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The rate constants for these reactions are orders of magnitude greater than those for the corresponding reactions of the diacid or diester reactants (Table 2-8) The use of such reactants in a novel low-temperature polymerization technique called interfacial polymerization has been extensively studied [Morgan and Kwolek, 1959a,b; Nikonov and Savinov, 1977] Temperatures in the range 0 50 C are usually employed Polymerization of two reactants is carried out at the interface between two liquid phases, each containing one of the reactants (Fig 2-11) Polyamidation is performed at room temperature by placing an aqueous solution of the diamine on top of an organic phase containing the acid chloride The reactants diffuse to and undergo polymerization at the interface The polymer product precipitates and is continuously withdrawn in the form of a continuous lm or lament if it has suf cient mechanical strength.



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(2.147) where H.c. stands for Hennitian conjugate. Substituting (2.146) and (2.147) in (2.133), we find the following expression for the Hamiltonian:





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Mechanically weak polymers that cannot be removed impede the transport of reactants to the reaction site and the polymerization rate decreases with time The polymerization rate is usually diffusion-controlled, since the rates of diffusion of reactants to the interface are slower than the rate of reaction of the two functional groups (This may not be the situation when reactions with small rate constants are employed) Interfacial polymerization is mechanistically different from the usual step polymerization in that the monomers diffusing to the interface will react only with polymer chain ends The reaction rates are so high that diacid chloride and diamine monomer molecules will react with the growing polymer chain ends before they can penetrate through the polymer lm to start the growth of new chains There is thus a strong tendency to produce highermolecular-weight polymer in the interfacial process compared to the usual processes.

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95 A Cayley On the application of quaternions to the theory of rotation Philosophical Magazine, 33: 196-200, February 1848 Online at http://homepipelineconV hbakerIlquaternioni 96 A Cayley On certain results relating to quaternions Philosophical Magazine, 26(3);141-145, February 1945 97 H B Chan, V A Aksyuk, R N Kleiman, D J Bishop, and F Capasso Quantum mechanical actuation of microelectromechanical systems by the casimir force Science, 291:1941-1944, March 9, 2001 98 K W Chan, C K Law, and J H Eberly Localized single-photon wave functions in free space Physical Review Letters, 88(10):100402, March 11,2002 99 K W Chan, C K Law, and J H Eberly Quantum entanglement in photon-atom scattering Physical Review A, 68(2):022110, August 2003 100 R R Chance, A Prock, and R Silbey Molecular fluorescence and energy transfer nearinterfaces Advances in Chemical Physics, 37: 1-65, 1978 101 K Chandrasekharan, editor Hennann Weyl Gesammelte Abhandlungen, volumes I-IV.

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Also, interfacial polymerization does not require overall bulk stoichiometry of the reactants in the two phases Stoichiometry automatically exists at the interface where polymerization proceeds There is always a supply of both reactants at the interface due to diffusion from the.

Springer-Verlag, Berlin, 1968 102 Y-J Cheng and A E Siegman Generalized radiation-field quantization method and the Petermann excess-noise factor Physical Review A, 68(4):043808, October2003 103 E S C Ching, P T Leung, A Maassen van den Brink, W M Suen, S S Tong, and K Young Quasinormal-mode expansion for waves in open systems Reviews of Modern Physics, 70(4):1545-1554, October 1998 104 J C K Chou Quaternion kinematic and dynamic differential equations IEEE Transactions on Robotics and Automation, 8:53-64, 1992 105 J C K Chou and M Kamel Finding the position and orientation of a sensor on a robot manipulator using quaternions International Journal of Robotics Research,10:240-253,1991 106 S Clark The Only Fools and Horses Story BBC, London, 1998 For more on this other del, see http://wwwcomedyzonebeebcomlofah 107 M H Cohen, L M Falicov, and J C Phillips Superconductive tunneling Physical Review Letters, 8(8):316-318, April 15, 1962.

Fig. 2-11 Interfacial polymerization; removal of polymer lm from the interface. From Morgan and Kwolek [1959 a,b] (by permission of Division of Chemical Education, American Chemical Society, Washington, DC and Wiley-Interscience, New York); an original photgraph, from which this gure was drawn, was kindly supplied by Dr. P. W. Morgan.

108 C Cohen-Tannoudji, J Dupont-Roc, and G Grynberg Photons and Atoms: Introduction to Quantum Electrodynamics Wiley-Interscience, New York, 1989 109 M J Collett and C W Gardiner Squeezing of intracavity and traveling-wave light fields produced in parametric amplification Physical Review A, 30(3): 13861391, September 1984..

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