DE2443058A1 - COORDINATION COMPLEX COMPOUNDS OF TRANSITION METALS OF GROUP VIII, THEIR PRODUCTION AND USE AS KATALYSA TOR - Google Patents

Description

Description of the patent application

RHONE PROGIL, SA
25, Quai Paul-Doumer, 92408 Courbevoie - France

concerning:

Coordination complex compounds of transition metals Group VIII, their manufacture and use as a catalyst

The invention relates to new insoluble metal complexes and their use as catalysts in different Reactions such as hydroformylation, hydrogenation and the production of tertiary amines by reacting an olefin with carbon monoxide, hydrogen and a secondary amine.

Generally, the catalysts used for such reactions are soluble catalysts that are a noble metal of Group VIII, which is often difficult to recover because the active catalyst as one coordinative complex compound dissolved in the reaction medium is present.

In contrast, the new insoluble metal complexes of the invention, which are also Group VIII metals contain extremely effective catalysts in this solid, insoluble form, which are used heterogeneously and by

O 9 R 3 V t Π

1A-45 252,

Allowing to settle or filtering can easily be separated again from the reaction medium. You can do this therefore reuse new catalysts as often as their catalytic activity lasts. .

Insoluble catalysts for heterogeneous implementation of the Reactions proceeding from soluble transition metal complex compounds have been used for various reactions. One made here Use of insoluble coordinative compounds or coordinative components (ligaments), to which, among other things belong:

organic polymers with certain functional groups such as amines or phosphines (FR-PS 1 583 037), or vinyl pyridine (U.S. Patent 3,636,159);

inorganic compounds in which a phosphorus-containing Group has been introduced, either starting from silica or alumina (GB-PS 1 275 733), or by condensation an alkoxysilane containing a phosphine group or a metal complex compound of this alkoxysilane with silica (FR-AS 70/45 824); this latter type of catalyst is used for the hydroformylation of ethylenic Hydrocarbons used to form aldehydes and alcohols (FR-AS 70/45 607).

It is required of such catalysts that they strongly hold back the metal, that is, this expensive one Noble metal is not given off in the exhaust gas or effluent from the reactor, but is retained in an active form that acts on a can be easily recovered.

This property of the solid catalyst to retain the metal after the reaction is due to the coordinating Element of the insoluble coordinative component (or ligand) bound and not to the other coordinating Elements (or ligands) that are optionally linked to the metal and not directly to the insoluble coordinative

5098 3 3/10 31 - 3 *

1A-45 252

Component are bound.

It can be said that up to now in all processes which lead to such catalysts, phosphorus is generally used as Hetero atom or used as donor atom, this phosphorus to an inorganic or organic polymer matrix or compound is bound.Although such catalysts have a significant catalytic Activity, the properties of the metal's restraint, are sufficient for economic use not out yet.

The contrast provided by this invention, suitable as catalyst compounds have an improved ability to retain the metals, so that it can be their uses should ■ dung in technically and economically viable manner contemplated.

The invention relates to solid catalysts which are insoluble in organic solvents and in water and are used heterogeneously and which consist of an insoluble coordinative component, a transition metal of group VIII and others bound to the transition metal which ligands exist; them corresponding general

formula

(A - Si - C) M (L ') _n (L ") _a

I.
in the A-Si-C the insoluble coordinative component

is, where A is a solid inorganic core based on silica or alumina and C is a group, which contains nitrogen in the form of an amine or polyamine, which is primary, secondary or tertiary as well as aliphatic, aromatic or may be heterocyclic, or is a group containing a carboxylic acid group; M represents the Group VIII transition metal with the exception of iron or nickel;

509833/1031

1A-45 252

L ¹ and L ^1f stand for divalent ligands such as carbon oxide, olefins, amines, phosphines, phosphites or arsines, and η and q each stand for an integer from 0 to 6.

