Vinyl monomers, chain-growth

An example of a commercial semibatch polymerization process is the early Union Carbide process for Dynel, one of the first flame-retardant modacryhc fibers (23,24). Dynel, a staple fiber that was wet spun from acetone, was introduced in 1951. The polymer is made up of 40% acrylonitrile and 60% vinyl chloride. The reactivity ratios for this monomer pair are 3.7 and 0.074 for acrylonitrile and vinyl chloride in solution at 60°C. Thus acrylonitrile is much more reactive than vinyl chloride in this copolymerization. In addition, vinyl chloride is a strong chain-transfer agent. To make the Dynel composition of 60% vinyl chloride, the monomer composition must be maintained at 82% vinyl chloride. Since acrylonitrile is consumed much more rapidly than vinyl chloride, if no control is exercised over the monomer composition, the acrylonitrile content of the monomer decreases to approximately 1% after only 25% conversion. The low acrylonitrile content of the monomer required for this process introduces yet another problem. That is, with an acrylonitrile weight fraction of only 0.18 in the unreacted monomer mixture, the low concentration of acrylonitrile becomes a rate-limiting reaction step. Therefore, the overall rate of chain growth is low and under normal conditions, with chain transfer and radical recombination, the molecular weight of the polymer is very low. 

Synthetic polymers are classified by their method of synthesis as either chain-growth or step-growth. The categories ate somewhat imprecise but nevertheless provide a useful distinction. Chain-growth polymers are produced by chain-reaction polymerization in which an initiator adds to a carbon-carbon double bond of an unsaturated substrate (a vinyl monomer) to yield a reactive inter-... 

Synthetic polymers can be classified as either chain-growth polymen or step-growth polymers. Chain-growth polymers are prepared by chain-reaction polymerization of vinyl monomers in the presence of a radical, an anion, or a cation initiator. Radical polymerization is sometimes used, but alkenes such as 2-methylpropene that have electron-donating substituents on the double bond polymerize easily by a cationic route through carbocation intermediates. Similarly, monomers such as methyl -cyanoacrylate that have electron-withdrawing substituents on the double bond polymerize by an anionic, conjugate addition pathway. 

Vinyl monomer (Sections 7.10, 31.1) A substituted alkene monomer used to make chain-growth polymers. 

The interest in hyperbranched polymers arises from the fact that they combine some features of dendrimers, for example, an increasing number of end groups and a compact structure in solution, with the ease of preparation of hn-ear polymers by means of a one-pot reaction. However, the polydispersities are usually high and their structures are less regular than those of dendrimers. Another important advantage is the extension of the concept of hyperbranched polymers towards vinyl monomers and chain growth processes, which opens unexpected possibilities. 

Hydroxyl containing polymers may be cross-linked with diisocyanates. Fordyce and Ferry cross-linked styrene-maleic anhydride copolymers through the action of glycols. The copolymerization of divinyl with vinyl monomers may be looked upon as a method of cross-linking chain polymers. The cross-linkages are introduced simultaneously with the growth of the linear polymer chains, rather than afterwards, but this difference is secondary. 

We can create crosslinks during chain growth polymerization by copolymerizing dienes with vinyl monomers. When the two vinyl functions of the diene are incorporated into separate chains, a crosslink is formed. This process is shown in Fig. 2.18. When we use a low concentration of dienes, we produce a long chain branched polymer, while high concentrations of dienes create a highly crosslinked polymer network... 

Most addition polymers are formed from polymerizations exhibiting chain-growth kinetics. This includes the typical polymerizations, via free radical or some ionic mode, of the vast majority of vinyl monomers such as vinyl chloride, ethylene, styrene, propylene, methyl methacrylate, and vinyl acetate. By comparison, most condensation polymers are formed from systems exhibiting stepwise kinetics. Industrially this includes the formation of polyesters and polyamides (nylons). Thus, there exists a large overlap between the terms stepwise kinetics and condensation polymers, and chainwise kinetics and addition (or vinyl) polymers. A comparison of the two types of systems is given in Table 4.1. 

The situation is quite different in chain polymerization where an initiator is used to produce an initiator species R with a reactive center. The reactive center may be either a free radical, cation, or anion. Polymerization occurs by the propagation of the reactive center by the successive additions of large numbers of monomer molecules in a chain reaction. The distinguishing characteristic of chain polymerization is that polymer growth takes place by monomer reacting only with the reactive center. Monomer does not react with monomer and the different-sized species such as dimer, trimer, tetramer, and n-trier do not react with each other. By far the most common example of chain polymerization is that of vinyl monomers. The process can be depicted as... 

Acetylene and its derivatives can be polymerized by chain growth in the presence of suitable transition metal catalysts to give high molecular weight (MW) polymers (Equations (l)-(4)). The monomers include acetylene, mono- and disubstituted acetylenes, and a,tv-diynes. The polymers possess carbon-carbon alternating double bonds along the main chain and exhibit unique properties (e.g., metallic conductivity) that are not expected with vinyl polymers. 

Commodity Chain-Growth Polymers. Two of the largest commodity wafer-soluble polymers are poly(vinyl alcohol) (PVA) and polyacrylamide (PAM). They are prepared by the free-radical initiation of vinyl monomers, a chain-growth polymerization technique. 

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