Preparation of biphosphine ligands for incorporation into...

Details Preparation of biphosphine ligands for incorporation into... Preparation of biphosphine ligands for incorporation into...

2001-02-02

2003-04-15

Vollano, Jean F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Phosphorus containing

C568S017000, C568S016000, C568S012000

Reexamination Certificate

active

06548708

ABSTRACT:

This is the natural phase of PCT/EP05748 filed Mar. 8, 1999, now WO00/08030.
This invention relates to processes for making phosphorus-containing compounds; to novel phosphorus-containing compounds themselves; to a process for making lithiated compounds useful in the aforesaid processes; to the use of phosphorus-containing compounds produced by the aforesaid processes, in the preparation of polymerization catalyst-compositions; to the use of said catalyst compositions in the preparation of polymers; and to polymers thereby produced.
The invention concerns particularly though not exclusively, processes for the preparation of phosphorus-containing compounds useful in the preparation of catalyst compositions which facilitate the copolymerization of carbon monoxide with an olefinically unsaturated compound to make linear alternating copolymers.
Such copolymers and catalyst compositions are described, for example, in EP-A-121965 and EP-A-248483. To set the present invention in the context in which it was made these copolymers, catalysts, compositions and associated preparative process will now be described but it should be noted that many of the compounds and processes of the present invention, described in detail hereinafter, will be useful also in other contexts.
Broadly, such catalyst compositions comprise a Group VIII (in more modern nomenclature a Group 8, 9 or 10) metal. Examples of suitable Group VIII metals for use in such catalyst compositions are nickel and cobalt. However, the Group VIII metal is preferably a noble Group VIII metal, of which palladium is most preferred.
The Group VIII metal of such a composition is typically employed as a cationic species. As the source of Group VIII metal cations conveniently a Group VIII metal salt is used. Suitable salts include salts of mineral acids, such as sulphuric acid, nitric acid, phosphoric acid, perchloric acid and sulphonic acids, and organic salts, such as acetylacetonates. Preferably, a salt of a carboxylic acid is used, for example a carboxylic acid with up to 8 carbon items, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid and citric acid. Palladium (II) acetate and palladium (II) trifluoroacetate represent particularly preferred sources of palladium cations. Another suitable source of Group VIII metal cations is a compound of the Group VIII metal in its zero-valent state.
Such a catalyst composition is preferably based, as an additional component, on a ligand which forms a complex with the Group VIII metal. It would appear that the presence of two complexing sites in one ligand molecule significantly contributes to the activity of the catalysts. It is thus preferred to use a ligand containing at least two dentate groups which can complex with the Group VIII metal. Although less preferred, it is also possible to employ a monodentate ligand, i.e. a compound which contains a single dentate group which can complex with the Group VIII metal, in particular a dentate group of phosphorous. Suitably a bidentate ligand is used which contains two phosphorus-, nitrogen- or sulphur-containing dentate groups. It is also possible to use a mixed bidentate ligand such as 1-diphenylphosphino-3-ethylthiopropane.
A preferred bidentate ligand for such a catalyst composition can be indicated by the general formula
R
2
M
1
—X—M
2
R
2
  (I)
In this formula M
1
and M
2
independently represent a phosphorus, nitrogen, arsenic or antimony atom, each group R independently represents an optionally substituted hydrocarbyl group, in particular of up to 10 carbon atoms, and X represents a bivalent bridging group.
In a ligand of formula (I) each group R may independently represent an optionally substituted alkyl, aryl, aralkyl or cycloalkyl group.
An aryl group R is preferably phenyl.
