Polymers of olefinically unsaturated monomers

Details Polymers of olefinically unsaturated monomers Polymers of olefinically unsaturated monomers

1997-11-20

2000-02-29

Wu, David W.

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

526170, 526172, 526161, C08F 480

Patent

active

06031057&

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to a process for preparing polymers of olefinically unsaturated monomers by polymerization of unsaturated monomers in the presence of a metal complex of the general formula (I) ##STR2## where the substituents and indices have the following meanings: M is a metal from group VIIIB of the Periodic Table of the Elements, the Elements, or VIA of the Periodic Table of the Elements, C.sub.1 -C.sub.20 -organic and C.sub.3 -C.sub.30 -organosilicon radicals, where the radicals can contain one or more elements of groups IVA, VA, VIA and VIIA of the Periodic Table of the Elements,
The polymerization of olefinically unsaturated monomers, for example of ethylene, C.sub.3 -C.sub.8 -alk-1-enes and acrylic acid derivatives, is well known for different polymerization processes, and the polyolefins obtainable are widely used commercially in many fields of application, for example as films, moldings and fibers.
The polymerization of the olefins is catalyzed or initiated, inter alia, by mixed catalysts comprising compounds of the early transition metals (titanium, zirconium, etc) and alkyl compounds of the main group metals (eg. aluminum alkyls), known as Ziegler catalysts, or else by means of free-radical initiators.
However, Ziegler catalysts have some disadvantages. They usually react, sometimes very vigorously, with moisture and oxygen, generally losing their catalytic activity.
Furthermore, these catalysts are generally not able to (co)polymerize unsaturated compounds containing functional groups such as carboxylic acid groups or ester groups.
In addition, the polymerization of cyclic, olefinically unsaturated monomers or olefinically polyunsaturated, linear monomers often does not proceed in the desired manner, namely as a polyinsertion reaction, but results in secondary reactions such as ring opening of the cyclic monomers or ring formation of the linear monomers. The polymers thus formed have high nonuniformity both of the chemical composition and of the molecular weight distribution.
Free-radical initiators are generally able, under high pressure, to copolymerize, for example, olefins with polar, unsaturated monomers, but the incorporation of the comonomer is often nonuniform and the polymer structure is branched, which leads, for example, to lower polymer film quality.
These characteristics restrict the field of application of the resulting polymers obtained by the various polymerization processes and it is therefore desirable to seek alternative polymers or polymerization processes which do not have said disadvantages or have them only to a subordinate degree.
EP-A 0 589 527 describes catalyst systems for olefin homopolymerization and olefin copolymerization which are based on specific palladium phosphine complexes. However, both the preparative accessibility and the polymerization behavior of these catalysts leave something to be desired. Thus, only low degrees of polymerization (oligomers having from 3 to 20 monomer units) are obtained in polar solvents such as methanol, ethylene glycol or water. In nonpolar solvents such as diethylene glycol dimethyl ether (diglyme) too, maximum molecular weights Mn of only 5600 are achieved, with only traces of the comonomer being incorporated. The use of internal olefins is also not described, and the double bond content of the polymers and their molecular weight distribution Mw/Mn is likewise not disclosed.
EP-A 0 454 231 describes catalyst systems for the polymerization of ethylene, olefins and alkynes which are based on cationic metal complexes of late transition metals (group VIII). However, these catalysts are very sensitive to impurities. The achievable roductivities likewise leave something to be desired. No polar opolymers are described.
It is an object of the present invention to provide a novel polyerization process which does not have the disadvantages indiated and which, in particular, also leads to copolymers having polar comonomers incorporated in a predominantly linear sequence.
We have found that this object is achieved by a process

REFERENCES:
patent: 3051694 (1962-08-01), Meriwether et al.
patent: 5373071 (1994-12-01), Drent et al.
J. Am. Chem. Soc. 1995, 117, pp. 6414-6415, Johnson et al., "New Pd and Ni-based catalysts for polymerization of Ethylene and .alpha.-olefins."
Grant et al., Grant & Hackh's Chemical Dictionary, McGraw-Hill, p. 337, 1987.
W. Keim, R. Appel, A. Storeck, C. Kruger and R. Goddard, Angew. Chem. Int. Ed. Eng. 20 (1981) No. 1, pp. 116-117, "Novel Nickel and Palladium Complexes with aminobis(imino)phosphorane Ligands for the Polymerization of Ethylene."

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