Polymerization, chain by free radical mechanism

CHAIN POLYMERIZATION BY FREE RADICAL MECHANISM 2.4.1 General Kinetics... 

Polymerizations by free-radical mechanism are typical free-radical reactions. That is to say, there is an initiation, when the radicals are formed, a propagation, when the products are developed, and a termination, when the free-radical chain reactions end. In the polymerizations, the propagations are usually chain reactions. A series of very rapid repetitive steps follow each single act of initiation, leading to the addition of thousands of monomers. 

Compounds possessing allylic structures polymerize by free-radical mechanism only to low molecularweight oligomers. In some cases the products consist mostly of dimers and trimers. The DP for poly(allyl acetate), for instance, is only about 14. This is due to the fact that allylic monomer radicals are resonance-stabilized to such an extent that no extensive chain propagations occur. Instead, there is a large amount of chain transferring. Such chain transferring essentially terminates the reactions [151]. The resonance stabilization can be illustrated on an allyl alcohol radical ... 

Commercially, poly(vinyl acetate) is formed in bulk, solution, emulsion, and suspension polymerizations by free-radical mechanism. In such polymerizations, chain transferring to the polymer may be as high as 30%. The transfer can be to a polymer backbone through abstraction of a tertiary hydrogen ... 

In catalytic polymerization the reactivity of the propagation center depends on the catalyst composition. Therefore, the dependence of the molecular structure of the polymer chain mainly on the catalyst composition, and less on the experimental conditions, is characteristic of catalytic polymerization. On the other hand, in polymerization by free-radical or free-ion mechanisms the structure of a polymer is determined by the polymerization conditions (primarily temperature) and does not depend on the type of initiator. 

Dimethacrylate monomers were polymerized by free radical chain reactions to yield crosslinked networks which have dental applications. These networks may resemble ones formed by stepwise polymerization reactions, in having a microstructure in which crosslinked particles are embedded in a much more lightly crosslinked matrix. Consistently, polydimethacrylates were found to have very low values of Tg by reference to changes in modulus of elasticity determined by dynamic mechanical analysis. 

The above examples of free-radical ring-opening polymerization, which have been explored by Bailey and Endo, produce polymers containing ketonic carbonyl and/or ester groups in the main chain. In addition, these cyclic monomers can be copolymerized with vinyl monomers by free-radical mechanism. Thus, the variety of the polymers produced by radical polymerization has been enlarged. 

Commercially, PFA is polymerized by free-radical polymerization mechanism usually in an aqueous media via addition polymerization of TFE and perfluoropropyl vinyl ether. The initiator for the polymerization is usually water-soluble peroxide, such as ammonium persulfate. Chain transfer agents such methanol, acetone and others are used to control the molecular weight of the resin. Generally, the polymerization regime resembles that used to produce PTFE by emulsion polymerization. Polymerization temperature and pressure usually range from 15 to 95°C and 0.5 to 3.5 MPa. 

Clearly, this technique can be extended to Include other monomers polymerizable by free radical mechanisms and work has begun using chloroprene. It must be stressed, however, that the specificity and purity of the product Is largely controlled by the detailed kinetics of the radical polymerization process. In particular the prominence of chain transfer reactions and the nature of the termination step which will, of course, vary from monomer to monomer. 

Free-radical polymerizations of 1,3-butadiene usually result in polymers with 78-82% of 1,4-type placement and 18-22% of 1,2-adducts. The ratio of 1,4 to 1,2 adducts is independent of the temperature of polymerization. Moreover, this ratio is obtained in polymerizations that are carried out in bulk and in emulsion. The ratio of trans-1,4 to cis-1,4 tends to decrease, however, as the temperature of the reaction decreases. Polybutadiene polymers formed by free-radical mechanism are branched because the residual unsaturations in the polymeric chains are subjects to free-radical attacks ... 

Common photopolymerization reactions by free radical mechanism follow the same laws of chemistry as do the thermal polymerizations. The differences are primarily in the formations of the initiating radicals. Typical chain growth polymerization reactions are initiated by Ifee radicals that come from thermal decomposition of the initiators. The initiating Ifee radicals in photo polymerizations, on the other hand, come If om photolyses of the photoinitiators. 

The classi cation of copolymers according to structural types and the nomenclature for copolymers have been described previously in Chapter 1. The present chapter is primarily concerned with the simultaneous polymerization of two monomers by free-radical mechanism to produce random, statistical, and alternating eopolymers. Copolymers having completely random distribution of the different monomer units along the copolymer chain are referred to as random copolymers. Statistical copolymers are those in which the distribution of the two monomers in the chain is essentially random but in uenced by the individual monomer reactivities. The other types of copolymers, namely, graft and block copolymers, are not synthesized by the simultaneous polymerization of two monomers. These are generally obtained by other types of reactions (see Section 7.6). 

It might be noted that most (not all) alkenes are polymerizable by the chain mechanism involving free-radical intermediates, whereas the carbonyl group is generally not polymerized by the free-radical mechanism. Carbonyl groups and some carbon-carbon double bonds are polymerized by ionic mechanisms. Monomers display far more specificity where the ionic mechanism is involved than with the free-radical mechanism. For example, acrylamide will polymerize through an anionic intermediate but not a cationic one, A -vinyl pyrrolidones by cationic but not anionic intermediates, and halogenated olefins by neither ionic species. In all of these cases free-radical polymerization is possible. 

Both modes of ionic polymerization are described by the same vocabulary as the corresponding steps in the free-radical mechanism for chain-growth polymerization. However, initiation, propagation, transfer, and termination are quite different than in the free-radical case and, in fact, different in many ways between anionic and cationic mechanisms. Our comments on the ionic mechanisms will touch many of the same points as the free-radical discussion, although in a far more abbreviated form. 

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