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There is theoretical justi cation for the independence of the reactivity of a functional group of molecular size [Rabinowitch, 1937] The common misconception regarding the alleged low reactivity of groups attached to large molecules comes from the lower diffusion rates of the latter However, the observed reactivity of a functional group is dependent on the collision frequency of the group, not on the diffusion rate of the whole molecule The collision frequency is the number of collisions one functional group makes with other functional groups per unit of time A terminal functional group attached to a growing polymer has a much greater mobility than would be expected from the mobility of the polymer molecule as a whole The functional group has appreciable mobility due to the conformational rearrangements that occur in nearby segments of the polymer chain.



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- 41T(p 1\ V)8(r),

The collision rate of such a functional group with neighboring groups will be about the same as for small molecules The lowered mobility of the polymer molecule as a whole alters the time distribution of collisions A lower diffusion rate means that any two functional groups will undergo more total collisions before diffusing apart Thus in any particular time interval (which is long compared to the interval required for diffusion of a group from one collision partner to the next) the number of partners with which a functional group undergoes collisions is less for a group attached to a polymer chain than for one attached to a small molecule But, most signi cantly, their overall collision frequencies are the same in the two cases.

(5.16) (5.17)

Excel moves or copies the worksheet. (Here, the worksheet was moved.)





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How To Convert PDF to Image Using Ghostscript API - CodeProject
15 Jan 2009 ... How to use Ghostscript library to create an image (or images) from a PDF file.

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Both single page and multi-page Tiff image files are acceptable.
Both single page and multi-page Tiff image files are acceptable.

If the diffusion of a functional group from one collision partner to the next were too slow to maintain the concentration of the reactive pairs of functional groups at equilibrium, one would observe decreased reactivity for the functional group The opposite is the case, since reaction between two functional groups in a step polymerization occurs only about once in every 1013 collisions [Flory, 1953] During the time interval required for this many collisions, suf cient diffusion of the molecule and of the functional group occurs to maintain the equilibrium concentration of collision pairs of functional groups The net result of these.

2To obtain (5.13) from (5.5), just solve the reciprocal space version of (5.5), which yields ell(k) -41T(k p)/k and invert:

5-75

= _~Jd3k(k'P)keik'"

The resulting polymerization is a copolymerization between the two monomers, not a homopolymerization of MMA. More importantly, this results in a slower reaction (and lower polymer molecular weight) since the carbanion derived from the ketone is not as reactive as the carbanion from MMA. Nucleophilic substitution by intramolecular backbiting attack of a

(21T)3

5-76

k 2 p,

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propagating carbanion lowers the polymer molecular weight and decreases the polymerization rate since methoxide is a weak initiator. Other reactions have been proposed nucleophilic attack by a propagating carbanion on monomer to displace methoxide and yield a polymer with an isopropenyl keto end group and the intermolecular analog of Reaction 5-76

Ell (r)

to yield branched polymer Acrylate monomers have an additional side reaction abstraction of the a-hydrogen of monomer by the initiator The effort to minimize side reactions and achieve polymers with controlled structures as well as living anionic polymerization (LAP) has involved control of temperature, solvent, and the addition of ligands [Baskaran, 2003] Side reactions are minimized by altering the reactivities of the propagating species (free ions and/or ion pairs) so that there is greater selectivity in favor of normal propagation To achieve LAP with narrow PDI requires fast initiation and fast exchange among free-ion- and ion-pair-propagating species and dormant (and associated) covalent species The side reactions predominate over normal polymerization in hydrocarbon solvents, yielding nonliving polymerization with lowered polymerization rate and polymer molecular weight Reaction 5-75 is the major reaction when n-butyllithium is the initiator.

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iText - I-Text PDF to TIFF Conversion
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