PROBLEMS 1-2 1-3 1-4 15 1-6 Show by equations the overall chemical reactions involved in the synthesis of polymers from a, CH;=CH=CO.H bs [] ec. HN—(CH;s-NH, + CICO—(CH,—COCI d. HO—(CH,),—CO;H a Ope 4 HO-CHjCH)-OH NCO ‘What is the structure of the repeating unit in each of the polymers in Problem 1-12 Can any other monomer(s) be used 10 obtain the same polymer structure for any of these polymer? Classify the polymers as to whether they are condensation or addition polymers. Classify the polymerizations as to whether they are step, chain, or ring-opening polymerizations. How would you experimentally determine whether the polymerization of an unknown monomer X was proceeding by a step or a chain mechanism? Name each of the polymers in Problem 1-1 by the IUPAC system. Indicate alternate names where applicable based on the polymer source, non-IUPAC structure system, or trade names. Name each of the following polymers by the IUPAC system a bocHt, CH,COOCH;1-7 A sample of polystyrene is composed of a series of fractions of different-sized molecules: Fraction Weight Fraction 0.10 o.19 O24 O18 O11 0.08 0.06 oo roamone> Molecular Weight 12,000 21,000 35,000 49,000 73,000 102,000, 122,000 146,000 ‘Calculate the number-average and weight-average molecular weights of this polymer sample. Draw a molecular weight distribution curve analogous to Fig. 1-4. 1-8 Indicate how the extent of polymer crystallinity is affected by chemical structure. 1-9 Define Tw and 7, and indicate how they are affected by chemical structure 1-10 Describe the differences in the properties and uses of flexible plastics, rigid plastics, fibers, and elastomers. What types of chemical structures are typical of each?PROBLEMS 2-1 Derive an expression for the rate of polymerization of stoichiometric amounts of adipic acid and hexamethylene diamine. Indicate the assumptions inherent in the derivation. Derive an expression for the rate of polymerization of nonstoichiometric amounts of the two reactants. 2-2 A 21.3-g sample of poly(hexamethylene adipamide) is found to contain 2.50 x 10-7 mol of carboxyl groups by both titration with base and infrared spectroscopy. From these data the polymer is calculated to have a number-average molecular weight of 8520. What assumption is made in the calculation? How can one experimentally obtain the correct value of Hf,? 2-3. Describe and draw the structure of the polyester obtained in each of the following polymerizations: a. HO.C-R—CO.H + HO-R'-OH b. HOC-R-COM + HO-R"—OH OH © HOC-R-COWH + HO-R"—GH + HO-R’—OH oH Will the structure of the polymer produced in each case depend on the relative amounts of the reactants? If so, describe the differences. 2-4 Describe and draw the structure of the polyester obtained in each of the following polymerizations: @ HO-R-COLH b. HO-R—-CO.H + HO-R’-OH ¢, HOTR-COsH + HO-R’—OH OH @ HO-R-CO.H + HO-R'-OH + HO-R"—OH OH Will the structure of the polymer produced in each of cases b, c, and d depend on the relative amounts of the reactants? If so, describe the differences. 2-5 Compare the molecular weight distributions that are expected for the polymerizations in Problems 2-34, 24a, 2-4b, and 2-4¢.27 28 29 2-10 2 2-13 Discuss the possibility of cyclization in the polymerization @ N(CH), — COH b. HO-(CH;)—OH + HO,C—(CHy),,-COH for the cases where m has values from ? to 10? At what stage(s) in the reaction is cyclization possible? What factors determine whether cyclization or linear polymer- ization is the predominant reaction? Show that the time required to go from p = 0.98 to p = 0.99 is very close to the time to reach p = 0.98 from the start of polymerization for the extemal acid-catalyzed polymerization of an equimolar mixture of a diol and diacid, The polymerization between equimolar amounts of a diol and diacid proceeds with an equilibrium constant of 200. What will be the expected degree of polymerization and extent of reaction if the