Polyolefins Ziegler-Natta

Cyclic Polyolefins (GPO) and Gycloolefin Copolymers (GOG). Japanese and European companies are developing amorphous cycHc polyolefins as substrate materials for optical data storage (213—217). The materials are based on dicyclopentadiene and/or tetracyclododecene (10), where R = H, alkyl, or COOCH. Products are formed by Ziegler-Natta polymerization with addition of ethylene or propylene (11) or so-called metathesis polymerization and hydrogenation (12), (101,216). These products may stiU contain about 10% of the dicycHc stmcture (216). 

B. C. Childress, Properties of homogeneous and heterogeneous polyolefins Metallocene catalyzed versus Ziegler-Natta catalyzed resins, MetCon 94 Proceedings, USA, May 1994. 

Keli, T., Doi, Y. Synthesis of Living Polyolefins with Soluble Ziegler-Natta Catalysts and Application to Block Copolymerization. Vol. 73/74, pp. 201 —248. 

Zucchini, U. and Cecchin,G. Control of Molecular-Weight Distribution in Polyolefins Synthesized with Ziegler-Natta Catalytic Systems. Vol. 51, pp. 101 — 154. 

With the exception of LDPE, polyolefins like other polyethylenes and polypropylene, which represent the largest amount of vinyl-type polymers produced in the world, are neither synthesized by radical nor by classical ionic polymerisation processes. Different types of polymerisation catalysts are in use for these purposes. The Cr-based Phillips catalyst, Ziegler-Natta type catalysts, metallocene or other more recently discovered catalysts, including late transition metal catalysts, are all characterized by their propagation step where the olefin monomer inserts into a carbon-transition metal link. ... 

A characteristic of polyolefins synthesized with metallocene catalysts is their significantly lower polydispersity compared to one obtained by using heterogeneous Ziegler-Natta catalysts. Such narrower molecular mass distributions can lead to different mechanical properties of the resulting material. 

Catalloy A gas-phase process for making olefin co-polymers, using Ziegler-Natta catalysts. It uses a series of three gas-phase reactors to which monomer is progressively added. The properties of the product can be varied according to the monomer grades used. Developed by Himont and first commercialized in 1990. Now operated by a joint venture of Montell Polyolefins and Japan Polyolefins. See also Hivalloy. 

Hivalloy A process for grafting styrenic polymers on to polyolefines, using a Ziegler-Natta catalyst. The products combine the physical properties of both polymer types. Developed by Montell and commercialized in the United States in 1997. See also Catalloy. Oxley, D. F., Chem. Ind. (London), 1998, (8), 307. 

Polyolefin industry, catalysts in, 26 503 Polyolefin (PO) resins, 17 699-700 technologies and uses for, 17 707-708 Polyolefin products, Ziegler-Natta catalysts for, 26 533-544 Polyolefins, 10 518... 

The annual production of various polymers can be measured only in billion tons of which polyolefins alone figure around 100 million tons per year. In addition to radical and ionic polymerization, a large part of this huge amount is manufactured by coordination polymerization technology. The most important Ziegler-Natta, chromium- and metallocene-based catalysts, however, contain early transition metals which are too oxophiUc to be used in aqueous media. Nevertheless, with the late transition metals there is some room for coordination polymerization in aqueous systems [1,2] and the number of studies published on this topic is steadily growing. 

High magnetic fields and in particular C-NMR spectroscopy allow the analysis of even longer configurational sequences (tetrads up to nonads). This proved to be important in particular for the analysis of polyolefins like polypropylene or cycloolefin copolymers (COC). These polymers are available via transition-metal mediated (Ziegler-Natta, metallocene) insertion polymerizations, and the configurational analysis provides deep insight into the respective polymerization mechanisms as well as into the structure-property relationships. 

Reith RL, Eaton FR, Coates WG. Polymerization of ureidopyrimidinone-functionalized olefins by using late-transition metal Ziegler-Natta catalysts synthesis of thermoplastic elastomeric polyolefins. Angew Chem Int Ed 2001 40 2153-2156. 

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