Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Patent
1996-04-15
1999-08-24
Wu, David W.
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
502152, 502155, 526 93, 526 94, 526120, 526134, 526171, 5263482, 5263483, 5263486, 526351, 556 7, 556 13, 556 34, B01J 3100
Patent
active
059424613
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
This invention relates to polymerizable compositions comprising alpha-olefin hydrocarbon monomers and a method for their polymerization, wherein the method is tolerant of both oxygen and water. Catalysts for the polymerization include organometallic complexes of Group VIII metals (CAS version of the Periodic Table), preferably Pd or Ni. Methods for polymerizing the polymerizable composition in open air and in the presence of water to provide novel polymers are described.
BACKGROUND OF THE INVENTION
Non-free radical polymerizations of ethylenically-unsaturated monomers are well known. Typically, these polymerizations use catalysts instead of initiators to effect polymerizations. Examples of such catalyzed polymerizations include Ziegler-Natta (ZN) polymerizations of alpha-olefins, ring-opening metathesis polymerizations (ROMP) of cyclic olefins, group-transfer polymerizations (GTP), and cationic and anionic polymerizations of activated olefins such as styrene or acrylate esters. More recently, metallocene catalysts have received considerable attention for polymerization of alpha-olefins. ZN and metallocene catalysts for alpha-olefin polymerizations are susceptible to deactivation by adventitious oxygen and water, requiring that such deactivating materials be rigorously excluded from all reagents as well as the reaction vessel.
European Patent Application No. 454231 describes a polymerization catalyst and a method of polymerizing ethylene, other olefins, and alkynes using a polymerization catalyst whose cationic portion has the formula Group VIII metal, and R is H, a hydrocarbyl radical or a substituted hydrocarbyl radical, and a substituted tetraphenylborate anion as the counterion. A preferred cationic portion has the formula ##STR1## wherein L' is a two-electron donor ligand and ##STR2## are chelating ligands wherein each L" is a neutral two-electron donor ligand, and M is nickel or palladium. All olefin polymerizations were conducted with ethylene, were carried out under dry, oxygen-free nitrogen atmospheres and all solvents were thoroughly dried under nitrogen by distillation from, e.g., sodiun/benzophenone. High polymer (M.sub.w >90,000) was not disclosed.
Johnson et al., (J Am. Chem. Soc., 1995, 117, 6414-6415 and supplementary material) describe Pd(II)- and Ni(II)-based catalysts for alpha-olefin polymerizations wherein the catalysts are, for example, cationic metal methyl complexes of the general formula {BAr'.sub.4 }.sup.- 2,6-C.sub.6 H.sub.3 (R') where R' is isopropyl or methyl; R.sup.1 is H, methyl, or the two R.sup.1 groups taken together are 1,8-naphthalene-diyl. All polymerizations were carried out in inert atmospheres, and polymers of ethylene, propene, and 1-hexene are reported. The same authors and S. J. McLain et al. reported that the same catalysts copolymerized ethylene and methyl acrylate (see PMSE Abstracts, Vol. 73, p. 458, Fall 1995, Proceedings of the American Chemical Society, Fall 1995, Chicago, Ill.). A full publication describing these findings and a catalyst {(ArN.dbd.C(R.sup.1)C(R.sup.1).dbd.NAr)M(CH.sub.2 CH.sub.2 CH.sub.2 C(OR.sup.2)(C.dbd.O))}.sup.+ BAr'.sub.4.sup.- are reported by Johnson et al. (J. Am. Chem. Soc., 1996, 118, 267-268 and supplementary material), wherein R.sup.2 can be --CH.sub.3, t-butyl, or --CH.sub.2 (CF.sub.2).sub.6 CF.sub.3, and R.sup.1, Ar, and Ar' are as defined above. These findings also appeared in M. Brookhart, L. K. Johnson, C. M. Killian, S. Mecking, D. J. Tempel, Polymer Preprints, 1996, 37, 254-255.
These catalysts were prepared in a multi-step sequence shown in Scheme I, below. The ligand (ArN.dbd.C(R.sup.1)C(R.sup.1).dbd.NAr) (III) was prepared from 2,6-diisopropylaniline (II) and 1,2-dione O.dbd.C(R.sup.1)C(R.sup.1).dbd.O (I), optionally in the presence of formic acid (H. T. Dieck, M. Svoboda, T. Greiser Z. Naturforsch. 36b, 1981, 823-832.). In a separate procedure, (1,5-cyclooctadiene)PdCl.sub.2 (IV) was reacted with Me.sub.4 Sn to give (1,5-cyclooctadiene)PdCl (Me) (V) (R. Rulke, J. M. Emnsting, A. L. Spek, C
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Brown Katherine A.
Lamanna William M.
Siedle Allen R.
Stewart Edward G.
Swanson Penelope J.
Gover Melanie
Minnesota Mining and Manufacturing Company
Sherman Lorraine R.
Wu David W.
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