Chain-solvent reaction

In ionic polymerizations termination by combination does not occur, since all of the polymer ions have the same charge. In addition, there are solvents such as dioxane and tetrahydrofuran in which chain transfer reactions are unimportant for anionic polymers. Therefore it is possible for these reactions to continue without transfer or termination until all monomer has reacted. Evidence for this comes from the fact that the polymerization can be reactivated if a second batch of monomer is added after the initial reaction has gone to completion. In this case the molecular weight of the polymer increases, since no new growth centers are initiated. Because of this absence of termination, such polymers are called living polymers. 

Chain transfer reactions to monomer and/or solvent also occur and lower the kinetic chain length without affecting the rate of polymerization ... 

Chain transfer is an important consideration in solution polymerizations. Chain transfer to solvent may reduce the rate of polymerization as well as the molecular weight of the polymer. Other chain-transfer reactions may iatroduce dye sites, branching, chromophoric groups, and stmctural defects which reduce thermal stabiUty. Many of the solvents used for acrylonitrile polymerization are very active in chain transfer. DMAC and DME have chain-transfer constants of 4.95-5.1 x lO " and 2.7-2.8 x lO " respectively, very high when compared to a value of only 0.05 x lO " for acrylonitrile itself DMSO (0.1-0.8 X lO " ) and aqueous zinc chloride (0.006 x lO " ), in contrast, have relatively low transfer constants hence, the relative desirabiUty of these two solvents over the former. DME, however, is used by several acryhc fiber producers as a solvent for solution polymerization. 

By polymerising styrene in solution many problems associated with heat transfer and the physical movement of viscous masses are reduced, these advantages being offset by problems of solvent recovery and the possibility of chain transfer reactions. In 1955 Distrene Ltd started a plant at Barry in South Wales for the production of styrene by such a solution polymerisation process and some details have been made available. The essential details of this process are indicated by Figure 16.7. 

At the opposite influence on the change of local rigidity and chain-solvent interaction change on R- there may exist two probable places of the reaction, symmetric relative to the chain middle (Figs. 12-14). 

Figure 13 The dependence of probability of the reaction proceeding on the position of active center in chain on different chain-solvent influence. The active center after the reaction proceeding has a lower local rigidity than the initial chain a = influence of solvent on deflection of reacted and unreacted place of the same chain b = influence of solvent on deflection is compensated by the influence of the local rigidity c influences of solvent and local rigidities on deflection are equal, but have opposite directions of action, d = influence of solvent on the deflection is stronger than the influence of the local rigidity.

Chain transfer reaction during propagation gives homopolymers as well as block copolymers. Separation of the homopolymers is performed by extraction with suitable solvents. Homopolymer A together with a small amount of block copolymer rich in component A are extracted... 

In solution polymerization, an organic solvent dissolves the monomer. Solvents should have low chain transfer activity to minimize chain transfer reactions that produce low-molecular-weight polymers. The presence of a solvent makes heat and viscosity control easier than in bulk polymerization. Removal of the solvent may not be necessary in certain applications such as coatings and adhesives. 

Typical chain transfer reactions involve the abstraction of an atom from a neutral saturated molecule, which may be solvent or a chain transfer agent added to the polymerisation mixture specifically to control the final size and distribution of molar masses in the polymer product. The chain transfer reaction may be represented as in Reaction 2.7. 

PEDRIELLI p, PEDULLi G F and SKIBSTED L H (2001a) Antioxidant mechanism of flavonoids. Solvent effect on rate constant for chain-braining reaction of quercetin and epicatechin in autoxidation of methyl linoleate, JAgric Food Chem, 49, 3034-40. 

The pinacol formation reaction follows a radical mechanism. Benzopinacol, benzophenone and the mixed pinacol are formed jointly with many radical species [72, 74]. In the course of the reaction, first a high-energy excited state is generated with the aid of photons. Thereafter, this excited-state species reacts with a solvent molecule 2-propanol to give two respective radicals. The 2-propanol radical reacts with one molecule of benzophenone (in the ground state, without photon aid) to lengthen the radical chain. By combination of radicals, adducts are formed, including the desired product benzopinacol. Chain termination reactions quench the radicals by other paths. 

Free radical polymerization Relatively insensitive to trace impurities Reactions can occur in aqueous media Can use chain transfer to solvent to modify polymerization process Structural irregularities are introduced during initiation and termination steps Chain transfer reactions lead to reduced molecular weight and branching Limited control of tacticity High pressures often required... 

Anionic polymerization Narrow molecular weight distribution Limited chain transfer reactions Predictable molecular weight average Possibility of forming living polymers End groups can be tailored for further reactivity Solvent-sensitive due to the possibility of chain transfer to the solvent Can be slow Sensitive to trace impurities Narrow molecular weight distribution... 

