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tually any physical system for which he could write down Hamilton's equations just by replacing the Poisson brackets by commutators multiplied by a certain constant. Here is how the analogy between Poisson brackets and commutators comes about. 5 The Poisson bracket of any two dynamical variables, U and v, in classical mechanics is defined by (2.1) where qn and Pn are any set of canonical coordinates and momenta that describe the system. In terms of Poisson brackets, the classical equation of motion of any dynamical variable 7} is given simply by



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The alternating copolymer of composition XXXV cannot be synthesized. However, it is possible to synthesize an alternating copolymer in which R00 R by using a two-stage process [Ueda, 1999]. In the rst stage, a diamine is reacted with an excess of diacid to form a trimer

i] =

2-193

(7},

1 2 3 4

The trimer is then reacted with an equimolar amount of a second diamine in the second stage:

(2.2)

2-194

where H is the Hamiltonian. From (2.1) it follows that Poisson brackets satisfy the identity (U, (v, w)) + (v, (w, u)) + (w, (u, v)) = 0 (2.3) and have the following properties:

Alternating copolymers with two different functional groups are similarly synthesized by using preformed reactants [Adduci and Amone, 1989; Gopal and Srinivasan, 1986; Liou and

(U, v) = -(v, u),





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Hsiao, 2001b; Mormann et al., 1989]. For example, polyamideurethanes analogous to XXXIV and XXXV are obtained by the polymerizations

(u, C) = 0,

OCN R CONH R OSi(CH3)3

2-195

(2.4)

2-196

(2.5)

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The silyl ether derivative of the alcohol is used in Eq. 2-195 since the corresponding alcohol OCN CONH 0 R R OH cannot be isolated because of the high degree of reactivity of isocyanate and alcohol groups toward each other.

(UI +U2,V) = (UI,v) +(U2,V),

2-13b-3

(2.6)

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There are two general methods for synthesizing block copolymers [Gaymans et al., 1989; Hadjichristidis, 2002; Hedrick et al., 1989; Klein et al., 1988; Leung and Koberstein, 1986; Reiss et al., 1985; Speckhard et al., 1986]. The two methods, referred to here as the one-prepolymer and two-prepolymer methods, are described below for block copolymers containing different functional groups in the two repeat units. They are equally applicable to block copolymers containing the same functional group in the two repeating units. The two-prepolymer method involves the separate synthesis of two different prepolymers, each containing appropriate end groups, followed by polymerization of the two prepolymers via reaction of their end groups. Consider the synthesis of a polyester-block-polyurethane. A hydroxy-terminated polyester prepolymer is synthesized from HO OH and HOOC R R0 COOH using an excess of the diol reactant. An isocyanate-terminated polyurethane R OH using an excess of the prepolymer is synthesized from OCN 00 R NCO and HO 000 diisocyanate reactant. The a,o-dihydroxypolyester and a,o-diisocyanatopolyurethane prepolymers, referred to as macrodiol and macrodiisocyanate respectively, are subsequently polymerized with each other to form the block copolymer.

(2.7)

2-197

Cu, VI + V2) = (U, vI) + (U, V2),

The block lengths n and m can be varied separately by adjusting the stoichiometric ratio r of reactants and conversion in each prepolymer synthesis. In typical systems the prepolymers have molecular weights in the range 500 6000. The molecular weight of the block copolymer is varied by adjusting r and conversion in the nal polymerization. A variation of the two-prepolymer method involves the use of a coupling agent to join the prepolymers. For example, a diacyl chloride could be used to join together two different macrodiols or two different macrodiamines or a macrodiol with a macrodiamine.

(UIU2, v)

The one-prepolymer method involves one of the above prepolymers with two small reactants. The macrodiol is reacted with a diol and diisocyanate

2-198

(U, VI V2) =

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