Polymers polypropene

A short section of the polymer polypropene is shown helow. 

Mention should be made of the nomenclature for the polymer. Industrially the materially is invariably known in the English-speaking world as polypropylene. However, the lUPAC name for the monomer is propene and until 1975 the recommended lUPAC name was polypropene, a term very rarely used. The latest lUPAC rules base the name of a polymer on the constitutional repeating unit, which in this case is a propylene unit (c.f. a methylene unit for polyethylene) and this leads to the name poly(propylene) (i.e. with brackets). In this volume the more common, unbracketed but still unambiguous name will be used. 

Atactic polymethacrylate esters, glass transition temperatures of, 16 273t Atactic polypropene, 16 104 20 524 Atactic polystyrene, 10 180, 182 Atactic propylene polymers, 17 704, 705 Atactic PSSA, 20 468 Atenolol, 5 102, 160... 

Steric hindrance may hamper the correct stereochemistry required for 13-elimination, and perhaps this can be used to stabilise our metal alkyl complex. In the modem polymerisation catalysts for polypropene this feature has actually been observed, which leads to higher molecular weight polymers. This now forms part of the design of new catalysts. 

Ewen was the first to report the synthesis of stereoregular propene polymers with soluble Group 4 metal complexes and alumoxane as the co-catalyst [13], He found that Cp2TiPh2 with alumoxane and propene gives isotactic polypropene. This catalyst does not contain an asymmetric site that would be able to control the stereoregularity. A stereo-block-polymer is obtained, see Figure 10.6. Formation of this sequence of regular blocks is taken as a proof for the chain-end control mechanism. 

Modification of the cyclopentadienyl ligands has led to a very rich chemistry and today a great variety of microstructures and combination thereof can be synthesised as desired including isotactic polymer with melting points above 160 °C, syndiotactic polypropene [16], block polymers, hemi-isotactic polymers etc. 

The name of a polymer is usually written with the prefix poly-(meaning many ) before the name of the monomer. Often the common name of the monomer is used, rather than the lUPAC name. For example, the common name of ethene is ethylene. Polyethene, the polymer that is made from ethene, is often called polyethylene. Similarly, the polymer that is made from chloroethene (common name vinyl chloride) is named polyvinylchloride (PVC). The polymer that is made from propene monomers (common name propylene) is commonly called polypropylene, instead of polypropene. 

The addition polymers are formed by the repeated addition of monomer molecules possessing double or triple bonds, e.g., the formation of polythene from ethene and polypropene from propene. However, the addition polymers formed by the polymerisation of a single monomeric species are known as homopolymers, e.g., polythene,... 

For many processes, how ever, it is necessary to employ a divided cell in which the anode and cathode compartments are separated by a barrier, allowing the diffusion of ions but hindering transfer of reactants and products between compartments. This prevents undesirable side reactions. Good examples of the need for a divided cell are seen in the reduction of nitjobenzenes to phenylhydroxylamines (p. 379) or to anilines (p. 376). In these ca.scs the reduction products are susceptible to oxidation and must be prevented from approaching the anode. The cell compartments can be divided with a porous separator constructed from sintered glass, porous porcelain or a sintered inert polymer such as polypropene or polytetra-... 

The pioneering work of Natta and co-workers introduced the concept of tacticity, i.e. the orderliness of the succession of configurational repeating units in the main chain of a polymer. For example, in polypropene (polypropylene), possible steric arrangements are (shown in Fischer projections displayed horizontally) ... 

Low- and high-density polyethylene, polypropene, and polymers of other alkene (olefin) monomers constitute the polyolefin family of polymers. All except LDPE are produced by coordination catalysts. Coordination catalysts are also used to produce linear low-density polyethylene (LLDPE), which is essentially equivalent to LDPE in structure, properties, and applications (Sec. 8-1 lc). The production figures given above for LDPE do not include LLDPE. The production of LLDPE now exceeds that of LDPE, with about 10 billion pounds produced in 2001 in the United States. (Copolymers constitute about one-quarter of all low density polyethylenes see Sec. 6-8b.)... 

Enormous commerical applications flowed from the revolution initiated by Ziegler and Natta. These include high-density and linear low-density polyethylenes (HDPE, LLDE), polypropene, ethene-propene co- and terpolymers, and polymers from 1,3-dienes (Sec. 8-10). The annual United States production of these polymers exceeded 40 billion pounds in 2000 the global production was about 3-3.5 times the U.S. production. Ziegler-Natta chemistry accounts for the production of one-third of all polymers. 