reaction is carried out in a closed system without removal of the by-product water? To what level must [H,0] be lowered in order to obtain a degree of polymerization of 200 if the initial concentration of carboyxl groups is 2M? A heat-resistant polymer Nomex has a number-average molecular weight of 24.116. Hydrolysis of the polymer yields 39.31% by weight maminoaniline, 59.81% terephthalic acid, and 0.88% benzoic acid, Write the formula for this polymer. Calculate the degree of polymerization and the extent of reaction. Calculate the effect on the degree of polymerization if the polymerization had been carried out with twice the amount of benzoic acid. Calculate the number-average degree of polymerization of an equimolar mixture of adipic acid and hexamethylene diamine for extents of reaction 0.500, 0.800, 0.900, 0.950, 0.970, 0.990, 0.995. Calculate the feed ratio of adipic acid and hexamethylene diamine that should be employed to obtain a polyamide of approximately 15,000 molecular weight at 99.5% conversion. What is the identity of the end groups of this product? Do the same calculation for a 19,000-molecular-weight polymer. What proportion of beazoic acid should be used with an equimolar mixture of adipic acid and hexamethylene dianiine to produce a polymer of 10,000 molecular weight at 99.5% conversion?Do the same calculation fer 19,000 and 28,000 molecular weight products, Calculate the extent of reaction at which gelation occurs for the following mixtures: a. Phthalic anhydride and glycerol in stoichiometric amounts, b. Phthalic anhydride and glycerol in the molar ratio 1.500: 0.980 ¢. Phthalic anhydride, glycerol, and ethylene glycol in the molar ratio 1.500 : 0.990 = 0.002 d Phthalic anhydride, glycerol, and ethylene glycol in the molar ratio 1.500 : 0.500: 0.700 ‘Compare the gel points calculated from the Carothers equation (and its modifications) with those using the statistical approach. Describe the effect of unequal functional groups reactivity (¢.g., for the hydroxyl groups in glycerol) on the extent of reaction at the gel point.2-14 2-15 2-16 2-17 2-18 2-19 Show by equations the polymerization of melamine and formaldehyde to form a crosslinked structure, Describe by means of equations how random and block copolymers having the following compositions could be synthesized: a. -tc0-ensf co— (Cn hb foo Q)-co-- 10ers - 0,-1.0} A How would you synthesize a block copolymer having segments of the following structures? -CH.CH;CH:— 0 and O-CHsCH, —OCONH: NHCO Distinguish between spiro, laddet. and semiladder polymers. Give examples of each. Describe the difference between the convergent and divergent approaches to synthe- sizing dendrimers. For each of the following reactions system indicate whether the product is a linear, branched, crosslinked, or hyperbranched polymer. a. As + By b. AB, ce AB, id As +By e. AB) +B; f. AB+B,;PROBLEMS #1 32 3-3 35 When one considers the various polymers produced from carbon-carbon double bond monomers, the following generalizations are apparent: a. The polymers are produced almost exclusively from ethylene, monomers that have one substituent on the double bond, or monomers that have two substituents on the same carbon atom of the double bond. Monomers containing one substituent on each carbon of the double bond seldom polymerize. b. Most of the chain polymerizations are carried out by radical initiation; relatively few are produced by ionic initiation, Why? Are there good reasons for these generalizations or are they simply a matter of chance? Discuss. Show by chemical equations the polymerization of acrylonitrile initiated by the thermal decomposition of cumy! hydroperoxide: Using “C-labeled AIBN as an initiator, a sample of styrene is polymerized to an number-average degree of polymerization of 1.52 x 10*, The AIBN bas an activity of 9.81 x 107 counts min~! mot”! in a scintillation counter. If 3.22 g of the polystyrene