A carbonylation reaction catalyst and its application

Abstract

The present invention discloses a carbonylation reaction catalyst and its application, wherein the catalyst comprises at least one metal or compound of group VIB or group VIII; a bidentate nitrogen ligand; an acid; and the catalyst is used for carbonylation of olefinic unsaturated compounds. The catalyst of the present invention has excellent catalytic activity, stable catalyst activity, high reaction selectivity and high conversion rate.

Description

Technical Field

[0001] The invention relates to the field of carbonylation reaction, in particular to a carbonylation reaction catalyst and its role in the carbonylation reaction of olefinic unsaturated compounds. Background Art

[0002] The products of carbonylation reactions are widely used in the synthesis of fine chemicals and bulk chemicals; at the same time, the high value-added products of carbonylation reactions also have very important uses in people's lives. The carbonylation reaction with olefinic unsaturated compounds as substrates is the most widely used.

[0003] At present, the carbonylation reaction mainly adopts the catalytic system of palladium metal and phosphine ligand, for example EP-A-0386833, EP-A-0235864, EP-A-0489472, EP-A-0282142, EP-A-0106379, EP-A-0055875, EP-A-0499329, EP-A-0495548, EP-A-0274795, EP-A-0441447, EP-A-0495547 and EP-A-0227160. The above patents disclose a method for carbonylating ethylene using carbon monoxide in the presence of alcohol or water and a catalyst system, wherein the catalyst system includes a Group VIII metal such as palladium and a phosphine ligand. In particular, EP-A-0227160, EP-A-0495547 and EP-A-0495548 disclose that certain bidentate phosphine ligands provide catalyst systems capable of achieving higher reaction rates.

[0004] The common problem of the above-disclosed catalyst systems is that although a high reaction rate can be obtained, the metal active sites are easily reduced and deactivated during the reaction, so the catalyst needs to be frequently added. At the same time, the metal active sites are easily clustered after precipitation during the reaction and form mirror images on the reactor wall, resulting in difficulties in catalyst recovery, low recovery rate and high recovery cost, making these methods uncompetitive in industry.

[0005] How to develop a new carbonylation catalyst with stable activity, high catalytic activity and high reaction selectivity is of great significance. Summary of the invention

[0006] The object of the present invention is to provide a carbonylation reaction catalyst and application, which has excellent catalytic activity, stable catalyst activity, high reaction selectivity and high conversion rate. The methylene structure of the diphosphine ligand used in the prior art is easily oxidized, resulting in a decrease in catalyst activity. Along with the oxidative decomposition of the ligand, the metal active site is prone to form clusters, which further reduces the catalytic activity. The nitrogen ligand provided by the present invention is a relatively stable aromatic ring structure, which can be tightly chelated with the metal active center to form a stable metal complex, thereby improving the stability of the catalyst system.

[0007] According to a first aspect of the present invention, there is provided a carbonylation reaction catalyst comprising the following components:

[0008] (a) at least one Group VIB or Group VIII metal or a compound thereof;

[0009] (b) a bidentate nitrogen ligand of the general formula (I);

[0010] (c) Acid.

[0011]

[0012] R represents an alkyl group, an aryl group or a heterocyclic group having a large steric hindrance, preferably tert-butyl, neopentyl, 1-adamantyl, 2-pyridyl, 2-quinolyl, indenyl and 1-indolyl.

[0013] Wherein, the metal of Group VIB or Group VIII includes one or more of Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt or Pd, preferably selected from Ru, Pt or Pd, more preferably the metal is Pd;

[0014] Wherein, X represents O, S or an amino group; the amino group may further be connected to a substituent.

[0015] Preferably, X is an aryl-substituted amino group, and more preferably the structure represented by general formula (II):

[0016]

[0017] R is as defined in the general formula (I).

[0018] R' represents a substituent on the benzene ring, which can be hydrogen, a monosubstituted or polysubstituted alkyl, alkoxy, perfluoroalkyl, mercapto, ester, aryl, heterocyclic, halogen, cyano, nitro, preferably hydrogen, 4-methyl, 4-methoxy, 4-trifluoromethyl, 4-tert-butyl.