The new catalysts work in two ways manufactured and insulated:

1) It is implemented as defined above, a salt or a coordinative complex compound ^component of a metal of group VIII with an insoluble coordination ^Kom P °. The insoluble coordinative components are obtained in particular as follows:

a) by using an alkoxysilane or a chlorosilane, the one Amino group or a carboxylic acid group, brings with silica or alumina to the reaction. Such coordinative components A-Si-C can either be already known compounds or in one older proposal (P 24 33 409.6) described porous anion exchanger on the basis of a porous inorganic Carrier which has hydroxyl groups on the surface and on which organic groups are grafted via a Intermediate member containing silicon atoms; the organic groups contain 1 or more silicon atoms and in addition Amino groups by at least 3 carbon atoms containing organic groups are removed from the silicon atom; these connections can be made by the general formula

ßi B -N

- 5 509833/1031

1A-45 252

are reproduced in which

Vehicle implies and

■ A- —Ο the porous mineral O' -B- O O
= Si S- - O

is the organic moiety in which B is an organic link between the silicon atom and the Represents amino group; R ^ and R "are the same or different Alkyl groups, which usually contain 1 to 3 carbon atoms, but also a chain length of up to Can have 12 carbon atoms *

You can also use the connections according to another older Use suggestion (P 24 39 088.3); these are aminoaromatically substituted silanes of general formula

NH

- O - (CH ₂ ) _p - Si ----

in which ρ is an integer from 2 to h , X is a linear or branched alkoxy group having 1 to 8 carbon atoms and Y and Y ^{1 can be the} same or different and each is a methyl, ethyl or phenyl group or a linear one or branched alkoxy groups having 1 to 8 carbon atoms; The dimers and linear or crosslinked polymers of such silanes are also suitable for this purpose.

5 0 9 8 3 3/1031

1A-45 - 6 - '

244305S

b) By a umtsetzt Vinylalkoxysilah or vinylchlorosilane with silica or alumina and the efhäliseüö product with a vinylpyridine or a AörylsMufäs eat a known manner öopolyöiei'isier't ^1.

2) A salt or fine coordinative complex compound is left an overrun details of Öruppe VIII with one Chlorosilane or with an alkoxysilane »the one anliesty or contains a carboxylic acid group react in part a new coordinative complex compound, this nliii in a second stage with some inorganic Fe & isiöff, which contains hydroxyl groups (silicic acid or "foherde") is brought to implementation.

The catalysts can be prepared in isolation and then used are or are produced in Äitu, ihdäm at the same time the insoluble co-ordinative in the reactor Brings component and the metal salt or the metal complex.

Contains that used to manufacture the catalytic converter Metal salt or the metal complex does not have a ligand of the trivalent phosphorus or arsenic such as phosphines, phosphites and arsine, the addition of a ligand of this "type in the stage of preparation of the catalyst or its use represent an advantageous means of the catalytic ^ activity of the entire system even further to increase if necessary or desired * fts it should be pointed out that in this latter ^ aile daö Phosphorus or arsenic atom are not an integral part of the insoluble coordinative component.

The invention is explained in more detail with the aid of the examples below. First, the production of the kooMlnaisiVert components is described, which are then brought into reaction with a courtship or a complex of a Group VIII metal.

6O9 8 3'3V1O'31 · " ⁷ ^

1A-45 - 7 -

Production of coordinative component A

In 500 ml of xylene, 500 g of silica gel beads with a specific surface area of 415 m / g, as previously dried under reduced pressure at 150 ° C. for 4 h

6ZT

had been, and 100 g of Silane Et

^ N - (CH ₂ J ₃ Si (OMe) ₃

Et

Me = -CH _x
j

iJ »U = -Upilc

brought in. The mixture was heated with stirring for 8 hours at 19O ⁰ C and then filtered.

The residue was washed with acetone and dried under reduced pressure h 4 at 12O ⁰ C; the solid product obtained contained 7 % carbon, 1 % nitrogen and had an exchange capacity of 0.4 meq / g.

Production of the coordinative component B

In the same manner as for component A, 500 g of silica gel beads and 100 g of silane were obtained

reacted ^{with each other.} The reaction product contained 0.8% nitrogen.

