DE1946437A1 - Process for the hydroformylation of olefins and suitable catalysts therefor - Google Patents

Description

Σ81η, the 3 Fu / ta / H *

Brltannie House. Moor Lan *. London. 1.0.2 (imlaad).

Process for the hydroforlation of olefins as well as suitable catalysts

The invention relates to a new process B ^ droformylation of olefins to aldehydes and / or alcohols and a new rhodium complex.

In the oxor process, olefins are reacted with carbon and hydrogen at elevated temperature and pressure. Aldehydes and / or alcohols are obtained as products. Cobalt compounds, especially Ootaoarbonyl, aind die most frequently used catalysts, but a number of other transition metal terbi charges are also used

In British patent application 6293/66 by Aaaelderin It is agreed that certain square-planar complexes of monovalent rhodium with an Oarboxylatligand very active catalysts for the formation of alcohols and / or Aldehydes by which the oxo reaction is. In the deutsohen

Patent specification ......... (patent application P 17 68 101.5) of

Applicant is informed that the actiom is divided into two stages and that as a product · aldehydes or alcohols duroh regulation of the conditions can be obtained.

009IS./22ÖI

BAD ORfQiNAt

It was subsequently found by the applicant that by Incorporation of a bidentate ligand which coordinates via at least one oxygen atom, instead of a carboxylate ligand, gives a different class of complexes will that can have high activity. Ketoenolates and their Schiff's have been identified as particularly suitable ligands Bases mentioned

It has now been found that certain bidentate ligands which coordinate via nitrogen and oxygen, the SfCKterstoff in the free ligand, form an acidic catalyst, which can be even more active.

In one aspect, the invention thus relates to the hydroformylation of olefins to alcohols and / or aldehydes naaheinem Terfahrea, which is characterized in that one olefins with coal & oxide and hydrogen at increased Temperature in the presence of a complex of a metal of the group TZXI with Ausnalim clay iron, nickel, palladium or Platinum hydroformylierii, of at least one neutral complex-forming ligand, which is an atom of an element of the Contains group Vb or VIb, which has a single pair of electrons Surfe, since the ponation is available, and a two- * Contains lahsifen ligand, which coordinates via oxygen and Stickateff, whereby the oxygen is free ligand

25 Ifil is an acidic group.

These · »white-like ligands include nitrogenous acidW phenols. If they« coordinate metal »with a transition, they form complex«, which the metal, ßiokäitoff- uad Oxygen atom · contained in a Sing * For example are formed according to the following type!

QG9888 / 2208

Herein, M is one of the above-mentioned metals of the group VIII.

The six-membered ring system is similar to the ring system, that using the ship's view base or one Ketoenolate is formed as a ligand, and is generally preferred as the more active catalysts tend to be have this fora

Suitable ligands are

COOH

The salicylaldoxy ligand is particularly preferred:

CH - NOH

Preferred catalyst metals are cobalt and bhodiua, especially Bhodiua

Suitable neutral complex-forming ligands are molecules which contain an atom of an element from group Vb or VIb which has a single pair of electrons that are available for donation (ff donors), in particular nitrogen or oxygen.Suitable nitrogen donor ligands of this type are monoalkyl and monoarylamines, e.g. methylamine, ethylamine, n-propylamine, and similar dialkyl, tri- alkyl and triarylamines, e.g. dirnethylamine, diphenylamine, Trimethylamine and sriphenylaain. Diamines and triamines, e.g. Ethylenediaain, diethylenetriamine, ammonia, hydroxylamine and other neutral molecules of the formula HI ,, where Z is any suitable group, are suitable as ligands.

009886/2206

Suitable oxygen donors are those of the formula g z * B »Ither.

In addition, the donor atom can have free orbitals that complement the Gf bond by accepting electrons (electron density) from occupied metal orbitals (TT acceptors). Examples of such donor atoms are phosphorus, arsenic, antimony and sulfur. Suitable ligands of this type are phosphines, arsines and stibines of the general formula. (E) (R ¹ XhOd, phosphites (BO) (E ¹ O) (E ^) D, mercaptans EE ¹ S and sulfoxides EE ⁹ SO *

Other suitable molecules have delocalized tT ^ orbitals and are able to take up electrons from the metal orbitals into the tr ♦ anti-bond sorbitol ale of the ring system (17 ** - acceptors). These ligands include pyridine and substituted pyridines, for example α-picoline, 2,2 ^I- dipyridyl, 1,10-phenanthroiene.