In solution polymerization, monomers mix and react while dissolved in a suitable solvent or a liquid monomer under high pressure (as in the case of the manufacture of polypropylene). The solvent dilutes the monomers which helps control the polymerization rate through concentration effects. The solvent also acts as a heat sink and heat transfer agent which helps cool the locale in which polymerization occurs. A drawback to solution processes is that the solvent can sometimes be incorporated into the growing chain if it participates in a chain transfer reaction. Polymer engineers optimize the solvent to avoid this effect. An example of a polymer made via solution polymerization is poly(tetrafluoroethylene), which is better knoivn by its trade name Teflon . This commonly used commercial polymer utilizes water as the solvent during the polymerization process,... 

Chain transfer reactions with solvent or some other component of the reaction system also occur (Eq. 33). 

Radicals are also formed in solution by the decomposition of other radicals, which are not always carbon free radicals, and by removal of hydrogen atoms from solvent molecules. Because radicals are usually uncharged, the rates and equilibria of radical reactions are usually less affected by changes in solvent than are those of polar reactions. If new radicals are being made from the solvent by hydrogen abstraction, and if the new radicals participate in chain reactions, this may not be true of course. But even in cases of non-chain radical reactions in which no radicals actually derived from the solvent take part in a rate-determining step, the indifference of the solvent has perhaps been overemphasized. This will be discussed more fully when radical and polar reactions are compared in Chapter XII. 

In some processes, a diluent, like benzene or chlorobenzene are used as the solvent. At high pressure and temperature, both the polyethylene and the monomers dissolve in these solvents so that the reaction occur in a solution phase. In a typical process, 10-30 per cent of the monomer is converted to polymer per cycle. Rest of monomer is recycled. Extensive chain transfer reactions take place during polymerisation to yield a branched polyethylene. Apart from long branches it is also having a large number of short branches of unto 5 carbon atoms formed by intramolecular chain transfer reactions. A typical molecule of Low density polyethylene is having a short branch for about every 50 carbon atoms and one or two long branches per molecule. 

The proportions of the different end-groups depend upon the relative rates of the various chain-breaking reactions by which they are formed. These are determined by the temperature, the solvent, the nature of the catalyst and co-catalyst, and the concentration of the chain-breaking agents. These features will be discussed below. 

The adventitious chain-breaking reactions are those which involve the adventitious components of the polymerization system in other words, the impurities. The inherent chain-breaking reactions are those which are characteristic of the system, such as reactions between cation and anion, monomer transfer, solvent transfer. Each system has its own inherent chain-breaking reactions and for any one monomer the relative importance of these can be changed by changing the solvent, catalyst or co-catalyst [27b, 101]. 

The DPs obtained in cationic polymerizations are affected not only by the direct effect of the polarity of the solvent on the rate constants, but also by its effect on the degree of dissociation of the ion-pairs and, hence, on the relative abundance of free ions and ion-pairs, and thus the relative importance of unimolecular and bimolecular chain-breaking reactions between ions of opposite charge (see Section 6). Furthermore, in addition to polarity effects the chain-transfer activity of alkyl halide and aromatic solvents has a quite distinct effect on the DP. The smaller the propagation rate constant, the more important will these effects be. 

This second molecule might be a monomer, polymer, or solvent. Because of chain transfer the end of one polymer chain might be a hydrogen atom, and the beginning of the next the radical formed by removing the hydrogen atom from the solvent molecule. In the same paper, he proposed the two most probable chain termination reactions, mutual combination and disproportionation. 

For entries 3-5 the increase in molecular weight observed can be assigned to the increase in the rate of insertion and the rate of termination remains practically the same. An increase of the rate of polymerisation with the steric bulk of the ligand is usually ascribed to the destabilisation of the alkene adduct while the energy of the transition state remains the same. As a chain transfer reaction presumably P-hydride elimination takes place or traces of water might be chain transfer agents. Chain transfer does occur, because a Schulz-Flory molecular weight distribution is found (PDI 2, see Table 12.2). Shorter chains are obtained with a polar ortho substituent (OMe, entry 2) and in methanol as the solvent, albeit that most palladium is inactive in the latter case. 

Porous organic polymers (Figure 10) are potential electrochromatographic stationary phases for the analysis of pharmaceuticals. The polymer network is generally formed inside the capillary by a stepwise chain polymerization reaction. Polymerization reaction mixtures usually consist of a combination of monomers and cross-linker, initiator, and a porogenic mixture of solvents. 

The chain transfer reaction decreases the average chain length in accordance with the concentration of the chain-transfer agent (S) and the tendency to chain transfer. The resulting DP is equal to that which would have been obtained without the solvent or additive plus a factor related to the product of the ratio of the rate of propagation (Rp) and the rate of chain transfer (Rtv), and the ratio of the concentration of the monomer [M] to the concentration of chain-transfer agent [S]. 

Chain transfer reactions almost always decrease DP and will often introduce branching as it occurs within or between polymer chains. Solvent can also act as effective chain-transfer agents lowering chain length. 

---