has an activity of 203 counts min”', what is the mode of termination? Poly(vinyl acetate) of number-average molecular weight 100,000 is hydrolyzed to poly(vinyl alcohol). Oxidation of the latter with periodic acid to cleave 1,2-diol linkages yields a poly(vinyl alcohol) with KX, = 200, Calculate the percentages of head-to-tail and head-to-head linkages in the poly(vinyl acetate). ‘The benzoyl peroxide-initiated polymerization of a monomer follows the simplest Kinetic scheme, that is, 2, = ky[M](f&yIl] [Ke )? with all tate constants and f being independent of conversion. For a polymerization system with [Mj], = 2M and [1], = 10°? M, the limiting conversion px. is 10%. To increase: px to 20%: a. Would you increase or decrease (MJ) and by what factor? b. Would you increase or decrease [I], and by what factor? How would the rate and degree of polymerization be affected by the proposed changes in {I],? e. Would you increase or decrease the reaction temperature for the case of thermal initiated polymerization? For the case of photopolymerization (assuming that an increase in temperature does not cause thermal decomposition of initiator)? Eq, E,, and E, ate 124, 32, and 8 kJ mol He respectively. For a radical polymerization with bimolecular termination, the polymer produced contains 1.30 initiator fragments per polymer molecule. Calculate the relative extents of termination by disproportionation and coupling. assuming that no chain-transfer feactions occur.37 38 ao 3-10 el 3-12 313 A solution 0.20 M in monomer and 4.0 x 10°3.M in a peroxide initiator is heated at 60°C. How long will it take to achieve 50% conversion? k, = 145 L mol! s~t, =7.0x 10" L mols!) ¢ = 1. and the initiator half-life is 44h. Show that a plot of the fraction of monomer polymerized versus time # yields a straight line for ¢ > t, and that the extension of this line cuts the time axis at ¢ =, Ln 2 Hine: Use [Me] = [Me], tanh (1/1,) as a starting point and assume low conversion. ‘The following data were obtained in the thermal initiated bulk polymerization of monomer Z ([M] = 8.3 M) using radical initiator W at 60°C: R, x10 (mol Ls Xa 0.0050 8350 0.010 5550 0.020 3330 0.050 1317 0.10 592 O15 358 Calculate Cy, hy/hi!", and Ry in this polymerization if it is experimentally observed that fp = 4.0 x 10-*{1}'". Le chain transfer to initiator important? If it is, describe how to calculate C, Consider the polymerization of styrene initiated by di-t-butyl peroxide at 60°C. For a solution of 0.01 M peroxide and 1.0 Mf styrene in benzene, the initial rates of initiation and polymerization are 4.0 x 10°‘! and 1.5% 10°? mol L' s'', respectively. Calculate the values of (fk,), the initial kinetic chain length, and the initial degree of polymerization. Indicate how often on the average chain wansfer occurs per each initiating radical from the peroxide. What is the breadth of the molecular weight distribution that is expected. that is, what is the value of X,,/X,? Use the following chain-transfer constants: Car = 8.0 x 10% G=32x10+ Cp = 1.9 x 10-4 Cs 23x10" For a particular application the molecular weight of the polystyrene obtained in Problem 3-10 is too high. What concentration of 1-butyl mercaptan should be used to lower the molecular weight to 85,000? What will be the polymerization rate for the reaction in the presence of the mercaptan? Consider the polymerization reaction in Problem 3-10, Aside from increasing the monomer concentration, what means are available for increasing the polymerization rate? Compare the alternate possibilities with respect to any changes that are expected in the molecular weight of the product. Show by chemical equations the reactions involved in chain tansfer by hexane, ‘benzene, isopropylbenzene, propanol, butyl iodide, carbon tetrabromide. n-butyl3-14 315 3-16 17 mercaptan, and di-n-butyl sulfide. Compare and discuss the differences in the transfer constants of these agents for vinyl acetate polymerization (Table 3-7). ‘The polymerization of methyl acrylate (one molar in benzene) is carried out using a photosensitizer and 3130 A light from a filtered mercury arc lamp. Light is absorbed by the system at the rate of 1.0 x 10° erg L~' s~!. Assuming that the quantum yield for radical production in this system is 0.50, caleulate the rates of initiation and polymerization. Consider the bulk polymerization of neat styrene by ultraviolet irradiation. The initi polymerization rate and degree of polymerization are 1.0 x 10°* mol L~! 