DE2022489A1 - Catalyst carrier - Google Patents

Description

DR.-ING. RICHARD GLAWE DlPL-ING. KLAUS DELFS DIPL-PHYS. DR. WAITER MOLL

MUNICH HAMBURG MÖNCHEN

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2000 Hamburg 52 · WaltafraBe 12 '■ Tel. (0411) 89 22 55 8000 Munich 22 · LiebherrstraBe 20 ■ Tel. (0811) 22 65 48

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E / Mh

P. 5685/70

HAMBURG

THE BRITISH. PETROLEUM 0OMPAEYLIMITED, Britannic House, Moor Lane, London E.CV.2 / England

Catalyst carrier

The present invention "relates to a catalyst support, catalysts derived from the support, and methods of making them.

The use of phosphine complexes of transition metals as homogeneous catalysts for numerous reactions, such as carboxylation, hydrogenation and oligomerization of Olefins are known. These catalysts often contain

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valuable metals, e.g. palladium and iridium, and it is therefore the recovery and recycling of the Catalysts of great importance. However, it is often a problem to recover the catalyst in to a high degree.

It has now been found that special polymeric carriers, which themselves contain trivalent phosphorus groups can be produced; these form macromolecular ones Transition metal complexes, which in many respects are equivalent to the above-mentioned catalysts and that are easier to regain.

The object according to the invention is achieved in that a polymeric material is proposed as the catalyst support _s 0.1 to 20 wt .- ^ phosphorus and units of the formula

■ (GH ₂ ) _X CR GHR (GH ₂ ) _y -

1 11
PR ¹ R ¹ '

11 contains, in which the groups R _$ R and R are aryl groups or alkyl groups; which contain up to 6 carbon atoms, or hydrogen, and in which one of the RG groups can be chlorine, and x, y, η and m NuIl or a

009885/2086
BATH

are integers up to 3 and ρ is an integer,

where the molecular weight of the polymeric material ■

greater than. 1000 is.

According to the invention, a Yerfahren for producing a support material for catalysts as defined above is created, which consists in that an olefinically unsaturated polymer with a molecular weight of at least 300 and which has a bromine number of at least 0.5, at a temperature in containing e bond, under conditions such _s reacting the phosphorus-containing compound itself attaches to the double bonds of the polymer - the range from room temperature to 250 C with a compound containing trivalent phosphorus and at least one]) T.

The unsaturated polymer preferably has a molecular weight in the range from 300 to 1/2 mil ₅ , although substances with a higher molecular weight can be used.

Suitable olefinically unsaturated polymers are polymers of dienes, especially conjugated dienes, z. B. polybutadiene, polychloroprene} poly-1, 3-pentadiene and polyisoprene. It has been found that it is easier to incorporate phosphorus in 1,2-polybutadiene than in 1,4-polybutadiene and therefore the former is preferred

009885/2086

■■■■■■. : '. ■■' ■■■ '- ■ .. "■ ■ ■■ - ■■■■ ■■■'. ■. · ^: -4-

^_:::; - .: ■■; bath

or dehydration of polyvinyl alcohol.

be as can graft, random, alternating or block Gopolymerisate of dienes with other monomers, for example styrene. Typical copolymers are butadiene / styrene and hexadiene terpolymers.

Suitable Phoyphorverbindungen are alkyl, cycloalkyl or arylphosphines or phosphine (PB ,,) and in particular Dialkyl, dicycloalkyl or diarylphosphines where the Alkyl, cycloalkyl or aryl radicals less than 20 carbon atoms per molecule. Jiis are phenylphosphine, diphenylphosphine, dicyciohexylphosphine, diethyl, Dipropyl, dibutyl and dihexyl phosphines are preferred.

In a typical case, it is believed that the reaction proceeds as follows:

- GH = GH -

η ⁺ < ^Q 6V

OH - OH ₂ -

The reaction can be carried out simply by converting the polymers into the phosphorus-containing compound stirred under an inert atmosphere such as dry nitrogen with a solvent if necessary. Jus

009885/2086

—5—

becomes a free radical initiator such as ultraviolet light, a peroxide such as t-ButylliydroperOxya s or an azo compound, such as:, cC '-azo-bis-isobutyronitrile, is added and the mixture is heated for as long as necessary. The degree of warming and the time during which it is required usually depends mainly on the properties of the initiator chosen and, in particular, on its half life, which is with the ! Temperature fluctuates.

