Metallocene elastomers

A number of other polymers have the characteristics of TPE and some are available commercially, such as (1) 1,2-polybutadiene, (2) tran -polyisoprene (PI), (3) modified polyethylene (PE) (e.g., ethylene vinyl acetate [EVA] and ethylene ethyl acrylate [EEA]), (4) nonhydrocarbon elastomer-based TPEs, (5) metallocene elastomers/TPEs (MEs/TPEs), and (6) graft copolymeric TPEs. 

In addition to the two-phase TPEs, two new technologies have emerged. They are the metallocene-catalyzed polyolefin plastomers (POPs, the name given to Exxon s EXACT product line) and polyolefin elastomers (POEs, DuPont Dow Elastomer s ENGAGE), and reactor-made thermoplastic polyolefin elastomers (R-TPOs). These new types of TPEs are often called metallocene elastomers-TPEs (MEs-TPEs) [87]. The new POPs and POEs are essentially very low-molecular-weight-Unear low-density PEs (VLMW-LLDPE). These new-generation TPEs exhibit mbber-like properties and can be processed on... 

Schlechter M., Metallocene Elastomers/TPEs, Business Communication, Wellesley, MA, 1996, 159. Figuly G.D. and Goldfinger M.B., Thermoplastic elastomers, US Patent 6300463, 2001. 

Stability (see Table 12.2). R talc is effective with ethylene propylene diene monomer (EPDM) and ethylene propylene rubbers (EPR) but not as effective with metallocene elastomers containing TPOs. Recently, Clark [11] presented evidence of improvements in scratch and mar resistance when talc is grafted to TPO. The need for higher performance materials will drive the development of new surface modification technologies [3]. 

Antec 96. Volume II. Conference proceedings. Indianapolis, 5th-10thMay 1996, p. 1995-2000. 012 PREPARATION OF METALLOCENE ELASTOMER MODIFIED fflGH FLOW THERMOPLASTIC OLEFINS YuTC... 

PE Resins. A thermoplastic, metallocene elastomer and plastomer grades supplied by Dupont-dow elastomer. Imperial Oil and Dow Chemical were utilized in the experiments. The peak melting temperature of these materials is reported to be aroimd 96°C 100°C. The original material was groimd to particle size of 20pm. 

Ethylene-cyclo-olefin copolymers have been known since 1954 (DuPont USP2 721 189) but these materials only became of importance in the late 1990s with the development of copolymers of ethylene and 2-norbomene by Hoechst and Mitsui using metallocene technology developed by Hoechst. The product is marketed as Topas by Ticona. By adjustment of the monomer ratios polymers with a wide range of Tg values may be obtained including materials that are of potential interest as thermoplastic elastomers. This section considers only thermoplastic materials, cyclo-olefins of interest as elastomers are considered further in Section 11.10. 

Markel E.J., Weng W., Peacock A.J., and Dekmezian A.H. Metallocene-based branched-block thermoplastic elastomers. Macromolecules, 33, 8541, 2000. 

Obviously, there exists severe interplastics competition, e.g. PP vs. ABS, clarified PP vs. PS, PA, PVC, HDPE and PS (Table 10.7). A wide range of cross-linked and thermoplastic elastomer applications, from footware to automotive parts and toothbrushes, are adopting new metallocene-catalysed polyolefin elastomers (POEs). These low-density copolymers of ethylene and octene were first accepted as impact modifiers for TPOs, but now displace EPDM, (foamed) EVA, flexible PVC, and olefinic thermoplastic vulcanisates (TPVs). Interpolymer competition may also result from... 

Polymers with blocks containing different tactcities can be produced, e.g., atactic PP (amorphous)/isotactic PP (semi-crystalline) can be made using metallocene catalysts. They behave in a manner similar to SBS thermoplastic elastomers. 

Eaves (92) distinguished between polyolefin plastomers (POP) with density >910 kg m and polyolefin (POE) elastomers with densities <910 kg m-3. The density of a polyethylene at 20 °C is a linear function of the crystallinity, with limiting values of 854 kg m 2 for zero crystallinity and 1000 kg m for 100% crystallinity. The polyolefin elastomer foams compete with EVA copolymer foams. Metallocene chemistry also allows the production of copolymers with a larger comonomer content in the high molecular weight part than in the low molecular weight part this... 

No.4, July 2001, p.333-52 INVESTIGATION OF THE RADIATION CROSSLINKED FOAMS PRODUCED FROM METALLOCENE POLYOLEFIN ELASTOMERS/ POLYETHYLENE BLEND Kim D W Kim K S... 