[0019] Suitable compounds of the above-mentioned Group VIB or Group VIII metals include salts of these metals with the following substances: nitric acid; sulfuric acid; lower alkanoic acids (up to C10), such as acetic acid and propionic acid; sulfonic acids or alkylsulfonic acids, such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid; halogenated carboxylic acids, such as trichloroacetic acid and trifluoroacetic acid; orthophosphoric acid; acids derived from the interaction of Lewis acids and Brewster acids.

[0020] The acid is selected from acids having a pKa value of less than 4, more preferably less than 3, most preferably less than 2, measured in aqueous solution at 18°C.

[0021] Preferably, the acid includes nitric acid, sulfuric acid, C1-C10 alkyl acids (such as acetic acid and propionic acid), sulfonic acids or alkylsulfonic acids (such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid), halogenated carboxylic acids (trichloroacetic acid and trifluoroacetic acid), orthophosphoric acid, and acids derived from the interaction of Lewis acids and Brewster acids.

[0022] Preferably, the acid is a sulfonic acid or an alkylsulfonic acid having a pKa value below 2 measured in aqueous solution at 18°C, even more preferably the acid is selected from the following sulfonic acids: methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, most preferably the acid is methanesulfonic acid.

[0023] Preferably, the molar ratio of Group VIB and Group VIII metals to bidentate nitrogen ligands in component (a) is 1:0.5 to 1:150, more preferably 1:1 to 1:50, most preferably 1:1 to 1:10.

[0024] Preferably, the molar ratio of Group VIB and Group VIII metals to acid in component (a) is from 1:1 to 1:150, more preferably from 1:1 to 1:50, most preferably from 1:2 to 1:10.

[0025] Preferably, the bidentate nitrogen ligand includes but is not limited to the following structure:

[0026]

[0027] The present invention also provides the use of the catalyst in a carbonylation reaction. Specifically, the catalyst of the present invention is used for the carbonylation reaction of olefinic unsaturated compounds, and the olefinic unsaturated compounds are subjected to a carbonylation reaction with carbon monoxide in the presence of a hydroxyl compound and the catalyst of the present invention.

[0028] The olefinic unsaturated compound is a straight-chain or branched olefin or alkyne containing one or more unsaturated bonds, preferably 1-3 unsaturated bonds, which may be unsubstituted or substituted by an alkyl group, an aryl group, or a heteroatom-containing group, preferably ethylene, propylene, heptene, octene, and 1,3-butadiene, and more preferably ethylene;

[0029] Preferably, the hydroxyl-containing compound is methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol or 1-hexanol, more preferably methanol;

[0030] The carbonylation reaction temperature is 50-180°C, preferably 70-110°C;

[0031] The carbonylation reaction pressure is 0-7 MPa, preferably 0.6-3.0 MPa.

[0032] The amount of the catalyst can be added according to common knowledge in the art. Preferably, the amount of the active metal component of Group VIB or Group VIIIB in each kilogram of the reaction solution is 1-200*10 -5 Mol preferably 2-100*10 -5 mol.

[0033] The catalyst system of the invention is used to catalyze the reaction of ethylene, carbon monoxide and methanol to prepare methyl propionate.

[0034] Compared with the prior art, the present invention has the following advantages: the nitrogen ligand provided by the present invention is a relatively stable aromatic ring structure, which can be tightly chelated with the metal active center to form a stable metal complex, thereby improving the stability of the catalyst system. The bidentate nitrogen structure chelates with the metal site, which can greatly improve the coordination insertion ability of the metal to the olefinic unsaturated compound; and the large steric hindrance R group makes it easier to remove the product from the intermediate, thereby significantly improving the reaction rate; the quinoline group and the nitrogen-containing five-membered ring in the ligand can both serve as proton transport media for the alcohol, promoting the alcoholysis of the palladium acyl substance, which is beneficial to the carbonylation reaction of the olefinic unsaturated compound. Therefore, the catalyst system provided by the present invention has the advantages of stable catalytic activity, high reaction conversion rate, and high selectivity. DETAILED DESCRIPTION

[0035] The following examples further illustrate the present invention. These embodiments should be considered as the description of the disclosed specific materials falling into the wider range stated above, and should not be considered as limiting the disclosure of the wider range in any way. Raw material sources: 8-quinolinecarboxylic acid (cas: 86-59-9, Macklin), tert-leucinol (cas: 3907-02-6, Shanghai Kairui Biotechnology Co., Ltd.), valinol (cas: 16369-05-4, Myril), phenylglycinol (cas: 7568-92-5, Myril).

