Macroradicals

Block copolymers of vinyl acetate with methyl methacrylate, acryflc acid, acrylonitrile, and vinyl pyrrohdinone have been prepared by copolymeriza tion in viscous conditions, with solvents that are poor solvents for the vinyl acetate macroradical (123). Similarly, the copolymeriza tion of vinyl acetate with methyl methacrylate is enhanced by the solvents acetonitrile and acetone and is decreased by propanol (124). Copolymers of vinyl acetate containing cycHc functional groups in the polymer chain have been prepared by copolymeriza tion of vinyl acetate with A/,A/-diaIlylcyanamide and W,W-diaIl5lamine (125,126). 

Polymerization of acrylamide is usually performed in aqueous solutions. The principal factors that determine popularity of this polymerization technique are a high rate of polymer formation and the possibility to obtain a polymer with a large molecular weight. The reason for a specific effect produced by water upon acrylamide polymerization lies in protonation of the macroradical, leading to localization of an unpaired electron, which leads to an increase in the reactivity of the macroradical ... 

Initiation-formation of macroradicals due to the polymeric-chain scission under the action of heating. 

Chain reaction followed by the detachment of monomer from the end macroradicals. 

Monomolecular chain transfer caused by the detachment of hydrogen macroradicals from other macromolecuie accompanied by the breaking of C—C bond. 

Destruction of macroradicals—scission of kinetic chains. A disproportionation reaction is most common at this stage ... 

Thus, suppression of the radical-chain thermal destruction reaction of olefins necessitates an addition of substances having the ability to react with active macroradicals and to yield inactive or low-reactivity products. 

At 300°C and in the presence of KOH an increase in the molecular weight is observed, i.e., the reaction of macropolymerization is realized [38,39]. Potassium hydroxide is effectively inhibiting thermal destruction of polyethylene at temperatures from 350-375°C. The per cent change in molecular weight is half or one-third as high as that without the use of an inhibitor. At 400°C the efficiency of inhibition is insignificant. Potassium hydroxide with an ABC carrier is effective up to the temperature of 440°C due to the increased contact surface of the inhibitor with macroradicals. 

The inhibitive efficiency of alkali metal hydroxides increases with increased branching of polyethylene. This is confirmed by more pronounced effect of these hydroxides diminishing the yield of propane and propylene than in case of ethane and ethylene. The decreased yield of propane and propylene is also conditioned by more efficient inhibition of the macroradical isomerization stage by alkali metal hydroxides. Upon thermal destruction of polyethylene with the use of inhibitors the... 

At the first stage of polyethylene thermal destruction the metallizing of polyethylene macroradical by the metal radical takes place. 

In the process of inhibition polypyrocatechin borate interacts with polyethylene macroradicals to form the B—O—C bonds. This is confirmed by the fact that the absorption spectrum of polyethylene inhibited with polypyrocatechin borate revealed the bands in the region of 1350 cm" characteristic for the B—O—C bond. There is no such a band in the spectrum of pure polypyrocatechin borate after heating under the same conditions. Chemical analysis of boron in polyethylene provides support for the IR-spectroscopy data concerning the presence of chemically bonded boron in polyethylene after destruction. 

High thermostabilizing efficiency of polyamine disulphides relative to chemically cross-linked polyethylene is conditioned by the ability to accept macroradicals at the disulphide bridge and imine group. Besides, the presence of paramagnetic centers causes the adherence of macroradicals providing for an extra stabilizing effect [49]. 

When the emulsion polymerization is conducted in the absence of an emulsifier, this process is termed emulsifier free or soapless emulsion polymerization [68-73]. In this case, the particle formation occurs by the precipitation of growing macroradicals within the continuous... 

According to the other kinetic model proposed for the soapless emulsion process, the growing macroradicals may also form micelle structures at earlier polymerization times since they have both a hydrophilic end coming from the initiator and a hydrophobic chain [74]. 

Figure 9 The schematical representation of dispersion polymerization process, (a) initially homogeneous dispersion medium (b) particle formation and stabilizer adsorption onto the nucleated macroradicals (c) capturing of radicals generated in the continuous medium by the forming particles and monomer diffusion to the forming particles (d) polymerization within the monomer swollen latex particles, (e) latex particle stabilized by steric stabilizer and graft copolymer molecules (f) list of symbols.

The radicals created in (1) and (2) interact with monomer molecules to produce macroradicals, and ulti-... 

This grafting technique proved to possess several advantages (1) the initiating macroradicals [shown in... 

It was found that the sulfate radical anion S04 produced photochemically in Scheme (46) is responsible for generating the cellulose derivative macroradicals by hydrogen abstraction, which added the vinyl monomer to produce the grafted copolymer. The main disadvantage of this method is the production of large quantities of undesirable homopolymers in addition to the grafted copolymers. 

Upon photolysis of polypropylene hydroperoxide (PP—OOH) a major absorption at 1726 and 1718 cm has been observed in the IR spectrum, which is attributed to the carbonyl groups. Sometimes the macroradical having free radical site reacts with a neighboring newly born hydroperoxide causing the formation of a macroalkoxy radical [116]. 

The presence of an azo group as a side group in the polymer structure can be used to produce a macroradical via its decomposition under the effect of metallic ions [3,4]. This macroradical reacts with vinyl monomers leading to grafting with a minimum amount of homopolymers. This reaction was first applied to a polymer by Chapman et al. [5]. The reaction proceeds as follows (See structure below.)... 

The presence of sulphonic and carboxylic groups enables the iron ions to be in the vicinity of the cellulose backbone chain. In this case, the radicals formed can easily attack the cellulose chain leading to the formation of a cellulose macroradical. Grafting of methyl methacrylate on tertiary aminized cotton using the bi-sulphite-hydrogen peroxide redox system was also investigated [58]. 

In this case, two kinds of free radicals are formed leading to the formation of homopolymer and graft copolymer. The latter is due to the formation of cellulosic macroradicals. 

The xanthate method [62] is considered as one of the most promising methods for industrial chemical modification. The principal involved in the xanthate method of grafting is that cellulosic xanthate either ferrated or in acidic conditions reacts with hydrogen peroxide to produce macroradicals. The following reaction mechanism has been proposed ... 

In presence of the monomer cellulose, macroradicals are added to the double bond of the monomer. 

Grafting reactions of polybutadiene with macrazo-inimers or polyazoesters produced polyethylene gly-col-polybutadiene crossHnked graft copolymers. Macroradicals thermally formed from macroazoinimers or polyazoesters attack 1,2-linked vinyl pendant groups of polybutadiene ... 

However, when MAIs are thermolyzed in solution, the role of the cage effect has to be taken into account. The thermolytically formed macroradicals can, due to their size, diffuse only slowly apart from each other. Therefore, the number of combination events will be much higher for MAIs than for low-molecular weight AIBN derivatives. As was shown by Smith [16], the tendency toward radical combination depends significantly on the rigidity and the bulkiness of the chain. Species such as cyclohexyl or diphenylmethyl incorporated into the MAI s main chain lead to the almost quantitative combination of the radicals formed upon thermolysis. In addition, combination chain transfer reactions may... 

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