Macromonomer

Poly(ethylene oxide). The synthesis and subsequent hydrolysis and condensation of alkoxysilane-terniinated macromonomers have been studied (39,40). Using Si-nmr and size-exclusion chromatography (sec) the evolution of the siUcate stmctures on the alkoxysilane-terniinated poly(ethylene oxide) (PEO) macromonomers of controlled functionahty was observed. Also, the effect of vitrification upon the network cross-link density of the developing inorganic—organic hybrid using percolation and mean-field theory was considered. 

Several macrointermediates to obtain this kind of copolymer were used via free radical, ionic, and/or free radical-ionic coupling polymerization. In this manner, macroinitiators, macromonomers, and macromono-meric initiators will be discussed in this chapter. 

The cationic ring opening polymerization of oxolane (THF) or of N-substituted aziridines can be initiated by oxocarbenium salts [42]. The methacrylic ester unsaturation is insensitive to cationic sites, and polyoxolanes (poly-THF) macromonomers are obtained in good yields. 

Radical polymerizations of macromonomers are greatly influenced by the diffusion control effect [44]. Segmental diffusivity and translational diffusivity of the growing chains of macromonomers are strongly affected by the feed concentration and the molecular weight of the macromonomers. Furthermore, there is little difference in the degree of polymerization between macro-... 

Macromonomers always lead to the formation of graft copolymers. For example, the vinyl-terminated polystyrene can be copolymerized with ethylene to produce a graft copolymer of polyethylene, whereby the vinyl moiety of polystyrene is integrally polymerized into the linear polyethylene backbone ... 

PDMS macromonomer was used as a component of block segment to obtain a graft block copolymer with PMMA (Scheme 1) [51-53]. This graft block copolymer is characteristic of surface water repellence, easy peeling, and weatherability superior to simple graft copolymers of the same members. PDMS-b-PVC film also shows long life surface water repellency with weatherability and very low coefficiency of abrasion [18,54]. 

Watanabe et al,25-5 52s applied AMS dimer (116) as a radical trap to examine the reactions of oxygen-centered radicals (e.g. r-butoxy, cumyloxy, benzoyloxy). AMS dimer (116) is an addition fragmentation chain transfer agent (see 6.2.3.4) and reacts as shown in Scheme 3,96. The reaction products are macromonomers and may potentially react further. The reactivity of oxygen centered radicals towards 116 appears to be similar to that of S.2 1 Cumyl radicals are formed as a byproduct of trapping and are said to decay mainly by combination and disproportionation. 

The high temperature polymerization of acrylates with the backbiting-fragmentation process has been used to synthesize macromonomers based on acrylate esters. 277,312 Interestingly, fragmentation shows a strong preference for giving the polymeric macromonomer 64 and a small radical 65. 276.277 An explanation for this specificity has yet to be proposed. 

The chain transfer agents (11 X=CH2, A=CH2) are misnamed macrornonomcrs since in this context they do not behave as macromonomers. Copoiymerization when it occurs is a side reaction. The mechanism is shown in Scheme 6.19 for MAA Mrimer (63). The final product (65) is a also a macromonomer5 and formation of the adduct (64) and chain transfer is reversible (see also Section 6.2.7.2 and Section 9.5.2)/6 76 79 109... 

The most used transfer agents in this class are the methacrylate macromonomers (e.g. 66-68) and AMS dimer (76). The applications of these compounds are summarized in a review.110... 

Transfer constants of the methacrylate macromonomers in MMA polymerization do not depend on the ester group but are slightly higher for MAA trimer. Compounds 72 and 73 are derived from the MMA trimer (67) by selective hydrolysis or hydrolysis and reesterification respectively. They offer a route to telechelic polymers. 

In the case of polymerization of monosubstituted monomers S, RA) with 66-68, copolymerization of the macromonomer to form a graft copolymer is a significant side reaction.76... 

Macromonomers such as 66, 68 and 94 are themselves catalytic chain transfer agents (Section 6.2.3.4) and transfer to macromonomer is one mechanism for chain extension of the initially formed species. The adduct species in the case of monomeric radical adding dimer (100) may also react by chain transfer to give 101 which is inert under polymerization conditions (Scheme 6.25). Polymerizations to... 