The phosphorus-containing support material preferably contains 0.1 to 15 wt ·, -fo phosphorus. '

Any suitable inert organic solvent can be used such as cyclohexane, can be used »■

The olefinically unsaturated polymer is usually with a stoichiometric excess of the phosphorus-containing Mixed connection »It has been found to be useful

'.- ■ - ■ ""' ■■ ■ '.

proved, the phosphorus-containing compound as Lö- ■ ...- (J

to use a means for the polymer; ·

~. These polymers can have a number of about = transition metal compounds are converted to macromolecular transition metal complexes, which in many ways · .. sees the above mentioned catalysts are equivalent and which are generally easier to retrieve. These masses can also be used as heat and flame resistant Fabrics or be useful as pigmented fabrics.

0Q988B / 2086 BAD ORIGINAL

According to an invention, a catalyst is also created, which contains a catalyst support material as defined above, in which the phosphorus atoms to the extent of transition metal atoms are bound that the catalyst contains 0.01 to 20 wt .- $ metal.

Preferred transition metals are Group VIII metals, although Cr, Mo, Mn, W, Re ₉ Ti, V, Cu, and Au can also be used. Suitable compounds of Group VIII metals are those that react with phosphines or substituted phosphines assets. Examples are halides, such as chlorides of formula RhCl. ,, MCIp (in which M ₅ zweiiirertiges Ii Pd, Pt or Co), Na ₉ PdCl _4, IrCl, _s TIGL., CrCl ₇₉ Äthylenkomplexe of iridium palladium ₅ - or platinum halide or carboxylates ^ II-ally! compounds, such as II-allylnickel chloride or its complexes with aluminum, alkyl, olefin cyclopentadienyl or! - aromatic complexes »

Also suitable are metal carbonyls and carbonyl-containing metal complexes, S ₀ B ₀ Ni (COKj Co _v (CO) aa Rh (G0) ₉ -acaC ;, Fe (GO) _rs Mn ₂ (CO) ₁₀ , M (CO) g, where M'Gr _{9 is} Mo or W, V (GO) ₆ , Rh ₂ (CO) 4 Gl ₂ and RCO Go (CO) ₄₉ where R is an alkyl = or aryl group »

The Katalysatorzusammensetzungeri containing transition metal are manufactured at temperatures in the range 20 to 25O = ⁰ G under such Bediagungan that the Übergangsmetallatom® Ea cii® phosphorus atoms are bound. The reaction is often effected by putting the transition metal compound and the phosphorus-containing carrier in a 008885/2086 BADORiGINAL

Si

heated appropriate solvent for one or both reactants. In some cases it is useful to to carry out the reaction at room temperature or below. Saturated or aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ethers or mixtures of these can be used as solvents.

Heating is usually continued for 1/2 to 6 hours, but the reaction time may be longer in special cases

or be shorter. Ä

When the metal-containing polymer is formed, one of the following reactions often takes place!

a) the transition metal compound contains a shiftable ligand, such as carbonyl, olefin, diolefin, phosphine or a solvent molecule, e.g. tetrahydrofuran, and the ligand is shifted under the reaction conditions, while the transition metal atom forms chelates with the phosphorus, e.g. i

R ₃ P + Ki (CO) ₄ -> ( ^R 3 ^p ) _n ^Ki ^ ^G0 Un ^{where n = 1 or 2}

R ₃ P + Fe (UO) ₅ > R ₃ P Fe (CO)

₅ > R ₃ P Fe (CO) ₄

R ₃ P + Rh ₂ (CO) ₄ Cl ₂ »(R ₃ P) ₂ Rh Cl (CO)

R ₃ P + M (CO) ₆ > ( ^R 3 ^p ) _n ^{M (G0)} 6-n

where IK = Cr, LIo or W, η = 1 or 2 and R, P + Rh (CO) ₂ -acac »K ₃ P Rh (C0) -acac, where acac is acetylacetonate.

b) The transition metal is able to increase its coordination number under the reaction conditions and is allowed