Tertiary phosphines, in particular triethylphoaphine, tri-n-propylphosphine and tri-n-butylphosphine, are preferred as ligands. In addition, a carbonyl ligand is usually present, at least under reaction conditions.

The starting materials are olefins with 2 to 20 carbon atoms in the molecule, in particular ethylene, propylene, hexene, heptene and octene. The double bond is preferably terminal, but can also be internal.

The catalyst can be used as a solution in an inert solvent or in the feed or in the recycle product to be introduced. Saturated or aromatic hydrocarbons or alcohols can be used as solvents. Normal paraffins, e.g. η-hexane, n-heptane, are suitable

30 and n-octane.

Alcohols are generally not formed if no alcoholic solvent is used or more than there is about 3000 moles of olefin per gram of catalyst

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or the pressure falls below about 5 | 6 atii.

The hydroformylation is conveniently atu at a pressure between O and 280, preferably between O and 140 atm, and preferably performed at a! Temperature between 20 and 25O ⁰ C, a temperature is particularly preferably from 60 to 180 ⁰ C.

The hydrogen / carbon oxide ratio in the feed can be between 4: 1 and 1: 4. A ratio of 2: 1 is preferred, which favors the formation of alcohol, and a ratio of 1: 1, which favors the formation of aldehydes.

The molar ratio of catalyst to olefin feed is preferably 1:30 to 1: 25,000,000, with one molar ratio between 1: 360 and 1: 5,000,000 is particularly preferred.

In a further aspect, the compound comprises one Catalyst which is a complex of a Group VIII metal other than iron, nickel, palladium and fiatin and at least one bidentate ligand coordinating via oxygen and nitrogen, the oxygen im free ligand is part of an acidic group and contains at least one neutral complex-forming ligand, which contains an atom of an element of group Vb or VTb, which has a single pair of electrons, which is necessary for donation is available. The metal is preferably rhodium.

Examples 1 to 5

50 ml of hexene-1 and 100 ml of an n-heptane solution which contained sufficient catalyst that the olefin / catalyst molar ratio was 1000: 1 were placed in an autoclave. The autoclave was flushed, pressurized to 2.1 atmospheres with carbon oxide and ^{heated to about 80 °} C. with shaking. At this temperature, the autoclave was pressed to 42 atmospheres with a mixture containing hydrogen and carbon oxide in a molar ratio of 1 μl. The pressure was kept in the range from 24.5 to 42 atm

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presses ", the temperature was maintained at about 80 ⁰ C. The results are shown in Table 1.

Example 5 does not illustrate the invention but rather is for comparison only · It should also be noted that the The initial speed when using the salicylaldox mat residue, which results in a six-membered Hing, is noticeable is higher than when using an acetylacetonate as a catalyst «

The previous biX4 © t® catalyst was placed in a 500 ml stainless steel bridge vessel together with 50 ml of hexene 1 and 100 ml of hexene. The vessel was placed in a heating and shaking device, rinsed three times and with a previously formed mixture of hydrogen and carbon oxide in a Mo! ratio of 1i1 pressed © The pouring mechanism was switched on and. the repeal started. After completion 4 © r Heaktion wtxsde des? Let the autoclave cool down. The excess Sas © was blown off and the products removed and analyzed »

20 Example 14

An experiment was to gleishe Weiae, as for the examples w games described 6 to 13, carried out, but using 1-heptene as Bltisatssmaterial and nO ^ tan was used as the solvent ·

■ 25. Example 1 ^

An experiment was described on di © for Examples 6 to 13® Weis® carried out, but octene-1 as Inlay material and often used as a solvent became.