Production of the coordinative component C

In the same manner as the component A, 500 g of silica gel beads and 100 g of silane were obtained

NH ₂ -CH ₂ -CH ₂ NH (CH ₂ ) ^ - Si (OMe). The reaction product contained 2 % nitrogen. -

609833/1031

1A-45 252

Production of the coordinative components D, E and F

These components were prepared according to the method of F. Runge et al, Makromolecular Chem. 1965 81_, p. 68.

Coordinatiye component D

Vinyltrichlorosilane was reacted with silica gel beads (specific surface area 400 m / g) and the product obtained was copolymerized with 4-vinylpyridine. The reaction product contained 1.6 % nitrogen.

Coordinative component E

The procedure was as for component D, but alumina was used instead of silica. The product obtained contained 0.7 % nitrogen.

Coordinative component F

Vinyltrichlorosilane was reacted with silica gel beads (specific surface area 400 m / g) and the obtained Product then copolymerized with acrylic acid.

The following examples now explain the preparation of catalysts according to the invention with the aid of those as described manufactured coordinative components, as well as their applications * All manufacturing took place under oxygen-free Nitrogen; the solvents had previously been dried over molecular sieves and flushed with nitrogen been degassed. .

example 1

37.8 mg of Rh ₂ Cl ₂ (CO) ^ (dichlorotetracarbonyldiriiodium) were added to a suspension of 2 g of coordinative component A in 20 ml of toluene. The mixture was stirred for a few minutes at room temperature and then for 1 hour at 50 ° C. * Man received

509 8 33/103

1A-45 252

a brown solid substance washed with toluene and hexane and dried under reduced pressure for 24 hours. The complex compound contained 1% by weight of rhodium.

Example 2

180 mg of RhCl / P (CgH ₅ ) ^ Z tris (triphenylphosphine) chlorrhodium were added to a suspension of 2 g of component A in 20 ml of toluene. The mixture was stirred for 10 min at room temperature and 2 h at 80 ^° C. and then allowed to settle. A slightly yellow colored liquid phase and a solid substance were obtained which were ^{washed three times with 10 ml of toluene at 80 °} C. and then 10 ml of hexane and then dried for 24 hours under reduced pressure at room temperature. The complex compound contained 0.8 % rhodium.

Example 3

52 mg of ruthenium trichloride hydrate containing 20 mg of ruthenium were added to a suspension of 2 g of component A in 20 ml of ethanol. The mixture was stirred for 10 min at room temperature and then for 1 1/2 h at 80 ^° C. and then allowed to settle. A solid substance and a colorless liquid phase were obtained. The solid substance was washed three times with ethanol and dried under reduced pressure at room temperature for 24 hours. The ruthenium content of the solid complex compound was 1% by weight.

Example 4

In the same way as in Example 1, 4.1 mg of Rh ₂ Clp (CO) ^ and 2.2 g of component B were reacted. A catalyst was obtained which contained 0.1% rhodium.

Example 5

In the same way as in Example 2, 29.3 mg of RhCl (CO) ₂ -p-toluidine (p-toluidinedicarbonylchloro-rhodium) and 1 g of component B were reacted with one another; the? finished catalyst contained 0.93% Rh.

509833/1031 -10-

1 & -45 252

Example 6 2443058

In the same way as in Example 1, 38 mg and 2 g of component C were reacted; the catalyst contained

1 % Rh.

Example 7

According to Example 2, 38 mg of Rh ₂ Cl ₂ (CO) ^ and 2 g of component D were reacted; the solid catalyst contained 1 % Rh.

Example 8

70 mg of Rh ₂ Cl ₂ (C _Q H ₁ ^) ^ (tetracylooctendichlorodirhodium) and 2 g of component D were reacted as in Example 2. The reaction product contained 1 % Rh.

