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are examples of active ligands Longer alkyl chains in 4,4-dialkyl-2,20 -bipyridine are useful for achieving solubility of the catalyst in the less polar monomers such as styrene Phosphorus ligands such as triphenyl phosphine are useful for most other transition metals, but not for copper The optimum ligand to Cu ratio depends in a complex manner on the ligand and counterion For complex anions such as tri ate and hexa uorophosphate, two bidentate or one tetradentate ligands are needed per Cu For bromide counterion, one bidentate ligand or one-half tetradentate ligand is needed per Cu The optimal ratio may change with temperature and solvent Polymerization rates are lower below the optimum ratio and constant above It was noted previously that the addition of some Cu2 at the beginning of ATRP decreases the amount of normal termination.



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You can use Excel s AutoFill feature to add duplicate entries or a data series to your worksheet. This can greatly expedite data entry. You can use Excel s built-in lists of common entries to create text series for example, to enter a list containing the days of the week or months in the year or number series. You can also create your own custom data lists, When you click a cell, a small fill handle appears in the lower right corner of the selector; you use this to create an AutoFill series.

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The initial addition of metallic copper is sometimes advantageous for achieving a faster polymerization as excess Cu2 undergoes redox reaction with Cu to form Cu ATRP has been carried out in bulk, solution, suspension, and aqueous emulsion A range of solvents have been used for solution polymerization, including toluene, ethyl acetate, alcohols, water, ethylene carbonate, DMF, and supercritical carbon dioxide Apart from the usual considerations, one needs to consider if a solvent interacts with and affects the catalyst system, such as by displacement of ligands Some polymer end groups (eg, polystyryl halide) can undergo substitution or elimination in polar solvents at polymerization temperatures ATRP can be carried out in aqueous heterogeneous systems (suspension and emulsion) with proper choice of the components of the reaction system (initiator, activator, deactivator).

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The components need to be chosen so that they are stable in the presence of water and soluble in the organic phase with minimal solubility in the aqueous phase In addition to copper catalyst systems [Perrier and Haddleton, 2002], various Ru(II) and Fe(II) halide complexes with triphenylphosphine and cyclopentadienyl or indenyl ligands have been studied [Sawamoto and Kamigaito, 2002] Temperatures for ATRP are generally in the range 60 120 C, with some polymerizations proceeding at lower temperatures The polymerization rate increases with increased temperature because both kp and K ( ka =kd ) increase with increasing temperature K increases since the equilibrium process is endothermic in the forward direction (toward propagating radicals) For example, H 20:1 kJ mol 1 for styrene polymerization with RBr/CuBr ( S 22 J K 1 mol 1 ).

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The tendency toward a living polymerization is enhanced at higher temperature since Ep > Et and kp =kt increases with temperature However, an excessively high temperature is counterproductive because chain transfer increases with increasing temperature There is an optimum temperature for any speci c ATRP reaction system Temperature has other effects on ATRP, such as catalyst solubility, changes in catalyst structure, and changes in the equilibrium constant between dormant species and propagating radicals, which need to be considered Depending on the monomer, one needs to adjust the components of the system as well as reaction conditions so that radical concentrations are suf ciently low to effectively suppress normal termination The less reactive monomers, such as ethylene, vinyl chloride, and vinyl acetate, have not been polymerized by ATRP Acidic monomers such as acrylic acid are not polymerized because they interfere with the initiator by protonation of the ligands.

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The carboxylate salts of acidic monomers are polymerized without dif culty New ATRP initiators and catalysts together with modi cation of reaction conditions may broaden the range of polymerizable monomers in the future ATRP as discussed to this point is normal ATRP which uses RX and a transition metal in its lower oxidation state to establish the equilibrium between dormant and propagating species Reverse ATRP involves generating the same ATRP system by using a combination of a.

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