5”! and 200, respectively, at 27°C. What will be the corresponding values for polymerization at TPC? ‘The same initial polymerization rate and degree of polymerization as in Problem 3-15 are obtained at 27°C for a particular AIBN thermal-initiated polymerization of styrene. Caleulate the R,, and X,, values at 77°C. A radical chain polymerization following R, conversions for specified initial monomer and times: [M]k Rul] ky)!" shows the indicated iator concentrations and reaction Temperature IM] [|x 10° Reaction Time Conversion Experiment (Cy mol L~' mol L~! (min) (%) 1 oO 1.00 25 500 50 2 80 oso Lo 700 75 3 60 O.80 Lo 600 40 4 60 0.25 10.0 ? 50 3-18 319 3-20 Calculate the reaction time for $0% conversion in experiment 4. Calculate the overall activation energy for the rate of polymerization. Calculate the equilibrium monomer concentration [M], for radical polymerization of 1,3-butadiene at 27°C, assuming that AH" and AS° are given by the values in Table 3-14. Repeat the calculations for 77°C and 127°C. Most radical chain polymerizations show one-half-order dependence of the poly- merization rate on the initiation rate R; (or the initiator concentration [I]}. Deseribe and explain under what reaction conditions [i.c., what type(s) of initiation and/or termina- tion] radical chain polymerizations will show the following dependencies: a. First-order b. Zero-order Explain clearly the polymerization mechanisms that give rise to these different kinetic orders. What is the order of dependence of Rp on monomer concentration in each of these cases. Derive the appropriate kinetic expressions for R, for at least one case Where R, is first-order in [I] and one where &,, is zero-order in (I]. ‘What is the breadth of the size disiribution to be expected for a low conversion polymerization where termination is entirely by coupling. Discuss the manner in which each of the following situations alters the size distribution:3-21 3-22 3-23 3-24 3-25 a. Chain transfer to n-butyl mereaptan b. High conversion. ¢. Chain transfer to polymer d. Autoacceleration For those situations where there is a tendency toward a broadening of the size distribution, discuss the possible process conditions that may be used to decrease this tendency. ‘Calculate the rate and degree of polymerization of methyl methacrylate initiated by AIBN at 50°C at 2500 atm relative to the corresponding quantities at 1 atm if AVg — 19.0 em’ mol~! and AV] = 3.8 em’ mol!. ATRP of 5.0.M styrene is carried out at 110°C using 1-phenylethyl bromide (0.050 Mf) and CuBr (0.050 M) in the presence of 4.4’-di(3-nonyl)-2,2’-bipyridine (0.10 M). The number-average molecular weight at 72% conversion is 7150. Compare the observed molecular weight to the theoretical value expected for this polymerization. ‘The living character of LRP is limited under certain conditions, such as high monomer conversion, high initister concentration, and high targeted molecular weight (100,000). Explain why these conditions result in broadening of PDI and some difficulty in producing block copolymers with well-defined block lengths of the different monomers. Describe how NMP is used to synthesize a block copolymer of styrene and 4-vinylpyridine. Describe how ATRP is used to graft styrene onto a vinyl chloride—vinylchlomacetate copolymer.PROBLEMS S-1 §-2 5-3 5-4 Consider the following monomers and initiating systems: Initiating Systems (CO) (CHs);CCOOH + Fe?