Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymer of an ethylenically unsaturated reactant with a...
Patent
1994-05-26
1998-02-03
Acquah, Samuel A.
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymer of an ethylenically unsaturated reactant with a...
528392, 524755, 524765, 524770, 524785, 502150, C08G 6702
Patent
active
057145741
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to a process for preparing polyketones by reacting one or more olefins with carbon monoxide in the presence of a palladium catalyst. In particular the invention relates to the use of certain preferred solvents in which the process is carried out. Polyketones are potentially useful polymers from which a wide range of plastic containers and packaging materials may be fabricated.
It is known to produce polyketones, which are linear alternating polymers of (a) one or more olefins and (b) carbon monoxide, by a liquid phase process in which the olefins(s) and carbon monoxide are polymerised together in methanol, ethanol or propanol solvent in the presence of a palladium catalyst. Such a process, which is disclosed in more detail in for example EP 121965 and EP 314309, typically employs a catalyst derived from (a) a palladium compound (b) a source of an anion which is either non-coordinating or only weakly coordinating to palladium and (c) a bisphosphine of formula R.sup.1 R.sup.2 P-R-PR.sup.3 R.sup.4 where R.sup.1 to R.sup.4 are independently aryl groups which can optionally be polar substituted and R is a divalent organic bridging group such as --(CH.sub.2).sub.n --(n=2 to 6). The source of the anion is typically its conjugate acid.
From U.S. Pat. Nos. 4,810,774 and 4,877,860 it is known that in such processes the molecular weight of the product is inversely proportional to the reaction temperature. As a consequence, in order to prepare products of acceptable molecular weight it is necessary to work at relatively low temperatures where the rate of polymerisation is relatively slow.
U.S. Pat. No. 4,810,774 teaches that an increase in the molecular weight of the polyketone product can be obtained by replacing at least part of the methanol, ethanol or propanol solvent by an aliphatic ketone having up to 10 carbon atoms, an aliphatic carboxylic acid ester or an aliphatic hydrocarbon. However, the use of such solvents systems is in general accompanied by a decrease in the rate of polymerisation and a fall in the bulk density of the polymer.
U.S. Pat. No. 4,877,860 teaches that improved rates of polymerisation for high bulk density polymers can be obtained using a ketone/alcohol mixture having more than 50% by volume of aliphatic ketones having at most 10 carbon atoms and more than 5% by volume of an aliphatic alcohol having at most 10 carbon atoms. Whilst, the primary or secondary alcohol/ketone mixtures disclosed therein go some way to solving this problem it remains an objective to further improve the polymerisation rate for a given molecular weight of product.
EP 322018 teaches that, when copolymerisation of a C.sub.3 to C.sub.10 olefin and carbon monoxide is effected, a preferred solvent system comprises (a) at least 75% by volume of either an aliphatic tertiary alcohol or an aromatic hydrocarbon having up to 10 carbon atoms and (b) at least 5% by volume of one or more aliphatic primary alcohols having up to 10 carbon atoms. However, Example 6 of this patent application teaches that when tertiary butanol is used in the absence of the other components of the solvent system no polymerisation occurs.
It has now been found that when polymerising carbon monoxide with mixtures of ethylene and at least one C.sub.3 to C.sub.10 alpha olefin at a given temperature, high molecular weights and good reaction rates can be obtained by using a solvent comprised of a C.sub.4 to C.sub.10 tertiary aliphatic alcohol optionally admixed with up to 80% by volume of a C.sub.3 to C.sub.10 aliphatic ketone or C.sub.4 to C.sub.10 cyclic aliphatic ether. Furthermore, it has been found that solvent systems containing a tertiary alcohol are superior to those disclosed in U.S. Pat. No. 4,877,860.
According to the present invention there is provided a process for preparing a polyketone comprising polymerising together carbon monoxide, ethylene and optionally at least one C.sub.3 to C.sub.10 alpha-olefin in the presence of a solvent and a catalyst composition derivable from a palladium salt, an anion which is eithe
REFERENCES:
patent: 3689460 (1972-09-01), Nozaki
patent: 3694412 (1972-09-01), Nozaki
patent: 4810774 (1989-03-01), Drent
patent: 4835250 (1989-05-01), Drent
patent: 4877860 (1989-10-01), van Broekhoven et al.
patent: 4925918 (1990-05-01), Brown et al.
patent: 5026674 (1991-06-01), Brown et al.
Acquah Samuel A.
BP Chemicals Limited
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