Generally, unless stated otherwise in this specification, any alkyl group or alkyl moiety of a larger group may be linear or branched and may suitably contain 1 to 10, preferably 1 to 6, and most preferably 1 to 4 carbon atoms, suitable examples being methyl, ethyl and propyl. Generally, unless stated otherwise in this specification, any cycloalkyl group may be monocyclic or polycyclic and may contain 3-15, preferably 3-12, most preferably 3-8 carbon atoms, for example cyclohexyl.
Generally, unless stated otherwise in this specification, preferred substituents for an aryl group or an aryl moiety within a larger group include halogen, especially fluorine, chlorine and bromine atoms, and nitro, cyano, hydroxyl, alkyl, haloalkyl, haloalkoxy, alkoxyalkyl, aryloxy, alkoxy, alkoxyalkoxy, amino, mono- and di-alkylamino, aminoalkyl, mono- and di-alkylaminoalkyl, amido, and mono- and di-alkylamido groups.
Generally, unless otherwise stated in this specification, any substituted aryl group may suitably be substituted by 1-3 substituents, preferably by 1 substituent.
Generally, unless stated otherwise in this specification, preferred substituents of an alkyl or cycloalkyl group or of an alkyl or cycloalkyl moiety within a larger group include halogen, especially fluorine, chlorine or bromine atoms, and nitro, cyano, hydroxyl, alkoxy, haloalkoxy, alkoxycarbonyl, and amino and mono- and di-alkylamino groups.
Preferably a hydrocarbyl group R carries a polar moiety. Suitable polar moieties include halogen atoms, especially fluorine and chlorine, haloalkoxy groups, alkoxy groups, such as methoxy and ethoxy groups, amino, mono- and di-alkylamino groups, such as methylamino, dimethylamino and diethylamino groups, aminoalkyl, mono- and dialkylaminoalkyl groups, amido, mono- and di-alkylamido groups, alkoxyalkoxy, alkylthio, alkylsulfonyl, dialkylamidosulfonyl, alkylsulfonate, lithio-oxy, aryloxy groups such as phenoloxy and sulfonates (—SO
3
M, with M being Li, Na, K or H).
Preferably at least one group R represents an aromatic group, in particular an aromatic group which is polar substituted.
It is preferred that one or more of the groups R in the ligand of formula (I) represents an aryl group, preferably a phenyl group, substituted at an ortho position with respect to M
1
or M
2
by a polar moiety, preferably an alkoxy group, especially a methoxy group, or an aryloxy group, especially a phenoloxy group.
It is preferred that at least one of the groups R attached to the atom M
1
, and at least one of the groups R attached to the atom M
2
, is as defined above, in accordance with any of the definitions given in the preceding three paragraphs. It is preferred that all four groups R are as defined above, in accordance with any of the definitions given in the preceding paragraph.
Preferably all the groups R are identical. In especially preferred ligands each group R is an 2-methoxyphenyl group (hereinafter called 2-anisyl). In another preferred ligand each group R is a 2-phenoxyphenyl group.
In a ligand of formula (I), X preferably represents a bivalent bridging group containing at least 1 bridging atom, preferably containing from 2 to 4 bridging atoms. Bridging atoms may be selected from C, N, O, Si and S atoms. Preferably X is an organic bridging group containing at least one carbon atom. More preferably X is an organic bridging group containing from 2 to 4 bridging atoms, at least two of which are carbon atoms. Examples of such groups R are —CH
2
—CH
2
—, —CH
2
—CH
2
—CH
2
, —CH
2
—CH(CH
3
)—CH
2
—, —CH
2
—C(CH
3
)
2
—CH
2
—, —CH
2
—C(C
2
H
5
)
2
—CH
2
—, —CH
2
—Si(CH
3
)
2
—CH
2
—, —CH
2
—CH
2
—CH
2
—CH
2
—, —CH
2
—CH(C
2
H
5
)CH
2
—, —CH
2
—CH(n-Pr)—CH
2
and —CH
2
—CH(n-Bu)—CH
2
.
In a ligand of formula (I) M
1
and M
2
preferably represent phosphorus atoms and it is to the preparation of such ligands that certain aspect of the present invention relate.
The amount of a said bidentate ligand supplied may vary considerably, but is usually dependent on the amount of Group VIII metal present in the catalyst composition. Preferred amounts of a said phosphorus-containing bidentate ligand are in the range of from 0.5 to 8, more preferably in the range of from 0.5 to 2 moles per gram atom of Group VIII metal.
Such a Group VIII metal containing catalys

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