* Na + naphthalene H,SO4 BF; + H,0 a-CyHgLi 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? 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 polyisoburylene. The rates of most reactions increase with increasing temperature. For certain poly- meri; ns, 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 SnCl, as the coinitiator and water as the initiator. Under certain reaction conditions, the polymerization rate was found to be first-order in SaCl,. first-order in water, and second-order in isobutylene.5-7 The number-average molecular weight of the initially formed polymer is 20,000. A 1.00-g sample of the polymer contains 3.0 x 10 moles of OH groups: it does not contain chlorine. Show the reaction sequence of initiation, propagation, and termina- tion steps for this polymerization and derive the appropriate expressions for the rate and degree of polymerization. Indicate clearly any assumptions made in the derivations. Under what reaction conditions might a cationic polymerization with Sal, plus water show a dependence of the polymerization rate that is a. Zero-order in water or SaCly b, Second-order in water or SnCly 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. e. The degree of polymerization is first-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. A 2.0 Mf solution of styrene in ethylene dichloride is polymerized at 25°C using 4.0 x 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 x 105 M? Use the following data as needed: ky = 7.6 L mol”! so kag = 1.2% 10°! L mol! sk, =4.9 x 0? s-!, &, (combination) = 6.7 x lo? sc, =45x« 107. ‘What experimental approaches are available for determining whether the polymeriza- tion 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 poly- merization rate? Discuss the effect of solvent on the relative concentrations of the different types of propagating centers. 5-10 Assume that 1.0 x 10-* 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 final total volume of the solution is | 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. S-11 A 1.5 M solution of styrene in tetrahydrofuran is polymerized at 25°C by sodium naphthalene at a concentration of 3.2 x 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°? M sodium naphthalene.5-12 Consider propagation by polystyryl sodium ion pairs in a 1 M styrene solution in tetrahydrofuran. For an ion pair concentration of 2.0 x 10°? M, caleulate the relative contributions of contact and solvent-separated ion pairs to the propagation process. Use appropriate data from Table 5-12. 5-13 Show by equations the synthesis of the following types of block copolymers a. ABA b. CABAC where A, B, and C represent styrene, butadiene, and isoprene, respectively.PROBLEMS 6-1 6-2 6-3 6-5 6-6 Discuss the differences in the structures of random, alternating, graft, and block copolymers, What is the difference between the ideal and alternating behaviors in copolymerization? Consider the following monomer reactivity ratios for the copolymerization of various pairs of monomers: Case rn n 1 ot 02 2 Oo. 10 3 ol 3 4 a 03 5 0 0 6 as 2 7 1 15 What is the composition of the copolymer that would be formed at low conversion from equimolar mixtures of the two monomers in each case? Using the 7; and rs values from Table 6-2, construct plots showing the initial copolymer composition as a function of the comonomer feed composition for the radical copolymerizations of methyl acrylate-methyl methacrylate and styrene—maleic anhydride. Are these examples of ideal or alternating copolymerization? Calculate the Composition of the initial terpolymer that would be produced from the radical polymerization of a solution containing acrylonitrile, styrene, and 1,3-butadiene in mole fractions of 0.47, 0.47, and 0.06, respectively. Ferrocenylmethyl acrylate (FMA) and 2-ferrocenylethyl acrylate (FEA) have been synthesized and