Hyperbranched materials, preparation

These theoretical results are confirmed experimentally. In attempts to prepare a resin with a ratio of the starting materials of HHPA diisopropanolamine 2.3 1 the mixture gelated. This is reflected in Scheme 1, example 1 (n = 2). If a ratio of HHPA diisopropanolamine 3.2 1 is chosen (Scheme 1, example 2, n = 5/6), the system does not gelate. By GPC analysis it was verified that the theoretical assumptions made in Scheme 1 are valid for this system. Besides the hyperbranched material, the presence of hexahydrophthalic acid is demonstrated. The quantity of the acid is in close agreement (29 %) with the calculated value (28%). 

Reichert and Mathias prepared related branched aramids, to those of Kim,t5-34] from 3,5-dibromoaniline (23) under Pd-catalyzed carbonylation conditions (Scheme 6.7). These brominated hyperbranched materials (24) were insoluble in solvents such as DMF, DMAc, and NMP, in contrast to the polyamine and polycarboxylic acid terminated polymers that Kim synthesized, which were soluble. This supports the observation that surface functionality plays a major role in determining the physical properties of hyperbranched and dendritic macromolecules J4,36 A high degree of cross-linking could also significantly effect solubility. When a four-directional core was incorporated into the polymerization via tetrakis(4-iodophenyl)adamantanc,1371 the resultant hyperbranched polybromide (e.g., 25) possessed enhanced solubility in the above solvents, possibly as a result of the disruption of crystallinity and increased porosity. 

The actual formation of hyperbranched material proceeds during the polymerization of 3,5-difluoro-4 -hydroxydiphenyl sulfone in the presence of 3,4,5-trifluorophenylsulfonyl benzene or tris(3,4,5-trifluorophenyl)phos-phine oxide as a core molecule. Cyclic oUgomers formed dining this polymerization contribute to a low-molecular-weight polymer ranging from 3400 to 8400 Dalton. A triazin-based AB2 monomer has also been described. This monomer is shown in Figure 7.8. A hyperbranched aromatic poly(ether sulfone) with sulfonyl chloride terminal groups has been prepared by the polycondensation of 4,4 -(m-phenylenedioxy)-bis-(benz-enesulfonyl chloride). The polymerization was carried out in nitrobenzene at 120°C for 3 h in the presence of a catalytic amount of FeCls. ... 

Hyperbranched polymers can be prepared by a variety of techniques, including the polycondensation of AB monomers as originally described by Flory [113], the reaction of A2 + B3 monomers, and self-condensing vinyl polymerization [139-141]. The first report [142] of using click chemistry in the synthesis of hyperbranched materials appeared at about the same time as the initial report for dendrimers prepared using CuAAC however, but much fewer examples have been reported that describe hyperbranched materials involving click chemistry. Nevertheless, these polymers represent an important class of materials, and both CuAAC [142-147] and thiol-ene [148] chemistry have found their way into the hyperbranched hterature. 

Hyperbranched Polyimides Prepared from 4,4, 4 -Triaminotriphenylmethane and Mixed Matrix Materials Based on Them... 

In order to compare general properties of hyperbranched polymers and dendrimers, Wooley et al. examined a model hyperbranched polyester and corresponding dendrimer. Pol)miers prepared from 3-hydroxy-5-( eri-butyldi-methylsiloxy)benzoic acid, as branching point, showed that thermal properties, such as Tg and those shown by thermogravimetic analysis (TGA), were independent of pol)mier architecture. However, the dendritic and hyperbranched materials demonstrated comparative solubilities that were much greater than that found for the linear polymer [99]. Their conclusions on the thermal properties may contradict some other findings. For examples, the of hyper-... 

An interesting novel approach to the synthesis of (metallo)dendrimer catalysts could be the use of random hyperbranched polymers [38]. Obviously, these hyperbranched polymers have comparable but less defined structures, but to arrive at dendrimers with similar sizes, a larger number of preparative steps are required, which may be an economic disadvantage. Furthermore, materials involving heterogeneous supports with well-defined metallodendritic subunits [15] can be a promising future direction giving rise to new types of supramolecu-lar catalysts that can easily be recovered from production streams. 

In the search to develop new materials for immobilization of homogeneous transition metal catalyst to facilitate catalyst-product separation and catalyst recychng, the study of dendrimers and hyperbranched polymers for application in catalysis has become a subject of intense research in the last five years [68], because they have excellent solubility and a high number of easily accessible active sites. Moreover, the pseudo-spherical structure with nanometer dimensions opens the possibility of separation and recycling by nanofiltration methods. Although dendrimers allow for controlled incorporation of transition metal catalysts in the core [69] as well as at the surface [70], a serious drawback of this approach is the tedious preparation of functionalized dendrimers by multi-step synthesis. 

Hyperbranched polymers are a relatively new type of highly branched materials, which in contrast with dendrimers, often can be prepared in a one-step synthesis of AB ... 

Preparation of dendrimers requires a high degree of purity of the starting materials and high yields of the individual synthetic steps, all of which generally increases the effort involved. Polydisperse, hyperbranched compounds, which admittedly show defects yet often display properties similar to their ideally perfect dendritic relations, can readily be synthesised. 

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