Olefins metallocenes

Finally, from the dynamics simulations it was found that the Cp rings are very flexible, and during the simulation they are not very closely attached to the metal centre as often anticipated. For further details regarding the metallocene and mono-cyclopentadienyl based olefin polymerisation studied by quantum molecular dynamics simulation we refer to [2] and [8-10]. 

Commercial production of PE resias with densities of 0.925 and 0.935 g/cm was started ia 1968 ia the United States by Phillips Petroleum Co. Over time, these resias, particularly LLDPE, became large volume commodity products. Their combiaed worldwide productioa ia 1994 reached 13 X 10 metric t/yr, accouatiag for some 30% market share of all PE resias ia the year 2000, LLDPE productioa is expected to iacrease by 50%. A aew type of LLDPE, compositioaaHy uniform ethylene—a-olefin copolymers produced with metallocene catalysts, was first introduced by Exxon Chemical Company in 1990. The initial production volume was 13,500 t/yr but its growth has been rapid indeed, in 1995 its combiaed production by several companies exceeded 800,000 tons. 

The second type of solution polymerization concept uses mixtures of supercritical ethylene and molten PE as the medium for ethylene polymerization. Some reactors previously used for free-radical ethylene polymerization in supercritical ethylene at high pressure (see Olefin POLYMERS,LOW DENSITY polyethylene) were converted for the catalytic synthesis of LLDPE. Both stirred and tubular autoclaves operating at 30—200 MPa (4,500—30,000 psig) and 170—350°C can also be used for this purpose. Residence times in these reactors are short, from 1 to 5 minutes. Three types of catalysts are used in these processes. The first type includes pseudo-homogeneous Ziegler catalysts. In this case, all catalyst components are introduced into a reactor as hquids or solutions but form soHd catalysts when combined in the reactor. Examples of such catalysts include titanium tetrachloride as well as its mixtures with vanadium oxytrichloride and a trialkyl aluminum compound (53,54). The second type of catalysts are soHd Ziegler catalysts (55). Both of these catalysts produce compositionaHy nonuniform LLDPE resins. Exxon Chemical Company uses a third type of catalysts, metallocene catalysts, in a similar solution process to produce uniformly branched ethylene copolymers with 1-butene and 1-hexene called Exact resins (56). 

Chemical Properties. Higher a-olefins are exceedingly reactive because their double bond provides the reactive site for catalytic activation as well as numerous radical and ionic reactions. These olefins also participate in additional reactions, such as oxidations, hydrogenation, double-bond isomerization, complex formation with transition-metal derivatives, polymerization, and copolymerization with other olefins in the presence of Ziegler-Natta, metallocene, and cationic catalysts. All olefins readily form peroxides by exposure to air. 

The introduction of metallocene and single-site polyethylene catalyst systems may eventually change the demand for higher olefins used as comonomers. Some sources indicate that their use will increase the demand for comonomers, but others feel that they will reduce comonomer use. At any rate, it is not expected that their introduction will have a significant effect on comonomer growth rates for the period 1992—1996 (see Olefin polymers). 

Polymerization Reactions. Polymerization addition reactions are commercially the most important class of reactions for the propylene molecule and are covered in detail elsewhere (see Olefin polymers, polypropylene). Many types of gas- or liquid-phase catalysts are used for this purpose. Most recently, metallocene catalysts have been commercially employed. These latter catalysts requite higher levels of propylene purity. 

Olefin Polymerization. Titanates having a carbon—titanium bond are extensively kivolved ki Ziegler-Natta and metallocene polymerization of... 

Metallocene catalysis can also make possible the production of copolymers of propylenes with monomers such as long-chain olefins, cyclic olefins and styrene which is not possible with more conventional Ziegler-Natta catalysts. 

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. 

U. Moll and M. Lux, Manufacture of ethylene/alpha olefin copolymers with metallocene catalysts in slurry loop... 

Linear low-density polyethylene (LLDPE) is produced in the gas phase under low pressure. Catalysts used are either Ziegler type or new generation metallocenes. The Union Carbide process used to produce HDPE could be used to produce the two polymer grades. Terminal olefins (C4-C6) are the usual comonomers to effect branching. 

Bent ansa-metallocenes of early transition metals (especially Ti, Zr, Hf) have attracted considerable interest due to their catalytic activity in the polymerization of a-olefins. Ruthenium-catalyzed olefin metathesis has been used to connect two Cp substituents coordinated to the same metal [120c, 121a] by RCM or to connect two bent metallocenes by cross metathesis [121b]. A remarkable influence of the catalyst on E/Z selectivity was described for the latter case while first-generation catalyst 9 yields a 1 1 mixture of E- and Z-dimer 127, -127 is the only product formed with 56d (Eq. 19). 

The need to paint the blends has also resulted in new painting systems. Recently, a nonpolar color coat based on a hydrogenated polybutadiene diol and melamine resin for TPO bumper fascia was invented. The breakthrough technology allows the elimination of the TPO pretreatment step such as adhesion promoter, flame, or plasma during manufacturing. The paintability of two different types of E-plastomers was evaluated. The olefinic white paint was found to provide excellent paint adhesion for both types of metallocene plastomers. Paint peeling was not observed in any of the test... 

Sumi K, Kumobayashi H (2004) Rhodium/Ruthenium Applications. 6 63-96 Suzuki N (2005) Stereospecific Olefin Polymerization Catalyzed by Metallocene Complexes. 8 177-215... 

Constrained Gteometry and Other Single Site Metallocene Polyolefin Catalysts A Revolution In Olefin Polymerization... 

The sterically unencumbered catalyst active site allows the copolymerization of a wide variety of olefins with ethylene. Conventional heterogeneous Ziegler/Natta catalysts as well as most metallocene catalysts are much more reactive to ethylene than higher olefins. With constrained geometry catalysts, a-olefins such as propylene, butene, hexene, and octene are readily incorporated in large amounts. The kinetic reactivity ratio, rl, is approximately... 

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