Reactively modified polymers

Approach ii is applicable to all thermoplastic polymers and offers considerable practical advantage since reactively modified polymers can be readily produced by normal commercial high-shear mixing procedures at no additional cost. 

As discussed in the previous section, this book focusses on reactive polymer systems, from network-forming polymers to reactively modified polymer systems. Network polymers may be defined as polymer systems that contain chemical or physical networks between the constituent molecules of the system. Within the term reactively modified polymers we include polymer systems that have been modified by grafting, chemical reaction or high-energy radiation. Typically network or reactively modified polymers are manufactured by various... 

We will now briefly introduce and differentiate between network and reactively modified polymers. 

Reactively modified polymers are polymer systems that have been chemically or physically changed during processing. Reactively modified polymers may be classified in terms of their production by the following processing techniques ... 

Xiong J, Liu Y, Yang X, Wang X. Thermal and mechanical properties of polyurethane/ montmorillonite nanocomposites based on a novel reactive modifier. Polym Degrad Stab December 2004 86(3) 549-55. 

Homogeneous GopolymeriZation. Nearly all acryhc fibers are made from acrylonitrile copolymers containing one or more additional monomers that modify the properties of the fiber. Thus copolymerization kinetics is a key technical area in the acryhc fiber industry. When carried out in a homogeneous solution, the copolymerization of acrylonitrile foUows the normal kinetic rate laws of copolymerization. Comprehensive treatments of this general subject have been pubhshed (35—39). The more specific subject of acrylonitrile copolymerization has been reviewed (40). The general subject of the reactivity of polymer radicals has been treated in depth (41). 

Blends based on polyolefins have been compatibilized by reactive extrusion where functionalized polyolefins are used to form copolymers that bridge the phases. Maleic anhydride modified polyolefins and acrylic acid modified polyolefins are the commonly used modified polymers used as the compatibilizer in polyolefin-polyamide systems. The chemical reaction involved in the formation of block copolymers by the reaction of the amine end group on nylon and anhydride groups or carboxylic groups on modified polyolefins is shown in Scheme 1. 

Al-Malaika, S. In Reactive Modifiers for Polymers, Al-Malaika, S., Ed. Chapman llall London, 1996 p 266. 

A great variety of suitable polymers is accessible by polymerization of vinylic monomers, or by reaction of alcohols or amines with functionalized polymers such as chloromethylat polystyrene or methacryloylchloride. The functionality in the polymer may also a ligand which can bind transition metal complexes. Examples are poly-4-vinylpyridine and triphenylphosphine modified polymers. In all cases of reactively functionalized polymers, the loading with redox active species may also occur after film formation on the electrode surface but it was recognized that such a procedure may lead to inhomogeneous distribution of redox centers in the film... 

The nucleophilic substitution on poly(vinyl chloroformate) with phenol under phase transfer catalysis conditions has been studied. The 13c-NMR spectra of partly modified polymers have been examined in detail in the region of the tertiary carbon atoms of the main chain. The results have shown that the substitution reaction proceeds without degradation of the polymer and selectively with the chloroformate functions belonging to the different triads, isotactic sequences being the most reactive ones. 

Properly functionalised additives can react with polymer substrates to produce polymer-bound functions which are capable of effecting the desired modification in polymer properties, hence the use of the term reactive modifiers. As an integral part of the polymer backbone, reactive modifiers are useful vehicles for incorporating the desired chemical functions to suit the specialised application. Being molecularly dispersed, the problem of solubility expressed under 2 above is avoided. Implicitly, the bound-nature of the function is not subjected to the normal problems of the loss of additives from the surface which are common with both high and low molecular mass additives. The bound nature of the function must be fully defined for the conditions of service. 

Current interest in reactive modifiers is in the areas of polymer property enhancement and improvement in additive performance. Reactive modifiers can be incorporated into commercial polymers by,... 

Tieing of reactive modifiers into polymers after their manufacture (via route 2), on the other hand, can be achieved (5.10) by either,... 

In the absence of oxygen or any other radical trap, however, mechanochemically formed macroalkyl radicals (scheme I, I) can be made to react with chemically reactive modifiers, RM, (see scheme Id) this forms the basis of an in-situ synthesis of polymer adducts i.e., the functionalised additive/modifier becomes chemically bound onto the polymer backbone. 

A good example of a reactive modifier which has been used (14) to enhance properties of polyolefins is maleic anhydride (MA). The formation of maleic adduct in polypropylene (PP), for example, can be used to effect several modifications e.g. to improving hydrophilicity, adhesion and dyeabflity. Moreover, the polymer-maleic adduct has an availabla additional functionality to effect other chemical modifications for achieving the desired material design objectives. Reactions of MA with polymers in solution are described in the patent literature (15). 

Radiation chemistry in polymer research, 168-169 Reactive macroalkyl radicals, formation, 409 Reactive modifiers addition of reactive antioxidants on rubbers, 417 adhesion, 420,422 demanding applications, 414,416 improving additive performance during melt processing, 412 polymer bound antioxidant, 418-419/ Reduced poly(vinyl chloride),... 

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