End groups reactive

The molecular size of polybenzimidazoles has in the pertinent literature been expressed in terms of inherent (j7i h) or intrinsic ([ ]) viscosities, determined on sulfuric acid solutions or, less frequently, on solutions in formic acid or aprotic solvents. The effect of structure on viscosity behavior appears to be less pronounced than that of the polymerization methods used and of the monomer sensitivity to the employed reaction conditions. In general, melt polymerizations by Marvel s method give products with higher molecular mass than obtained in solution condensations, which may partly be due to increased end group reactivity and interaction at the much higher reaction temperatures encountered in the former process (Cf. Table 1). Furthermore, monomers like bis(phenoxycar-bonyl)ferrocene, diphenyl tetrafluoroterephthalate, or l,7-bis(phenoxycarbonyl)car-... 

Scheme 8.21 Schematic representation of the synthesis of polyfcyclic poly(tetrahydrofnran)), bottom right, utilizing a bifunctional alkyne-modifled initiator for the living CROP followed by end-capping with -phenyl-pyrrolidine to moderate the end-group reactivity. Subsequent end-group modification with a bifunctional acid modified with an azide moiety yields the cyclic poly(tetrahydrofuran) comprising both aUcyne and azide functionalities, which is subsequently polymerized by cycloaddition in the presence of copper(I).

The procedures for the two cases are similar with a slight difference due to high end group reactivity in the second case involving methyl methacrylate (MMA). The synthesis in both cases is carried out in three steps. 

Proteins and peptide can be cmijugated with end-group reactive polymers. There are several methods and reactive groups suitable for this purpose, as pointed out in recent reviews [92, 94, 112]. Therefore, we will focus here on systems in which homopolypeptides prepared by NCA polymerization are conjugated with polymers. 

One of the most sensitive tests of the dependence of chemical reactivity on the size of the reacting molecules is the comparison of the rates of reaction for compounds which are members of a homologous series with different chain lengths. Studies by Flory and others on the rates of esterification and saponification of esters were the first investigations conducted to clarify the dependence of reactivity on molecular size. The rate constants for these reactions are observed to converge quite rapidly to a constant value which is independent of molecular size, after an initial dependence on molecular size for small molecules. The effect is reminiscent of the discussion on the uniqueness of end groups in connection with Example 1.1. In the esterification of carboxylic acids, for example, the rate constants are different for acetic, propionic, and butyric acids, but constant for carboxyUc acids with 4-18 carbon atoms. This observation on nonpolymeric compounds has been generalized to apply to polymerization reactions as well. The latter are subject to several complications which are not involved in the study of simple model compounds, but when these complications are properly considered, the independence of reactivity on molecular size has been repeatedly verified. 

Diisocyanates or Polyisocyanates. The thiol end groups of the hquid polysulfides are quite reactive with isocyanates (eq. 3). Typical chisocyanates, such as 1,3-toluene chisocyanate (m-TDl) and diphenylmethane-4,4 -diisocyanate (MDl), ate effective in curing hquid polysulfides. Using hquid polysulfides in-... 

Reactions of the Disulfide Group. Besides the thiol end groups, the disulfide bonds also have a marked influence on both the chemical and physical properties of the polysulftde polymers. One of the key reactions of disulfides is nucleophilic attack on sulfur (eq. 4). The order of reactivity for various thiophiles has been reported as (C2H O) P > R, HS , C2H5 S- >C,H,S- >C,H,P,... 

Chelation itself is sometimes useful in directing the course of synthesis. This is called the template effect (37). The presence of a suitable metal ion facihtates the preparation of the crown ethers, porphyrins, and similar heteroatom macrocycHc compounds. Coordination of the heteroatoms about the metal orients the end groups of the reactants for ring closure. The product is the chelate from which the metal may be removed by a suitable method. In other catalytic effects, reactive centers may be brought into close proximity, charge or bond strain effects may be created, or electron transfers may be made possible. 

It is now generally used ia the form of a Hquid, low molecular-weight polymer, having reactive end groups obtained by degradation of the base polymer, as foUows ... 

Low molecular weight liquid nitrile rubbers with vinyl, carboxyl or mercaptan reactive end groups have been used with acrylic adhesives, epoxide resins and polyesters. Japanese workers have produced interesting butadiene-acrylonitrile alternating copolymers using Ziegler-Natta-type catalysts that are capable of some degree of ciystallisation. 

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