Functionalized cyclopentene-derived oligomer mixtures, their...

Details Functionalized cyclopentene-derived oligomer mixtures, their... Functionalized cyclopentene-derived oligomer mixtures, their...

1999-06-21

2002-03-05

Gitomer, Ralph (Department: 1623)

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

Organic compounds

Oxygen containing

C568S667000, C568S816000, C560S114000

Reexamination Certificate

active

06353141

ABSTRACT:

The present invention relates to functionalized cyclopentene-derived oligomer mixtures, processes for their preparation by hydroformylation and, where appropriate, further reaction of corresponding oligomer mixtures which contain ethylenic double bonds, and their use.
The processing of petroleum by steam cracking results inter alia in a hydrocarbon mixture which is called the C
5
cut and has a high total olefin content of, for example, about 50%, of which about 15% is made up of cyclopentene and the remainder of acyclic monoolefins, especially n-pentene (about 15% by weight) and other isomeric pentenes (about 20% by weight). This mixture can, if required, before further processing be subjected to partial catalytic hydrogenation so that dienes are essentially no longer present then. To isolate the cyclopentane which comprises about 8% of the C
5
cut and which is employed, for example, as propellent as substitute for the CFCs and HFCs which are of concern with regard to damage to the atmosphere, and where appropriate to isolate the other saturated acyclic pentanes, it is necessary in the prior art to subject the C
5
cut to work up by distillation. This is technically a very complicated process when acyclic and cyclic C
5
olefins, in particular cyclopentene, are simultaneously present. There is thus a need for a process for removing cyclopentene and, where appropriate, other monoolefins from the C
5
cut other than by distillation, where possible with simultaneous production of a new product of value.
It is possible for this purpose to subject the C
5
cut to a metathesis reaction in the presence of a transition metal catalyst, resulting in new cyclopentene-derived oligomer mixtures with ethylenic double bonds.
A known process for the functionalization of polymers with ethylenic double bonds is hydroformylation. Thus, for example, M. P. McGrath et al., describe, in J. Appl. Polym. Sci. 56, (1995) 533 et seq., the hydroformylation of EPDM polymers and polybutadienes with HRhCO(PPh
3
)
3
or Rh(CO)
2
acac (acac=acetylacetonato) as hydroformylation catalysts in toluene. Reviews on the hydroformylation of polymers with olefinic double bonds, such as polyisoprene or styrene/butadiene copolymers, are given by N. T. McManus et al. in J. Macromol. Sci., Rev. Macromol. Chem. Phys. C35(2) (1995) 239-285.
Aldehyde-functionalized polymers of this type in turn permit reactions to be carried out on the polymer, ie. conversion into or attachment of new functionalities which confer new properties on the polymer.
C. Azuma et al. describe in J. Polym. Sci., Polymer Chemistry Edition, 18, (1980) 781 et seq. the hydroformylation of a polypentenamer with a number average molecular weight of 94,000 in the presence of an HRhCO(PPh
3
)
3
catalyst, and the subsequent conversion into the oxo alcohols with various reducing agents such as sodium borohydride. The amounts of catalyst needed for this hydroformylation are extremely high at about 5000 ppm. Hydroformylation of the polymer is possible only to a maximum aldehyde content of 30 mol %, otherwise insoluble products result. It is likewise necessary for the hydroformylated polymers to be reacted further immediately, without isolation, otherwise crosslinking occurs, likewise resulting in completely insoluble products.
K. Weissermel, H. J. Arpe, Industrielle Organische Chemie, 4th edition, 1994, VCH Weinheim, pages 137 et seq. describe the hydroformylation (oxo synthesis) of olefins by reaction with carbon monoxide and hydrogen in the presence of a catalyst and generally at elevated temperatures under elevated pressures. The oxo aldehydes obtained therefrom have virtually no importance as final products but are important reactive intermediates for preparing oxo alcohols, oxo carboxylic acids and aldol condensates. It is furthermore possible for oxo aldehydes to be converted by reductive amination with ammonia or a primary or secondary amine in the presence of a reducing agent into the corresponding amines.
The oxo alcohols can in principle be prepared together with the hydroformylation, usually at elevated temperature, in a one-stage synthesis because the hydroformylation catalysts are generally also suitable for further hydrogenation of the oxo aldehydes. However, the oxo aldehydes are usually first isolated and then subjected to a catalytic hydrogenation on a specific hydrogenation catalyst selected from metals in group VIII or Ib, eg. a Cu or Ni catalyst.
To prepare oxo carboxylic acids, the oxo aldehydes can be oxidized with mild oxidizing agents, in the simplest case with air or with H
2
O
2
in the presence of acids. The oxidation with air can take place either catalytically in the presence of metal salts or else in the absence of catalysts at up to about 100° C. under pressures up to about 7 bar.
Houben-Weyl, Methoden der organischen Chemie, Volume XI/1, 1957, pages 602 et seq., describes the reduction of condensates of ammonia or amines and carbonyl compounds, and the reductive amination of carbonyl compounds, the latter, eg. an aldehyde, being reacted with ammonia or a primary or secondary amine in the presence of a reducing agent without isolation of an intermediate. The reducing agent generally used is hydrogen in the presence of a hydrogenation catalyst, but it is also possible to use other reducing agents, such as formic acid and its derivatives. None of the abovementioned publications refers to a process for functionalizing oligomers derived from cyclopentene and obtainable by a metathesis reaction of the C
5
cut from petroleum processing.
It is an object of the present invention to provide a process for further processing of the new oligomer mixtures produced by a metathesis reaction on the C
5
cut.
We have found that this object is achieved by a process for preparing functionalized cyclopentene-derived oligomer mixtures, where the cyclopentene-derived oligomer mixtures which contain ethylenic double bonds are subjected to a hydroformylation and, where appropriate, further functionalizations.
The invention thus relates to a process for preparing functionalized cyclopentene-derived oligomer mixtures by a single stage or multistage functionalization of at least some of the ethylenic double bonds present in an oligomer mixture of the formula I
R
1
R
2
C
CH—(CH
2
)
3
—CH
n
CR
3
R
4
  (I)
where n is an integer from 1 to 15, and R
1
, R
2
, R
3
and R
4
are, independently of one another, hydrogen or alkyl.
The value of n in the formula I is the number of cyclopentene units introduced by a ring-opening metathesis reaction into the cyclopentene-derived oligomer mixtures. The oligomer mixtures of the formula I preferably used for the process according to the invention are those where the value of n is >1 in a proportion which is as large as possible, eg. at least 40% by weight (determined by integration of areas in the gas chromatograms). The value of n and thus the extent of the ring-opening metathesis can be influenced by the activity of the metathesis catalyst used and the ratio of acyclic to cyclic olefins.
The radicals R
1
, R
2
, R
3
and R
4
in the formula I are, independently of one another, hydrogen or alkyl, where the term “alkyl” embraces straight-chain and branched alkyl groups.
These are preferably straight-chain or branched C
1
-C
15
-alkyl, preferably C
1
-C
10
-alkyl, particularly preferably C
1
-C
5
-alkyl, groups. Examples of alkyl groups are, in particular, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl, etc.
The degree of branching and the number of carbon

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