^;: ■■. ■ - ■ ^

Example 9

There were 70 mg of Rh ₂ Cl ₂ (CqH ^^) r on a suspension

2 g of component D are given. The mixture was heated for 15 min with stirring to 80 ⁰ C and then i ⁿ 20 ml of toluene with 54 mg of triphenylphosphine P (CgHc) T. ₅ The mixture was stirred for a further 2 h at 80 ^° C. and then allowed to settle. A colorless liquid phase and a solid substance were obtained, which was washed with toluene and then with hexane and dried under reduced pressure at room temperature for 24 hours. A yellow solid substance containing 0.93 % Rh was obtained. .

example

265 mg of catalyst according to Example 8 were suspended in 5 ml of toluene; _{8.1 mg of P (OCgH 5} ), dissolved in 10 ml of toluene, were added to the suspension, while stirring, and the mixture was then heated to 80 ° C. for 1 1/2 h. After allowing to settle, a solid substance was obtained which was washed with hot toluene (2 × 10 ml) and then with hexane and dried in vacuo. The rhodium content of the finished catalyst was 1 %,

- 11 - 509833/1031

"IA-V) 252

Example 11

A catalyst containing 0.125 % Rh was prepared by reacting 39.5 mg of Rh ₂ Cl ₂ (CO) ^ and 1.990 g of component E according to Example 2.

Example 12

In the same way as in Example 2, 148 mg of Pt / JP (OC ₆ H ₅ ), ~ /, (tetrakistriphenylphosphite platinum) and 2 g of component E were reacted; the finished catalyst contained 0.496 platinum.

Example 13

A catalyst with 0.1% Rh was prepared by reacting 7.7 mg of Rh ₂ Cl ₂ (CgH ₁ ^) with 2.2 g of component F according to Example 2.

Example 14

39.8 mg of Rh ₂ Cl ₂ (CO) 1 and 2 g of component F were reacted with one another as in Example 2; the resulting catalyst contained 0.3 % Rh.

Example 15

Were reacted mg PdCl ₂ 73 (CGH ₅ CN) ₂ with 2 g of component F as in Example 2; the reaction product contained 0.63 % palladium.

Example 16

In a solution of 18.9 mg of Rh ₂ Cl ₂ (CO) ^ in 10 ml of xylene, 28 mg of soluble coordinative components were added

- O - (CH ₂ ) ₃ - Si (OMe) ₃

given. The mixture was stirred at 50 ° C. for 1 h and a suspension of 1 g of silica (specific surface area 400 m ² / g) in 10 ml of toluene was then added to the solution obtained.

■■■■: ■ -. - 12 -

509833/1031

iA-45 252

r 12 «.

The whole was heated to 80 ° C. for 4 h and then allowed to settle. A solid substance was obtained, which was washed with toluene and with hexane and dried ^{under reduced pressure 1;} the reaction product contained 1 % Rh,

Example 17

100 mg of RhCl, (Py), (Tripyridintrichlorrhodiumjl

implemented with 2 g of component D as in Example 3? the reaction product contained 1 % Rh.

The new catalysts are particularly suitable for the following reactions:

Hydroformylation of olefins with a degree of conversion to aldehydes of 30 to 99 % \

Preparation of tertiary amines with a considerable selectivity for the amines formed from 70 to 93 % (based on the olefin consumed);

Hydrogenation of

a) Olefins with a degree of conversion to higher alkaries of 40% up to 95 % _t

b) Nitro compounds with a degree of conversion to the corresponding higher amines of 90%.

The catalysts are effective under moderate pressure conditions:

In the hydroformylation 10 to 120 bar, preferably 20 to 90 bar, in a solvent such as ketones _t alcohols, ethers, hydrocarbons, preferably saturated hydrocarbons;

in the production of tertiary amines 30 to 120 bar, preferably 60 to 120 bar, in a solvent such as alcohols, ethers and hydrocarbons, preferably saturated Hydrocarbons ;. '■

509933/1031 ' ^{T 1} ^ "

1A-45 252 - 13 -

in the hydrogenation 1 to 100 bar, preferably 20 to 50 bar, in a solvent such as alcohols, ethers, hydrocarbons, preferably saturated hydrocarbons.

The reaction temperatures are below 220 ^° C., preferably in the range from 100 to 200 ^° C.