copolymerized with styrene, methyl acrylate. and vinyl acetate (C. U. Pittman, Jr., Macrmotecules, 4, 298 (1971)]. The following monomer reactivity ratios were found:6-7 M, Mz A rn FEA Styrene oat 1.06 FEA Methyl acrylate 0.76 0.69 FEA Vinyl acetate 34 0.074 FMA Styrene ame 23 FMA Methyl acrylate Olt 44 FMA Vinyl acetate 14 0.46 a. Predict whether FEA ot FMA will have the higher &, in homopolymerization. Explain the basis of your prediction. How can the difference in ky values be explained in relation to the structures of FEA and FMA? b, Which of the comonomer pairs above could lead to azeotropic copolymerization? c. Is styrene monomer a more or less reactive monomer than FMA monomer toward the FMA propagating center? By what factor? d. List styrene, methyl acrylate, and vinyl acetate in order of increasing reactivity toward the FEA propagating center. Is the trend in reactivity toward the FMA propagating center the same? ¢. List the styrene, methyl acrylate, and vinyl acetate propagating centers in order of increasing reactivity toward FEA monomer. f. Are the copolymerization data above indicative of radical, cationic, or anionic copolymerization? Explain. Consider the radical copolymerization of a benzene solution that is 1.5 M in styrene and 3.0 M in methyl acrylate. a, What is the initial copolymer composition if the polymerization is curried out at 60°C using benzoyl peroxide at a concentration of 5.0 x 10' M? How is the copolymer composition affected if 3.0 x 10° M benzoyl peroxide is used? b, How will the presence of 5.0 x 10° M a-butyl mercaptan affect the initial copely- mer composition? ©. What would you expect (qualitatively) for the copolymer composition if the reaction were initiuted by n-butyllithium? by BF; plus water? List the following monomers in order of their increasing tendency toward altemation with 1,3-butadiene in radical copolymerization: a. m-Butyl vinyl ether b, Methyl methacrylate c. Methyl acrylate d. Styrene . Maleie anhydride f. Vinyl acetate g. Acrylonitrile Explain the relative alternating tendencies in these copolymerizations.69 10 Gil 612 6-13 6-14 6-15 If the copolymerizations in Problema 6-8 were carried out using cationic initiation, what would be expécted qualitatively for the copolymer compositions? List the copolymers in order of their increasing 1.3-butadiene content, Would copolymers be formed from each of the comonomer pairs? Explain. What would be observed if one used anionic ation’? Using the @ and ¢ values in Table 6-7, calculate the monomer reactivity ratios for the comonomer pairs styrene—1,3-butadiene and styrene—methyl methacrylate, Compare the results with the ri and m values in Table 6.2. Discuss the general effects of temperature, solvent, and catalyst on the monomer reactivity ratios in ionic copolymerizations. How do these compare with the corre- sponding effects in radical copolymerizations? ‘What are the differences between the two treatments (kinetic penultimate effect and depropagation) used to account for the deviations observed in the capalymer composi- tion equation? Discuss quatitatively the course of the radical copolymerization of each of the following comonomer pairs in terms of the degree of reaction at which gelation would be expected to occur: a. Styrene—divinylbenzene b. Methyl methactylate—allyl methacrylate Vinyl acetate-ethylene glycol dimethacrylate a. Methyl methacrylate~diviny! adipate e. Styrene—1.3-butadiene The product obtained in the polymerization of 4-methyl-1,6-heptadiene contains no residual unsaturation. What is its chemical structure? Calculate the monomer reactivity ratios for chloroprene-2-vinylpyridine using the data from Table 6-8 for the “patterns of reactivity” scheme.PROBLEMS 7-1 7-2 13 7-4 Consider the following initiators and monomers: Initiator Monomer Grubbs initiator Propylene oxide r-Buty! lithium -Caprolactam bpyNitCODy Cyclooctene BF, + 1,0 Oxacyclobutane