Poly graft copolymers, anionic polymerization

In a similar manner polyisoprene-polyethylene oxide block copolymers can prepared301. It is surprising that the poly(methyl methacrylate) anion can be successfully used for the polymerization of ethylene oxide without chain transfer302. Graft copolymers are also prepared by successive addition of ethylene oxide to the poly-... 

A radical initiator based on the oxidation adduct of an alkyl-9-BBN (47) has been utilized to produce poly(methylmethacrylate) (48) (Fig. 31) from methylmethacrylate monomer by a living anionic polymerization route that does not require the mediation of a metal catalyst. The relatively broad molecular weight distribution (PDI = (MJM ) 2.5) compared with those in living anionic polymerization cases was attributed to the slow initiation of the polymerization.69 A similar radical polymerization route aided by 47 was utilized in the synthesis of functionalized syndiotactic polystyrene (PS) polymers by the copolymerization of styrene.70 The borane groups in the functionalized syndiotactic polystyrenes were transformed into free-radical initiators for the in situ free-radical graft polymerization to prepare s-PS-g-PMMA graft copolymers. 

A combination of TEMPO living free radical (LFRP) and anionic polymerization was used for the synthesis of block-graft, block-brush, and graft-block-graft copolymers of styrene and isoprene [201]. The block-graft copolymers were synthesized by preparing a PS-fo-poly(styrene-co-p-chloromethylstyrene) by LFRP [Scheme 110 (1)], and the subsequent re-... 

During the last 5 years, there have been several reports of multiblock copolymer brushes by the grafting-from method. The most common substrates are gold and silicon oxide layers but there have been reports of diblock brush formation on clay surfaces [37] and silicon-hydride surfaces [38]. Most of the newer reports have utilized ATRP [34,38-43] but there have been a couple of reports that utilized anionic polymerization [44, 45]. Zhao and co-workers [21,22] have used a combination of ATRP and nitroxide-mediated polymerization to prepare mixed poly(methyl methacrylate) (PMMA)Zpolystyrene (PS) brushes from a difunctional initiator. These Y-shaped brushes could be considered block copolymers that are surface immobilized at the block junction. 

Here we discuss dispersion polymerizations that are not related to vinyl monomers and radical polymerization. The first one is the ring-opening polymerization of e-caprolactone in dioxane-heptane (30). A graft copolymer, poly(dodecyl acrylate)-g-poly(e-caprolactone), is used as a stabilizer. The polymerization proceeds via anionic or pseudoanionic mechanism initiated by diethylaluminum ethoxide or other catalysts. The size of poly(caprolactone) particles depends on the composition of stabilizer, ranging from 0.5 to 5 i,m. Lactide was also polymerized in a similar way. Poly(caprolactone) and poly(lactide) particles with a narrow size distribution are expected to be applied as degradable carriers of drugs and bioactive compounds. 

Graft copolymer, polyclhylene-gra/f-poly(propylcnc oxide) (PE-g-PPG), has been synthesized by ring opening anionic polymerization of propylene oxide with a phosphazene catalyst and hydroxylated polyethylene (Mn = 12400, [OH] = 5 units/chain). Polymerization of propylene oxide was carried out in tetraline at 120 °C for 20 hours. The 13C NMR analysis of PE-g-PPG suggested that all the hydroxyl groups were consumed for propylene oxide polymerization (Fig. 6). 

In another approach, PMMA- g-poly(/j-butyrolac-tone) copolymers were synthesized using the grafting from technique.149 Anionically polymerized PMMA was treated with the 18-crown-6 complex of potassium hydroxide in toluene, resulting in an macro-molecular initiator (Scheme 67). The average number... 

Se et al. presented the synthesis of poly[(VS- -I)-b-S] block—graft copolymers.157 The backbone, a diblock copolymer of 4-(vinyldimethylsilyl)styrene (VS) and styrene, was prepared first by anionic polymerization. The VS monomer was polymerized selectively through the styryl double bond at low... 

Poly(amino acids)2892 and polypeptides2893 can also be grafted onto starch. Starch was first alkylated in the presence of lithium naphthalene, and then the alkoxy derivatives were reacted with /V-carboxy anhydrides. Poly(amide amines) were produced by reacting amines with dioic acids on starch and then crosslinking with epichlorohydrin or 1,2-dichloroethane 2894 Grafting of starch with a synthetic polymer chain, for instance, polystyryl carboxylate anions prepared by an anionic polymerization, can be carried out on a blend of starch and cellulose functionalized by sulfonation, mesylation, or tosylation. In this manner, cellulose-starch graft copolymers were prepared.2895... 

Using anionic polymerization techniques poly[styrene-b-(4-vinyl phenyl-dimethylsiloxane-g-isoprene)), P[S-fr-(VS-,g-I)] block-graft copolymer was prepared [66,67] according to the following reaction sequence (Scheme 20). 

---