Side-chain dendritic polymers

A GGS model was used to treat side-chain dendritic polymers [78]. The model is given in Fig. 21 it consists of chains bearing dendritic wedges (CBDW) in their middles. A dendritic wedge (DW) differs from a conventional classical dendrimer in that its core has one main branch less /c = (/ - 1). For such DW the results of the previous section hold [74,78]. In particular, the maximal relaxation time of a DW is the same as that of a classical dendrimer, because this time corresponds to the motion of two main branches against each other. 

This theoretical result is in quahtative agreement with rheological data obtained for side-chain dendritic polymers that consist of a polymethane main chain and of polyether wedges of second, third, and fourth generations [201]. 

The bulkiness of dendritic side chains can force the polymer backbone to adopt special geometries [84]. The overall contour of the polymer can then be spherical or rod-hke so that the polymers adopt Uquid crystalUne phases. Even when the driving force of this behavior is caused by the bulkiness of the side chain, these polymers show MCLCP-Uke behavior. 

It is also possible to incorporate dendritic design motifs into polymeric systems. Sato and Aida have recently demonstrated the feasibility of constructing lightharvesting dendritic side chains on polymer chains of fluorophores [149]. The repeat... 

When a linear polymer is grafted with a large number of much shorter side chains, cylindrical polymer brushes are formed [33, 108-111]. They are also denoted as bottlebrushes or molecular brushes. Although most cylindrical polymer brushes contain linear side chains, dendritic or even hyperbranched space demanding grafts can also render cylindrical shapes, which leads to the so-called dendronized [112-116] andhypergrafted[117, 118] polymers, respectively. In this review, we will focus on cylindrical brushes with linear side chains. Due to their anisotropic nature in topology, they have attracted more and more research interest in their synthesis, bulk, or solution properties, as well as applications. 

Jen a al. have developed dendronized polymeric NEO materials that have shown significantly improved poling efficiency by encapsulating chromophore with dendritic substituents that can electronically shield the core, ii-electrons, and form spherical molecular shapes." "" " Figure 6 illustrates different molecular architectures of dendronized side-chain NLO polymers with crosslinkers. The diverse selections of molecular architectures provide additional flexibility in the molecular engineering of high-performance polymeric NLO materials. Moreover, the unique nanoscale environment created by the shape and size, dielectric properties, and distribution of chromophores in crosslinkable polymers with dendrons and dendrimers can all play critical roles in maximizing the macroscopic EO properties of polymeric NEO materials. 

The concept of making brush-type polymers in which a linear polymer is funtionalized with dendritic side-chains was first suggested by Tomalia in a 1987 patent, though actual experimental work on his approach was only reported recently recently [15]. Hawker and Frechet were first to document the preparation of a vinyl copolymer containing a few pendant Frechet-type dendrons (Figure 7.9). 

In one of several important studies on dendronized polymers [4c, 4d]. Schluter and coworkers explored the stiffening of polystyrene chains through the incorporation of Frechet-type dendrons as side chains [28, 29]. While the G-l and G-2 dendrons were not sufficiently bulky to effectively stiffen the polystyrene chain, the G-3 dendron provides enough steric bulk to force the hybrid polymer into adopting a cylindrical shape in solution [28b], In a complementary study, Neubert and Schluter demonstrated that adding charges to the dendritic wedges leads to an expansion of the chains of the hybrid copolymer in aqueous solution [29],... 

The affinity of Cgo towards carbon nucleophiles has been used to synthesize polymer-bound Cgo [120] as well as surface-bound Cjq [121]. Polymers involving G q [54, 68, 69] are of considerable interest as (1) the fullerene properties can be combined with those of specific polymers, (2) suitable fullerene polymers should be spin-coatable, solvent-castable or melt-extrudable and (3) fullerene-containing polymers as well as surface-bound Cgo layers are expected to have remarkable electronic, magnetic, mechanical, optical or catalytic properties [54]. Some prototypes of polymers or solids containing the covalently bound Cjq moiety are possible (Figure 3.11) [68,122] fullerene pendant systems la with Cjq on the side chain of a polymer (on-chain type or charm bracelet ) [123] or on the surface of a solid Ib [121], in-chain polymers II with the fullerene as a part of the main chain ( pearl necklace ) [123], dendritic systems III, starburst or cross-link type IV or end-chain type polymers V that are terminated by a fullerene unit For III and IV, one-, two-and three-dimensional variants can be considered. In addition, combinations of all of these types are possible. 

Dendronized polymers are a class of polymers produced by the combination of linear polymers and dendritic molecules as side chain pendant moieties [67-69],... 

When dendritic fragments are attached to polymer chains, the conformation of the polymer chain is strongly affected by the size and chemical structure of the dendritic wedges attached. Dense attachment of dendritic side chain converts a linear polymer into a cylindrically shaped, rigid and nanoscopic dimension. Frechet and Flawker [70] were one of the first to recognize these hybrid architectures . 

The self-assembly of the various polymer systems described in the above sections is only a brief summary of the attempts by chemists to create multifunctional materials based on noncovalent interactions. The unique regions present within a polymer including the (1) main-chain/backbone, (2) end groups, (3) side-chains and (4) dendritic periphery, along with the ability to functionalize any of these regions with recognition units, provide chemists with a wide array of self-assembly possibilities with which to build and create multifunctional materials. 

Norbornene-based and oxa-norbornene-based monomers bearing dendritic side chains, XXX and XXXI (Fig. 19), were synthesized and polymerized via ROMP with initiator 6 [83]. Based on size exclusion chromatography data, the polymerization shows hving-like character up to DP=70. H- and C-NMR-spectroscopy revealed 35% cis and 65% tram sequences. These polymers displayed enantiotropic nematic and smectic mesophases, except for DP=5. In contrast to other classes of SCLCPs, the dependence of the DP on the transition temperatirre of the polymer was very weak. Glass transition and isotropization temperatures became independent of molecular weight above a degree of polymerization of about 10. 

Beside classical SCLCPs, attaching dendritic side chains to poly(norborn-enes) and poly(7-oxanorbornenes) leads to highly-ordered columnar mesophases (Sect. 2.5). In these polymers, the dendritic side chains force the polymer to adopt a rod-like structure. 

Polymeric materials have advantages because of their stability and structureforming properties. Electron- and ion-active organic polymeric materials have attracted attention for new devices. In Chapter 5, Kato and co-workers focus on polymeric liquid crystalline materials that are used for the development of functional materials transporting ions and electrons. The nanostructures such as smectic and columnar phases exhibited by side-chain, main-chain, dendritic, and network polymers may exhibit one- and two-dimensional transportation properties. 

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