Highly branched polymers

StmcturaHy, arabinogalactan is a complex, highly branched polymer of arabinose and galactose in a 1 6 ratio (67). It is composed of one fraction with an average molecular weight of 16,000, and one of 100,000 (68). 

The polymerization of ethyleneimine (16,354—357) is started by a catalyticaHy active reagent (H or a Lewis acid), which converts the ethyleneimine into a highly electrophilic initiator molecule. The initiator then reacts with nitrogen nucleophiles, such as the ethyleneimine monomer and the subsequendy formed oligomers, to produce a branched polymer, which contains primary, secondary, and tertiary nitrogen atoms in random ratios. Termination takes place by intramolecular macrocycle formation. 

High pressure (60—350 MPa) free-radical polymerization using oxygen, peroxide, or other strong oxidizers as initiators at temperatures of up to 350°C to produce low density polyethylene (LDPE), a highly branched polymer, with densities from 0.91 to 0.94 g/cm. ... 

If a polymer molecule has a sufficiently regular structure it may be capable of some degree of crystallisation. The factors affecting regularity will be discussed in the next chapter but it may be said that crystallisation is limited to certain linear or slightly branched polymers with a high structural regularity. Well-known examples of crystalline polymers are polyethylene, acetal resins and polytetrafluoroethylene. 

The first commercial grades were introduced by Phillips Petroleum in 1968 under the trade name Ryton. These were of two types, a thermoplastic branched polymer of very high viscosity which was processed by PTFE-type processes and an initially linear polymer which could be processed by compression moulding, including laminating with glass fibre, and which was subsequently oxidatively cross-linked. 

Highly branched polymers, polymer adsorption and the mesophases of block copolymers may seem weakly connected subjects. However, in this review we bring out some important common features related to the tethering experienced by the polymer chains in all of these structures. Tethered polymer chains, in our parlance, are chains attached to a point, a line, a surface or an interface by their ends. In this view, one may think of the arms of a star polymer as chains tethered to a point [1], or of polymerized macromonomers as chains tethered to a line [2-4]. Adsorption or grafting of end-functionalized polymers to a surface exemplifies a tethered surface layer [5] (a polymer brush ), whereas block copolymers straddling phase boundaries give rise to chains tethered to an interface [6],... 

This group includes a set of anionic polysaccharides secreted by unrelated bacteria. The common theme, however, is that their main chains have the same tetrasaccharide repeat. Although (high acyl) native gellan (42) and (deacylated) gellan (40,41) are linear polymers, welan (43) is a branched polymer in which a monosaccharide side chain is regularly attached to each repeat. Other members of this family, such as S-657 and rhamsan, are also branched, like welan."0... 

A polymer is a large molecule built up from numerous smaller molecules. These large molecules may be linear, slightly branched, or highly interconnected. In the latter case the structure develops into a large three-dimensional network. 

There are a number of methods of classifying polymers. One is to adopt the approach of using their response to thermal treatment and to divide them into thermoplastics and thermosets. Thermoplastics are polymers which melt when heated and resolidify when cooled, while thermosets are those which do not melt when heated but, at sufficiently high temperatures, decompose irreversibly. This system has the benefit that there is a useful chemical distinction between the two groups. Thermoplastics comprise essentially linear or lightly branched polymer molecules, while thermosets are substantially crosslinked materials, consisting of an extensive three-dimensional network of covalent chemical bonding. 

Indeed, cumyl carbocations are known to be effective initiators of IB polymerization, while the p-substituted benzyl cation is expected to react effectively with IB (p-methylstyrene and IB form a nearly ideal copolymerization system ). Severe disparity between the reactivities of the vinyl and cumyl ether groups of the inimer would result in either linear polymers or branched polymers with much lower MW than predicted for an in/mcr-mediated living polymerization. Styrene was subsequently blocked from the tert-chloride chain ends of high-MW DIB, activated by excess TiCU (Scheme 7.2). 

Gauthier, M. and Mdller, M. Uniform highly branched polymers hy anionic grafting Arborescent graft polymers. Macromolecules, 24, 4548, 1991. 

Branching also occurs in polymers. The branches are extensions of hnked monomer units that protrude from the polymer trunk chain. Branched polymers can also form random coils, but the branches prevent a highly irregular arrangement and, therefore, less crystalhnity results because the molecules cannot line up and pack as well. 

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]. 

---