Unbridged metallocenes rarely achieve highly stereoselective polymerizations because free rotation of the r 5-ligands results in achiral environments at the active sites. An exception occurs when there is an appreciable barrier to free rotation of the r 5-ligands. Fluxional (con-formationally dynamic) metallocenes are initiators that can exist in different conformations during propagation. Stereoblock copolymers are possible when the conformations differ in stereoselectivity and each conformation has a sufficient lifetime for monomer insertion to occur prior to conversion to the other conformation(s). Isotactic-atactic stereoblock polymers would result if one conformation were isoselective and the other, aselective. An isotactic-atactic stereoblock polymer has potential utility as a thermoplastic elastomer in which the isotactic crystalline blocks act as physical crosslinks. 

Metallocene catalysts are the latest innovations to make a big impact in the polymer industry. They have been used mostly to make new polyolefin plastics, such as very-high-molecular-weight, bullet-proof polyethylene, but they have also been used to make elastomers. The catalysts make very regular stereospecific polymers similar to the Ziegler-Natta catalysts. 

They are based on various metals. Such as zirconium, complexed with cyclopentadienide anions. This type of compound is called a zirconocene and is used with organoalu-minum to make highly regular polymers. The catalyst has the ability to flip back and forth from making atactic to isotactic polypropylene in the same polymerization. The alternating tacticity of the polymer breaks up the crystallinity of the chains and yields an elastomer. Metallocene catalysts are currently very expensive and cannot yet polymerize dienes such as butadiene, so they have only enjoyed limited commercial success in elastomers. However, this is one of the most intense fields of polymer research and many new product breakthroughs are expected in the near future. 

Of great industrial interest are the copolymers of ethene and propene with a molar ratio of 1/0.5, up to 1/2. These EP-polymers show elastic properties and, together with 2-5 wt% of dienes as third monomers, they are used as elastomers (EPDM). Since they have no double bonds in the backbone of the polymer, they are less sensitive to oxidation reactions. As dienes, ethylidenenorbomene, 1,4-hexadiene, and dicyclopentadiene are used. In most technical processes for the production of EP and EPDM rubber in the past, soluble or highly disposed vanadium components are used [69]. Similar elastomers can be obtained with metallocene/MAO catalysts by a much higher activity which are less colored [70-72]. The regiospecificity of the metallocene catalysts toward propene leads exclusively to the formation of head-to-tail enchainments. The ethylidenenor-bornene polymerizes via vinyl polymerization of the cyclic double bond and the tendency to branching is low. The molecular weight distribution of about 2 is narrow [73]. 

For the production of ethylene/l-octene copolymers, metallocenes in combination with oligomeric methylalumoxanes or other compounds are now used [31, 63]. Half-sandwich transition metal complexes such as [(tetramethyl- / -cyclopentadienyl) (A-/-butylamido)dimethylsilyl]titanium dichloride are applied to synthesize linear low-density copolymers and plastomers, called constrained geometry catalysts [31]. Ethylene and styrene can be copolymerized to products ranging from semicrystalline mbber-like elastomers to highly amorphous rigid materials at room temperature [64]. 

Within the past five years, commercial interest in metallocene catalyst components for the polymerization of olefins has increased enormously. Commercial production of a rising number of polyolefin types from different companies is creating a burgeoning and highly diversified demand for metallocenes. New brand names (e. g., Metocene (Basell), Elite (Dow Chemical), Engage (DuPont), Exact (ExxonMobil), Luflexen (Basell), Apel (Mitsui Chemicals), Borecene (Borealis), Finathene (TotalFinaElf), Topas (Ticona), just to name a few) characterize polyolefins such as PE, elastomers, PP, cycloolefin copolymers (COCs) and PS from metallocene-type catalysts [1-3]. 

Parikh, D. R. Edmondson, M. S. Smith, B. W. Winter, J. M. Castille, M. J. Magee, J. M. Patel, R. M. Karajala, T. P. Structure and Properties of Single-site Constrained Geometry Ethylene-Propylene-Diene (EPDM) Elastomers. In Metallocene-catalyzed Polymers -Materials, Properties, Processing Markets, Benedikt, G. M., Goodall, B. L., Eds. Plastics Design Library New York, 1998 p 113. 

Ho, T. Martin, J. M. Structure, Properties and Applications of Polyolefin Elastomers Produced by Constrained Geometry Catalysts. In Metallocene-based Polyolefins Preparation, Properties and Technology, Scheirs, J., Kaminsky, W., Eds. Wiley Chichester, 2000 Vol. 2 175. 

With metallocene catalysts, not only homopolymers such as polyethylene or polypropylene can be synthesized but also many kinds of copolymers and elastomers, copolymers of cyclic olefins, polyolefin covered metal powders and inorganic fillers, oligomeric optically active hydrocarbons [20-25]. In addition, metallocene complexes represent a new class of catalysts for the cyclopolymerization of 1,5- and 1,6-dienes [26]. The enantio-selective cyclopolymerization of 1,5-hexadiene yields an optically active polymer whose chirality derives from its main chain stereochemistry. 

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