Ethylene enhancement of processes for synthesis of high melting

Details Ethylene enhancement of processes for synthesis of high melting Ethylene enhancement of processes for synthesis of high melting

1998-06-12

2000-12-12

Wu, David W.

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

526134, 526943, C08F 444

Patent

active

061600644

ABSTRACT:
This invention relates generally to low ethylene insertions into .alpha.-olefin polymers and processes for production of such polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalyst systems in methods of production of high melting point .alpha.-olefin homo- and co-polymers, particularly elastomeric crystalline and amorphous block homo- and co-polymers of .alpha.-olefins. The activity of fluxional unbridged metallocene polymerization catalysts containing at least one 2-arylindene ligand is increased 10.times. or more by the addition of small (typically 0.1-10 wt. %) amounts of ethylene to the polymerization system, which increase is termed the Polymerization Rate-Enhancement effect (PRE), which is measured in terms of an Ethylene Enhancement Factor (EEF) as a dimensionless ratio in the range of from about 1.1 to about 10 or above. A second important aspect of this invention is the ability to use a PRE activity-enhancing amount of ethylene in an olefin polymerization without substantially affecting the physical properties of the elastomer. In a third important aspect of this invention, .alpha.-olefin elastomers are produced through incorporation of ethylene using unbridged fluxional catalyst systems which may not otherwise produce acceptable elastomeric homopolymers. Preferred polymers of this invention retain sufficient crystallinity to provide a high melting point (by DSC) of about 80.degree. C., preferably above 100.degree. C., including in the range of from about 120.degree. C. to about 140.degree. C. and above. Novel flexible .alpha.-olefin homo and copolymers having elongation in excess of 600% and substantially no retained force are disclosed.

REFERENCES:
patent: 3873642 (1975-03-01), Jezl
patent: 4334040 (1982-06-01), Fujii et al.
patent: 4668752 (1987-05-01), Tominari et al.
patent: 4677172 (1987-06-01), Zimmerman et al.
patent: 4792595 (1988-12-01), Cozewith et al.
patent: 4797461 (1989-01-01), Aubanel et al.
patent: 4871705 (1989-10-01), Hoel
patent: 4981760 (1991-01-01), Naito et al.
patent: 5001205 (1991-03-01), Hoel
patent: 5055535 (1991-10-01), Spitz et al.
patent: 5086134 (1992-02-01), Antberg et al.
patent: 5192732 (1993-03-01), Druanel et al.
patent: 5229478 (1993-07-01), Floyd et al.
patent: 5278272 (1994-01-01), Lai et al.
patent: 5279999 (1994-01-01), DeBoer et al.
patent: 5459217 (1995-10-01), Todo et al.
patent: 5475075 (1995-12-01), Brant et al.
patent: 5491207 (1996-02-01), Hoel et al.
patent: 5585448 (1996-12-01), Resconi et al.
patent: 5594080 (1997-01-01), Waymouth et al.
patent: 5747621 (1998-05-01), Resconi et al.
patent: 5780659 (1998-07-01), Schmid et al.
patent: 5936050 (1999-08-01), Sangokoya
patent: 5986024 (1999-11-01), Wilson
Quirk, Roderic P., Transition Metal Catalyzed Polymerizations, 1988, Cambridge University Press, Cambridge, pp. 719-728.
Spitz, R., et al., Propene Polymerization with MgCl.sub.2 supported Ziegler catalysts: Activation by hydrogen and ethylene, 1988, Makromol. Chem. 189, pp. 1043-1050.
Valvassori, A., et al., Kinetics of the Ethylene-Propylene Copolymerization, 1963, Makromol. Chem. 161, pp. 46-62.
Brintzinger, H, et al., Stereospecific Olefin Polymerization with Chiral Metallocene Catalysts, 1995, Angew. Chem Int. Ed. Engl. 34, pp. 1143-1170.
Pasquet, v., and Spitz, R., Irreversible activation effects in ethylene polymerization, 1993, Makromol. Chem. 194, pp. 451-461.
Busico, V., et al., Siegler-Natta oligomerization of 1-alkenes: a catalyst's "fingerprint", 2, Preliminary results of propene hydrooligomerization in the presence of the homogeneous isospecific catalyst system rac-(EBI) ZrCl.sub.2 /MAO, 1993, Makromol. Chem., Rapid Commun. 14, pp. 97-103.
Herfert, N., et al., Elementary processes of the Xiegler catalysis, 7, Ethylene, .alpha.-olefin and norbornene copolymerization with the stereorigid catalyst stems iPr[FluCp]ZrCl.sub.2 /MAO, 1993, Makromol. Chem. 194, pp. 3167-3182.
Koivumaki, J. and Seppala, J., Observations on the Rate Enhancement Effect with MgCl.sub.2 /TiCl.sub.4 and Cp.sub.2 ZrCl.sub.2 Catalyst systems upon 1-Hexene Addition, 1993, Macromolecules 26 No. 21, pp. 5535-5538.
Corradini, P., et al., Hydrooligomerization of propene: a "fingerprint" of a Ziegler-Natta catayst, 2, A reinterpretation of results for isospecific homogeneous systems, 1992, Makromol. Chem., Rapid Commun. 13, pp. 21-24.
Busico, V., et al., Hydrooligomerization of propene: a "fingerprint" of a Ziegler-Natta catayst, 1, Preliminary results for MgCl.sub.2 supported systems, 1992, Makromol. Chem., Rapid Commun. 13, pp. 15-20.
Ystenes, M., Predictions from the Trigger Mechanism for Ziergler-Natta Polymerization of .alpha.-olefins, 1993, Makromol. Chem., Makromol. Symp. 66, pp. 71-82.
Hawley's Condensed Chemical Dictionary, John Wiley & Sons, p. 819, 1997.
Brintzinger et al., Sterospecific olefin polymerization with chiral metallocene catalysts, Angew. Chem. Int. Ed. Engl. vol. 34, pp. 1143-1170, 1995.

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