Catalyst with a base consisting of compounds of the rare...

Details Catalyst with a base consisting of compounds of the rare... Catalyst with a base consisting of compounds of the rare...

2000-04-18

2002-05-07

Wu, David W. (Department: 1713)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C502S103000, C502S104000, C526S164000, C526S161000, C526S172000, C526S335000, C526S348600

Reexamination Certificate

active

06383971

ABSTRACT:

The present invention relates to new catalysts based on compounds of the rare earth metals as well as the use of the new catalysts for the polymerisation of unsaturated compounds, in particular conjugated dienes.
The polymerisation of unsaturated organic compounds, in particular conjugated dienes, in the presence of catalysts based on rare earth metals has been known for a long time (see for example DE 28 33 721, U.S. Pat. No. 4,429,089, EP 76 535, EP 92 270, EP 92 271, EP 207 558. WO 93/05083, U.S. Pat. No. 5,627,119, EP 667 357, U.S. Pat. No. 3,478,901, EP 637 589). In this connection the Ziegler-Natta catalysts based on the rare earth metals have proved to be particularly suitable. For example, EP 11 184 proposes a catalyst system based on the rare earth metals, in particular based on neodymium compounds, which is particularly suitable for the polymerisation of conjugated dienes, in particular butadiene. In the polymerisation of for example butadiene these catalysts provide a polybutadiene in very good yields and with high selectivity, which is characterised in particular by a high proportion of cis-1,4 units. However, the disadvantage of the use of these catalysts for the polymerisation of conjugated dienes is the small proportion of laterally bound vinyl groups (1,2 units) in the polymer. The proportion of 1,2-double bonds in the polymer is thus often less than 1%.
Catalysts based on structurally defined allyl complexes of the rare earth metals have been described in WO 96/31 544, by means of which diene rubbers are obtained containing a high proportion of 1,4-cis-double bonds and more than 1% of 1,2-double bonds. A serious disadvantage of the use of these catalysts is that, being structurally defined allyl compounds, they are very difficult and expensive to produce and are thus not competitive with the generally more inexpensive Ziegler-Natta catalysts, which are moreover available in any desire amounts.
The aim of the present invention is accordingly to provide a catalyst system based on the rare earth metals, by means of which in the polymerisation of conjugated dienes a substantially higher proportion of laterally bound vinyl groups can be obtained in the polymer. Polydienes with a high proportion of lateral 1,2-double bonds in polymers have a great influence in particular with regard to their use as modifiers in plastics, in order to improve for example the impact strength. Examples of such rubber/plastics combinations are HIPS and ABS (Ullmann, 4th Edition, Vol. 19, p. 265 ff and p. 277 ff). It is furthermore desirable-for economic reasons—that the catalysts can be used in readily available aliphatic solvents and that, with their use, the 1,4-cis and 1,4-trans content in the polydienes can be controlled while at the same time maintaining a uniform content of 1,2-double bonds in the polymer.
The present invention thus relates to a catalyst based on compounds of the rare earth metals, comprising:
a) a compound of tile rare earth metals,
b) a cyclopentadiene, and
c) an alumoxane,
the molar ratio of the components (a):(b):(c) being in the range from 1:0.01 to 1.99:1 to 1000.
The molar ratio of the components (a):(b):(c) is preferably in the range from 1:0.2 to 1.8:3 to 500, particularly preferably in the range 1:0.5 to 1.5:5 to 100.
Compounds of the rare earth metals (component (a)) that are particularly suitable are those selected from
an alcoholate of the rare earth metals.
a phosphonate, phosphinate and/or phosphate of the rare earth metals,
a carboxylate of the rare earth metals,
a complex compound of the rare earth metals with diketones and/or
an addition compound of the halides of the rare earth metals with an oxygen donor or nitrogen donor compound.
The aforementioned compounds of the rare earth metals are for example described in more detail in EP 11 184.