30 Beiapi ·! 16

how. follows producedi 0 ₉ ö58'8 S Hhoäius

aldoximat was filled with Θ ₁ 05S4 »1 fi? ipfe © ay! pli © iipM% in toluene ®i® lüo'euag mmsä ^ -amf-1 © al on, and one

57210 © '' "

* ⁰ " ^m

One portion of only 1 toluene was placed in a vessel made of stainless steel. The vessel was purged with nitrogen and then first with ethylene in an amount equivalent to an "olefin / catalyst molar ratio of 2" · 9? Οΐ1 corresponds to, to 38 »5 * tii and then a with a more thoroughly formed mixture -of hydrogen and carbon oxide ia molar content · τοη 1: 1 pressed to 84 atm (seed pressure) · The vessel was then pressed to 83 ° ö heated and 10 hours, "wipe 83 and 90 ⁰ O kept, while gesehüttelt and the gas pressure in the range 89.6 to 105" ta was hold ge ·

After aa the Öaeaufnähme geaessenen cessation of Beaktion the autoclave cooling was left · excess Oasis were then analyzed by kept at -80 ⁰ O Cold trap blown off to remove entrained liquid products. The liquid products were extracted and analyzed. The product obtained was t5.3 g of a mixture which it analysis contained 99% propionaldehyde and Λ% diethyl ketone.

20 Example 17

Salioylaldoxiaatocarbonyltriphenylphosphitrhodiua was by implementing Rhodiuadicarbonylealicylaldoximat in Toluene made with tributyl phosphite. The catalyst solution was poured out into a nitrogen-purged vessel Stainless steel was added, whereupon about 100 μl of propylene were added, so that the olefin / catalyst oil ratio was 4900: 1. The jar was rinsed three times and then a with a previously formed mixture of hydrogen and carbon dioxide in general a ratio of 1: 1 to 63 atmospheres (total seed pressure) pressed on. The autoclave was heated to 85 ° C. with shaking and kept at 83 to 90 ° C. during the subsequent reaction. The pressure was maintained between 70 and 96 atmospheres by adding more olefin as required.

When the reaction stopped, i.e. no more gas absorbed the autoclave was left to cool, over-

009886/2206 BADORtOtNAt,

Schüeeige grasses were blown off by a cold trap kept ^{at -80 0} C to remove entrained liquids. The products were removed and analyzed. The propylene had been completely converted. The product obtained was 83.7 g of a mixture of n-butyraldehyde and isobutyraldehyde in a molar ratio of 1.01: 1.

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Tabel Hydroformylation reactions ii

catalyst

Response time 3 hours ^from

Temperature gO i 2 ° C

Hg / CO molar ratio ί ^ 1 * ^{Χ8 2} ^ ' ⁵ ***

1000: 1 olefin / catalyst molar ratio

Insert (50 ml) Hexen-1

Solvent (100 ml) n-heptane

Attempt. Bidentate Ligand Relative Initial Olefin Hr. ^ jf, -. speed turnover,

The reaction % product distribution %. olefin-free)

Hexane branching normal alcohols ■

ter aldehyde aldehyde

1 picolinate (III) 1.0

2 Quinaldin «* (Ü) 3.3

3 8-Oxyquinolate (I) 7t0

4 Salicylaldoximate (IV) 13.0

5 acetylacetonate 8.3

negligible - 32 bar

32

neglect ^. casual- 33 bar

66 69

68 68

66

Table 2

ρ
mm
it

Hydroforaoliergng by witches, hepten, xaaä. Oe ten

Solvent: η-heptane for hexene, n-oetane for heptene * . -and ". Honing for octene

Example catalyst

Wr.

Time
Hour min

Pressure, atü olefin / olefin product distribution Max · Min · Catalyst rate ₉ (mol- $ «olefin-free)

Alka

Molar ratio never

neYerJBweig-Koraale te aldehydes

Aldehydes

Temp, ° 0

Sa (PrIH ₂ ) (00) 8-oxyehin

BhCEt ₂ HH) (GO) -

Eh _ («- pi ©) (00) - 10

10
11

12th

Sa (^ y) (CO) saldox11

Bh (Eh _x Sb) (OO) -balance 11

Ha (Me ^ BrH) SaIdOX

14 KhOHaQ) (OQ) -

eel & ox

15 *

10

10

17th

»
4?

56 43.2

56
? 0

70
70

56
56
70

40.5 26.4

40.5 54.4

- 70 47.5

58.7 34.4

24.5

56 55 500ϊ1

2000ι1
500s1

500: 1
500s1

500s1

500: 1
500; 1
500: 1

500: 1

100

76 99

100 100

75

97

87

100

99

1 1 5

56

54 63

56 59

36

57 58 59

37

42

46 35

42 39

62

42 41 36

62

78-84

80-86 «83-85 f

82-85 82-89

80-r85

82-85 85-86 75-85

83-87

ohinald «

U JL ±

8-oxyehin

balance

I "1

CB - HOH

β-pic -

et

bipy - 2,2'-py - pyridine;

- DiMethj-IsulXoxyd.

