Interfacial grafting

Heterogeneous alloys can be formed when graft or block copolymers are combined with a compatible polymer. Alloys of incompatible polymers can be formed if an interfacial agent can be found. 

Most elastomers that are used for nylon modification contain a small amount of maleic anhydride (0.3 to 2%). In the melt blending process, these elastomers react with the primary amine end groups in nylon, giving rise to nylon grafted elastomers. These grafts reduce the interfacial tension between the phases and provide steric stabili2ation for the dispersed mbber phase. Typically, thermally stable, saturated mbbers such as EPR, EPDM, and styrene—ethylene/butylene—styrene (SEBS) are used. 

The study of acid-base interaction is an important branch of interfacial science. These interactions are widely exploited in several practical applications such as adhesion and adsorption processes. Most of the current studies in this area are based on calorimetric studies or wetting measurements or peel test measurements. While these studies have been instrumental in the understanding of these interfacial interactions, to a certain extent the interpretation of the results of these studies has been largely empirical. The recent advances in the theory and experiments of contact mechanics could be potentially employed to better understand and measure the molecular level acid-base interactions. One of the following two experimental procedures could be utilized (1) Polymers with different levels of acidic and basic chemical constitution can be coated on to elastomeric caps, as described in Section 4.2.1, and the adhesion between these layers can be measured using the JKR technique and Eqs. 11 or 30 as appropriate. For example, poly(p-amino styrene) and poly(p-hydroxy carbonyl styrene) can be coated on to PDMS-ox, and be used as acidic and basic surfaces, respectively, to study the acid-base interactions. (2) Another approach is to graft acidic or basic macromers onto a weakly crosslinked polyisoprene or polybutadiene elastomeric networks, and use these elastomeric networks in the JKR studies as described in Section 4.2.1. 

Polypropylene block and graft copolymers are efficient blend compatibilizers. These materials allow the formation of alloys, for example, isotactic polypropylene with styrene-acrylonitrile polymer or polyamides, by enhancing the dispersion of incompatible polymers and improving their interfacial adhesion. Polyolefinic materials of such types afford property synergisms such as improved stiffness combined with greater toughness. 

Compatibility and various other properties such as morphology, crystalline behavior, structure, mechanical properties of natural rubber-polyethylene blends were investigated by Qin et al. [39]. Polyethylene-b-polyiso-prene acts as a successful compatibilizer here. Mechanical properties of the blends were improved upon the addition of the block copolymer (Table 12). The copolymer locates at the interface, and, thus, reduces the interfacial tension that is reflected in the mechanical properties. As the amount of graft copolymer increases, tensile strength and elongation at break increase and reach a leveling off. 

Els and McGill [48] reported the action of maleic anhydride on polypropylene-polyisoprene blends. A graft copolymer was found in situ through the modifier, which later enhanced the overall performance of the blend. Scott and Macosko [49] studied the reactive and nonreactive compatibilization of nylon-ethylene-propylene rubber blends. The nonreactive polyamide-ethylene propylene blends showed poor interfacial adhesion between the phases. The reactive polyamide-ethylene propylene-maleic anhydride modified blends showed excellent adhesion and much smaller dispersed phase domain size. 

The graft polymer formed during melt mixing results in good interfacial adhesion between the phases. The... 

ATBN - amine terminated nitrile rubber X - Flory Huggins interaction parameter CPE - carboxylated polyethylene d - width at half height of the copolymer profile given by Kuhn statistical segment length DMAE - dimethyl amino ethanol r - interfacial tension reduction d - particle size reduction DSC - differential scanning calorimetry EMA - ethylene methyl acrylate copolymer ENR - epoxidized natural rubber EOR - ethylene olefin rubber EPDM - ethylene propylene diene monomer EPM - ethylene propylene monomer rubber EPR - ethylene propylene rubber EPR-g-SA - succinic anhydride grafted ethylene propylene rubber... 

Interfacial polycondensation between a diacid chloride and hexamethylenediamine in the presence of small amounts of ACPC also yield polymeric azoamid, which is a macroazo initiator.[27] In this manner, azodicarbox-ylate-functional polystyrene [28], macroazonitriles from 4,4 -azobis(4-cyano-n-pentanoyl) with diisocyanate of polyalkylene oxide [29], polymeric azo initiators with pendent azo groups [3] and polybutadiene macroazoinitiator [30] are macroazoinitiators that prepare block and graft copolymers. 

After this treatment the surface energy of the fibers is increased to a level much closer to the surface energy of the matrix. Thus, a better wettability and a higher interfacial adhesion are obtained. The polypropylene (PP) chain permits segmental crystallization and cohesive coupling between modified fiber and PP matrix [40]. The graft copolymerization method is effective, but complex. 

In cases where additive molecules have been grafted to the polymer all of the methods that require extraction are less than quantitative. Graft copolymers acting as interfacial agents [587] are quite inaccessible to extraction. 

Copolymers of styrene, especially with acrylonitrile, also attained increasing importance both in the unmodified form (30) and modified with rubber as ABS copolymers. The first products of this kind were blends of nitrile rubber and SAN (31). However, these only had mediocre mechanical properties because the interfacial compatibility was insufficient. The breakthrough came when nitrile rubber was replaced by a polybutadiene rubber which was grafted in emulsion with styrene and acrylonitrile... 

Reactive impact modifiers are preferred for toughening of PET since these form a stable dispersed phase by grafting to the PET matrix. Non-reactive elastomers can be dispersed into PET by intensive compounding but may coalesce downstream in the compounder. Reactive impact modifiers have functionalized end groups. Functionalization serves two purposes - first, to bond the impact modifier to the polymer matrix, and secondly to modify the interfacial energy between the polymer matrix and the impact modifier for enhanced dispersion. Some examples of commercially available reactive impact modifiers for PET are shown in Table 14.3. An example of a non-reactive elastomer that can be used in combination with reactive impact modifiers is ethylene methyl acrylate (EMA), such as the Optema EMA range of ethylene methyl acrylates manufactured by the Exxon-Mobil Chemical Company (see Section 4.2). 

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