Stereoselective polymerizations yielding isotactic and syndiotactic polymers are termed isoselective and syndioselective polymerizations, respectively. The polymer structures are termed stereoregular polymers. The terms isotactic and syndiotactic are placed before the name of a polymer to indicate the respective tactic structures, such as isotactic polypro-pene and syndiotactic polypropene. The absence of these terms denotes the atactic structure polypropene means atactic polypropene. The prefixes it- and st- together with the formula of the polymer, have been suggested for the same purpose it-[CH2CH(CH3)] and st-[CH2 CH(CH3)] [IUPAC, 1966],... 

Both isotactic and syndiotactic polypropenes are achiral as a result of a series of mirror planes (i.e., planes of symmetry) perpendicular to the polymer chain axis. Neither exhibits... 

It should be noted that other polymer structures can be postulated—those where one substituent is atactic while the other is either isotactic or syndiotactic or those where one substituent is isotactic while the other is syndiotactic. However, these possibilities are rarely observed since the factors that lead to ordering or disordering of one substituent during polymerization generally have the same effect on the other substituent. An exception is the formation of hemiisotactic polypropene where isotactic placements alternate with atactic placements [Coates, 2000]. 

While the properties and applications of isotactic polymers have been extensively studied, those of syndiotactic polymers received less attention until relatively recently. The reason is the relative ease of forming isotactic polymers. Syndioselective polymerizations were less frequently encountered or proceeded with less efficiency compared to isoselective polymerizations. But the situation is changing fast as initiators and reaction conditions have been developed for syndioselective polymerizations. In the case of polypropene, the properties of the syndiotactic polymer have been examined [Youngman and Boor, 1967]. Syndiotactic polypropene, like its isotactic counterpart, is easily crystallized, but it has a lower Tm by about 20°C and is more soluble in ether and hydrocarbon solvents. 

C NMR of isotactic polypropene shows the main error is pairs of racemic dyads instead of isolated racemic dyads (Table 8-3) [Heatley et al., 1969 Resconi et al., 2000 Wolfsgruber et al., 1975]. A stereoerror in the addition of a monomer molecule is immediately corrected when stereocontrol is by the chiral active site. If stereocontrol was due to the propagating chain end, an error would continue to propagate in an isotactic manner to yield a polymer, referred to as an isotactic stereoblock, containing long isotactic all-R and all-5 stereoblocks on each side of the error. 

C NMR of ethylene-propene copolymers of low ethylene content produced by initiators that yield isotactic polypropene shows that the isotactic propene units on each side of an ethylene unit have the same configuration (i.e., all-R or all-5) [Zambelli et al., 1971, 1978, 1979]. For stereocontrol by the propagating chain end, the amount of polymer in which the polypropene blocks on either side of an ethylene unit have the same configuration would equal that in which the blocks have the opposite configuration. 

The polymer chain end control model is supported by the observation that highly syndiotactic polypropene is obtained only at low temperatures (about —78°C). Syndiotacticity is significantly decreased by raising the temperature to —40°C [Boor, 1979]. The polymer is atactic when polymerization is carried out above 0°C. 13C NMR analysis of the stereoerrors and stereochemical sequence distributions (Table 8-3 and Sec. 8-16) also support the polymer chain end control model [Zambelli et al., 2001], Analysis of propene-ethylene copolymers of low ethylene content produced by vanadium initiators indicates that a syndiotactic block formed after an ethylene unit enters the polymer chain is just as likely to start with an S- placement as with an R-placement of the first propene unit in that block [Bovey et al., 1974 Zambelli et al., 1971, 1978, 1979]. Stereocontrol is not exerted by chiral sites as in isotactic placement, which favors only one type of placement (either S- or R-, depending on the chirality of the active site). Stereocontrol is exerted by the chain end. An ethylene terminal unit has no preference for either placement, since there are no differences in repulsive interactions. 

Bis(2-arylindene)zirconium dichlorides have been studied for the purpose of synthesizing isotactic-atactic stereoblock polymers [Busico et al., 2001 Lin et al., 2000 Lin and Way-mouth, 2002 Nele et al., 2000], Without the phenyl substituents, bisindenylzirconium dichloride yields atactic polypropene because there is rapid rotation of the r 5-ligands. The 2-phenyl substituents in bis(2-arylindene)zirconium dichloride interfere with each other suf-ficently that rotation is slowed to produce isotactic-atactic stereoblock polypropene. Three conformational isomers (conformers) are possible in this metallocene (Eq. 8-54). There is... 

Optically active polymers are rarely encountered. Most syndiotactic polymers are optically inactive since they are achiral. Most isotactic polymers, such as polypropene and poly(methyl methacrylate), are also inactive (Sec. 8-la-l). Optically active polymers have been obtained in some situations and these are discussed below. 

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