Chain in polymerization

Kobayashi, K., Vaerman, J. P., Bazin, H and Lebaq-Verheyden, A. M. 1973. Identification of J-chain in polymeric immunoglobulins from a variety of species by crossreaction with rabbit antisera to human J-chain. J. Immunol 111, 1590-1594. 

Smal0 HS, Uggerud E (2012) Ring opening vs. direct bond scission of the chain in polymeric triazoles under the influence of an external frace. Chem Comm 48 10443-10445... 

Several mechanisms were offered to explain steric control in polymerizations of polar monomers. Furukawa and co-workers based their mechanism on infrared spectroscopy data of interactions between the cations and the growing polymeric chains in polymerizations of methyl methacrylate and methacrylonitrile. They observed a correlation between the tacticities of the growing molecules and the carbonyl stretching frequencies. The higher the frequency, the higher is the amount of isotactic placement in the resultant chains. The adducts, as in the initiation reactions, are resonance hybrids of two structures, A and B ... 

Boeffel C, Spiess FIW, Hisgen B, Ringsdorf H, Ohm H, Kirste RG (1986) Molecular order of spacer and main chain in polymeric side-group liquid-crystals. Makromol Chem Rapid Commun 7(12) 777-783... 

We have tacitly assumed that the rate constants depend only on the last unit of the chain. In such a situation, the copolymerization is called a Markov copolymerization of first order. The special case (i), r r- = 1, is a Markov copolymerization of order zero. If reactivity also depends on the penultimate unit of the chain, the polymerization is a Markov copolymerization of second order. 

FIGURE 1111 Cham propagation in polymerization of styrene The growing polymer chain has a free radical site at the benzylic carbon It adds to a molecule of styrene to extend the chain by one styrene unit The new polymer chain is also a benzylic radical it attacks another molecule of styrene and the process repeats over and over again... 

Positional isomerism is conveniently illustrated by considering the polymerization of a vinyl monomer. In such a reaction, the adding monomer may become attached to the growing chain in either of two orientations ... 

We shall have considerably more to say about this type of kinetic analysis when we discuss chain-growth polymerizations in Chap. 6. 

Our primary purpose in this section is to point out some of the similarities and differences between step-growth and chain-growth polymerizations. In so doing we shall also have the opportunity to indicate some of the different types of chain-growth polymerization systems. 

Step-growth polymerizations can be schematically represented by one of the individual reaction steps VA + B V —> Vab V with the realization that the species so connected can be any molecules containing A and B groups. Chain-growth polymerization, by contrast, requires at least three distinctly different kinds of reactions to describe the mechanism. These three types of reactions will be discussed in the following sections in considerable detail. For now our purpose is to introduce some vocabulary rather than develop any of these beyond mere definitions. The principal steps in the chain growth mechanism are the following ... 

Elsewhere in this chapter we shall see that other reactions-notably, chain transfer and chain inhibition-also need to be considered to give a more fully developed picture of chain-growth polymerization, but we shall omit these for the time being. Much of the argumentation of this chapter is based on the kinetics of these three mechanistic steps. We shall describe the rates of the three general kinds of reactions by the notation Rj, Rp, and R for initiation, propagation, and termination, respectively. 

Photoinitiation is not as important as thermal initiation in the overall picture of free-radical chain-growth polymerization. The foregoing discussion reveals, however, that the contrast between the two modes of initiation does provide insight into and confirmation of various aspects of addition polymerization. The most important application of photoinitiated polymerization is in providing a third experimental relationship among the kinetic parameters of the chain mechanism. We shall consider this in the next section. 

There is a great deal more that could be said about emulsion polymerization or, for that matter, about free-radical polymerization in general. We shall conclude our discussion of the free-radical aspect of chain-growth polymerization at this point, however. This is not the end of chain-growth polymerization, however. There are four additional topics to be considered ... 

Chain-growth polymerization through cationic active species. This is taken up in Sec. 6.11. 

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. 

DNA polymerases normally use 3 -deoxynucleotide triphosphates as substrates for polymerization. Given an adequate concentration of substrate, DNA polymerase synthesizes a long strand of new DNA complementary to the substrate. The use of this reaction for sequencing DNA depends on the inclusion of a single 2/3 -dideoxynucleoside triphosphate (ddNTP) in each of four polymerization reactions. The dideoxynucleotides ate incorporated normally in the chain in response to a complementary residue in the template. Because no 3 -OH is available for further extension, polymerization is... 

Polyethylene (PE) is a genetic name for a large family of semicrystalline polymers used mostiy as commodity plastics. PE resins are linear polymers with ethylene molecules as the main building block they are produced either in radical polymerization reactions at high pressures or in catalytic polymerization reactions. Most PE molecules contain branches in thek chains. In very general terms, PE stmcture can be represented by the following formula ... 

Molecular Weight. PE mol wt (melt index) is usually controlled by reaction temperature or chain-transfer agents. Reaction temperature is the principal control method in polymerization processes with Phillips catalysts. On the other hand, special chemical agents for chain transfer are requited for... 

Effect of Fiber Properties. Acid dyes are attracted to the accessible amine ends of the nylon chains located in the amorphous regions of the fiber. Acid dye affinity of nylon can be adjusted by a dding excess diamine or diacid to the polymer salt or by changing the molecular weight in polymerization. A light acid-dyeable nylon-6,6 is spun with 15—20 amine ends, expressed in terms of gram equivalents per 10 g of polymer. A medium or... 

OC-Methylstyrene. This compound is not a styrenic monomer in the strict sense. The methyl substitution on the side chain, rather than the aromatic ring, moderates its reactivity in polymerization. It is used as a specialty monomer in ABS resins, coatings, polyester resins, and hot-melt adhesives. As a copolymer in ABS and polystyrene, it increases the heat-distortion resistance of the product. In coatings and resins, it moderates reaction rates and improves clarity. Physical properties of a-methylstyrene [98-83-9] are shown in Table 12. 

Distribution of the monomer units in the polymer is dictated by the reactivity ratios of the two monomers. In emulsion polymerization, which is the only commercially significant process, reactivity ratios have been reported (4). IfMj = butadiene andM2 = acrylonitrile, then = 0.28, and r2 =0.02 at 5°C. At 50°C, Tj = 0.42 and = 0.04. As would be expected for a combination where = near zero, this monomer pair has a strong tendency toward alternation. The degree of alternation of the two monomers increases as the composition of the polymer approaches the 50/50 molar ratio that alternation dictates (5,6). Another complicating factor in defining chemical stmcture is the fact that butadiene can enter the polymer chains in the cis (1), trans (2), or vinyl(l,2) (3) configuration ... 

This combination of monomers is unique in that the two are very different chemically, and in thek character in a polymer. Polybutadiene homopolymer has a low glass-transition temperature, remaining mbbery as low as —85° C, and is a very nonpolar substance with Htde resistance to hydrocarbon fluids such as oil or gasoline. Polyacrylonitrile, on the other hand, has a glass temperature of about 110°C, and is very polar and resistant to hydrocarbon fluids (see Acrylonitrile polymers). As a result, copolymerization of the two monomers at different ratios provides a wide choice of combinations of properties. In addition to providing the mbbery nature to the copolymer, butadiene also provides residual unsaturation, both in the main chain in the case of 1,4, or in a side chain in the case of 1,2 polymerization. This residual unsaturation is useful as a cure site for vulcanization by sulfur or by peroxides, but is also a weak point for chemical attack, such as oxidation, especially at elevated temperatures. As a result, all commercial NBR products contain small amounts ( 0.5-2.5%) of antioxidant to protect the polymer during its manufacture, storage, and use. 

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