S + C6H5C CH2Cl S CH2S CC6H5 S in .NET

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The grafting-through method has been used to graft polymers onto solid surfaces such as silica, gold, and polymers via the NMP and ATRP techniques [Davis and Matyjaszewski, 2002]. The solid surfaces include those on at wafers and spherical particles. Appropriate reagents are used to introduce functional groups that initiate NMP or ATRP. For example, a thiol reacts with gold surfaces through sul de formation. If the thiol reagent also contains a halogen or alkoxyamine group, ATRP or NMP can be achieved. Alternately, the thiol contains a functional group that is reacted with some other reagent to attach a halogen or alkoxyamine group to the surface. A chlorosilane is used to introduce funtional groups onto silica surfaces [Zhao and Brittain, 2000].
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Anionic Graft Polymerization
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Metallation of a polymer by treatment with strong base, for example, t-butyllithium, yields polymeric anions that initiate the grafting of monomers such as styrene, acrylonitrile, and
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ethylene oxide [Adibi et al., 1979, 1981; Hadjichristidis and Roovers, 1978; Kashani et al., 1978; Takayangi and Katayose, 1983].
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Polymers with carboxylate anionic groups (COOH and COOR are precursors) initiate graft polymerization [Harris and Sharkey, 1986; Sundet, 1978].
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Coupling of polymers to form graft copolymers is accomplished by nucleophilic reaction between living polystyryl carbanion and various chlorine-containing polymers such as
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poly(vinyl chloride) [Kucera et al., 1983, 1985; Majid et al., 1982]. Elimination is a side reaction, and the overall yield is also limited by steric hindrance. 9-9c Cationic Graft Polymerization
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Polymeric carbocations have been formed from a chlorine-containing polymer such as chlorinated SBR and polystyrene, poly(vinyl chloride), and polychloroprene, by reaction with (C2 H5 2 AlCl, for example
CH2CH Cl + (C2H5)2AlCl CH2CH
(C2H5)2AlCl2 +
The polymeric carbocation initiates polymerization of isobutylene, styrene, tetrahydrofuran, and other monomers [Cai and Yan, 1987; Cameron and Sarmouk, 1990; Kennedy and Ivan, 1992; Martinez et al., 2001; Pi and Kennedy, 2001]. A hydroxy-containing polymer can be coupled with living polytetrahydrofuran carbocation [Cameron and Duncan, 1983]:
P OH + O
Other Approaches to Graft Copolymers
Nonionic coupling reactions between appropriate polymers is another approach to graft copolymers. An example is the use of a telechelic polymer such as polystyrene containing one carboxyl end group per molecule. Graft copolymers are formed by coupling of carboxyl groups with the pendant epoxy groups of a copolymer of methyl methacrylate and glycidyl methacrylate [Miyauchi et al., 1988]. The carboxyl-terminated polystyrene can be obtained by living anionic polymerization followed by reaction with carbon dioxide or radical polymerization in the presence of a chain-transfer agent such as 3-mercaptopropionic acid.
A telechelic polystyrene containing two carboxyl groups at one end of a polymer can be used as a macromonomer in a step polymerization with a diol or diamine to yield a polyester or polyamide containing graft chains of polystyrene. The required telechelic polymer is obtained by radical polymerization of styrene in the presence of 2-mercaptosuccinic acid. Macromonomers containing a norbornene group have been polymerized by ROMP (Sec. 7-8) to form graft copolymers [Breunig et al., 1995; Heroguez et al., 1997]. ROMP combined with living anionic polymerization produces an interesting architecture referred to as a double-brush polymer by using compound XXXII [R (CH2 10 OCH2 ], which contains both norbornene and 1,1-diphenylethylene (DPE) groups [Cheng et al., 2002]. ROMP of XXXII through the norbornene group produces a polymer (XXXIII) with pendant DPE groups. Reaction of XXXIII with living polystyryl anions produces XXXIV, a polymer with polystyrene graft chains. Subsequent reaction of XXXIV with monomer M2 (E-caprolactam, ethylene oxide, or hexamethylcyclotrisiloxane) yields the double-brush polymer XXXV, in which there is one brush of polystyrene graft chains and a second brush of polyM2 graft chains.
Most of the methods for synthesizing block copolymers were described previously. Block copolymers are obtained by step copolymerization of polymers with functional end groups capable of reacting with each other (Sec. 2-13c-2). Sequential polymerization methods by living radical, anionic, cationic, and group transfer propagation were described in Secs. 315b-4, 5-4a, and 7-12e. The use of telechelic polymers, coupling and transformations reactions were described in Secs. 5-4b, 5-4c, and 5-4d. A few methods not previously described are considered here. Block copolymers have been obtained from polymeric radicals, which unlike those employed for graft polymerization have the radical centers at the ends of the polymer chains. This can be achieved by breaking chemical bonds in the polymer backbone by mastication (mixing) of the polymer [Ceresa, 1973, 1976, 1978; Sakaguchi and Sohma, 1978]. If