Functional Polymers and Other Modifiers

The interaction between the surface of particulate and fibrous fillers and a polymer matrix plays a key role in deterrnining the processability and properties of filled composites. Unmodified filler surfaces often give poor interactions and this has led to the growth of an industry based on the use of additives to modify filler surfaces and improve their interactions with polymers. Several types of additives have been evolved for this purpose. Two of these, organofunctional silanes and titanates, have been described in Chapters 4 and 5. This chapter covers other approaches that have been studied, although only a few of these, notably fatty and unsaturated carboxylic acids and functionalized polymers, have achieved much commercial importance. 

While division into coupling and noncoupling types is often based on chemical structures, this can be misleading. As will be shown later, some modifiers can act as either noncoupling or coupling types, depending on the formulation. The concept of reinforcement promoters, first introduced by Ancker et al. [1], and discussed in Section 6.2.3, is a potentially useful alternative way of classifying modifiers in some cases. 

The coverage has largely been restricted to additives that can be considered to have some form of chemical attachment to the filler surface. This eliminates species such as glycols and some surfactants, which are only physically adsorbed. There is still a gray area, however, as some additives cannot only function as 

General Types of Modifiers and Their Principal Effects 

These additives form a strong, essentially permanent, attachment to the filler surface, 

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It is well known that the surface chemical and physical properties play a dominant role in the separation characteristics of a membrane. Most of the currently used membranes are made of polymers because they have excellent bulk physical and chemical properties, they are inexpensive, and are easy to process. However, the surface properties of polymers, their hydrophobicity, and their lack of functional groups stand in the way of many other applications (Chan et al. 1996). So far, various polymers have been used for membrane fabrication. However, due to the limited number of polymeric materials on the market, one cannot expect any significant increase in the variety of the membranes offered. What is more, large-scale production of brand-new polymers has not been commercialized during the last decade, nor is it expected to be launched in the near future. These observations have forced material scientists to search for alternative methods to increase the number and variety of membranes being prepared. There are two directions for new membrane manufacturing (i) to modify a polymer in bulk and then prepare the membrane from it or (ii) to prepare the membrane from a standard polymer and then modify its surface. The first method needs the optimization of the membrane formation for the particular derivative separately. The second seems to be less complicated and less expensive, and it can offer a wide variety of new membranes based on one starting matrix. The authors intention is to present the plasma methods for membrane modification and tailor them based on the end-user requests. 

Polar side groups are useful to improve the adhesion of copolymers on surfaces, to reduce incompatibility with other polymers and to modify the solubility of polymers, or to synthesize graft copolymers. Common functional monomers for free-radical copolymerization with acrylic monomers are listed in Table 2 [132]. 

Sonochemistry is also proving to have important applications with polymeric materials. Substantial work has been accomplished in the sonochemical initiation of polymerisation and in the modification of polymers after synthesis (3,5). The use of sonolysis to create radicals which function as radical initiators has been well explored. Similarly the use of sonochemicaHy prepared radicals and other reactive species to modify the surface properties of polymers is being developed, particularly by G. Price. Other effects of ultrasound on long chain polymers tend to be mechanical cleavage, which produces relatively uniform size distributions of shorter chain lengths. 

Other immobilization methods are based on chemical and physical binding to soHd supports, eg, polysaccharides, polymers, glass, and other chemically and physically stable materials, which are usually modified with functional groups such as amine, carboxy, epoxy, phenyl, or alkane to enable covalent coupling to amino acid side chains on the enzyme surface. These supports may be macroporous, with pore diameters in the range 30—300 nm, to facihtate accommodation of enzyme within a support particle. Ionic and nonionic adsorption to macroporous supports is a gentle, simple, and often efficient method. Use of powdered enzyme, or enzyme precipitated on inert supports, may be adequate for use in nonaqueous media. Entrapment in polysaccharide/polymer gels is used for both cells and isolated enzymes. 

The thiocarbonylthio group can be transformed post-polymerization in a variety of ways to produce end-functional polymers or it can be removed. The presence of the thiocarbonylthio groups also means that the polymers synthesized by RAFT polymerization are usually colored and they possess a labile end group that may decompose to produce sometimes odorous byproducts. Even though the color and other issues may be modified by appropriate selection of the initial RAFT agent, these issues have provided further incentive to develop effective methods for treatment of RAFT-synthesized polymer to transform the thiocarbonylthio groups post-polymerization. 

Another approach was developed by Scott in the 1970 s (7.8) which utilises the same mechanochemistry used previously by Watson to initiate the Kharacsh-type addition of substituted alkyl mercaptans and disulphides to olefinic double bonds in unsaturated polymers. More recently, this approach was used to react a variety of additives (both antioxidants and modifiers) other than sulphur-containing compounds with saturated hydrocarbon polymers in the melt. In this method, mechanochemically formed alkyl radicals during the processing operation are utilised to produce polymer-bound functions which can either improve the additive performance and/or modify polymer properties (Al-Malaika, S., Quinn, N., and Scott, 6 Al-Malaika, S., Ibrahim, A., and Scott, 6., Aston University, Birmingham, unpublished work). This has provided a potential solution to the problem of loss of antioxidants by volatilisation or extraction since such antioxidants can only be removed by breaking chemical bonds. It can also provide substantial improvement to polymer properties, for example, in composites, under aggresive environments. 

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). 

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