Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Patent
1998-06-26
2000-04-25
Cain, Edward J.
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
526151, 526153, 526170, 526281, 526282, C08F 206
Patent
active
060545437
DESCRIPTION:
BRIEF SUMMARY
BACKGROUND OF THE INVENTION
The invention is related to the amorphous olefin co/ter-polymers and their manufacture. The invention is especially concerned with the improvement of the softness, flexibility and impact properties of amorphous co/ter-polymers by using substituted cyclic co-monomers.
Cycloolefin--copolymers (COC) are manufactured commercially using metathesis ring-opening polymerization providing thermoplastic COC--polymers with high glass transition temperatures (Tg) and good optical properties (used in compact discs etc.). Furthermore COC--polymers are manufactured commercially by co-polymerizing ethylene and cycloolefins using vanadium type Ziegler-Natta-catalysts, also providing good optical properties and heat resistance, but rather poor impact properties. Also ethylene-cycloolefin-copolymers with high Tg values have been obtained by the use of metallocene catalysts. Based on the patent examples, however, these technologies are focusing on using norbornene or tetracyclododecene as comonomer. Typical for both these co-monomers is the poor impact properties of their COC--polymers. This is due to the fact that the forces between the polymer chains are very weak (van der Waal's forces), because the polymer chains are fully saturated hydrocarbons (paraffinic). Furthermore there is a very low degree of entanglement of these polymer chains due to their stiffness.
THE INVENTION
In the present invention the cyclic comonomer is substituted with a chemical group which increases the forces between the polymer chains as well as decreases the rotation of the cyclic comonomer around the polymer chain (stiffens the chain). When the substituent is a phenyl-group, or any other kind of aromatic group the forces between the polymer chains increase due to the interaction of -electrons. In this respect a non-condensed aromatic group, such as phenyl-group can move more freely and find another phenyl-group in a neighboring chain, which results in improved impact properties which is greater than if the aromatic group is condensed or otherwise linked to the cycloolefin via several bonds (like the indanyl-group). The phenyl-group also reduces the rotation around the polymer chain but not to the extent as when the substituent is linked to the cycloolefin via several bonds (tetracyclododecene, indanyl-norbornene etc.). Less rotation around the polymer chain increases the Tg more efficiently.
By using metallocene catalysts and methylaluminoxane (MAO) as cocatalyst, one can produce amorphous ethylene-co/ter-polymers which have both high heat resistance (high glass transition temperature, Tg) and good impact properties. When ethylene is co-polymerized with phenyl-norbornene, indanyl-norbornene or any other aryl-substituted norbornene, stiffer polymer chains (higher Tg:s) are obtained as when incorporating the same amount of norbornene. In addition one obtains a softer, more flexible and more impact resistant product. The greatest disadvantage with the present cyclo-olefin-coplymers (COC) is their poor impact resistance. Due to the fact that the above mentioned substituted norbornenes have a greater stiffening effect on the polymer chains than norbornene, substantially lower incorporations are needed which is a great advantage from a production as well as economical point of view. Furthermore phenyl-norbornene (5-phenyl-bicyclo-2,2,1-hept-2-ene) is made from styrene and indanyl-norbornene (1,4- methano-1,4,4a,9a-tetrahydrofluorene) from indene using dicyclopentadiene as the other component in a Diels-Alder-reaction. These raw-materials are readily available liquids which are easy to transport and store and also the corresponding cyclic monomers are liquids and can therefore be easily purified and fed to the polymerization process. Norbornene on the other hand is made from ethylene and dicyclopentadiene which requires that the monomer reactor is connected to an ethylene pipe-line or to an ethylene cold-storage and the reactor is able to withstand higher pressures. Draw-backs of norbornene include that it is present in a
REFERENCES:
patent: 5559199 (1996-09-01), Abe et al.
patent: 5637400 (1997-06-01), Brekner et al.
patent: 5650471 (1997-07-01), Abe et al.
Bergstrom, Christer H., et al., "Influence of the Polymerization Conditions on the Rigidity of Phenylnorbornene-Ethylene Copolymers Made Using Ethylene bis (indenyl) zirconium dichloride and MAO", Journal of Applied Polymer Science, vol. 67, 385-393 (1998) [Encl. 1].
Bergstrom, Christer H., et al., "Influence of the Polymerization Conditions on Microstructure of Norbornene-Ethylene Copolymers Made Using Metallocene Catalysts and MAO", Journal of Applied Polymer Science, vol. 63, 1071-1076 (1997) [Encl. 2].
Bergstrom, Christer H., "New and Unique Cyclic Comononers for Improvement of the Technical Performance of Metallocene Catalyzed COC", presented at Met Con '97, Jun. 5, 1997: Cyclic Olefin Copolymers-Materials and Processes, .COPYRGT.Christer Bergstrom, Apr. 7, 1997, unpublished. [Encl. 3].
Ahjopalo Lisbeth
Bergstrom Christer Hans
Hase Tapio
Paavola Sari
Pietila Lars-Olof
Cain Edward J.
Optatech Corporation
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