Polymer, branched Modification

The hydroxyl group at the end of the polymer branches can be used for further desired chemical modification. In the above case the hydroxyl groups on the PVC were reacted with benzoyl chloride forming benzoyl terminated grafted oligomer. The NMR spectrum of such a product appears in Figure 11. 

An example of a branched modification of a linear polymer is amylo-pectin, a type of starch. The difference due to branching is shown in Fig. 26.2. 

ADMET is quite possibly the most flexible transition-metal-catalyzed polymerization route known to date. With the introduction of new, functionality-tolerant robust catalysts, the primary limitation of this chemistry involves the synthesis and cost of the diene monomer that is used. ADMET gives the chemist a powerful tool for the synthesis of polymers not easily accessible via other means, and in this chapter, we designate the key elements of ADMET. We detail the synthetic techniques required to perform this reaction and discuss the wide range of properties observed from the variety of polymers that can be synthesized. For example, branched and functionalized polymers produced by this route provide excellent models (after quantitative hydrogenation) for the study of many large-volume commercial copolymers, and the synthesis of reactive carbosilane polymers provides a flexible route to solvent-resistant elastomers with variable properties. Telechelic oligomers can also be made which offer an excellent means for polymer modification or incorporation into block copolymers. All of these examples illustrate the versatility of ADMET. 

The molecular distributions for polymers formed by condensations involving polyfunctional units of the type R—A/ resemble those for the branched polymers mentioned above, except for the important modification introduced by the incidence of gelation. The generation of an infinite network commences abruptly at the gel point, and the a-mount of this gel component increases progressively with further condensation. Meanwhile, the larger, more complex, species of the sol are selectively combined with the gel fraction, with the result that the sol fraction decreases in average molecular complexity as well as in amount. It is important to observe that the distinction between soluble finite species on the one hand and infinite network on the other invariably is sharp and by no means arbitrary. 

An important polymer modification reaction is the grafting to or from a polymer backbone by some chemical method to produce a branched structure Q). The characterization of the products of these reactions is often somewhat less well defined than block copolymers (2) due to the complexity of the mixture of products formed. It is therefore useful to prepare and characterize more well defined branched systems as models for the less well defined copolymers. The macromonomer method (3 ) allows for the preparation of more well defined copolymers than previously available. 

We can introduce short chain branching into polymers by three methods copolymerization, "backbiting , and chemical modification. The first two occur during polymerization, while the last requires a secondary chemical reaction. Short chain branches have well defined chemical structures, the nature of which we can accurately determine via analytical methods or know, from the structure of the reactants. 

There are five prime factors that determine the properties of starches 1. starch is a polymer of glucose (dextrose) 2. the starch polymer is of two types linear and branched 3 the linear polymeric molecules can associate with each other giving insolubility in water 4. the polymeric molecules are organized and packed into granules which are insoluble in water and 5 disruption of the granule structure is required to render the starch polymer dispersible in water. The modification of starch takes into account these factors. 

Favorable rheological properties are an essential requirement for the commercialization of polyolefins like polyethylene. The ease of processability of the polymer melt, obtained through modifications in the microstructural features, is as important as the end use mechanical properties of these polymers. Presence of long-chain as well as short-chain branching, LCB and SCB, respectively, more or less dictates the rheological behavior of most commercial... 

The most common of all natural polymers is cellulose. It is ubiquitous in plant life in various molecular modifications and structural arrangements. Large quantities are found in the trunks, branches and leaves of trees as well as in... 

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