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1-4 MOLECULAR WEIGHT The molecular weight of a polymer is of prime importance in the polymer s synthesis and application. Chemists usually use the term molecular weight to describe the size of a molecule. The more accurate term is molar mass, usually in units of g mol 1 . The term molecular 1 weight is the ratio of the average mass per formula unit of a substance to 12th of the mass of 12 an atom of C and is dimensionless (IUPAC, 1991, in press). This text will use molecular weight throughout irrespective of the units, because molecular weight is the more familiar term for most chemists. The interesting and useful mechanical properties that are uniquely associated with polymeric materials are a consequence of their high molecular weight. Most important mechanical properties depend on and vary considerably with molecular weight as seen in Fig. 1-3. There is a minimum polymer molecular weight (A), usually a thousand or so, to produce any signi cant mechanical strength at all. Above A, strength increases rapidly with molecular weight until a critical point (B) is reached. Mechanical strength increases more slowly above B and eventually reaches a limiting value (C). The critical point B generally corresponds to the minimum molecular weight for a polymer to begin to exhibit suf cient strength to be useful. Most practical applications of polymers require higher molecular weights to obtain higher strengths. The minimum useful molecular weight (B), usually in the range 5000 10,000, differs for different polymers. The plot in Fig. 1-3 generally shifts to the right as the magnitude of the intermolecular forces decreases. Polymer chains with stronger

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The stability of credit customs in Mesopotamia over thousands of years has been mentioned Evolution, development, and great change there must have been, especially considering the long history of wars, destruction, invasion, and conquest And yet in broad outline the financial usages of the year 1800 BC and earlier still seemed to be current in the sixth century BC After 600 BC there grew up a more advanced form of banking practice in private hands For example, the Egibi Sons and the Murassu, merchant bankers of Babylon, carried on large and complicated businesses, lending large sums to governments and to individuals, transferring deposits on order from one merchant to another, paying interest on deposits, buying loans on land, and entering business ventures as partners The use of modern terminology, however, must not suggest a picture of modern finance in Babylonia.

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There are two possible points of attachment on monosubstituted (X H) or 1,1-disubstituted monomers for a propagating radical on either carbon 1

3-8

FIGURE 2-1: Suminagashi by Ghazala, 2002

or carbon 2:

An absolute Oriental monarch ruled as a god It is sufficient to note that by 600 BC Neo-Babylonian finance was at least as far ahead of the primitive as twentieth-century finance is ahead of the Neo-Babylonian The history of Assyria long antedates the period when Assyria ruled over Babylonia Assyrian dynasties are known as early as 2000 BC, but the nation s rise to empire came much later Financial usage in Assyria did not differ greatly from financial usage in Babylonia However, credit transactions appeared less frequently and were more primitive Assyrian loans were scarcely ever granted without real security in the form of a substantial pawn Collateral changed hands at the granting of a loan rather than at default, as in Babylonia Loans free of interest for a short term were frequent in Assyria, but with heavy penalties for default.

3-9

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If each successive addition of monomer molecules to the propagating radical occurs in the same manner as Eq. 3-9 or Eq. 3-8, the nal polymer product will have an arrangement of monomer units in which the substituents are on alternate carbon atoms:

Interest rates were probably higher in Assyria than in Babylonia We do not know of formal legal limits for interest in Assyria, but customary rates were recognized There, too, the temples loaned money As in Babylonia, wives, slaves, and children could be given as pledge for a.

This type of arrangement (III) is usually referred to as a head-to-tail (H-T) or 1,3-placement of monomer units. An inversion of this mode of addition by the polymer chain propagating alternately via Eqs. 3-9 and 3-8 would lead to a polymer structure with a 1,2-placement of substituents at one or more places in the nal polymer chain. 1,2-Placement is usually referred to as head-to-head (H-H) placement.

The head-to-tail placement would be expected to be overwhelmingly predominant, since successive propagations by Eq. 3-9 are favored on both steric and resonance grounds. The propagating radical (radical II) formed by attachment of a radical at carbon 2 is the more stable one. Radical II can be stabilized by the resonance effects of the X and Y substituents. The substituents cannot stabilize radical I, since they are not attached to the carbon bearing the unpaired electron. Further, the approach (and subsequent attachment) of a propagating radical at the unsubstituted carbon (carbon 2) of a monomer molecule is much less sterically hindered compared to the approach at the substituted carbon (carbon 1). A propagation proceeding with predominantly H-T placement is a regioselective process, that is, one orientation (H T) is favored over another (H H). The term isoregic has been used to indicate a polymer structure with exclusive head-to-tail placements. The terms syndioregic and aregic would be used for polymer structures with alternating and random arrangements, respectively, of H T and H H placements.

This art was held supreme by the Japanese people, the paper so valued that gold flakes were integrated into the material and only the highest poetry was penned upon it, the script following the surreal lines of ink. Chance art is behind the changing configurations of Calder s mobiles and many other kinetic pieces, and is certainly behind the work of many abstract painters. We don t need to go as far as the action painting of the American abstract expressionists for an example. Just look how oil paints might blend within a single impressionist stroke of even a controlled painting, or how watercolors bleed out into the paper and into each other, quite freely, to define their medium. To one degree or another, art is often chancy.

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