[0036] Glossary:

[0037] (1) TON = the amount of methyl propionate generated during the reaction in mol / the total amount of metal added in mol;

[0038] (2) TOF = molar amount of methyl propionate generated per unit time / molar amount of metal required for the reaction.

[0039] Ligand Preparation Example 1

[0040] Preparation of 4-tert-butyl-2-(8-quinolyl)-4,5-dihydrooxazole (L1):

[0041]

[0042] 8-Quinolinecarboxylic acid (17.3 g, 0.1 mol) was dissolved in thionyl chloride (135.0 g, 1.0 mol), heated to reflux for 3 hours, and 8-quinolinecarbonyl chloride was obtained after rotary evaporation. 8-Quinolinecarbonyl chloride was dissolved in chloroform (200 mL), and then tert-leucine alcohol (14.1 g, 0.12 mol) and triethylamine (60 mL) were added dropwise at -10 ° C. After stirring at room temperature for 24 hours, a white solid was obtained by column chromatography. It was then dissolved in thionyl chloride (135.0 g, 1.0 mol), heated to reflux for 2 hours, and a yellow solid was obtained after rotary evaporation. The yellow solid and sodium hydroxide (6.0 g, 0.15 mol) were dissolved in methanol (500 mL), heated to reflux for 15 hours, dried over potassium carbonate and filtered through a Buchner funnel. The volatiles were removed by rotary evaporation and finally dried in a vacuum to obtain a milky white powder L1 with a yield of 14.3 g.

[0043] 1 H NMR (400MHz, CDCl3): δ9.03(dd,J=4.2and 1.8Hz,1H), 8.16(dd,J=8.3and1.8Hz,1H), 8.08(dd,J=7.1and 1.5Hz,1H), 7.90(dd,J=8.2and 1.5Hz,1H),7.56(dd,J=8.2and 7.2Hz,1H),7.42(dd,J=8.3and 4.2Hz,1H),4.57(dd,J=10.1and 8.6Hz,1H),4.39(t,J=8.0Hz,1H),4.20(dd,J=10.1and 8.0Hz, 1H), 1.05 (d, J = 3.4Hz, 9H).

[0044] Ligand Preparation Example 2

[0045] Preparation of 4-isopropyl-2-(8-quinolyl)-4,5-dihydrooxazole (L2):

[0046]

[0047] The main difference between the preparation method of L2 and the preparation method of L1 is that 12.4 g (0.12 mol) of valinol is used instead of tert-leucinol, and the rest is the same as the preparation method of L1.

[0048] 1 H NMR (400MHz, CDCl3): δ8.96(dd,J=4.2and 1.7Hz,1H), 8.07(dd,J=8.3and1.7Hz,1H), 8.02(dd,J=7.2and 1.3Hz,1H), 7.80(dd,J=8.3and 1.4Hz,1H),7.46(dd,J=8.0and 1.3Hz,1H),7.33(dd,J=8.3and 4.2Hz,1H),4.15–4.30(m,2H),4.43–4.60(m,1H),1.82–2.00(m,1H),1.01(d,J=6.8Hz,3H),0.92(d,J=6.8Hz,3H).

[0049] Ligand Preparation Example 3

[0050] Preparation of 4-phenyl-2-(8-quinolyl)-4,5-dihydrooxazole (L3):

[0051]

[0052] The main difference between the preparation method of L3 and the preparation method of L1 is that 16.5 g (0.12 mol) of phenylglycinol is used instead of tert-leucinol, and the rest is the same as the preparation method of L1.

[0053] 1 H NMR (400MHz, CDCl3): δ9.11(dd,J=4.3and 1.7Hz,1H), 8.25(dd,J=7.2and1.3Hz,1H), 8.21(dd,J=8.3and 1.7Hz,1H), 7.96(dd,J=8.2and 1.3Hz,1H),7.60(t,J=7.8Hz,1H),7.20–7.55(m,6H),5.58(dd,J=10.2and 8.1Hz,1H),4.98(dd,J=10.2and1.7Hz,1H),4.45(t,J=8.3Hz,1H).

