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the counterion of the propagating center) with both the propagating chain end and the incoming monomer occurs so as to orient the monomer with respect to the growing chain end and bring about stereoselective addition Many different mechanisms have been advanced to explain the usual isotactic placement obtained with coordination initiators [Corradini et al, 1989; Kuran, 2001; Tait and Watkins, 1989] Stereoselective polymerization is a concerted, multicentered reaction Figure 8-10 depicts the general situation for an anionic coordination polymerization proceeding with isotactic placement The polymer chain end has a partial negative charge with the initiator fragment G (the counterion) having a partial positive charge (Cationic coordination polymerization involves a similar mechanism except for reversal of the signs of the partial charges) The initiator fragment G is coordinated with both the propagating chain end and the incoming monomer molecule.

In testing the bent SK-1, you ve already nearly reassembled it. Replace the remaining screws and hope that you don t have to reopen it someday to prove to airline security that it s only art. By the way, airline security always asks me if what I m carrying is dangerous. I look concerned and say, Well, sure, it s art. This gives me a chance to practice my licks while I m detained.

Rates on medium-maturity loans will usually be lacking Nevertheless, the definition of maturity will usually be precise For the Middle Ages, we will often have to be satisfied with two broad.

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Monomer is oriented and held in place by coordination during addition to the polymer chain Coordination between the initiator fragment and the propagating center is broken simultaneously with the formation of bonds between the propagating center and the new monomer unit and between the initiator fragment and the new monomer unit Propagation proceeds in the four-center cyclic transition state by the insertion of monomer between the initiator fragment and the propagating center The initiator fragment essentially acts as a template or mold for the successive orientations and isotactic placements of the incoming monomer units Isotactic polymerization occurs because the initiator fragment forces each monomer unit to approach the propagating center with the same face This mechanism is referred to as catalyst (initiator) site control or enantiomorphic site control For the polymerization described in Fig 8-10, monomer approaches the propagating center with its re face facing the propagating center.

The face of a monomer molecule is labeled as the re face if viewing that face of the molecule shows the groups attached to the CHR carbon decreasing in priority in a clockwise manner ( C > R > H) The opposite face is the si face, in which.

maturity categories, long and short, because the bulk of the data is not more precise Long-term loans will include the perpetual debt of Italian cities, the French rentes, the perpetual annuities issued by many European towns, and other loans that were clearly intended to run for many years Short-term loans will include bills of exchange, bank deposits, pawnshop and other collateral loans, and the floating debt of princes Much of this short-term debt, in fact, probably ran for years, but the form of contract was short term There is uncertainty, however, as to the term of many medieval credits; when there is doubt, they have been classified as short term, but a description of the term is given to the reader whenever it has come down to us For ancient times, distinctions between interest rates arising from maturity are almost nonexistent.

priorities decrease in a counterclockwise manner when the face is viewed from the propagating center The re and si faces of a monomer such as propene are enantiotopic; that is, the products formed by additions of a propagating center to the two faces have opposite con gurations (The term prochiral has been used for a carbon atom such as the CHR carbon of a monomer molecule to indicate additions to the si and re face yield, respectively, one enantiomer or the other of a pair of enantiomers) The description in Fig 8-10 for isotactic polymerization could also have been shown with the R and H groups of the last monomer unit in the polymer chain reversed (R in back and H in front), in which case isotactic propagation consists of monomer always approaching the propagating center with its si face.

The property of the initiator fragment that forces successive placements of monomer to occur with the same face is chirality There is a stereochemical t between initiator and monomer, which overrides the usual tendency toward moderate syndiotacticity The initiator in isotactic polymerization is usually a racemic mixture of two enantiomers One of the enantiomers yields isotactic polymer by forcing all propagations via the re face of monomer; the other enantiomer, via the si face The isotactic polymer structures formed from the enantiomeric initiators are the same polymer; that is, they are superposable (ignoring the effects of end groups) for most monomers (Exceptions are some ring-opening polymerizations, eg, propylene oxide, and 1,4-polymerizations of some substituted 1,3-dienes, eg, 1,3-pentadiene, where the two isotactic polymers are enantiomeric.

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