POLYMERISATION CATALYST

Sodium trichloroacetate [650-51-17, C2Cl202Na, is used as a herbicide for various grasses and cattails (2). The free acid has been used as an astringent, antiseptic, and polymerisation catalyst. The esters have antimicrobial activity. The oral toxicity of sodium trichloroacetate is quite low (LD q rats, 5.0 g/kg). Although very corrosive to skin, trichloroacetic acid does not have the skin absorption toxicity found with chloroacetic acid (28). 

Current Polymerisation Catalysts—Peroxide, and Other Initiators, muIti-cHent study. Catalyst Consultants, Inc., Spring House, Pa., Nov. 1991. 

High density polyethylene (HDPE) is defined by ASTM D1248-84 as a product of ethylene polymerisation with a density of 0.940 g/cm or higher. This range includes both homopolymers of ethylene and its copolymers with small amounts of a-olefins. The first commercial processes for HDPE manufacture were developed in the early 1950s and utilised a variety of transition-metal polymerisation catalysts based on molybdenum (1), chromium (2,3), and titanium (4). Commercial production of HDPE was started in 1956 in the United States by Phillips Petroleum Company and in Europe by Hoechst (5). HDPE is one of the largest volume commodity plastics produced in the world, with a worldwide capacity in 1994 of over 14 x 10 t/yr and a 32% share of the total polyethylene production. 

This involves first the preparation of lower molecular weight polymers with a degree of polymerisation of about three. These are then reacted with bis-phenol A in the presence of a suitable polymerisation catalyst such that the reaction takes place without the evolution of by-products. ... 

A number of highly active ethylene polymerisation catalysts have resulted from the combination of functionalised NHC ligands with Ti, the first of these was the bis(phenolate)carbene ligated complex 3 [8], Upon activation with modified MAO (MMAO), this species gave an activity of 290 kg-mol bar h in the one test reported, making it one of the most active carbene-based olefin polymerisation catalysts known. In later work the same complex was evaluated with straight MAO activation, and activities of up to ca. 100 kg mol -bar" -h" were reported for linear polyethylene production [9],... 

There has also been some interest in NHC-lanthanide complexes as polymerisation catalysts. Indenyl and fluorenyl functionalised NHC complexes of structures 14 and 15 (Fig. 4.5) were evaluated for isoprene polymerisation following activation... 

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. ... 

Iron-Based and Cobalt-Based Olefin Polymerisation Catalysts... 

For more general overviews of post-metallocene a-olefin polymerisation catalysts, the reader is referred to a series of reviews [8, 9, 10, 11, 12], while recent reviews pertaining to the importance of 2,6-bis(imino)pyridines and to iron and cobalt systems per se have also been documented [13, 14],... 

The introduction of metal alkyls to an MAO-activated bis(imino)pyridine iron catalyst has also been the subject of a number of studies. Both AlMe3 and AlEt3 have been added to 5a/MAO-based polymerisation catalysts leading to polyethylene displaying a bimodal distribution similar to that observed using 5a/M AO,... 

Prior to the development of polymerisation catalysts based on the bis(imino)pyridine framework, the bis(imino)pyridine moiety was widely incorporated into macrocycles [163, 164], As an extension of this design strategy to polymerisation applications, several groups have been attempting to incorporate sterically bulky bis(arylimino) pyridine units into macrocycles. In a similar fashion, the introduction of the bis(imino)pyridine unit into polymeric chains in which polymerisation-active metal centres are bound has been the subject of study. 

In addition, cyclodextrins incorporating a 2,6-bis(imino)pyridine unit have been used to support active iron polymerisation catalysts. Using the (i-cyclodextrin-based system 52, in the presence of a large excess of MAO, ethylene can be converted into HDPE (Fig. 16). Only low activities are, however, observed, which... 

While the 2,6-bis(imino)pyridine ligand frame has continued to lead the way, the past 10 years has also seen the development of alternative ligand sets that can act as compatible supports for iron and cobalt ethylene oligomerisation/polymerisation catalysts (Table 4) [46, 50, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192,193,194,195,196,197,198,199,200, 201,202,203,204,205, 206,207,208, 209] active catalysts based on bimetallic iron and cobalt precatalysts have also started to emerge (Table 5) [54, 210, 211, 212, 213, 214, 215], In the main, these systems show lower activities than the prototype bis(imino)pyridine-based catalysts, although several of these systems have significantly started to approach their catalytic performances (e.g. 65/MAO [46, 188], 69/MAO [191,192,193], 70/MAO [194], 71/MMAO [195]). 

It now remains to place the concept of an ester as an active species into a wider chemical context, with special reference to polymerisation catalysts. Sinn and Patat [39] have emphasised the distinction between monofunctional and bifunctional catalytic systems and this distinction is obviously and necessarily related to the idea, explained above, that there is a difference in kind between polarised molecules and the ions which can be formed from them. Whereas the carbonium and other cations as reactive species are monofunctional, the esters evidently belong to the class of bifunctional catalysts their mode of action - the addition of their constituent parts across a double bond - is, in modern terminology, an insertion reaction. In this context, we must note the important... 

Selection of those metals where the metal alkyl complexes are stable with respect to hydride and liberated alkene. For the metals on the left-hand side of the periodic table, the Early Transition Metals and the Lanthanides, the alkyls are relatively stable. Therefore it is not surprising that the best alkene polymerisation catalysts are found amongst these metals. 

Steric hindrance may hamper the correct stereochemistry required for 13-elimination, and perhaps this can be used to stabilise our metal alkyl complex. In the modem polymerisation catalysts for polypropene this feature has actually been observed, which leads to higher molecular weight polymers. This now forms part of the design of new catalysts. 

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