Grafting reactions

Typical values for mf n are 0.5 to 2.5. Gommercially used bases include sodium hydroxide, potassium hydroxide, calcium hydroxide (lime), magnesium hydroxide, sodium carbonate, sodium alurninate, calcium carbonate, or various mixtures. For certain appHcations, PAG can be made from waste grades of aluminum chloride [7446-70-0] such as spent catalyst solutions from Friedel-Grafts synthesis (see Friedel-Grafts reaction). 

Friedel-Grafts Reaction. Until quite recently, the manufacture of anthraquiaone ia the United States was by the Friedel-Crafts reaction benzene [71-43-2] and phthaUc anhydride [85-44-9] condense ia the preseace of anhydrous aluminum chloride to give o-benzoylbenzoic acid [85-52-9] which, on treatment with concentrated sulfuric acid, is converted iato anthraquiaoae ia high yields and purity (33). 

Friedel-Grafts Reactions. In the presence of Friedel-Crafts catalysts, succinic anhydride reacts with alkyl benzenes to form alkylben2oylpropionic acids (103), eg, the reaction with iadane gives a 97% yield of 4-oxo-(4,5-iQdanyl)butyric acid (eq. 6). 

N. J. Earhart, The Grafting Reactions ofPoly(vinyl alcohol) During the Emulsion Copolymerisyation of Poly(vinyl acetate—co-butyl acrylate), Ph.D. dissertation. 

A series of graft polymers on polychloroprene were made with isobutjiene, /-butyl vinyl ether, and a-methylstyrene by cationic polymerization in solution. The efficiency of the grafting reaction was improved by use of a proton trap, eg, 2,6-di-/-butylpyridine (68). 

A large number of hard polymer/elastomer combinations made by the last technique have been investigated (30). In some cases, the components are technologically compatibilized by use of a grafting reaction, but usually a fine dispersion of the two phases is formed that is sufficient to give the product the properties of a thermoplastic elastomer. 

Polymers containing oxazoline groups are obtained either by grafting the 2-oxazoline onto a suitable existing polymer such as polyethylene or polyphenylene oxide or alternatively by copolymerising a monomer such as styrene or methyl methacrylate with a small quantity (<1%) of a 2-oxazoline. The grafting reaction may be carried out very rapidly (3-5 min) in an extruder at temperatures of about 200°C in the presence of a peroxide such as di-t-butyl peroxide Figure 7.13). 

Scheme 13 Grafting reactions of some reactive antioxidants.

T. C. Chung, New utilities of metallocene catalysts and borane reagents in the functionalization and block/graft reactions of polyolefins, MetCon 95 Proceedings, USA, May 1995. 

We modified polyanionic polymers by use of a grafting reaction of hydrophobic groups onto the polymers. After an extensive evaluation for the affinity of the hy-drophobically modified (hydrophobized) polymers to cell membrane, the immuno-stimulating activity of polymers was investigated by in vitro or ex vivo experiments. Consequently, the increased biological activity was found in the hydrophobized polymer, indicating that... 

Graft reactions on cellulosics are well studied and are well known to incorporate desired properties in polymers [61,72,73,76,77,99-102], but commercialization of the processes on cellulosics are not increasing. (Table 4 gives a summary of the techniques of grafting.) A fresh imaginative approach is required to solve this problem. 

When tertiary butyl hydrogen peroxide (TBHP) was used alone as the radical initiator, no grafting of methylmethacrylate (MMA) onto wool was observed. However, TBHP in conjunction with mineral acids, such as H2SO4, HNO3, or HCIO4 afforded good results [26]. Protonation of TBHP by the acid aided in the dissociation of TBHP to yield free radicals, which initiated grafting reaction. 

These two parameters give the quantitative measurement of the grafting reaction. The general characterization of the graft copolymer is based on the following ... 

Grafting reactions alter the physical and mechanical properties of the polymer used as a substrate. Grafting differs from normal chemical modification (e.g., functionalization of polymers) in the possibility of tailoring material properties to a specific end use. For example, cellulose derivatization improves various properties of the original cellulose, but these derivatives cannot compete with many of the petrochemically derived synthetic polymers. Thus, in order to provide a better market position for cellulose derivatives, there is little doubt that further chemical modification is required. Accordingly, grafting of vinyl monomers onto cellulose or cellulose derivatives may improve the intrinsic properties of these polymers. 

In this case, the grafting reactions start with the photolysis of carbonyl groups. 

The advantage of this technique is that the intermediate peroxy polymers may be kept for long periods of time before performing the final grafting step. The grafting reactions using this technique can be described as follows ... 

Cotton linters and viscose grade wood pulp were grafted with acrylamide using the xanthate method. The effects of monomer concentration, reaction time, hydrogen peroxide concentration, reaction temperature, and liquor ratio on the grafting process were studied. Optimum conditions for the grafting reaction were established [26]. 

The grafting reaction depends upon the degree of substitution as well as the kind of pulp used. Introducing acetyl groups in the cellulose chains (high substitution) causes a large reduction of its swellability, which reduces the diffusion of the reactants. Thus, acetylation lowers the graftability of the cellulose. 

The structural effect of alkyl groups such as methyl, ethyl, and -butyl on the Rp is small. Alkyl 4-methyl-phenylcarbamate can be chosen as a model compound for the hard segment of poly(ether-urethane) (PEU). This group can initiate grafting reaction with Ce(IV) ion and the grafting site was proposed at the hard segment of PEU [3,15] as shown in Scheme (1). 

CH2-AcAc)], the grafting reactions of this polymer initiated with Ce(IV) ion will be discussed in Sec. VI.B. Furthermore, the order of the promoting activity of diketone is always greater than that of monoketone. 

A. Grafting Reaction of Macromolecules Having 4-Tolylcarbamoyl Pendant Group... 

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