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PROBLEMS 5-1 Consider the following monomers and initiating systems: Initiating Systems (fCO2 )2 (CH3 )3 CCOOH Fe2 Na naphthalene H2 SO4 BF3 H2 O n-C4 H9 Li Monomers fCH CH2 CH2 CHCN CH2 C(CH3 )2 CH2 CH n-C4 H9 O Cl CH2 CH CH2 C(CH3 ) 2 CH3 CO CH2 O CF2 S
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What is the actual initiating species that initiates polymerization for each of the initiating systems Show equations. Which initiating system(s) can be used to polymerize each of the various monomers Explain. What general reaction conditions (e.g., temperature, solvent) are required for each polymerization 5-2 Isobutylene is polymerized under conditions where chain transfer to monomer is the predominant chain-breaking reaction. A 4.0-g sample of the polymer was found to decolorize 6.0 mL of an 0.01 M solution of bromine in carbon tetrachloride. Calculate the number-average molecular weight of the polyisobutylene. The rates of most reactions increase with increasing temperature. For certain polymerizations, the rate decreases with temperature. Under what different conditions can this type of behavior occur Explain. Consider step polymerizations as well as radical and ionic chain polymerization in answering this question. Consider the cationic polymerization of isobutylene using SnCl4 as the coinitiator and water as the initiator. Under certain reaction conditions, the polymerization rate was found to be rst-order in SnCl4 , rst-order in water, and second-order in isobutylene.
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The number-average molecular weight of the initially formed polymer is 20,000. A 1.00-g sample of the polymer contains 3:0 10 5 moles of OH groups; it does not contain chlorine. Show the reaction sequence of initiation, propagation, and termination steps for this polymerization and derive the appropriate expressions for the rate and degree of polymerization. Indicate clearly any assumptions made in the derivations. 5-5 Under what reaction conditions might a cationic polymerization with SnCl4 plus water show a dependence of the polymerization rate that is a. Zero-order in water or SnCl4 b. Second-order in water or SnCl4 c. First-order in monomer A monomer Z is polymerized in the presence of an initiating system Y. The following experimental observations are made: a. The degree of polymerization decreases as the reaction temperature increases. b. The degree of polymerization is affected by the solvent used. c. The degree of polymerization is rst-order in monomer concentration. d. The rate of polymerization increases as the reaction temperature increases. Is this polymerization proceeding by a step, radical chain, cationic chain, or anionic chain mechanism Discuss clearly how each experimental observation is consistent with your answer. 5-7 A 2.0 M solution of styrene in ethylene dichloride is polymerized at 25 C using 4:0 10 4 M sulfuric acid. Calculate the initial degree of polymerization. What would be the degree of polymerization if the monomer solution contains isopropylbenzene at a concentration of 8:0 10 5 M Use the following data as needed: kp 7:6 L mol 1 s 1 , ktr;M 1:2 10 1 L mol 1 s 1 , kts 4:9 10 2 s 1 , kt (combination) 6:7 10 3 s 1 , Cs 4:5 10 2 . What experimental approaches are available for determining whether the polymerization of a particular monomer by ionizing radiation proceeds by a radical or ionic mechanism The sodium naphthalene polymerization of methyl methacrylate is carried out in benzene and tetrahydrofuran solutions. Which solution will yield the highest polymerization rate Discuss the effect of solvent on the relative concentrations of the different types of propagating centers.
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5-10 Assume that 1:0 10 3 mol of sodium naphthalene is dissolved in tetrahydrofuran and then 2.0 mol of styrene is introduced into the system by a rapid injection technique. The nal total volume of the solution is 1 liter. Assume that the injection of styrene results in instantaneous homogeneous mixing. It is found that half of the monomer is polymerized in 2000 s. Calculate the propagation rate constant. Calculate the degree of polymerization at 2000 and at 4000 s of reaction time. 5-11 A 1.5 M solution of styrene in tetrahydrofuran is polymerized at 25 C by sodium naphthalene at a concentration of 3:2 10 5 M. Calculate the polymerization rate and degree of polymerization using appropriate data from Table 5-11. What fractions of the polymerization rate are due to free ions and ion pairs, respectively Repeat the calculations for 3:2 10 2 M sodium naphthalene.
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