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Discuss the effect of ring size on the tendency of a cyclic monomer toward ringopening 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, S. Kobayashi, H. Ando, and R. Kawase, Macromolecules, 6, 26 (1973), have found that the polymerization rate for the BF3 polymerization of oxetane follows the equation:

b. The values of kp at 20 C are 0.18 and 0.019 L mol 1 s 1 , respectively, for polymerizations carried out in methylcyclohexane and methylene chloride. Explain why propagation is faster in the less polar solvent. c. The following rate constants and activation parameters for propagation were observed for oxetane and 3-methyloxetane: Oxetane kp at 20 C (L mol 1 s 1 ) Gz (kJ mol 1 ) p z Hp (kJ mol 1 ) z Sp (J mol 1 K 1 ) 0.019 71.2 57.4 50.7 3-Methyloxetane 0.11 65.7 65.3 5.4

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We have seen that for the matrix of weights, the ICs will all be bounded, but they do not necessarily redescend to 0. Observe, however, that as either or is equal to zero (for > 0), either (8.10) or (8.11) will be equal to 0. Hence, moving perpendicularly to the decision hyperplane, the IC will be redescending in either one direction or the other. We note, however, the arbitrary nature of this. If we take the MLP model (8.7) and set

Discuss why 3-methyloxetane is more reactive than oxetane. Is a negative entropy of activation for propagation consistent with the proposed propagation mechanism 7-6 The polymerization of an epoxide 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 BF3 even though epichlorohydrin is much less basic than tetrahydrofuran. b. The addition of small amounts of water to the polymerization of oxetane by BF3 increases the polymerization rate but decreases the degree of polymerization. An equilibrium polymerization is carried out with an initial concentration of 12.1 M tetrahydrofuran, M 2:0 10 3 M, and kp 1:3 10 2 L mol 1 s 1 . Calculate the initial polymerization rate if M c 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

Up to this point in the book, we have laid a foundation for mobility and have covered in detail the threats that BlackBerrys bring to the enterprise. The next part of the book deals with PDAs.

7-10 Consider the equilibrium polymerization of E-caprolactam initiated by water at 220 C. For the case where I 0 0:352, M 0 8:79 and M c 0:484, the degree of polymerization at equilibrium is 152, calculate the values of Ki and Kp at equilibrium. 7-11 Discuss by means of equations the occurrence of backbiting, ring-expansion reactions in the polymerizations of cyclic ethers, acetals, and amines. 7-12 E-Caprolactone is polymerized using aluminum isopropoxide as the initiator in THF at 25 C [A. Duda and S. Penczek, Macromolecules, 28, 5981 (1995)]. The initial monomer concentration is 1.47 mol L 1 ; the initial aluminum isopropoxide concentration is 1:63 10 4 mol L 1 . The reaction mixture is subjected to hydrolysis at the point where 100% conversion has been reached. The number-average degree of polymerization of the hydrolyzed polymer is 2:99 103 . Compare this value with the theoretical degree of polymerization.

Constitutional (formerly: structural) isomerism is encountered when polymers have the same overall chemical composition (i.e., same molecular formula) but differ in connectivity the order in which the atoms are connected to each other. Polyacetaldehyde, poly(ethylene oxide), and poly(vinyl alcohol) are constitutional isomers. The rst two polymers are

- (W0,WI) - 'v1,

Poly(ethylene oxide)

Poly(vinyl alcohol)

obtained from isomeric monomers, acetaldehyde and ethylene oxide. The third is obtained by hydrolysis of poly(vinyl acetate) since vinyl alcohol does not exist (it is the enol form of acetaldehyde). Poly(methyl methacrylate) and poly(ethyl acrylate) are isomeric polymers

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