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Claims (1)

- 12 - Claims / IV Process for the hydroformylation of olefins to alcohols and / or aldehydes by reacting olefins with carbon monoxide and hydrogen at elevated temperature In the presence of catalysts, thereby characterized in that one is in the presence of a complex of a Group VIII metal with the exception of iron, Nickel, palladium or platinum works, which has at least one neutral complex-forming ligand, which is an atom of an element from group Vb or IQ VIb, which has a single pair of electrons available for donation, and which contains a bidentate ligand which coordinates via oxygen and nitrogen, the oxygen in the free ligand being part of an acidic group. 2) The method according to claim 1, characterized in that it worked in the presence of complex compounds the bidentate ligand containing a nitrogen-containing acid or a nitrogen-containing Have phenol, the bidentate ligand 1 especially quinaldinate, 8-oxyohinoline or a Salcylaldoximate 1st. 3) Method according to claim 1 and 2, characterized in that containing cobalt and / or rhodium Catalysts is working. ^) Method according to claim 1 - 3, characterized in that complex compounds are used, in which at least one of the ligands is a carbonyl group. 009886/2206 5) Method naoh claim 1-4 «characterized« that it works with catalysts containing ligands of the following type: alkyl or arylamine, Phosphine, arsine, stibine, phosphite, arsenite, stibinite, Mercaptan, sulfoxide, pyridine or substituted pyridine. 6) method naoh claim 5> characterized in that that you work with catalysts that contain ligands of the following types: methylamine, ethyl amine, n-propylamine, triphenylphosphine, triphenylarsine, triphenylstibine, triphenyl phosphite, triethyl phosphite, Pyridine or α-PiColine, with trialkylphosphine ligands are particularly preferred. 7) Method according to claim 1 - ß, characterized in that « that it works with catalysts, the ligands contain the following types: triethylphosphine, trin-propylphosphine, tri-n-butylphosphine, trioyolohexylphosphine or triootylphosphine. 8) Method naoh claim 1 - 7 * gekennzeiohnet that olefins with 2-20 carbon atoms and preferably Ethylene, propylene, a hexene, heptene or octene can be used, olefins with a terminal double bond being preferred. 9) Method according to claim 1-8, characterized in that the catalyst dissolved in a solvent, in the hairdresser or in the circulatory product in the reaction zone is introduced, preferably saturated or aromatic hydrocarbons or alcohols being used as solvents, of which η-paraffins, for example η-hexane, n-heptane or n-octane are preferred, 009888/2208 10) Method according to claims 1-9 »characterized gekennzeiohne t that it works at pressures between 0 and 2θθ atü, preferably between 0 and 14o atü. 11) Method na oh claim 1-10 »thereby gekeraiseiohnet, dad at temperatures between 20 and 250 ° C, preferably between 60 and 180 ° C is carried out. 12) Method according to claims 1-11, characterized in that Biit WaRseretoff / Kohlenaonoxyd-Ver ratios in fresh food between h s 1 and 1 ι 4 is worked, the preferred ratio of hydrogen to Konlenmonoxyd 2: 1 or 1: 1. A method NaOH claim 1 »12, characterized in 'that with a. The ratio of catalyst to ca® £ tafils © hein * atz in the range from 1:30 to 1 ι 25,000,000, preferably in the range from 1: 300 to 1: 5,000,000 - in each case mol / mol - is used. 14) catalyst for the hydroformylation of olefins, characterized in that it is a complex compound of a Group VIII metal with the exception is from bis-iron, nickel, palladium or platinum and contains at least one bidentate ligand, who coordinates via oxygen and nitrogen, wherein the oxygen in the free ligand is part of a is acidic group, and which further has at least one neutral complex-forming ligand which is an atom of an element of group Vb or VIb includes having a lone pair of electrons available for donation to. 988S / 2298 15) KatalyjMitor according to claim 14, characterized daduroh that the metal of group VIII rhodium let. 009886/2206