Metal alkoxide polymerisation

The mode of lactone ring opening depends on the kind of catalyst. It is characteristic that -lactone polymerisation with a catalyst containing a metal alkoxide active bond (Mt-X X = OR) involves C(0)-0 bond scission in the coordinating monomer (via the metal orthocarbonate species) with regeneration of the metal alkoxide active bond [scheme (7)] [87]. On the other hand, the application of a catalyst with a metal carboxylate active bond [Mt-X X = 0C(0)R] for -lactone polymerisation results in Cp — O bond scission in the coordinating monomer with regeneration of the metal carboxylate active bond [scheme (8)] [88-90],... 

Syndiotactic polystyrene was first obtained only recently by Ishihara et al. [5] in polymerisation with a homogeneous catalyst derived from a transition metal compound such as monocyclopentadienyltitanium trichloride and methylalu-minoxane in toluene. Since then, several authors have reported on the synthesis of syndiotactic polystyrene promoted by different catalysts based on metal hydrocarbyls such as benzyl compounds, half-sandwich metallocenes (e.g. monocyclopentadienyl, monopentamethylcyclopentadienyl and monoindenyl metal derivatives), metal alkoxides, metallocenes and some other compounds. These catalysts are commonly derived from titanium or zirconium compounds, either activated with methylaluminoxane or aluminium-free, such as those activated with tris(pentafluorophenyl)boron, and promote the syndiospecific polymerisation of styrene and substituted styrenes [5-10,21,48-70], Representative examples of the syndiospecific polymerisation of styrene using catalysts based on various titanium compounds and methylaluminoxane are shown in Table 4.2 [6,52,53,56,58],... 

Most coordination catalysts have been reported to be formed in binary or ternary component systems consisting of an alkylmetal compound and a protic compound. Catalysts formed in such systems contain associated multinuclear species with a metal (Mt)-heteroatom (X) active bond ( >Mt X Mt—X > or — Mt—X—Mt—X— Mt = Al, Zn, Cd and X = 0, S, N most frequently) or non-associated mononuclear species with an Mt X active bond (Mt = Al, Zn and X = C1, O, S most frequently). Metal alkyls, such as triethylaluminium, diethylzinc and diethylcadmium, without pretreatment with protic compounds, have also been reported as coordination polymerisation catalysts. In such a case, the metal heteroatom bond active in the propagation step is formed by the reaction of the metal-carbon bond with the coordinating monomer. Some coordination catalysts, such as those with metal alkoxide or phenoxide moieties, can be prepared in other ways, without using metal alkyls. There are also catalysts consisting of a metal alkoxide or related compound and a Lewis acid [1]. 

The coordination polymerisation of lactones with a six- and seven-membered ring (5- and e-lactones respectively) occurs via ring opening at the C(0)-0 linkage to generate metal alkoxide chain terminals, following a reaction analogous to that presented by scheme (9). 

More recently, a very efficient yttrium-based catalyst, yttrium 2-methoxyeth-oxide, has been applied successfully for /f-butyrolactone polymerisation which proceeded easily at room temperature [99], It is worth mentioning that rare-earth metal alkoxides (derived from yttrium and lanthanum) exhibit outstanding efficiency as catalysts for the polymerisation of cyclic esters such as e-caprolactone [132] and lactide [133]. 

Furukawa et al. [274] and Natta cl al. [275,276] succeeded independently in the preparation of crystalline polyacetaldehyde by using some organometallic compounds, such as diethylzinc or triethylaluminium, for the low-temperature polymerisation of acetaldehyde. Metal alkyls and metal alkoxides, e.g. aluminium isopropoxide, zinc ethoxide or ethyl orthotitanate, have also polymerised other aldehydes such as propionaldehyde and trichloroacetaldehyde to give crystalline polymers (Table 9.3) [270,275,277], A highly crystalline isotactic polymer has been obtained from the polymerisation of w-butyraldehyde with triethylaluminium or titanium tetrachloride-triethylaluminium (1 3) catalysts. Combinations of metal alkyl, e.g. diethylzinc, with water [278] or amine [279] appeared to give very efficient catalysts for aldehyde polymerisations. 

The formation of a complex between the carbonyl oxygen atom of the aldehyde monomer and the catalyst metal atom, followed by its rearrangement to the respective metal alkoxide of secondary alcohol, has been suggested to be the first polymerisation step [274,277,280,281], In the case of alumina as a catalyst, the aldehyde coordination was confirmed by IR spectroscopy [282],... 

In anionic ROP, nucleophilic metal alkoxides initiate the polymerisation reaction. Some bulky alkoxides, however, will rather act as a base thereby introducing a new anionic centre on a monomer unit, which can subsequently act as the anionic initiator [30,31]. Two... 

Ring-opening polymerisation initiated by metal alkoxides according to the insertion-coordination mechanism. 

The faster kinetics is aceounted for the coordination of the Lewis base onto the metal, which polarises the metal alkoxide bond and makes the monomer insertion easier (Fig. 4.12). An excess of triphenylphosphine is however not beneficial to polymerisation. Worse, this excess can compete with the monomer for coordination to aluminium, which is detrimental to the kinetics. 

Despite the fact that the metal ions enable to control the polymerisation, they also pose an important downside as the formed polymers will always contain metal residues. These metal ions might have detrimental health effects. Aluminium derivatives have already been linked to Alzheimer s disease, although this hypothesis is controversial [50], while tin octoate, despite being FDA approved, has already been shown to be cytotoxic. As tin levels often exceed 1000 ppm, the FDA has set a limit of 20 ppm for polyesters used for biomedical applications [51]. To circumvent this problem, attention has already been paid to less toxic catalysts including magnesium and calcium alkoxides. Conversely, attempts are being made to remove the catalyst residues from the polymer. 

The earliest work on polyester synthesis used no catalyst or a simple acid catalyst such as p-toluenesulfonic acid, but use of weakly basic metallic salt catalysts is now almost universal. Many salts have been claimed to be useful in this context, but the best known examples are alkaline earth and transition metal acetates, tin compounds and titanium alkoxides [21-23]. Care must be exercised in selecting ester-interchange catalysts because some may cause degradation/ discoloration in the polymer during the subsequent polymerisation reaction [24], especially for PET and PEN. To prevent this occurrence, catalysts are often sequestered/complexed at the end of the ester-interchange phase by addition of phosphorus compounds such as phosphites, phosphates or polyphosphoric acid [25]. Titanium and tin compounds operate as catalysts for ester-interchange and polymerisation reactions, and in general do not require such procedures. 

In order to overcome the drawbacks related to metal contamination of polyesters prepared in the presence of tin and aluminium alkoxides, supercritical carbon dioxide is a promising polymerisation medium in order to prepare biomedical grade aliphatic polyesters, due to the possibiUty to extract the... 

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