[0054] Ligand Preparation Example 4

[0055] Preparation of 4-tert-butyl-2-(8-quinolyl)-4,5-dihydrothiazole (L4)

[0056]

[0057] 8-Quinolinecarboxylic acid (17.3 g, 0.1 mol) was dissolved in thionyl chloride (135.0 g, 1.0 mol), heated to reflux for 3 hours, and 8-quinolinecarbonyl chloride was obtained after rotary evaporation. 8-Quinolinecarbonyl chloride was dissolved in chloroform (200 mL), and then tert-leucine alcohol (14.1 g, 0.12 mol) and triethylamine (60 mL) were added dropwise at -10 ° C. After stirring at room temperature for 24 hours, a white solid was obtained by column chromatography. Then it was dissolved in pyridine (400 mL) together with phosphorus pentasulfide (44.5 g, 0.2 mol), heated to reflux for 20 hours, washed with 20% potassium hydroxide solution and 2.0 M hydrochloric acid, dried with magnesium sulfate and filtered with a Buchner funnel. The volatiles were removed by rotary evaporation, and finally dried in a vacuum to obtain a bright yellow powder L4 with a yield of 22.1 g.

[0058] 1 H NMR (400MHz, CDCl3): δ9.08(dd,J=4.2and 1.8Hz,1H),8.22(dd,J=8.3and1.8Hz,1H),8.11(dd,J=7.1and 1.5Hz,1H),7.96(dd,J=8.2and 1.5Hz,1H),7.61(dd,J=8.2and 7.2Hz,1H),7.48(dd,J=8.3and 4.2Hz,1H),4.62(dd,J=10.1and 8.6Hz,1H),4.52(t,J=8.0Hz,1H),4.22(dd,J=10.1and 8.0Hz,1H),0.94(d,J=3.4Hz,9H).

[0059] Ligand Preparation Example 5

[0060] Preparation of 8-[2-(4-tert-butyl-1-p-tolyl-4,5-dihydroimidazolyl)]quinoline (L5)

[0061] 8-Quinolinecarboxylic acid (17.3g, 0.1mol) was dissolved in thionyl chloride (135.0g, 1.0mol), heated under reflux for 3 hours, and 8-quinolinecarbonyl chloride was obtained after rotary evaporation. 8-Quinolinecarbonyl chloride was dissolved in chloroform (200mL), and then tert-leucine alcohol (14.1g, 0.12mol) and triethylamine (60mL) were added dropwise at -10°C. After stirring at room temperature for 24 hours, a white solid was obtained by column chromatography. It was then dissolved in thionyl chloride (135.0g, 1.0mol), heated under reflux for 2 hours, and a yellow solid was obtained after rotary evaporation. The yellow solid was dissolved in ether (500mL) with p-methylaniline (12.1mL, 0.11mol), and stirred at room temperature for 12 hours. It was washed with 10% sodium hydroxide solution, dried with magnesium sulfate, and filtered through a Buchner funnel. The volatiles were removed by rotary evaporation and finally dried in vacuo to afford brown powder L5 with a yield of 20.1 g.

[0062] 1 H NMR (400MHz, CDCl3): δ8.80(dd,J=4.0,2.0Hz,1H),8.06(dd,J=8.0,2.0Hz,1H),7.86–7.81(m,2H),7.52(dd,J=8.0,7.2Hz,1H),7.29 (dd,J=8.0,4.0Hz,1H),6.70(d,J=8.4Hz,2H),6.56(d,J=8.4Hz,2H),4.21–4.14(m,2H),3.91-3.83(m,1H),2.08(s,3H),1.08(s,9H).

[0063] Ligand Preparation Example 6

[0064] Preparation of 8-[2-(4-methoxy-1-p-tolyl-4,5-dihydroimidazolyl)]quinoline (L6):

[0065]

[0066] The main difference between the preparation method of L6 and the preparation method of L5 is that (12.8 mL, 0.11 mol) of p-methoxyaniline is used instead of tert-p-methylaniline, and the rest is the same as the preparation method of L5.

[0067] 1H NMR (400MHz, CDCl3): δ8.80(dd,J=4.0,1.6Hz,1H),8.05(dd,J=8.4,1.6Hz,1H),7.88(dd,J=7.2,1.6,Hz,1H),7.81(dd,J=8.4,1.6Hz,1H),7.52(dd,J=8. 0,7.2Hz,1H),7.30(dd,J=8.4,4.4Hz,1H),6.71(d,J=8.8Hz,2H),6.46(d,J= 9.2Hz,2H),4.23–4.16(m,2H),3.89–3.84(m,1H),3.59(s,9H),1.09(s,9H).