00988 5/2086 '-8-

in that the Ghelat "forms, / e.g. s

Ni (GI) T) + R ₃ P _} (R ₅ P) _n Ni (OO) ₄ _ _n where n = 1 or

R ₇ P + Fe (GO) _{5 )} RJ? Fe (GO) ₄

R ₃ P + Rh ₂ (GO) ₄ Ol ₂ . ( ^R 3 ^p ) 2 ^{Rh G1}

R ₃ P + M (GO) _6? (R ₅ P) _n M (00) ₆ _ _n

where M = Gr, Mo or W, n = 1 or 2 and RJP + Rh (G0) ₂ -acac -j>

RJP Rh- (C0) -acac, where acac is acetylaeetonate.

b) The transition metal is able to increase its coordination number under the reaction conditions and is allowed in that the chelate is formed, or e.g .:

Wi (GDT) + R ₃ P _χ R ₃ P Ni (GDT)

where GDT is 1, 5, 9 - cyclododecatriene

RJP + MGl ₉ ν (RP) _o + MGl ₀

where M is divalent nickel, ₉ palladium platinum, or obalt

τ? P 4- Ph η inert
3 ^{P + Iih} - ¹ S reading center <« ₃ ^P > ₂ ^Kh01 ₅

c) The reaction takes place in the presence of a solvent that enters into the reaction, for example 0 H ₁ -OH in a mixture with KOH, which introduces a GO group as in

G ₀ H ₁ -OH
RJ? + Rh Gl _x and __ ~ Jl-_w ( ^R * ^p ) o Rh (GO) Eq

₀ p

or RP + Ir Gl ₃ ^ά ° ^ (R ₃ P) ₂ Ir CO Gl

θχΧΘχη

or R-P + Rh 01,> (K, P), Rh (H) CO,

YY 3 »5 5

works either in HGHO in ethanol or NaHi in ethanol.

009885/2086 -9-

In the above formula, at least one of the R-G groups is one polymer chain, while the other is alkyl or aryl could be.

Many of the compositions of the invention are active as catalysts and are such homogeneous phosphine-containing complexes as IrH ₃ (Ph ₅ P) ₃ or IrH ₂ (OOGCH ₅ ) (Ph ₅ P) ₅ for the hydrogenation of aldehydes or PdCl ₉ (Bu ^ p) ρ for the carboxylation of olefins is similar. .

It can be a co-catalyst, such as an aluminum alkyl, Aluminum alkyl halide or aluminum trihalide or Sodium borohydride may be necessary to remove the phosphine Complex to make active.

A number of catalyst systems consists of a mixture of a transition metal compound, a phosphine and a reducing agent such as an aluminum alkyl, such as:

M (acac) n + Ph ₃ P + It ₂ Al (OAt) for the cyclodimerization *

of butadiene, where MPe is (III), Co (III) or M (II), η is 2 or 3 and acac means acetylacetonate.

Ni (acac) ₂ + R ₃ P + At ₃ Al ₂ Cl ₃ for the Propylenoligomerisa- '

tion and (RGOO) ₂ Ii + Ph ₃ P + R ₂ AlGl for the propylene

dimerization. In these cases the active species is formed in situ.

The PhoBphin connections can be found in this Ffille by the

-10-

by the phosphorus-containing polymers of the invention be replaced, with the active species on the polymer surface and a catalyst using a composition of the present invention is provided.

The polymeric carriers of the invention can also be used as heat and flame retardants in certain cases are, for example flame retardant polybutadiene and polyisoprene, lubricating oil additives (where the solubility it allows) and as sequestrating agents for transition metals in solution »

The invention is explained in more detail by the following examples »

example 1

In Examples 1 to 3, the polybutadiene was 98 μfa and had a molecular weight in excess of 30,000 and was made using a titanium-aluminum Ziegler catalyst. 2.7 grams of polybutadiene was placed in a quartz flask under nitrogen, 40 ml (approximately 0.2 moles) of diphenylphosphine added under nitrogen and the reaction mixture was stirred until the polymer dissolved. The piston was then irradiated with UV light with stirring for 24 hours. The excess Dipheny! Phosphine was under ■, Vacuum distilled from the reaction mixture and that resulting polymer dissolved in 150 ml of toluene and precipitated with methanol. The polymer was then evacuated.

