated at 80° The co-reactant is suitably used in excess, thereby avoid C. with the difference that as phosphine 1 mmol (0.33 g) of ing the need of a separate diluent or solvent. However, a bis(3-chlorophenyl)(2-pyridyl)phosphine was used. liquid diluent may be applied, if so desired. Preferably, The reaction time was 10 hours. Analysis showed that non-alkaline diluents are used, such as ketones, e.g. MMA had been formed with a selectivity of 98.5% at a methylisobutylketone, or ethers, e.g. dipropylether or 2.5.8- propyne conversion of about 86%. The average reaction rate trioxanonane. was calculated to be 7,200 mol/mol.hr, Owing to the high activity of the catalysts, the process of c) The experiment described under b) was repeated with the invention proceeds readily at moderate reaction condi the difference that as phosphine 2 mmol (0.66 g) of bis(3- tions. Suitable reaction temperatures are, for instance, in the chlorophenyl)(2-pyridyl)phosphine was used. range of 20 to 150° C. preferably in the range of 30 to 100° The reaction time was 2 hours. Analysis showed that C. MMA had been formed with a selectivity of 98.5% at a The reaction pressure is usually selected in the range of 1 5 propyne conversion of about 100%. The average reaction to 100 bar. Preferably, the pressure is in the range of 5 to 70 rate was calculated to be 48,800 mol/mol.hr. bar. The invention is illustrated with the following, non Example III limiting examples. An experiment was carried out in the manner as outlined 55 above, whereby as phosphine 4 mmol (1.42 g) of bis(3- EXAMPLES chlorophenyl)(6-chloro-2-pyridyl)phosphine and as pro All experiments were carried out in a 250 ml "Hastelloy tonic acid 5 mmol (325 ul) of methanesulfonic acid were C” (trade mark) magnetically stirred autoclave. The auto used. The feed was propyne, containing 3.6% of propadiene. clave was charged with 0.025 mmoles (5.6 mg) of palladium The reaction temperature was 80° C. (II) acetate, the selected phosphine and protonic acid in the The reaction time was 1 hour. Analysis showed that MMA amounts indicated hereafter, and 50 ml of methanol. had been formed with a selectivity of 99.6% at a propyne Air was evacuated from the autoclave, whereupon 30 ml conversion of about 100%. The average reaction rate was of a feedstock containing propyne and propadiene was calculated to be 12,000 mol/mol.hr. added. Subsequently, carbon monoxide was supplied up to a 65 Example IV pressure of 60 bar. The autoclave was sealed and heated to An experiment was carried out in the manner as outlined the desired reaction temperature. above, whereby as phosphine 2 mmol (0.71 g) of bis(3- 5,719,313 5 6 chlorophenyl)(6-chloro-2-pyridyl)phosphine and as pro 5. The catalyst of claim 1 wherein component b) com tonic acid 2 mmol (180 ul) of trifluoromethanesulfonic acid prises a phosphine wherein R represents a phenyl group were used. The feed was propyne, containing 5.1% of having one or more chlorine atoms substituted thereon. propadiene. The reaction temperature was 85 C. 6. A catalyst of claim 1 wherein component b) comprises The reaction time was 5 hours. Analysis showed that 5 a phosphine wherein R or each of the R's represents a MMA had been formed with a selectivity of 99.6% at a substituted or non-substituted pyridyl, alkyl or aryl group. propyne conversion of about 86%. The average reaction rate 7. A catalyst of claim 5 wherein component b) comprises was calculated to be 12,500 mol/mol.hr, aphosphine wherein both RandR represent a halogenated These examples demonstrate that the catalyst systems of phenyl group. the present invention (alike the comparative catalyst system 10 8. A process for the carbonylation of acetylenically unsat based on a non-substituted phosphine) are sufficiently stable urated compounds, the process comprising the steps of: at elevated temperatures. providing a feedstock, the feedstock comprising an acety In comparative Examples (a) and I(a), with a non lenically unsaturated compound and a relatively minor substituted phosphine as catalyst component, the reaction amount of an 12-alkadiene compound; rates for convening feedstocks containing propadiene are 5 contacting the feedstock, under conditions effective to low even at high temperatures due to the (inhibitive) pres carbonylate the feedstock, with carbon monoxide and a ence of the propadiene. In Examples I(b), I(b), and I(c), hydroxylated co-reactant, in the presence of a catalyst however, the use of the halogenated phosphines of the system comprising present invention results in considerably higher reaction 20 a) a source of cations of one or more metals of Group VIII rates. Indeed, in Examples III and IV, a feedstock compris of the Periodic Table, ing 3.6%, respectively 5.1% of propadiene was convened at b) a phosphine selected from the group consisting of high yield and selectivity, RRM-R-PRR and RRM-R-PRR, We claim: wherein R' represents a substituted or non-substituted 1. A carbonylation catalyst comprising: 25 6-membered heteroaryl group having at least one imino a) a source of cations of one or more metals of Group VIII nitrogen atom next to the carbon atom that is attached of the Periodic Table; to the phosphorus atom; R represents a halogenated b) a phosphine of the general formula selected from the aryl group; R or each of the R's represents a substi group consisting of R'R'M-R-PRR, and tuted or non-substituted (hetero)hydrocarbyl group, M RRM-R-PR'R'', wherein R' represents a substi 30 is an element of Group Va., R represents a bridging tuted or non-substituted 6-membered heteroaryl group hydrocarbyl group having 1 to 4 carbon atoms in the having at least one imino nitrogen atom next to the bridge, and carbonatomthat is attached to the phosphorus atom; R' c) a source of protons; and recovering the carbonylated represents a halogenated aryl group; R or each of the feedstock. R's represents a substituted or non-substituted (hetero) 35 9. The process of claim 8, wherein the amount of 1.2- hydrocarbyl group, M is an element of Group Va, R alkadiene compound in the feedstock is less than 0.1 mole represents a bridging hydrocarbyl group having 1 to 4 per mole of acetylenically unsaturated compound. carbon atoms in the bridge; and 10. The process of claim 9, wherein the molar amount of c) a source of protons. 1.2-alkadiene compound in the feedstock per mole of acety 2. The catalyst of claim 1, wherein the metal of compo 40 lenically unsaturated compound is in the range of 0.002 to nent a) is selected from the group consisting of nickel, 0.05. platinum and palladium. 11. The process of claim 8 wherein the recovered carbo 3. The catalyst of claim 1, wherein the metal of compo nylated feedstock is methyl methacrylate and the feedstock nent a) is palladium. comprises propyne and 1,2-propadiene. 4. The catalyst of claim 1, wherein component b) com 45 prises a phosphine wherein R' represents a 2-pyridyl group. ck sk x 2k xk