The compounds of the rare earth metals are in particular based on the elements with the atomic numbers 21, 39 and 57 to 71. Lanthanum, praseodymium or neodymium or a mixture of elements of the rare earth metals that contains at least one of the elements lanthanum, praseodymium or neodymium in an amount of at least 10 wt. % are preferably used as rare earth metals. Lanthanum or neodymium are particularly preferably used as rare earth metals, which again may be used mixed with other rare earth metals. The proportion of lanthanum and/or neodymium in such a mixture is particularly preferably at least 30 wt. %.
Suitable alcoholates, phosphonates, phosphinates and carboxylates of the rare earth metals or suitable complex compounds of the rare earth metals with diketones are in particular those in which the organic group contained in the compounds contains in particular straight-chain or branched alkyl radicals with 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopropyl, isobutyl, tert.-butyl, 2-ethylhexyl, neo-pentyl, neo-octyl, neo-decyl or neo-dodecyl radicals.
As alcoholates of the rare earth metals there may for example be mentioned:
Neodymium(III) n-propanolate, neodymium(III) n-butanolate, neodymium(III) n-decanolate, neodymium(III) iso-propanolate, neodymium(III) 2-ethly-hexanolate, praseodymium(III) n-propanolate, praseodymium(III) n-butanolate, praseodymium(III) n-decanolate, praseodymium(III) iso-propanolate, praseodymium(III) 2-ethyl-hexanolate, lanthanum(III) n-propanolate, lanthanum(III) n-butanolate, lanthanum(III) n-decanolate, lanthanum(III) iso-propanolate, lanthanum(III) 2-ethyl-hexanolate, preferably neodymium(III) n-butanolate, neodymium(III) n-decanolate, neodymium(III) 2-ethyl-hexanolate.
As suitable phosphonates, phosphinates and phosphates of the rare earth metals there may for example be mentioned: neodymium(III) dibutyl phosphonate, neodymium(III) dipentyl phosphonate, neodymium(III) dihexyl phosphonate, neodymium(III) diheptyl phosphonate, neodymium(III) dioctyl phosphonate, neodymium(III) dinonyl phosphonate, neodymium(III) didodecyl phosphonate, neodymium (III) dibutyl phosphinate, neodymium(III) dipentyl phosphinate neodymium(III) dihexyl phosphinate, neodymium(III) diheptyl phosphinate neodymium(III dioctyl phosphinate neodymium(III) dinonyl phosphinate, neodymium(III) didodecyl phosphinate, and neodymium(III) phosphate, preferably neodymium(III) dioctyl phosphinate and neodymium(III) dioctyl phosphinate.
Suitable carboxylates of the rare earth metals are:
Lanthanum(III) propionate, lanthanum(III) diethylacetate, lanthanum(III) 2-ethylhexanoate, lanthanum(III) stearate, lanthanum(III) benzoate, lanthanum(III) cyclohexanecarboxylate, lanthanum(III) oleate, lanthanum(III) versatate, lanthanum(III) naphthenate, praseodymium(III) propionate, praseodymium(III) diethylacetate, praseodymium(III) 2-ethylhexanoate, praseodymium(III) stearate, praseodymium(III) benzoate, praseodymium(III) cyclohexanecarboxylate, praseodymium(III) oleate, praseodymium(III) versatate, praseodymium(III) naphthenate, neodymium(III) propionate, neodymium(III) diethylacetate, neodymium(III) 2-ethylhexanoate, neodymium(III) stearate, neodymium(III) benzoate, neodymium(III) cyclohexanecarboxylate, neodymium(III) oleate, neodymium(III) versatate, neodymium(III) naphthenate, preferably neodymium(III) 2-ethylhexanoate, neodymium(III) versatate, neodymium(III) naphthenate. Neodymium versatate is particularly preferred.
As complex compounds of the rare earth metals with diketones, there may be mentioned:
Lanthanum(III) acetylacetonate, praseodymium(III) acetylacetonate, neodymium(III) acetylacetonate, preferably neodymium(III) acetylacetonate.
As addition compounds of the halides of the rare earth metals with an oxygen donor or a nitrogen donor compound, there may for example be mentioned: Lanthanum(III) chloride with tributyl phosphate, lanthanum(III) chloride with tetrahydrofuran, lanthanum(III) chloride with iso-propanol, lanthanum(III) chloride with pyridine, lanthanum(III) chloride with 2-ethylhexanol, lanthanum(III) chloride with ethanol, praseodymium(III) chloride with tributyl phosphate, praseodymium(III) chloride with tetrahydrofuran, praseodymium(III) ch

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