Chains poly

By enantioselective polymerization polymer chains, each containing only one configurational kind of monomeric unit, are produced from a mixture of stereoisomeric monomer molecules. The number of kinds of polymer chain generated therefore equals the number of various stereoisomers in the monomer mixture. In the course of propagation, the enantiomeric composition of the polymer and unreacted monomer remains identical to the intial composition. When optically active monosubstituted cyclic monomers are polymerized, stereoregular polymers are formed with both isotactic polyR and polyS chains... 

Conformational changes of poly chain (containing or interacting photo-ionizable groups) during 1 irradiation... 

Remark. Tertiary carbon atoms that are responsible for the atacticity initially exist in the monomer molecules. However, certain stereoselective polymerization by giving polyR and polyS chains from [R] and [S] monomer molecules can be isospecific. 

Several studies have demonstrated the successful incoriDoration of [60]fullerene into polymeric stmctures by following two general concepts (i) in-chain addition, so called pearl necklace type polymers or (ii) on-chain addition pendant polymers. Pendant copolymers emerge predominantly from the controlled mono- and multiple functionalization of the fullerene core with different amine-, azide-, ethylene propylene terjDolymer, polystyrene, poly(oxyethylene) and poly(oxypropylene) precursors [63,64,65,66,62 and 66]. On the other hand, (-CggPd-) polymers of the pearl necklace type were fonned via the periodic linkage of [60]fullerene and Pd monomer units after their initial reaction with thep-xy y ene diradical [69,70 and 71]. 

In polymers made of dis-symmetric monomers, such as, for example, poly(propylene), the stmcture may be irregular and constitutional isomerism can occur as shown in figure C2.1.1(a ). The succession of the relative configurations of the asymmetric centres can also vary between stretches of the chain. Configuration isomerism is characterized by the succession of dyads which are named either meso, if the two asymmetric centres have the same relative configurations, or racemo if the configurations differ (figure C2.1.1(b )). A polymer is called isotactic if it contains only one type of dyad and syndiotactic if the dyad sequence strictly alternates between the meso and racemo fonns. 

Figure C2.1.1. (a) Constitutional isomerism of poly (propylene). The upper chain has a regular constitution. The lower one contains a constitutional defect, (b) Configurational isomerism of poly(propylene). Depending on tire relative configurations of tire asymmetric carbons of two successive monomer units, tire corresponding dyad is eitlier meso or racemo.

The second category of polymerization reactions does not involve a chain reaction and is divided into two groups poly addition and poly condensation [4]. In botli reactions, tire growth of a polymer chains proceeds by reactions between molecules of all degrees of polymerization. In polycondensations a low-molecular-weight product L is eliminated, while polyadditions occur witliout elimination ... 

Anotlier model system consists of polymetliylmetliacrylate (PMMA) latex, stabilized in organic solvents by a comb polymer, consisting of a PMMA backbone witli poly-12-hydroxystearic acid (PHSA) chains attached to it [10]. The PHSA chains fonn a steric stabilization layer at tire surface (see section C2.6.4). Such particles can approach tire hard-sphere model very well [111. 

A polymer is a macromolecule that is constructed by chemically linking together a sequent of molecular fragments. In simple synthetic polymers such as polyethylene or polystyrer all of the molecular fragments comprise the same basic unit (or monomer). Other poly me contain mixtures of monomers. Proteins, for example, are polypeptide chains in which eac unit is one of the twenty amino acids. Cross-linking between different chains gives rise to j-further variations in the constitution and structure of a polymer. All of these features me affect the overall properties of the molecule, sometimes in a dramatic way. Moreover, or... 

FIGURE 7 16 Poly mers of propene The mam chain IS shown in a zigzag conformation Every other carbon bears a methyl sub stituent and is a chirality center (a) All the methyl groups are on the same side of the carbon chain in isotactic polypropylene (b) Methyl groups alternate from one side to the other in syndiotactic polypropy lene (c) The spatial orienta tion of the methyl groups IS random in atactic polypropylene... 

Polymerization of styrene is carried out under free radical conditions often with benzoyl peroxide as the initiator Figure 1111 illustrates a step m the growth of a poly styrene chain by a mechanism analogous to that of the polymerization of ethylene (Sec tion 6 21)... 

FIGURE 28 14 The poly merase chain reaction (PCR) Three cycles are shown the target region appears after the third cycle Additional cycles lead to amplification of the target region... 

Poly(tetmfluoroethylene). Poly(tetrafluoroethylene) is prepared from tetrafluoroethy-lene and consists of repeating units in a predominantly linear chain ... 

Poly(vinylidene Fluoride). Poly(vinylidene fluoride) consists of linear chains in which the predominant repeating unit is... 

Poly (dimethyl siloxane) offers the least steric hindrance of the polymers listed every other atom along the backbone of the chain is devoid of substituents in this case. 

Poly(ethylene oxide). Although AH j is more than double that of polyethylene, the effect is offset by an even greater increase for AS j. The latter may be due to increased chain flexibility in the liquid caused by the regular insertion of ether oxygens along the chain backbone. 

The melting points of a series of poly(a-olefin) crystals were studied. All of the polymers were isotactic and had chain substituents of different bulkinesses. Table 4.2 lists some results. Use Eq. (4.5) as the basis for interpreting the trends in these data. 

If the poorer solvent is added incrementally to a system which is poly-disperse with respect to molecular weight, the phase separation affects molecules of larger n, while shorter chains are more uniformly distributed. These ideas constitute the basis for one method of polymer fractionation. We shall develop this topic in more detail in the next section. 

Fig. 4. Chemistry of poly(vinyl cinnamate) negative-acting resist. Initial light absorption by the photosensitizer is followed by energy transfer to produce a pendant cinnamate group in a triplet electronic state. This combines with a second cinnamate on another polymer chain, forming a polymer—polymer...

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