When using these new precious metal compounds, the precious metal concentration in the liquid drain is increased The end of the reaction is considerably reduced, namely up to 1 ppm, based on the end product, in the case of the hydroformylation or in the hydrogenation. This represents a considerable improvement over the previous state of the art.

The use of the new catalysts for such reactions is described below.

1) hydroformylation

10 ml of olefin, 10 ml of solvent and 200 mg of catalyst were placed in a reaction vessel with gas inlet, stirrer and heating device. Subsequently, carbon monoxide and hydrogen were supplied under specified partial pressures and the whole thing was reduced to a specified value while stirring ^. Brought temperature, which was maintained for 5 min. After cooling and releasing the pressure, the catalyst was separated off by allowing it to settle. The liquid phase was then analyzed by gas chromatography and in this way the amount of olefin consumed and aldehyde formed and alcohol formed was determined; the metal content of the reaction effluent was determined by flame spectrometry. The various results are summarized in Table 1 below.

2) Production of tertiary amines

6.7 g of olefin, 10 ml of solvent, 3.6 g of dimethylamine and a certain weight of catalyst were placed in a reactor. The whole was ^{heated to 150 °} C. for 2 h (5 h in Example 32). After the completion of the reaction, the device was

509833/103 1

- 14 -

1A-45 252 - 14 -

Cooled in an acetone-carbonic acid snow bath and then relaxed. The amount of amines formed was determined by gas chromatography. The various results are summarized in Table 2 below. .

3) hydrogenation

The hydrogenation can be carried out with different substrates, for example with linear or branched substrates or cyclic olefins, with aliphatic or aromatic nitro compounds.

The respective substrate or starting material, the solvent and the catalyst were placed in a reactor, and hydrogen was introduced under a predetermined pressure. The whole was heated to the predetermined temperature for a given time. The various results are summarized in Table 3 below.

Those used for the various reactions described Catalysts can easily be recovered and then reused very often without loss of activity. For example, the catalyst according to Example 8 was 20 times in succession for a hydroformylation reaction with a subsequent reaction Recovery of the catalyst used without a reduction in the activity of this catalyst was established.

Tables 1. 2 and 3

5 0 9 8 3 3/1031

Table 1

ι Example olefin Octene-1 catalyst Hydroformylation H ₂
bar CO
bar T
⁰ C Transformation
degree of olefin to
alcohol Metal in
more fluid phase I.
VJl Pentene-3 Solution
middle to
aldehyde _ ppm 18th Witches-1 example 1 45 45 150 77 - 3.5 19th Decene-1
Witches-1 Example 2 toluene 20th 20th 150 64 7th 4th 20th Witches-1 Example 7 Heptane 45 45 150 89 10 (5) 0.5 IV)
VJl
ro 21
22nd Witches-1 200 mg
component
D + 4 mg
Rh ₂ Cl ₂
(CO) ₄
Example 8 Heptane 45
20th 45
20th 150
150 87 (85)
32. - 4 (3)
^ 0.5 5098: 23 Witches-1
Witches-1 Example 9 toluene
toluene 20th 20th 150 56 (56) - 0.8 (■ ^ 0.5) UJ 24 Helen-1 Example 10 toluene 20th 20th 150 66 2.5 25,
26th Witches-1 Example 9
+5.7 mg
P (OC ₆ H ₅ ) ₃
example 1 toluene 20th
45 20th
45 150
100 86
51 - 2.7
7.5 ;; ο 27 Witches-1 Example 12 toluene
toluene 45 45 150 30th 25 (-) ^ ■ 2 4> 28 Witches-1 Example 13 Heptane 45 45 150 52 (84) 14 (10) -O-
CO 29 Example 11 toluene 45 45 150 75 (87) - - O 30th Example 16 toluene 45 45 150 79 ■ '- Cn
OO toluene

example Olefin T a b e catalyst ). Gewi Ch ^- I
mg H ₂ lie 2 100 S. 95 15th I. tertiary At si 200 bar -3 amines 75 77 - O ¹ N
I. 31 Witches-1 1 200 60 CO solvent 98 97 7th 32 Decene-1 3 2000 90 bar 98 98 20th 33 Witches-1 4th 220 60 60 toluene 100 96 28 34 Dodecen 1 5 200 60 30th Ethanol 97 75 - 35 Witches-1 6th 670 60 60 toluene 36 Witches-1 14th 60 60 toluene 60 toluene 60 toluene cn
ο
CD
GO
CjO i
ο

