Polymers, chain type

BI20) may aggrepte even when located somewhat apart along the polymer chain (type III). On the other hand, when the side chains possess intermediate hydro-phobicity, as in the MIm-VP copolymer iS, the catalytic site is formed by a loop of the polymer segment which surroimds the substrate molecule (type I). Type II is an intermediate case of types I and III. 

Table 8.4. Dimension factors for different polymer chain types...

Once a rubberband is stretched beyond its elastic region, it becomes much harder to stretch and soon breaks. At this point, the polymer chains are linear and more energy must be applied to slide chains past one another and break bonds. Thus, determining the energy required to break the material requires a different type of simulation. 

Copolymerization. Copolymerization occurs when a mixture of two or more monomer types polymerizes so that each kind of monomer enters the polymer chain. The fundamental structure resulting from copolymerization depends on the nature of the monomers and the relative rates of monomer reactions with the growing polymer chain. A tendency toward alternation of monomer units is common. 

The second type of isomerism we discuss in this section is stereo isomerism. Again we consider the number of ways a singly substituted vinyl monomer can add to a growing polymer chain ... 

Figure 1.2 shows sections of polymer chains of these three types the substituent R equals phenyl for polystyrene and methyl for polypropylene. The general term for this stereoregularity is tacticity, a term derived from the Greek word meaning to put in order. ... 

When monomers of the type AlA or even greater functionality are involved, the effect of their incorporation into the growing polymer chain is to introduce a branch point into the polymer. 

The type of initiator utilized for a solution polymerization depends on several factors, including the solubiUty of the initiator, the rate of decomposition of the initiator, and the intended use of the polymeric product. The amount of initiator used may vary from a few hundredths to several percent of the monomer weight. As the amount of initiator is decreased, the molecular weight of the polymer is increased as a result of initiating fewer polymer chains per unit weight of monomer, and thus the initiator concentration is often used to control molecular weight. Organic peroxides, hydroperoxides, and azo compounds are the initiators of choice for the preparations of most acryUc solution polymers and copolymers. 

The thermal stability of polymers of types (1) and (2) is also dependent on the nature of the substituents on phosphoms. Polymers with methoxy and ethoxy substituents undergo skeletal changes and degradation above about 100°C, but aryloxy and fluoroalkoxy substituents provide higher thermal stability (4). Most of the P—N- and P—O-substituted polymers either depolymerize via ring-chain equilibration or undergo cross-linking reactions at temperatures much above 150—175°C. 

The Ts of methacryhc polymers may be regulated by the copolymerization of two or more monomers as illustrated in Figure 1. The approximate T value for the copolymer can be calculated from the weight fraction of each monomer type and the T (in K) of each homopolymer (15). Acrylates with low transition temperatures are frequently used as permanent plasticizers (qv) for methacrylates. Unlike plasticizer additives, once polymerized into the polymer chain, the acrylate cannot migrate, volatilize, or be extracted from the polymer. 

As with nearly all other polymers, HDPE resin is a collection of polymer chains of different lengths, varying from short, with molecular weights of 500—1000, to very long, with molecular weights of over 10 million. Relative contents of chains with different lengths (ie, the shape and width of MWD) depend mostly on production technology and on the type of catalyst used for polymerization. The MWD width of HDPE resins can be tailored to specific apphcations. 

The manufacture of siHcone polymers via anionic polymerization is widely used in the siHcone industry. The anionic polymerization of cycHc siloxanes can be conducted in a single-batch reactor or in a continuously stirred reactor (94,95). The viscosity of the polymer and type of end groups are easily controUed by the amount of added water or triorganosUyl chain-terminating groups. 

CMC hydrates rapidly and forms clear solutions. Viscosity buUding is the single most important property of CMC. DUute solutions of CMC exhibit stable viscosity because each polymer chain is hydrated, extended, and independent. The sodium carboxylate groups are highly hydrated, and the ceUulose molecule itself is hydrated. The ceUulose molecule is linear, and conversion of it into a polyanion (polycarboxylate) tends to keep it in an extended form by reason of coulombic repulsion. This same coulombic repulsion between the carboxylate anions prevents aggregation of the polymer chains. Solutions of CMC are either pseudoplastic or thixotropic, depending on the type. 

The distribution of chlorine atoms along the polymer chain has been studied in great detail. The distribution in various functional types is shown in Table 4 (18). High density polyethylene chlorosulfonated to 35% G1 and 1% S has been found to contain only 1.7% highly active chlorines, ie, reactive to weak bases. AH of these are attributed to the chlorine in the sulfonyl chloride group and those in beta position to SO2GI. No vicinal chlorides groups were found (19). 

In the ordered smectic or nematic phase, the rigid rods are arranged in parallel arrays that allow for close packing. The nematic phase is the most common type found with synthetic polymer molecules. The molecules long axes are parallel, but there is no layering. Aromatic polymer chains that have stiff ester or amide linkages are ideal. 

Nylon, also a linear polymer, is made by a condensation reaction. Two different kinds of molecule react to give a larger molecule, and a by-product (usually HjO) the ends of large molecules are active, and react further, building a polymer chain. Note how molecules of one type condense with those of the other in this reaction of two symmetrical molecules... 

The final variable to be mentioned here is the presence of impurities. These may be metallic fragments residual from Ziegler-type processes or they can be trace materials incorporated into the polymer chain. Such impurities as catalyst fragments and carbonyl groups incorporated into the chain can have a serious adverse influence on the power factor of the polymer, whilst in other instances impurities can have an effect on aging behaviour. 

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