[0068] Ligand Preparation Example 7

[0069] Preparation of 8-[2-(4-trifluoromethyl-1-p-tolyl-4,5-dihydroimidazolyl)]quinoline (L7):

[0070]

[0071] The main difference between the preparation method of L7 and the preparation method of L5 is that (13.8 mL, 0.11 mol) of p-trifluoromethylaniline is used instead of tert-p-methylaniline, and the rest is the same as the preparation method of L5.

[0072] 1 H NMR (400MHz, CDCl3): δ8.72(dd,J=4.0,1.6Hz,1H),8.10(dd,J=8.4,1.6Hz,1H),7.90(d,J=7.6Hz,2H),7.59(t,J=7.6Hz,1H) ,7.31(dd,J=8.4,4.4Hz,1H),7.11(d,J=8.4,2H),6.58(d,J=8.4Hz,2H),4.19–4.15(m,2H),3.97–3.93(m,1H),1.08(s,9H).

[0073] Example 1

[0074] In the glove box, 1.2 × 10 -5 moles of palladium acetate, 2.4×10 -5 moles of L5 ligand and 6.0×10 -5Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 85°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 1.0 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0075] After calculation, the catalyst TOF was 152169 molMeP / molPd / h, the cumulative TON was 420w molMeP / molPd, the selectivity of methyl propionate was as high as 99.9%, the Pd loss was less than 1%, and there was no obvious metal adhesion on the container wall.

[0076] Example 2

[0077] In the glove box, 1.2 × 10 -5 moles of palladium acetate, 2.4×10 -5 moles of L1 ligand and 6.0×10 -5 Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 85°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 1.0 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0078] After calculation, the catalyst TOF was 130165 molMeP / molPd / h, the cumulative TON was 392w molMeP / molPd, the selectivity of methyl propionate was as high as 99.9%, the Pd loss was less than 1%, and there was no obvious metal adhesion on the container wall.

[0079] Example 3

[0080] In the glove box, 1.2 × 10 -5 moles of palladium acetate, 2.4×10 -5 moles of L2 ligand and 6.0×10 -5Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 70°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 1.0 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0081] After calculation, the catalyst TOF was 111656 molMeP / molPd / h, the cumulative TON was 375w molMeP / molPd, the selectivity of methyl propionate was as high as 99.9%, the Pd loss was less than 1%, and there was no obvious metal adhesion on the container wall.

[0082] Example 4

[0083] In the glove box, 1.2 × 10 -5 moles of palladium acetate, 2.4×10 -5 moles of L3 ligand and 6.0×10 -5 Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 100°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 0.6 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0084] After calculation, the catalyst TOF was 105165 molMeP / molPd / h, the cumulative TON was 366w molMeP / molPd, the selectivity of methyl propionate was as high as 99.9%, the Pd loss was less than 1%, and there was no obvious metal adhesion on the container wall.

[0085] Example 5

[0086] In the glove box, 1.2 × 10 -4 moles of palladium acetate, 2.4×10 -4 moles of L4 ligand and 6.0×10 -4Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 100°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 1.5 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0087] After calculation, the catalyst TOF was 105165 molMeP / molPd / h, the cumulative TON was 366w molMeP / molPd, the selectivity of methyl propionate was as high as 99.9%, the Pd loss was less than 1%, and there was no obvious metal adhesion on the container wall.

[0088] Example 6

[0089] In the glove box, 1.2 × 10 -5 moles of palladium acetate, 1.2×10 -5 moles of L5 ligand and 2.4×10 -5 Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 110°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 1.8 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0090] After calculation, the catalyst TOF was 102019 molMeP / molPd / h, the cumulative TON was 361w molMeP / molPd, the selectivity of methyl propionate was as high as 99.9%, the Pd loss was less than 1%, and there was no obvious metal adhesion on the container wall.

[0091] Example 7

[0092] In the glove box, 1.2 × 10 -5 moles of palladium acetate, 1.2×10 -5 moles of L5 ligand and 1.2 × 10 -4Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 90°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 3.0 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0093] After calculation, the catalyst TOF was 96153 molMeP / molPd / h, the cumulative TON was 355w molMeP / molPd, the selectivity of methyl propionate was as high as 99.9%, the Pd loss was less than 1%, and there was no obvious metal adhesion on the container wall.

