Vinyl graft copolymerization

D.W. Jenkins, S.M. Hudson, Review of vinyl graft copolymerization featuring recent advances toward controlled radical-based reactions and illustrated with chitin/chitosan trunk polymers, Chem Rev. 101 (11) (2001) 3245-3274. 

Gross-Linking. A variety of PE resins, after their synthesis, can be modified by cross-linking with peroxides, hydrolysis of silane-grafted polymers, ionic bonding of chain carboxyl groups (ionomers), chlorination, graft copolymerization, hydrolysis of vinyl acetate copolymers, and other reactions. 

Another use is of minor proportions of polyfunctional aHyl esters, eg, diaHyl maleate, ttiaHyl cyanurate, and ttiaHyl isocyanurate, for cross-linking or curing preformed vinyl-type polymers such as polyethylene and vinyl chlotide copolymers. These reactions ate examples of graft copolymerization in which specific added peroxides or high energy radiation achieve optimum cross-linking (see Copolymers). 

Although they lack commercial importance, many other poly(vinyl acetal)s have been synthesized. These include acetals made from vinyl acetate copolymerized with ethylene (43—46), propjiene (47), isobutjiene (47), acrylonitrile (48), acrolein (49), acrylates (50,47), aHyl ether (51), divinyl ether (52), maleates (53,54), vinyl chloride (55), diaHyl phthalate (56), and starch (graft copolymer) (47). 

Issues to be considered in selecting the best stabilizing system are polymeric chain branching which increases with high temperature and the presence of some stabilizers, polydispersity of the particles produced, and grafting copolymerization, which may occur because of the reaction of vinyl acetate with emulsifiers such as poly(vinyl alcohol) (43,44). 

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-... 

Graft copolymerization of acrylonitrile with various vinyl comonomers such as methyl acrylate, ethyl acrylate, vinyl acetate, and styrene onto cellulose derivatives using ceric ion was studied [24]. The results showed that... 

In aqueous solutions the persulphate ion is known as a strong oxidizing agent, either alone or with activators. Thus, it has been extensively used as the initiator of vinyl polymerization [43-47]. However, only later, Kulkarni et al. [48] reported the graft copolymerization of AN onto cellulose using the Na2S203/K2S20s redox system. 

Graft Copolymerization of Vinyl Monomers Onto Macromolecules Having Active Pendant Group via Ceric Ion Redox or Photo-Induced Charge-Transfer Initiation... 

Recently, Li et al. [30], Yu et al. [31] reinvestigated the mechanism of graft copolymerization of vinyl monomers onto carbohydrates such as starch and cellulose initiated by the Ce(IV) ion with some new results as mentioned in Section II. Furthermore, they investigated the mechanism of model graft copolymerization of vinyl monomers onto chitosan [51]. They chose the compounds containing adjacent hydroxyl-amine structures, such as D-glucosamine, /mn5-2-amino-cyclohexanol, 2-... 

Therefore, the graft copolymerization of vinyl monomers onto macromolecules having active an pendant group can be achieved either by redox initiation with a Ce(IV) ion or by photo-induced charge-transfer initiation with BP, depending on the structure of the active groups. 

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. 

A number of other polymers have the characteristics of TPE and some are available commercially, such as (1) 1,2-polybutadiene, (2) tran -polyisoprene (PI), (3) modified polyethylene (PE) (e.g., ethylene vinyl acetate [EVA] and ethylene ethyl acrylate [EEA]), (4) nonhydrocarbon elastomer-based TPEs, (5) metallocene elastomers/TPEs (MEs/TPEs), and (6) graft copolymeric TPEs. 

The technique of graft copolymerization is used for the production of radiation-modified fabrics and fibers. The process consists of saturating the fabrics with vinyl monomers and then irradiating it in moist state with accelerated electrons. The fabrics thus produced have improved properties such as resistance to wrinkling and shrinkage, resistance to fire, color-fastness, good launderability, and dissipation of static charge. 

Reactive species can be generated prior to monomer exposure (preirradiation grafting), during contact with monomer, or, after the polymer surface has been saturated with monomer and isolated (postirradiation grafting). The radiation-induced (y-ray and EB) graft copolymerization of AA and vinyl acetate monomer onto PE surface has been reported [170]. The grafted sheets show excellent bonding with an epoxy adhesive and enhanced adhesion with aluminum. 

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-). 

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