Propylene-ethylene copolymers processes for the production there

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...

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C08F 406

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active

061568562

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BRIEF SUMMARY
TECHNICAL FIELD

This invention relates to propylene-ethylene copolymers, and more particularly it relates to propylene-ethylene copolymers having a characteristic ethylene units-chain, very small amounts of inverted propylene units and narrow molecular weight distribution and processes for the production thereof.
The invention also relates to molded articles made from the propylene-ethylene copolymers.


BACKGROUND ART

Prior propylene-ethylene copolymers have been extensively used in the field of films or the like, by utilizing the characteristics of lower crystallizability and lower glass transition point than linear crystalline polypropylene homopolymers. However, the use has been limited in other application fields, and more improved characteristics have been required for use in those applications.
For instance, low temperature heat-sealing characteristics have been required from a standpoint of energy-saving even in the film field as most extensively used. The prior art has employed a method of lowering the melting points of the copolymers with the sacrifice of the film stiffness. Thus it has been strongly demanded to reconcile stiffness and low temperature heat-sealing characteristics which conflict with each other.
These prior propylene-ethylene copolymers are usually produced by copolymerizing ethylene and propylene using a titanium catalyst. However, at improvement in various properties of the propylene-ethylene copolymers produced by such copolymerization method is considered to reach substantially the limit. In recent years, there have been investigated various methods for producing olefin (co)polymers by (co)polymerizing olefins using different catalyst systems in which metallocenes are combined with aluminoxanes.
For instance, Japanese Patent Kokai 3-12406, Japanese Patent Kokai 3-12407 and CHEMISTRY LETTERS, pp. 1853-1856, 1989 disclose that high stereoregular polypropylenes produced by polymerizing propylene using catalysts consisting of silylene-bridged metallocenes having the specific structures and aluminoxanes have narrow molecular weight distributions, high melting points and high rigidities. However, no concrete technique is disclosed therein on propylene-ethylene copolymers.
Further, Tsutsui et al. have considered that, for the propylene-ethylene copolymers produced by copolymerizing propylene and ethylene using an ethylenebis(1-indenyl)zirconium dichloride and methylaluminoxane catalyst system, the stereoregularities thereof defined by the meso--meso triad sequence are the same as those of the copolymers produced with prior titanium-containing catalyst components, but the melting points of said propylene-ethylene copolymers produced with said metallocene and aluminoxane catalyst system are lower than those of the copolymers obtained with the titanium catalyst components, and the causes are due to larger amounts of inverted propylene units in the propylene-ethylene copolymers obtained with the metallocene-aluminoxane catalysts (T. Tsutsui et al., POLYMER, 1989, Vol. 30, 1350). Larger amounts of inverted propylene units are due to the fact that the polymerization of propylene using the titanium catalysts proceeds substantially with 1,2-insertion, whereas the polymerization of propylene using known metallocene catalysts proceeds with 2,1- and 1,3-insertions in a constant ratio.


PROBLEMS TO BE SOLVED BY THE INVENTION

When prior propylene-ethylene copolymers are used for molding materials, e.g., films, it is very difficult to reconcile good stiffness and good low temperature heat-sealing characteristics.
The objects of the present invention are to provide propylene-ethylene copolymers having good stiffness and low temperature heat-sealing characteristics, processes for the production thereof, and molded articles made from said copolymers.
The present inventors have made extensive investigation in an effort to achieve the above-mentioned objects and succeeded in producing propylene-ethylene copolymers having a characteristic ethylene units-chain, very small amounts of inverted propylen

REFERENCES:
patent: 4931417 (1990-06-01), Miya et al.
patent: 5712323 (1998-01-01), Braga et al.
"Excellent Stereoregular Isotactic Polymerizations of Propylene with C2-Symmetric Silylene-Bridged Metallocene Catalysts" by Takaya Mise, Shinya Maya and Hiroshi Yamazaki, The Institute of Physical and Chemical Research, Wako Saitama 351-01; Chemistry Letters, The Chemical Society of Japan, 1989, pp. 1853-1856.
"Propylene Homo-and Copolymerization with Ethylene Using an Ethylenebis (1-Indenyl) Zirconium Dichloride and Methylaluminoxane Catalyst System", Toshiyuki Tsutsui, Naoshi Ishimaru, Akira Mizuno, Akinori Toyoda and Norio Kashiwa; Polymer, vol. 30, Jul. 1989.
"C NMR Determination of Monomer Sequence Distribution in Ethylene-Propylene Copolymers Prepared with TiCl.sup.3 -Al(C.sup.2 H.sup.5).sup.2 Cl", Masahiro Kakugo, Yukio Naito, Kooji Mizunuma, and Tatsuya Miyatake; Macromolecules, vol. 15, 1982, pp. 150-152.

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