[0094] Example 8

[0095] In the glove box, 1.2 × 10 -5 moles of palladium acetate, 6.0×10 -5 moles of L5 ligand and 2.4×10 -5 Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 85°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 2.5 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0096] After calculation, the catalyst TOF was 142583 molMeP / molPd / h, the cumulative TON was 409w molMeP / molPd, the selectivity of methyl propionate was as high as 99.9%, the Pd loss was less than 1%, and there was no obvious metal adhesion on the container wall.

[0097] Example 9

[0098] In the glove box, 1.2 × 10 -5 moles of palladium acetate, 1.2×10 -4 moles of L5 ligand and 6.0×10 -5Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 85°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 1.0 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0099] After calculation, the catalyst TOF was 129856 molMeP / molPd / h, the cumulative TON was 388w molMeP / molPd, the selectivity of methyl propionate was as high as 99.9%, the Pd loss was less than 1%, and there was no obvious metal adhesion on the container wall.

[0100] Example 10

[0101] In the glove box, 1.2 × 10 -5 moles of palladium acetate, 6.0×10 -5 moles of L6 ligand and 6.0×10 -5 Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 85°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 1.0 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0102] After calculation, the catalyst TOF was 114895 molMeP / molPd / h, the cumulative TON was 378w molMeP / molPd, the selectivity of methyl propionate was as high as 99.9%, the Pd loss was less than 1%, and there was no obvious metal adhesion on the container wall.

[0103] Embodiment 11

[0104] In the glove box, 1.2 × 10 -5 moles of palladium acetate, 3.6×10 -5 moles of L7 ligand and 9.6×10 -5Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 85°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 1.0 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0105] After calculation, the catalyst TOF was 101652 molMeP / molPd / h, the cumulative TON was 358w molMeP / molPd, the selectivity of methyl propionate was as high as 99.9%, the Pd loss was less than 1%, and there was no obvious metal adhesion on the container wall.

[0106] Comparative Example 1

[0107] In the glove box, 1.2 × 10 -5 moles of palladium acetate, 2.4×10 -5 moles of bis(di-tert-butylphosphine)-o-xylene and 6.0×10 -5 Molar methanesulfonic acid is dissolved in 200 mL of a mixed solution of methyl propionate / methanol (85% wt methyl propionate) (nitrogen deoxygenated). To avoid contact with air, the catalyst solution is pumped into a 2L stainless steel mechanically stirred autoclave filled with ethylene by a peristaltic pump. The autoclave and the solution are then heated to 85°C within 40 minutes. A 1:1 gas mixture of carbon monoxide and ethylene is then introduced at a pressure of 1.0 MPa. Feeds are continuously added to the system through a pressure regulating valve to maintain a constant pressure in the autoclave, and no product is removed during the reaction.

[0108] After calculation, the catalyst TOF was 42115 molMeP / molPd / h, the cumulative TON was 183w molMeP / molPd, the selectivity of methyl propionate was 99.9%, the Pd loss was 32%, and an obvious mirror image appeared on the container wall.

[0109] By comparing the activity and stability of the olefinic unsaturated compound catalysts prepared in the above examples, it can be seen that the catalyst prepared by this patent exhibits high reaction rate and product selectivity. In addition, the active metal is more stable during the above reaction process, and there is no phenomenon of Pd adhering to the container wall, showing excellent long-term stability.

Claims

1. A carbonylation reaction catalyst, characterized in that: Includes the following components: (a) at least one Group VIB or Group VIII metal or a compound thereof; (b) a bidentate nitrogen ligand of the general formula (I); (c) acid; R represents isopropyl, tert-butyl, neopentyl, phenyl, 1-adamantyl, 2-pyridyl, 2-quinolyl, indenyl and 1-indolyl; Wherein, the metal of Group VIB or Group VIII includes one or more of Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt or Pd, Here, X represents O, S or an amino group substituted with an aryl group.

2. The catalyst according to claim 1, characterized in that The metal of Group VIB or Group VIII is selected from Ru, Pt or Pd.

3. The catalyst according to claim 2, characterized in that The metal of Group VIB or Group VIII is Pd.

4. The catalyst according to claim 1, characterized in that The bidentate nitrogen ligand of general formula (I) is selected from the structure shown in general formula (II): R is defined the same as in the general formula (Ⅰ); R' represents a substituent on the benzene ring, selected from hydrogen, monosubstituted or polysubstituted alkyl, alkoxy, perfluoroalkyl, mercapto, ester, aryl, heterocyclic, halogen, cyano, and nitro.