Table 3

example Catalyst unsaturated
Substrate
Example weight
mg 800 Hexen-1 (40ml) Hydrogenation; H ₂
bar reaction time Reaction
product
(D % 0 IJ [JI (2) 37 1 800 Nitrobenzene
(40 ml) solvent 20th 3 h 40 min Hexane 94 0 , 5 ppm Rh 38 1 200 Octene-1 (10ml) Toluene (40ml) 20th 7 h Aniline 96 3 , 5 ppm Rh 39 3 800 Hexen-1 (40ml) Toluene (40ml) 20th 3 h Octane 74 0 ppm Ru 40 8th 500 Hexen-1 (10ml) Heptane (10ml) 20th 3 h Hexane 94 , 5 ppm Rh 41 12th 312 Decen-1 (10ml) Toluene (40ml) 20-
40+ 4 h
1 h 30 min Hexane 38 ppm Pt cn . 42 15th Heptane (10ml) 20th 5 h Dean 66 ppm Pd 3 9 833 Heptane (10ml) / ΊΟ 3

00 I.

ro -ο-

on OO

1A-45 25 ?:

Footnotes to Tables 244 3058

Table 1;

The numbers in brackets refer to Experiments carried out with the catalyst recovered after the reaction.

In Examples 19, 20 and 27, the reaction vessel was cooled to room temperature after completion of the reaction, auf'-80 in all the other examples ⁰ C abgekühlt.In Example 28 2000 mg of catalyst were used.

Table 2; (^ = Degree of conversion for olefin

S = selectivity to tertiary amines, based on consumed Olefin

^ i | 7 = metal concentration in the liquid phase after the Response, given in ppm. The amount of catalyst used corresponded to 2 mg of metal.

Table 3:

All experiments were carried out at 10 ° C. After the reaction had ended, the reactor was brought to room temperature (Examples 39, 41 and 42) or to -8Ö ^Q e ^! (37, 38, 40) cooled. (1) = Degree of conversion of the unsaturated substrate to hydrogenated product

(2) / S7 = metal concentration in the liquid phase after completed reaction. ■

Claims; 72XV

509 833 ^

Claims (5)

Claims 1. Solid coordination complex compounds of transition metals which are insoluble in water and organic solvents of group VIII of the periodic table of the general formula (A-Si-C) M (L ') _n (L ") _q ι
in which A-Si-C represents an insoluble coordinate component, A being a solid inorganic nucleus based on silica or alumina and C being a group containing a carboxylic acid group or nitrogen in the form of a primary, secondary or tertiary, aliphatic, aromatic or heterocyclic Contains amine or polyamine, M is a transition metal of Group VIII of the Periodic Table with the exception of iron and nickel and L ¹ and L ¹ ″ are 2-bond ligands such as carbon monoxide, olefins, amines, phosphines, phosphites or arsines and η and q respectively represent an integer from 0 to 6. 2. Process for the preparation of the compounds according to claim 1, characterized in that one a salt or a coordinative complex compound of a Group VIII metal either a) directly with the insoluble coordinative component A-Si-C or b) with a chlorosilane or alkoxysilane for the reaction brings which contains an amino group or a carboxylic acid group and. then the new complex compound formed Reacts with silica or alumina. 509833/1031 1A-45 252-20- 5. The method according to claim 2, characterized in that such a coordinative com brings component A-Si-C to the reaction, either by reaction of an alkoxysilane or a chlorosilane containing an amino group or a carboxylic acid group with silica or alumina or by reacting one Vinylalkoxysilane or a vinylchlorosilane with silica or alumina and subsequent copolymerization with a vinyl pyridine or alkyl acid. 4. Use of the compounds according to claim 1 for hydroformylation, hydrogenation and production of tertiary Amines. 5098 33/1031