Thermoplastic elastomeric olefin polymers

Details Thermoplastic elastomeric olefin polymers Thermoplastic elastomeric olefin polymers

1996-12-20

1999-10-19

Nagumo, Mark

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

5263482, 5263483, 5263486, 526348, 526160, 526943, 502117, C08F 1006

Patent

active

059690704

DESCRIPTION:

BRIEF SUMMARY
DESCRIPTION

1. Technical Field
This invention relates to novel catalysts, catalyst systems, methods of production of olefin polymers, and elastomeric olefin polymers, particularly crystalline and amorphous block polymers by use of the novel catalysts of the invention. A principal area of interest is the preparation and use of novel cyclopentadienyl or indenyl metallocene catalysts to produce elastomeric stereoblock polymers, and methods of control of catalyzed polymeric reactions to produce polymers having properties ranging from crystalline thermoplastics to thermoplastic elastomers to amorphous gum elastomers.
2. Background Art
Crystalline, amorphous, and elastic polypropylenes are known. Crystalline polypropylenes are generally regarded as comprising of predominantly isotactic or syndiotactic structures and amorphous polypropylene is regarded as comprising predominantly of an atactic structure. U.S. Pat. No. 3,112,300 and 3,112,301 both of Natta, et. al. describe isotactic and prevailingly isotactic polypropylene.
U.S. Pat. No. 3,175,199 to Natta et al. describes an elastomeric polypropylene which can be fractioned out of a polymer mixture containing prevailingly isotactic and atactic polypropylenes. When separated from the polymer mixture, a fraction of this polymer showed elastomeric properties which were attributed to a stereoblock structure comprising alternating blocks of isotactic and atactic stereosequences.
Previously, the catalysts used to produce stereoblock amorphous crystalline polypropylenes consisted of heterogeneous catalysts comprising titanium or vanadium halides on a support (Natta and Crespi (Montecatini), U.S. Pat. No. 3,175,999, 1965 (Chem. Abstr, 1961, 55,14985b); German Patent DD 300,293 of Arnold et al.), or tetralkyl zirconium or titanium on a metal oxide support U.S. Pat. No. 4,335,225 of Collette (du Pont). These heterogeneous catalysts do not consist of single sites, but of multiple sites and thus produce a mixture of polymeric materials which can be fractionated by extraction into suitable solvents. The various fractions typically have different molecular weights and molecular weight distributions and vary in their physical properties.
Metallocene catalysts are capable of polymerizing alpha olefins to atactic, isotactic, or syndiotactic structures. In particular, rigid bridged indenyl metallocenes represented by the general structure A and B are known in the art where M=Ti, Zr, and Hf: ##STR1##
As disclosed by Ewen ("Mechanisms of Stereochemical Control in Propylene Polymerizations with Soluble Group 4B Metallocene/Methylalumoxane Catalysts" J. Am. Chem. Soc. 1984, 106, 6355-6364), stereorigid catalysts of racemic geometry A produce isotactic polypropylene whereas stereorigid catalysts of meso geometry B produce atactic polypropylene.
A metallocene catalyst was disclosed which yields elastomeric polypropylene Chien, J. C. W.; Llinas, G. H.; Rausch, M. D.; Lin, G. YU.; Winter, H. H.; Atwood, J. L.; Bott, S. G., "Two-state Propagation Mechanism for Propylene Polymerization Catalyzed by rac-[anti-ethylidene (1-.eta..sup.5 -tetramethylcyclopentadienyl) (1-.eta..sup.5 - indenyl)] dimethylititanium" J Am. Chem. Soc. 1991, 113, 8569-8570; Cheng, H. N.; Babu, G. N.; Newmark, R. A.; Chien, J. C. W., "Consecutive Two-State Statistical Polymerization Models" Macromolecules 1992, 25 6980-6987; Lilinas, G. H.; Dong, S. H.; Mallin, D. T.; Rausch, M. D.; Lin, Y. G.; Winter, H. H.; Chien, J. C. W., "Crystalline-amorphous Block Polypropylene and Nonsymmetric ansa-Metallocene Catalyzed Polymerization" Macromolecules 1992, 25 1242-1253. This catalyst had rather low activity (3.5.times.10.sup.5 gm polymer/mol Ti.hr) and yielded polypropylenes with molecular weights less than M.sub.w =200,000. This polymer was more homogeneous in its composition, and was completely soluble in diethyl ether. Polypropylenes produced with this catalyst had melting points below 70.degree. C., with elongations up to 1300% and tensile strength of 1750 psi.
Accordingly, there is a need for more active catalyst systems

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Gauthier et al. Elastomeric Poly(propylene): Influence of Catalyst Structure and Polymerization Conditions on Polymer Structure and Properties, Macromolecules 1995, 28, 3771-3778.
Tsvetkova et al., Synthesis of Elastomeric Polypropynlene in Bulk Using The (2-Phlnd).sub.2 ZrCl.sub.2 Homogenous Catalyst, Polymer Science, Series A, vol. 39, No. 3 (1997), 235-240.
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