009885 / 208S

Phosphorus content = 1.7% by weight> ■:

Example 2

2.7 g of polybutadiene was placed in a flask under nitrogen and 20 ml of diphenylphosphine (approximately 0.1 mole) was added. The reaction mixture was stirred until the polymer dissolved, and then 10 drops of tert-butyl hydroperoxide were added. The reaction mixture was heated at 140 ⁰ G for 6 hours under reflux, and then treated in the manner described above. Phosphorus content = 2.0 f

Example 3

5.4 g of polybutadiene were taken in 200 ml of cyclohexane; Dissolved nitrogen. 19 ml (0.1 mol) Diphenylphosphiny dissolved in 50 ml Gyclohexan "followed by 5 gc was added £ is - C ^ j '-azo-bis-isobutyronitrile. The reaction mixture was heated for 12 hours at 80 ⁰ and G with UV light sawn m irradiated. The polymer was obtained by precipitation with methanol and then evacuated.
Phosphorus content = 0.9% by weight.

Example 4

2.5 g of 1) 2-polybutadiene were under nitrogen in a Put quartz flask and add 50 ml of diphenylphosphine. The reaction mixture was mechanically shaken until the polymer had dissolved and then with UV light for 72 hours at room temperature under nitrogen

009885/2086 'i ₂ ~

shine. Then the excess diphenylphosphine was evaporated. The resulting polymer was dissolved in 15 ml of toluene and then precipitated from the solution with 300 ml of η-hexane. This procedure was repeated 5 times. Finally, the polymer was dissolved in 50 ml of toluene, the toluene is evaporated und.das polymer under vacuum at 120 ⁰ C during 12 hours.

The polybutadiene was 88 $ 1.2, 4 $ trans-1,4, & 7 ° cis-1.4 and had a molecular weight of 28,000; it was made by anionic polymerization in tetrahydrofuran. Phosphorus content = 7.9 wt .

Example 5

1 g of the phosphorus-containing polymer (prepared as in Example 4) was dissolved in 50 ml of toluene and there were 0.26 g of anhydrous cobalt (II) chloride in 10 ml of n-butanol added. The reaction mixture was under nitrogen

Heated under reflux for 2 hours. A blue polymeric material precipitated out. This was briefly extracted with a 10 v / v% strength solution of n-butanol in toluene. The polymer was then heated in 300 ml of refluxing n-butanol, the resulting solution cooled and poured into 1 liter of pentane. $> - The polymer was abfiltxiert, washed with pentane and dried in vacuo * cobalt content = 3.1 wt.

-13- 009885/2086

Example 6

5 g of 1,2-polybutadiene as used in Example 4 was placed in a quartz flask under nitrogen and 50 ml of di-n-hexylphosphine was added. The reaction mixture was shaken mechanically when the polymer had dissolved and then irradiated with UV light "at room temperature under nitrogen" for 72 hours. The excess Din-hexylphosphin was evaporated at 200 ⁰ G under a vacuum of 0.5 mm Hg. The polymer was then redissolved in 25 ml of degassed toluene and precipitated with 400 ml of degassed methanol. This procedure was repeated 5 times. The polymer was finally redissolved in 100 ml of degassed toluene? the toluene was evaporated, and the polymer at 120 G ⁰ for 12 hours in vacuo.
Phosphorus content = 11.2 wt. = $ "

Claims (1)

Claims 1. Polymeric catalyst support material with a molecular weight of at least 1000, thereby ge indicates that there are units of the formula GR GHR (CH ^ 1 11 R ¹ R ¹ ' 1, in which the groups R, R and R are aryl or alkyl groups with "up to 6 carbon atoms or hydrogen and one of these R groups can be chlorine _s and S ₅ -J ₉ η \ mä m. O'oclcsr a © whole "number" up to 5 "mean and 'p sin © sens® number is = . Material according to Claim I _8, characterized in that the Ph ο θ ph ο rkt ο me are bound to transition metal atoms to the extent that the material contains 0.01 to 20 wt .- ^ metal <D O (O CO CO / 3./Verfahren for the production of a catalyst support material with a molecular weight of at least 100O _9, characterized in that an olefinically unsaturated polymer from 'molecular weight at least 300 and a bromine number of at least O ₉ S with a compound containing trivalent phosphorus and at least one> P - H bond contains ₉ "at a temperature in the range from room temperature - to 25O ⁰ G under such conditions , 1 alcn äi® containing phosphorus © Adds compound to the double bonds d @@ Pol ₅ i / m @ ria ©, ts "