5. The catalyst according to claim 4, characterized in that R' is hydrogen, 4-methyl, 4-methoxy, 4-trifluoromethyl, 4-tert-butyl.

6. The catalyst according to claim 1, characterized in that The bidentate nitrogen ligand is selected from the following structures:

7. The catalyst according to claim 1, characterized in that The acid is selected from acids having a pKa value of less than 4 when measured in aqueous solution at 18°C.

8. The catalyst according to claim 7, characterized in that The acid is selected from acids having a pKa value of less than 3 when measured in aqueous solution at 18°C.

9. The catalyst according to claim 8, characterized in that The acid is selected from acids having a pKa value lower than 2 when measured in aqueous solution at 18°C.

10. The catalyst according to claim 7, characterized in that The acid includes nitric acid, sulfuric acid, C1-C10 alkyl acid, sulfonic acid or alkylsulfonic acid, halogenated carboxylic acid, orthophosphoric acid, and acids derived from the interaction of Lewis acid and Brewster acid.

11. The catalyst according to claim 9, characterized in that The acid is a sulfonic acid or an alkylsulfonic acid having a pKa value of less than 2 measured in aqueous solution at 18°C.

12. The catalyst according to claim 11, characterized in that The acid is selected from methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid.

13. The catalyst according to claim 12, characterized in that The acid is methanesulfonic acid.

14. The catalyst according to claim 1, characterized in that The molar ratio of the Group VIB and Group VIII metals to the bidentate nitrogen ligand in the component (a) is 1:0.5 to 1:

150.

15. The catalyst according to claim 14, characterized in that The molar ratio of the Group VIB and Group VIII metals to the bidentate nitrogen ligand in the component (a) is 1:1 to 1:

50.

16. The catalyst according to claim 15, characterized in that The molar ratio of Group VIB and Group VIII metals to bidentate nitrogen ligands in the component (a) is 1:1 to 1:

10.

17. The catalyst according to claim 1, characterized in that The molar ratio of Group VIB and Group VIII metals to acid in the component (a) is 1:1 to 1:

150.

18. The catalyst according to claim 17, characterized in that The molar ratio of Group VIB and Group VIII metals to acid in the component (a) is 1:1 to 1:

50.

19. The catalyst according to claim 18, characterized in that The molar ratio of Group VIB and Group VIII metals to acid in component (a) is 1:2 to 1:

10.

20. Use of the catalyst according to any one of claims 1 to 19 for the carbonylation reaction of olefinically unsaturated compounds.

21. Use of the catalyst according to any one of claims 1 to 19 to carry out carbonylation reaction of an olefinically unsaturated compound with carbon monoxide in the presence of a hydroxyl compound and the catalyst according to any one of claims 1 to 19.

22. The use according to claim 20, characterized in that The olefinically unsaturated compound is a straight-chain or branched olefin or alkyne containing one or more unsaturated bonds.

23. The use according to claim 22, characterized in that The ethylenically unsaturated compound contains 1 to 3 unsaturated bonds.

24. The use according to claim 22, characterized in that The olefinically unsaturated compounds are ethylene, propylene, heptene, octene and 1,3-butadiene.

25. The use according to claim 24, characterized in that The ethylenically unsaturated compound is ethylene.

26. The use according to claim 21, characterized in that The hydroxyl-containing compound is methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol or 1-hexanol.

27. The use according to claim 26, characterized in that The hydroxyl-containing compound is methanol.

28. The use according to claim 20 or 21, characterized in that The carbonylation reaction temperature is 50-180°C.

29. The use according to claim 28, characterized in that The carbonylation reaction temperature is 70-110°C.

30. The use according to claim 20 or 21, characterized in that The carbonylation reaction pressure is 0-7 MPa.

31. The use according to claim 30, characterized in that The carbonylation reaction pressure is 0.6-3.0 MPa.

32. The use according to claim 20 or 21, characterized in that The active component of Group VIB or Group VIII metal in each kilogram of reaction solution is 1-200×10 -5 mol.

33. The use according to claim 32, characterized in that The active component of Group VIB or Group VIII metal in each kilogram of reaction solution is 2-100×10 -5 mol.

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