H;SO, &Valerolactone NaOCoHs NCA 1:0 1.5-Hexadiene Octamethylcyclotetrasiloxane Propylene sulfide Trioxane Which initiator(s) can be used to polymerize each of the monomers? For each monomer, give the structure of the polymer product. Give the cyclic monomer(s), initiator, and reaction conditions necessary tw synthesize each of the following polymers: a, -PNHCOICH,)y F. NH-CH-CO a ENTE Ot, CoH é N= CH)CH)CHs HOO dP 01CH)),0CH, ck e. -PCHSCHICH,) t f PSHCH:)0-f Discuss the effect of ring size on the tendency of a cyclic monomer toward ring- opening polymerization Anionic polymerization of propylene oxide is usually limited to producing a relatively low-molecular-weight polymer. Discuss the reasons for this occurrence. T. Saegusa, H. Fujii, §. Kobayashi, H. Ando, and R. Kawase, Macromolecules, 6, 26 (1973). have found that the polymerization rate for the BF polymerization of oxetane follows the equation: =a tp = sips a, Describe by an equation the mechanism for the propagation step in this polymer ization.1 TB 7-10 TLL 712 b, The values of &;, at —20°C are 0.18 and 0.019 L mol! s-!, respectively, for polymerizations carried out in methyleyclohexane and methylene chloride. Explain why propagation is faster in the less polar solvent. ©. The following rate constants and activation parameters for propagation were observed for oxetane and 3-methyloxetane: Oxetane —_-3-Methyloxetane ky at (L mol oo19 oul AG} (kd mol") m2 65.7 AH} (kd mol~!) S74 65.3 As. mol! K!) 50.7 54 Discuss why 3-methyloxetane is more reactive than oxetane. Is a negative entropy of activation for propagation consistent with the proposed propagation mechanism’? ‘The polymerization of an epaxide by hydroxide or alkoxide ion is often carried out in the presence of an alcohol. Why? How is the degree of polymerization affected by alcohol? Discuss how the presence of alcohol affects both the polymerization rate and molecular weight distribution. Explain the following observations: a. A small amount of epichlorohydrin greatly increases the rate of the polymerization of tetrahydrofuran by BF; even though epichlorohydrin is much less basic than tetrahydrofuran, b. The addition of small amounts of water to the polymerization of oxetane by BF; increases the polymerization rate but decreases the degree of polymerization. An equilibrium polymerization is carried out with an initial concentration of 12.1 Af tetrahydrofuran, [M"] = 2.0 x 107° M, and A, = 1.3 x 10°? L mol”! s7!. Calculate the initial polymerization rate if (MJ, = 1.5 M. What is the polymerization rate at 20% conversion? What are the roles of an acylating agent and activated monomer in the anionic polymerization of lactams? Consider the equilibrium polymerization of €-caprolactam initiated by water at 220°C. For the case where [I], =0.352, [M], = 8.79 and [M],=0.484, the degree of polymerization at equilibrium is 152, calculate the values of Kj and Ki, at equilibrium. Discuss by means of equations the occurrence of backbiting, ring-expansion reactions in the polymerizations of cyclic ethers, acetals. and amines. €-Caprolactone is polymerized using aluminum isopropoxide as the initiator in THF at 25°C [A. Duda and 8. Penczek, Macromolecules, 28, 5981 (1995)]. The initial monomer concentration is 1.47 mol L~; the initial aluminum isopropoxide concentra- tion is 1.63 x 10 mol L~!. The reaction mixture is subjected to hydrolysis at the point where 100% conversion has heen reached. The number-average degree of polymerization of the hydrolyzed polymer is 2.99 x 10°. Compare this value with the theoretical degree of polymerization.LEMS 8-1 Show by structural drawings the various (if any} stereoregular polymers that might possibly we obtained from each of the monomers. a. CH= CH-CH, 726 STEREOCHEMISTRY OF POLYMERIZATION b CECH ech cH ad CHECICH CH Cu-CHy Cy —CH=cH-c.oH) SCH, a 1, ‘ kK Gb-cr=crcHscH—cH, 4 HNIC, NI, + HOCH, COST 2. AN. = ccc ou cu.