Graft copolymerization radical

A waterborne system for container coatings was developed based on a graft copolymerization of an advanced epoxy resin and an acryHc (52). The acryhc-vinyl monomers are grafted onto preformed epoxy resins in the presence of a free-radical initiator grafting occurs mainly at the methylene group of the aHphatic backbone on the epoxy resin. The polymeric product is a mixture of methacrylic acid—styrene copolymer, soHd epoxy resin, and graft copolymer of the unsaturated monomers onto the epoxy resin backbone. It is dispersible in water upon neutralization with an amine before cure with an amino—formaldehyde resin. 

A number of metal chelates containing transition metals in their higher oxidation states are known to decompose by one electron transfer process to generate free radical species, which may initiate graft copolymerization reactions. Different transition metals, such as Zn, Fe, V, Co, Cr, Al, etc., have been used in the preparation of metal acetyl acetonates and other diketonates. Several studies demonstrated earlier that metal acetyl acetonates can be used as initiators for vinyl polymeriza-... 

In its simplest form the direct grafting method involves the irradiation of polymeric substrate in the absence or presence of oxygen. Graft copolymerization of the monomer to the polymer is then initiated through the free radicals generated in the latter. The reaction can be schematically written as ... 

The trapped radicals, most of which are presumably polymeric species, have been used to initiate graft copolymerization [127,128]. For this purpose, the irradiated polymer is brought into contact with a monomer that can diffuse into the polymer and thus reach the trapped radical sites. This reaction is assumed to lead almost exclusively to graft copolymer and to very little homopolymer since it can be conducted at low temperature, thus minimizing thermal initiation and chain transfer processes. Moreover, low-molecular weight radicals, which would initiate homopolymerization, are not expected to remain trapped at ordinary temperatures. Accordingly, irradiation at low temperatures increases the grafting yield [129]. 

When P[(St-NHCOCH3)-g-AAM] was hydrolyzed in the basic solution no PAAM was released. The scanning electron microscopy (SEM) micrograph of the copolymer shows that the hydrolyzed grafted beads are still covered with PAAMs with salient micrographs. The results reveal that AAM graft copolymerization is initiated by the nitrogen radical rather than any other radical. 

Based on the ESR studies of Ce(IV) ion-BzyAcAc-MNP, Ce(IV) ion BzAc-MNP systems as mentioned before, the grafting reaction of P(St-CH2-AcAc) will take place on the methene carbon of 1,3-dikeone via the abstraction of hydrogen by the Ce(I V) ion to form radicals and then initiate monomer graft copolymerization. The initiation mechanism of graft copolymerization is proposed in Scheme (10). 

An effective method of NVF chemical modification is graft copolymerization [34,35]. This reaction is initiated by free radicals of the cellulose molecule. The cellulose is treated with an aqueous solution with selected ions and is exposed to a high-energy radiation. Then, the cellulose molecule cracks and radicals are formed. Afterwards, the radical sites of the cellulose are treated with a suitable solution (compatible with the polymer matrix), for example vinyl monomer [35] acrylonitrile [34], methyl methacrylate [47], polystyrene [41]. The resulting copolymer possesses properties characteristic of both fibrous cellulose and grafted polymer. 

The investigations have shown, however, that graft copolymerization carried out according to this method is accompanied with a simultaneous reaction of monomer homopolymerization which, naturally, reduces the effectiveness of the method. This is explained by the presence of hydroxyl radicals in the reaction medium, which are formed as formulated in the above scheme. 

Bamford, Eastmond and coworkers have employed metal complexpolymeric halide redox systems to initiate block and graft copolymerization. The polymeric halides can be synthesized by a variety of techniques, including radical polymerization,281 anionic polymerization (Scheme 7.28),"so... 

A number of methods have been used to prepare graft copolymers in the past few decades including both conventional chemical and radiation-chemical methods [20,86,87]. In the latter case, graft copolymerization is usually initiated by creating active radical sites on existing polymer chains. The advantages of radiation-chemical methods are (i) ease of preparation as compared to... 

The modihcation of polymer surfaces by graft copolymerization of a monomer or monomers from active sites has been reported in numerous references [165-169]. The most common techniques are y- and EB radiations, which generate surface radicals. Monomers can be present in gas phase (sublimed solid), in solution or as neat liquid. 

Photoinduced free radical graft copolymerization onto a polymer surface can be accomplished by several different techniques. The simplest method is to expose the polymer surface (P-RH) to UV light in the presence of a vinyl monomer (M). Alkyl radicals formed, e.g. due to main chain scission or other reactions at the polymer surface can then initiate graft polymerization by addition of monomer (Scheme 1). Homopolymer is also initiated (HRM-). 

Graft copolymerization can be initiated by physical or chemical processes. This paper describes methods for chemical initiation of grafting onto cellulosic fibers with special emphasis on recent developments, i.e. studies from the last 10-15 years. The initiation reactions may be free radical or ionic processes. The grafting reaction may also be a condensation or addition process. 

Initiation of graft copolymerization by radical mechanisms can occur by (a) a redox process on the substrate or (bl a chain transfer process to the substrate. In addition to grafting, formation of homopolymer may occur in both cases. 

It is likely that Ce + and Mn ions initiate graft copolymerization by about the same mechanisms. Mn + ions have a lower redox potential ( 1.5 V) than CeH ions ( 1.7 V), and they appear to cause less side-reactions besides the radical formation. Industrial development of the Mn-5 initiator for grafting is under way. 

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