Poly organometallic monomer

The organometallic copolymer of ferrocenylethylacrylamide and isopropy-lacrylamide was prepared and was foimd to be soluble in water due to the minimal incorporation of the organometallic monomer. These polymers exhibited low critical solution temperatures (LCSTs) ranging from 26-29°C when compared to the LCST of 32°C for poly(A -isopropylacrylamide)." ... 

A final example of a stereoselective heterogeneous catalytic system is the work of Laycock, Collacott, Skelton and Tchir.17 Layered double hydroxide (LDH) synthetic hydrotalcite materials were used to stereospecifically polymerize propylene oxide [PO] to crystalline isotactic and liquid atactic poly(propyleneoxide) [PPO]. These authors suggest that the LDH surface acts as other inorganic or organometallic coordination initiators or catalysts by providing specific surface orientations for propylene oxide monomer. X-ray powder diffraction showed some loss of crystallinity after calcination and X-ray photoelectron spectroscopy showed an enhancement of Mg/Al content due to restructuring of the Mg and A1 surface atoms. The surface was also rich in Cl ... 

For instance, in the last decade synthesis of poly(ester-alt-ether) was intensively studied. A common enzyme used in these syntheses is CALB. Polymerization of l,5-dioxepan-2-one (DXO) was performed by enzyme-catalyzed ROP in order to avoid contamination of product polymers by toxic organometallic catalysts [92], High molecular weight of poly(DXO) was obtained (Mn = 56000 Mw = 112000, 97% yield) at 60 °C for 4h. The polymerization had the characteristics of a living polymerization, as indicated by the linearity of plots between M and monomer conversion, meaning that the product molecular weight could be controlled by the stoichiometry of the reactants. Similarly, Nishida et al. [91] carried out enzymatic ROP of l,4-dioxan-2-one at 60 °C catalyzed by Novozym 435 that resulted in a polymer with Mw = 41000 in 77% yield. 

The radical polymerization of various other organometallic vinyl monomers has been well studied. For example, in 1978, it was shown that vinylcymantrene 43 undergoes radical homopolymerization in the presence of AIBN as initiator at 50-80 °C in organic solvents such as benzene to yield poly(vinylcymantrene) 44 (Equation (15)). Molecular weights varied from = S x 10 to 3.6 x 10 with broad PDI values in the range 3.2-8.9. 

The first synthesis of a soluble and processible poly(2,7-fluorene) was reported by Yoshino and coworkers in 1989 [44,45]. Their approach involved coupling fluorene monomers with substituents at the C9 position by chemical oxidation with FeCls (see P3 in Scheme 1.2). However, the polymerization process was not regiospecific and the polymer backbone contained structural defects that influence the electronic delocalization. Thus, the synthesis of defect-free poly(fluorene)s became a major challenge and advances in carbon-carbon bond forming reactions promoted by organometallic catalysts provided the... 

Each monomer addition step interconverts the two organometallic components. The poly(methyl methacrylate) (PMMA) obtained is predominantly syndio-tactic, although isotactic PMMA has been obtained by using chiral indenyl zirconocenes in combination with non-zirconocene Lewis acids. No reports of attempted ethylene or a-olefin copolymerizations have been described. 

Organometallic derivatives of poly-p-xylylene (PPX) with Ge and Sn atoms covalently bonded to polymer chains have been synthesized by a vapor deposition technique using bridged [2,2]-paracyclophanes with corresponding organometallic groups [32, 33]. Pyrolysis of these cyclophanes, along with polymerization of the /7-xylylene monomer mixture, is shown in Scheme 2.2. 

Novel organometallic poly(arylene)s with 1,3-type (cyclobutadiene)cobalt moieties 27 in the main chain are prepared by Ni(0)-mediated dehalogenative polycondensation of monomers having (cyclobutadiene)cobalt moieties [51], The polymers with of 20 kDa exhibit thermotropic liquid crystallinity. The synthesis of a variety of homometallic and heterometallic oligomers and polymers such as 28 is possible via nucleophilic aromatic substitution reactions of dichlorophenylene-Fe Cp and dihydroxyphenylene-Ru Cp complexes in DMF in the presence of K2CO3 [52]. 

Recently, Abd-El-Aziz and colleagues reported different hyperbranched poly(arylethers) (4,5) and poly(arylthioethers) (6) containing cyclopentadienyliron moieties, which were successfully furnished by nucleophilic substitution of A + Bj type monomers (Scheme 2.3) [54], The polymers were thoroughly characterized by standard spectroscopic analysis techniques, they exhibited generally low viscosities, and the organometallic complexes were stable up to 230 °C, as evaluated by thermal gravimetric analysis (TGA). 

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