— ciency, e cH-cHO (emy:co Peer ct comects «8 Name the various polymer structures using the nomenclature described in this chapter. $2 What ae the mechanisms for syndiotactic and isotactic placements ia propene polymerization? Desceibe the reaction conditions that favor each type of steseoselective placement. 3° Discuss the use of homogencous versus heterogeneous reaction conditions for the caocdination and traditional Ziegler—Natta polymerizations of propene, isoprene, styrene. methyl methacrylate. and a-butyl vinyl ether 8-4 What reaction conditions determine the relative amounts of 1.2-,eis 1,4-, and trans 14- polymerization in the radical and anionic polymerizations oF 1,3-butadiene? Indicatethe effect of solvent and counterion in these polymerizations. What polymer structures are obtained using traditional Ziegler—Natta and metallocene initiators? &-5 Which of the stereoregular polymer structures in question 8-1 are capable of exhibiting optical activity? How would you synthesize optically active polymers of these structures? Explain the inability of certain stereoregular polymers to exhibit optical activity. $6 The polymerization cis-I-d-propene by traditional Ziegler-Natta initiators in hydro- carbon solvents yields the erythrodiisotactic structure, while under similar salvent conditions anionic polymerization of cis-B-d-methyl acrylate yields the threodiisotactic polymer. Explain the factor(s) responsible for this difference. $7 The polymerization of optically pure propylene oxide by FeCl;-clerived initiators yields an optically active polymer. E, J. Vandenberg (J. Polym. Sci.. A-M(7), 525 (1969) attempted to gain insight into the mechanism by polymerizing the 2.3-cpoxybutanes. ‘The optically active trans-2.3-epoxybutane was polymerized to an optically inactive crystalline polymer. Evaluate this result and discuss its implications on the propagation mechanism for propylene oxide polymerization. 8-8 Briefly explain each of the following: a. There is only one disyndiotactic structure for —-CHRCHR’}-, whereas there are erythro- and threodiisotactic structures. b. Addition of alursinura trialky! to a traditional Ziegler-Natta polymerization system (e-g.. BeTiCls, propene) increases the polymerization rate up to a maximum after which &,, either remains constant or decreases. ¢. Hydrogen lowers the molecular weight of polyethylene and polypropene synthe- sized using traditional ZieglerNatta and metallocene initiators 4d. Low temperatures enhance syndioselective polymerization. Metal-polymer bonds are sometimes found in polymers: synthesized using tradi- tional Ziegler-Natta and metallocene initiators. &9 SC NMR analysis of polypropene sample A showed (im) = 0.78, (r) = 0.22, (um) = 0.62, (mr) = 0.33, (rr) = 0.05, (mmm) = 0.44, (mmr) = 0.27, (nmr) = 0.06, (ron) = 0.04, (rm) = 0.13, (rrr) = 0.01. Polypropene sample B showed (in) = 0.80, (r) = 0.20, (mm) = 0.71, (nr) = 0.19, (rr) = 0.10. What type of propagation mechanism (Bernoulli, first-order Markov, catalyst site control) is indicated for the syothesis of samples A and B? 8-10 Methyl methacrylate polymerization was carried out using rac-C2Hi(Ind)s2fMez with C(CoHs))B(C,F)s in the presence of triisobutylaluminum at 0°C [H. Deng, T. Shiono, and K. Soga, Marcomolecules, 28, 3067 (1995)]. ®C NMR of the polymer showed the pentad structure (unm) = 0.869, (mmmr) = 0.0155, (rauar) = 0.0014, (mma) = 0.0008, (rnin) = 0.0027, (mmr) = 0.0177, (rmrr) = 0.0165, (mrnn} = 0.0089, (rrvm) = 0.0165, (rer) = 0.0510. Show by analysis of the steceoerrars whether polymerization occured by chain end control or catalyst site control. $-11 Consider each of the following metallocene initiators: a. CoHa(CphZrClyb. rac-MesSi(Hylnd);ZrCl c. meso-Me1Si{Hslnd}221Cl2 d. Me.C(Cp)(luj2rCl, ©. Mc2Si(3-isopropyl-Cp)(Flujérz For cach initiator, indicate the (1) type of symmetry, (2) symmetry elements, and (3) stereochemistry of polymer produced.