Macromonomers copolymerization with comonomers

Polycondensation techniques have been employed for the synthesis of macromonomers. Depending on the nature of the functional end group the copolymerization with comonomers can be performed with addition polymerization techniques, giving rise to very interesting graft copolymer structures. 

The chief application of macromonomers is, however, to provide easy access to graft copolymers 69,70,71,84,851 by free radical copolymerization with a vinylic or acrylic comonomer. This grafting through process offers graft length control and provides randomness of graft distribution. 

The next step concerned the synthesis of the polyester-polyimide copolymers. Triblock copolymers have been prepared by a step-growth copolymerization of stoichiometric amounts of an aromatic diamine and dianhydride (e.g., PMDA and 3FDA, as depicted in Scheme 41a) added with the single oo-amino polyesters as chain end-cappers. Graft copolymers can be prepared as well. In this case, the diamine end-functionalized oligomeric macromonomers are copolymerized with the polyimide condensation comonomers (Scheme 41b). 

Allyl PS macromonomers, which were synthesized by the ATRP of styrene with CuBr/bipyridine, have been used as comonomers in metallocene-catalyzed propylene copolymerizataions using Me2Si(2-Me-4,5-BzInd)2ZrCl2/ MAO [110]. It has been found that the incorporation of the PS macromonomers increases with a decrease in molar mass of the macromonomer and propylene concentration and increasing polymerization temperature. The highest comonomer incorporation (10.8 wt%) was achieved in the copolymerization at 70 °C. 

The S-PIB macromonomer was copolymerized by radical copolymerization with MMA and S, and the reactivity ratio of the small comonomer was calculated by a modified copolymer equation [85]. With MMA, rMMA=0.5 was obtained, i.e., close to that reported for conventional S/MMA system. With S however, rs= 2.1 was determined which suggested that the reactivity of S-PIB is lower than that of S, possibly due to steric interference. 

The relative reactivity of the macromonomer in copolymerization with a common comonomer, A, can be assessed by l/rA=kAB/kAA> i-e-> the rate constant of propagation of macromonomer B relative to that of the monomer A toward a common poly-A radical. In summarizing a number of monomer reactivity ratios in solution copolymerization systems reported so far [3,31,40], it appears reasonable to say that the reactivities of macromonomers are similar to those of the corresponding small monomers, i.e., they are largely determined by the nature of their polymerizing end-group, i.e., essentially by their chemical reactivity. 

Narrow distribution in the backbone length as well as in the chemical composition or the branch frequency may be expected from a living-type copolymerization between a macromonomer and a comonomer provided the reactivity ratios are close to unity. This appears to have been accomplished to some extent with anionic copolymerizations with MMA of methacrylate-ended PMMA, 29, and poly(dimethylsiloxane) macromonomers, 30, which were prepared by living GTP and anionic polymerization, respectively [50,51]. Recent application [8] of nitroxide (TEMPO)-mediated living free radical process to copolymerizations of styrene with some macromonomers such as PE-acrylate, la, PEO-methacr-ylate, 27b, polylactide-methacrylate, 28, and poly(e-caprolactone)-methacrylate, 31, may be a promising approach to this end. 

Use of macromonomers as reactive (copolymerizable) surfactants in heterogeneous systems such as emulsion and dispersion constitutes an increasingly important application in the design of polymeric microspheres, as will be discussed later in Sect. 6. Here the macromonomers copolymerize in situ with some of the substrate comonomers to afford the graft copolymers, the grafts (branches) of which serve as effective steric stabilizers by anchoring their backbone onto the surfaces of the particles. In general, however, the copolymerization reactivities of macromonomers in such systems are not well understood yet. 

These macromonomers have been copolymerized with various comonomers. 

It is well known that primary amines are efficient initiators for the polymerization of Leuch s anhydrides (oxazolidinediones) and that initiation proceeds by the addition of the amine to the monomer. This pathway has been utilized recently to synthesize polypeptide macromonomers bearing a terminal p-vinylbenzyl group 88). Copolymerization of these macromonomers with a vinylic or acrylic comonomer yields graft copolymers with polypeptide grafts. Alternately, the monomer adduct (IV) was copolymerized with styrene, and the primary amine functions of this polymer were used to initiate the polymerization of an oxazolidinedione whereby polypeptide grafts are formed 89). Such graft copolymers may be of interest for biomedical applications. 

The copolymerization of macromonomer with comonomer is governed by the general rules of copolymerization, the ability of any of the two polymerizable species present to participate in the process being determined by the radical reactivity ratios r. Let us denote the macromonomer as M and the comonomer as A. The well-known instantaneous composition law applies to the copolymer formed ... 

In a patent dated 1965 Stowe35) laid the basis for the copolymerization of PEO macromonomer with comonomers such as acrylonitrile. It was searched for an increased wettability of polyacrylonitrile films or fibers by a permanent surface modification. ro-Styryl poly(oxyethylene) macromonomers readily copolymerize with acrylonitrile in water emulsions. They can also be copolymerized with styrene-sulfonates in the presence of poly(vinylpyrrolidone). The presence of small amounts of such copolymers in polyacrylonitrile fibers was shown to increase their wettability and their receptivity to dyes and to make them more resistant to electric loading (antistatic fibers). No characterization data on the copolymers formed have been reported. 

Kennedy 67,77 118) studied the ability of w-styryl-polyisobutene macromonomers to undergo free-radical copolymerization with either styrene or butyl or methyl methacrylate. Here, the macromonomers exhibited a relatively high molecular weight of 9000, and the reaction was stopped after roughly 20% of the comonomer had been converted. The radical reactivity ratios of styrene and methyl methacrylate with respect to macromonomer were found to be equal to 2 and to 0.5, respectively. From these results, Kennedy concluded that in the ra-styrylpolyisobutene/styrene system the reactivity of the macromonomer double bond is reduced whereas with methacrylate as the comonomer the polar effect is the main driving force, yielding reactivities similar to those observed in the classical system styrene/MMA. 

Copolymerization of the CD-complexed macromonomer 8a with hydrophilic comonomers 2-acrylamido-2-methylpropansulfonate (AMPS) and A,A-dimethyl-acrylamide (DMAA) leads to formation of hydrophobically associative polymers (Fig. 14) [48],... 

Graft copolymers have also been prepared by grafting through techniques. Nitroxide mediated copolymerization has been successful using styrene as comonomer and p(CL), p(LA), or p(EG) [345] as macromonomers, also p(EO) [346], NVP and NBA have been copolymerized with p(St) [347] and p(MMA) macromonomers [348] and... 

The free radical copolymerization of a macromonomer M with a suitable comonomer A gives easy access to graft copolymers. The chief characteristic of this reaction is the large difference in molecular weights between the two species involved. Consequently, the mole fraction of macromonomer [M] in the copolymerization mixture is always low ([M] [A]). As a result, the classical... 

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