Poly hyperbranched polymers

Dendrimers have structures similar to that of hyperbranched polymer and can be taken as the perfectly branched polymer with monodispersity. However, they need to be prepared by a multistep procedure. Therefore, very little work has been done on dendritic polyfarylcnc ether)s. Morikawa et al. prepared a series of monomers with a various number of phenylene units.164,165 These monomer were used to prepare poly(ether ketone) dendrons with graded structures (Scheme 6.24). 

Hyperbranched poly(ethyl methacrylate)s prepared by the photo-initiated radical polymerization of the inimer 13 were characterized by GPC with a lightscattering detector [51]. The hydrodynamic volume and radius of gyration (i g) of the resulting hyperbranched polymers were determined by DLS and SAXS, respectively. The ratios of Rg/R are in the range of 0.75-0.84, which are comparable to the value of hard spheres (0.775) and significantly lower than that of the linear unperturbed polymer coils (1.25-1.37). The compact nature of the hyperbranched poly(ethyl methacrylate)s is demonstrated by solution properties which are different from those of the linear analogs. 

Experimental data on the solution properties and melt rheology of highly branched structures are scarcely found in the literature. This might be because of the structural nonuniformity of hyperbranched polymers, which makes it difficult to obtain reliable data. Because of the purely statistical nature of the poly-... 

Hyperbranched polymers have also been prepared via living anionic polymerization. The reaction of poly(4-methylstyrene)-fo-polystyrene lithium with a small amount of divinylbenzene, afforded a star-block copolymer with 4-methylstyrene units in the periphery [200]. The methyl groups were subsequently metalated with s-butyllithium/tetramethylethylenediamine. The produced anions initiated the polymerization of a-methylstyrene (Scheme 109). From the radius of gyration to hydrodynamic radius ratio (0.96-1.1) it was concluded that the second generation polymers behaved like soft spheres. 

Commercially available hyperbranched polymer, a poly(ester-amide) is currently being marketed by DSM under the product name Hybrane [13] (Figure 8.2). It is also a hydroxyl-functionalized product, but contains both amide and ester linkages. The synthesis is accomplished in two steps cyclic anhydrides are reacted with diisopropanolamine to give an amide-intermediate, possessing two hydroxyl groups and one carboxylic acid. The subsequent polymerization takes places via an oxazolinium intermediate which results in the formation of a... 

Since these reports, a number of new approaches based on vinyl monomers and various initiating systems have been explored to yield hyperbranched polymers such as, poly(4-acetylstyrene) [26], poly(vinyl ether) [27] and polyacrylates [28], In view of the fact that free radical polymerizations are most widely used in industrial polymerization processes the development of these procedures for vinyl monomers has opened a very important area for hyperbranched polymers. 

Fig. 14. Hyperbranched polymer grafts prepared on a mercaptoundecanoic acid (MUA) self assembled monolayer confined to a gold substrate. PAAM-c-PAA represents a random copolymer of poly(acrylamide) and poly(acrylic acid) prepared from the poly(acrylic acid) carboxylic acid groups and an amine [129]...

The molecular weight of the polymers is controlled by the initiator/monomer ratio. The first hyperbranched polymer obtained via ROP is poly(ethylene imine) (PEI) (Scheme 1). 

Although rigid-rod poly(p-phenyleneterephthalamide) analogues having alkyl side chains did not contain cyclic polymers, the polycondensation of silylated m-phenylenediamine and aliphatic dicarboxyhc acid chloride afforded cyclic polyamides predominantly (Scheme 49) [187]. Furthermore, cyclic polymers were also produced in polycondensations for polyesters, poly(ether ketone)s, polyimides, and polyurethanes [183]. These examples are the products in polycondensation of AB monomers or in A2 + B2 polycondensations, but cyclization of oligomer and polymer was also confirmed in polycondensation of AB2 monomers [ 188-195] and in A2 + B3 [ 196-202] and A2 + B4 polycondensations [203-206], which afford hyperbranched polymers. 

Massa, Voit, and coworkers1231 conducted a survey of the phase behavior of blends of these polyester hyperbranched polymers with linear polymers. Blend miscibility of a hydroxyl terminated polyester was comparable to that of poly(vinylphenol) indicating strong H-bonding interactions, whereas miscibility of an acetoxy terminated analog decreased relative to the hydroxy derivative. 

Miller, Neenan, et al.129,301 reported a general single-pot method (Scheme 6.5) for the preparation of poly(arylether) hyperbranched macromolecules (14 a-d), that are functionally analogous to linear poly(arylether) engineering plastics.129-3 1 The hyperbranched polymers were generated from phenolic A2B-type monomers (15 a-d), that were converted to the corresponding sodium phenoxides (16 a-d NaH, THF) and subjected to polymerization. 

The hyperbranched polymer, as obtained by the dehydropolymerization of n-Bu2SnH2 with a rhodium catalyst, has a kmax value of 394 nm98, which is slightly red-shifted with respect to high molecular weight poly(dibutyl)stannane (Table 7, entries 2-5). 

Son and coworkers also reported the syntheses of hyperbranched poly(carbosilanes) via hydrosilylation. In one report, they prepared a series of AB3 carbosilarylene monomers (5, 6 and 7)173 which polymerized cleanly and rapidly to form soluble hyperbranched polymers in high yields. The polymers, ranging in appearance from sticky solids to oils, were characterized by NMR spectroscopy, thermogravimetric analysis, differential scanning calorimetry and vapor pressure osmometry. The polymers possessed subambient Tg... 

Additional studies have focused on the structure, modification and characterization of hyperbranched poly(carbosilanes) synthesized via hydrosilylation. The structure of the hyperbranched polymer derived from methyldiallylsilane was examined using small-angle... 

Getmanova and coworkers attached polar groups to the periphery of the hyperbranched poly(carbosilane) obtained from the polymerization of methyldiallylsilane (Scheme 25)78. This modified hyperbranched polymer possessed certain properties, such as zero shear viscosity, 7 g and surface tension, that were similar to comparably modified carbosilane dendrimers81. 

In 1999, Muzafarov and coworkers published a preliminary report describing the synthesis of a hyperbranched poly(siloxane) from triethoxysilanol via a rapid, ammonia-catalyzed condensation process (Scheme 28)192. The authors acknowledged the potential difficulties of this process (e.g. head-head condensation leading to crosslinked products) but presented 29Si NMR data to support their conclusion that hyperbranched polymer was formed. The fact that no gel formation was observed also suggested that the polymerization proceeded as expected. The polymer, a transparent, yellow liquid, was characterized with NMR and IR spectroscopy, and GPC. 

Other hyperbranched polymers showed similar absorption and luminescence properties. Upon photoexcitation, the hb-PA solutions emitted deep-blue to blue-green lights, whose intensities were higher than that of poly(l-phenyl-l-octyne), a well-known highly emissive polyene. The PL efficiencies of the polymers varied with their molecular structures. Polymers hb-P(38-VI), hfo-P(45-V), hb-P(48-VI), M>-P(50-VI), fcfo-P(50-VII) and hb-P(59-VI) exhibited (P values higher than 70%, with hfc-P(50-VII) giving the highest value of 98%. 

As a basis for hydrogels, hyperbranched polymers [41] can also be used. These polymers can be connected by click chemistry in miniemulsion droplets in order to obtain hyperbranched polyglycerol (HPG)-based particles. Such materials are of great interest for drug release because they are nontoxic [42, 43] and show similar behavior to poly(ethylene glycol)s. 

---