There is a considerable body of evidence (kinetic studies, chemical and NMR analysis) indicating that transfer to VAc monomer involves largely, if not exclusively, the acetate methyl hydrogen to give radical 111 (Scheme 6.29).171,172 This radical (111) initiates polymerization to yield a reactive macromonomer (112). 

Stein166 has indicated that the reactivity of the terminal double bond of the macromonomer (112) is 80% that of VAc monomer. The kinetics of incorporation of 112 have also been considered by Wolf and Burchard175 who concluded that 112 played an important role in determining the time of gelation in VAc homopolymerization in bulk. 

In polymerization of methacrylates, the adducts formed by addition to the macromonomer radicals are relatively unreactive towards adding further monomer... 

Copolymerization of macromonomers formed by backbiting and fragmentation is a second mechanism for long chain branch formation during acrylate polymerization (Section 4.4.3.3). The extents of long and short chain branching in acrylate polymers in emulsion polymerization as a function of conditions have been quantified.20 ... 

Depending on the choice of transfer agent, mono- or di-cnd-functional polymers may be produced. Addition-fragmentation transfer agents such as functional allyl sulfides (Scheme 7.16), benzyl ethers and macromonomers have application in this context (Section 6.2.3).212 216 The synthesis of PEG-block copolymers by making use of PEO functional allyl peroxides (and other transfer agents has been described by Businelli et al. Boutevin et al. have described the telomerization of unsaturated alcohols with mercaptoethanol or dithiols to produce telechelic diols in high yield. 

Radical induced grafting may be carried out in solution, in the melt phase,292 29 or as a solid state process.296 This section will focus on melt phase grafting to polyolefin substrates but many of the considerations are generic. The direct grafting of monomers onto polymers, in particular polyolefins, in the melt phase by reactive extrusion has been widely studied. Most recently, the subject has been reviewed by Moad1 9 and by Russell.292 More details on reactive extrusion as a technique can be found in volumes edited by Xanthos," A1 Malaika and Baker et a 21 7 The process most often involves combining a frcc-radical initiator (most commonly a peroxide) and a monomer or macromonomer with the polyolefin as they are conveyed through the extruder. Monomers commonly used in this context include MAII (Section 7.6.4.1), maleimidc derivatives and malcate esters (Section 7.6.4.2), (meth)acrylic acid and (meth)acrylate esters (Section 7.6.43), S, AMS and derivatives (Section 7.6.4.4), vinylsilancs (Section 7.6.4.5) and vinyl oxazolines (Section 7.6.4.6). 

Various macromonomers have been described in the literature many are based on polymers of S or (mcth)aerylatc esters [e.g. 43-46]. The relative merits of macromonomers have been assessed in reviews by Hadjichrislidis, 67 Capek and eoworkers,368" 69 Ito and coworkers, 70 371 Meijs and Rizzardo, 72 Gnanou and I ut/ and Rempp and Franla274... 

The reactivity of macromonomers in copolymerizalion is strongly dependent on the particular comonomer-macromonomer pair. Solvent effects and the viscosity of the polymerization medium can also be important. Propagation may become diffusion controlled such that the propagation rate constant and reactivity ratios depend on the molecular weight of the macromonomer and the viscosity or, more accurately, the free volume of the medium. 

It is of interest that thermogravimetric analysis has been used as a means of determining end group purity of PM VIA macromonomers formed by catalytic chain transfer. 

As in the case of PS (Section 8.2.1) polymers formed by living radical polymerization (NMP, ATRP, RAFT) have thermally unstable labile chain ends. Although PMMA can be prepared by NMP, it is made difficult by the incidence of cross disproportionation.42 Thermal elimination, possibly by a homolysis-cross disproportionation mechanism, provides a route to narrow polydispersity macromonomers.43 Chemistries for end group replacement have been devised in the case of polymers formed by NMP (Section 9.3.6), ATRP (Section 9.4) and RAFT (Section 9.5.3). 

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