Molecular weight hyperbranched polymers

The use of epoxidized hyperbranched polyesters as toughening additives in carbon-fiber reinforced epoxy composites has been demonstrated (Boogh et al., 1995). Since a hyperbranched resin has a substantially lower viscosity and much shorter drying time than a conventional (less branched) resin of comparable molecular weight, hyperbranched polymers have been used as the base for various coating resins (Pettersen and Sorensen, 1994). 

The two different molecular weight hyperbranched polymers with a phosphonic acid group at the periphery (HBP-PA(H, L)) were synthesized according to the procedure as shown in Scheme 13.3. The hyperbranched polymer with a hydroxyl group (HBP-OH), prepared by the polymerization of methyl 3,5-bis[(8 -hydroxy-3, 6 -dioxaoctyl)oxy]benzoate monomer... 

High molecular weight Hyperbranched PAMAM Hyperbranched polymer Inhibitory concentration Kilo Dalton Linear unit... 

The branched architecture has great influence on the packing of molecular chains. In general, dendrimers have smaller hydrodynamic radius and the melt and solution viscosity of a hyperbranched polymer is expected to be lower than that of a parent linear polymer. Viscosity measurements performed with a cone viscometer confirmed the decrease of viscosity of star-shape polymers compared to the respective high molecular weight arms (polymers B-R-4 and C-R-4, Tables 1 and 2). This observation is consistent with the decrease of hydrodynamic volume observed for... 

As early as 1952, Flory [5, 6] pointed out that the polycondensation of AB -type monomers will result in soluble highly branched polymers and he calculated the molecular weight distribution (MWD) and its averages using a statistical derivation. Ill-defined branched polycondensates were reported even earlier [7,8]. In 1972, Baker et al. reported the polycondensation of polyhydrox-ymonocarboxylic acids, (OH)nR-COOH, where n is an integer from two to six [ 9]. In 1982, Kricheldorf et al. [ 10] pubhshed the cocondensation of AB and AB2 monomers to form branched polyesters. However, only after Kim and Webster published the synthesis of pure hyperbranched polyarylenes from an AB2 monomer in 1988 [11-13], this class of polymers became a topic of intensive research by many groups. A multitude of hyperbranched polymers synthesized via polycondensation of AB2 monomers have been reported, and many reviews have been published [1,2,14-16]. 

A series of theoretical studies of the SCV(C)P have been reported [38,40,70-74], which give valuable information on the kinetics, the molecular weights, the MWD, and the DB of the polymers obtained. Table 2 summarizes the calculated MWD and DB of hyperbranched polymers obtained by SCVP and SCVCP under various conditions. All calculations were conducted, assuming an ideal case, no cyclization (i.e., intramolecular reaction of the vinyl group with an active center), no excluded volume effects (i.e., rate constants are independent of the location of the active center or vinyl group in the macromolecule), and no side reactions (e.g., transfer or termination). 

A challenging goal in this field, particularly from the synthetic point of view, is the development of general AB polymerization methods that achieve control over DB and narrow MWDs. Experimental results and theoretical studies mentioned above suggest that the SCV(C)P from surfaces, which are functionahzed with monolayers of initiators, permit a controlled polymerization, resulting structural characteristics (molecular weight averages, DB) of hyperbranched polymers. In particular, it is expected that the use of polyfunctional initiators with a different number of initiator functionahty, copolymerization, and slow monomer addition techniques lead to control the molecular parameters. 

Random hyperbranched polymers are generally produced by the one-pot polymerization of ABX monomers or macromonomers involving polycondensation, ring opening or polyaddition reactions hence the products usually consist of broad statistical molecular weight distributions. 

Frechet [49, 89] was the first to compare viscosity parameters for (A) linear topologies, as well as (B) random hyperbranched polymers and (C) dendrimers. More recently, we reported such parameters for (D) dendrigraft polymers [111] as shown in Figure 1.19. It is clear that all three dendritic topologies behave differently than the linear. There is, however, a continuum of behavior wherein random hyperbranched polymers behave most nearly like the linear systems. Dendrigrafts exhibit intermediary behavior, whereas dendrimers show a completely different relationship as a function of molecular weight. 

High functionality precursors of/ > 10-20 are primary chains if they participate in crosslinking by vulcanization each monomer unit of primary chain is a potential site for crosslinking. Also, dendrimers and random hyperbranched polymers of higher molecular weight, rank among high-functionality precursors. 

If the crosslinking reaction is interrupted before the gel point, the molecular weight and functionality distributions of such functional precursors are wider but not basically different from that of polymers of BAf monomer. It was stressed recently that they resemble hyperbranched polymers [24] in a certain respects. The pre-gel polymers are generally not stable because the crosslinking reaction can occur during storage. Stable precursors, e.g. for RAf + R Ba, can be obtained in two ways ... 

Average values of molecular weight and functionality of the hyperbranched polymer. 

For a theoretical description of crosslinking and network structure, network formation theories can be applied. The results of simulation of the functionality and molecular weight distribution obtained by TBP, or by off-space or in-space simulations are taken as input information. Formulation of the basic pgf characteristic of TBP for crosslinking of a distribution of a hyperbranched polymer is shown as an illustration. The simplest case of a BAf monomer corresponding to equation (4) is considered ... 

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